Transparent conductive electrode, preparation method thereof and semiconductor device

Abstract

The invention discloses a transparent conductive electrode, a preparation method thereof and a semiconductor device applying the transparent conductive electrode, a metal wire layer is arranged on the surface of a transparent conductive layer or in at least part of the transparent conductive layer, and the metal wire layer comprises a plurality of metal wires, so that the surface resistance of the transparent conductive layer can be reduced, and the conductivity of the transparent conductive layer is improved. The conductivity of the whole formed by the transparent conducting layer and the metal wire layer is improved, and the transparency of the whole formed by the transparent conducting layer and the metal wire layer is kept to a great extent. Moreover, the transparent conductive layer is arranged to expose at least part of the metal wire layer, so that the transparent conductive layer is flat and not easy to break, particularly, the protective layer is arranged on the surface of the metal wire layer exposed on the transparent conductive layer, and the protective layer is made of metal oxide in the metal wire layer. The whole body formed by the transparent conductive layer and the metal wire layer also keeps good chemical / electrochemical inertness, and the stability of the transparent conductive electrode is improved.

Description

Technical Field

[0001] The present application relates to the field of semiconductor technology, and in particular to a transparent conductive electrode and a preparation method thereof, and a semiconductor device using the transparent conductive electrode. Background Art

[0002] Transparent conductive electrodes are an important component of various optoelectronic devices such as solar cells, liquid crystal displays, light-emitting diodes and touch screens. For example, transparent conductive electrodes are widely used in smart surfaces of automotive interiors and on-board display touch screens. With the development of intelligent automobiles, the demand for transparent conductive electrodes is also growing rapidly.

[0003] Currently, the most widely used transparent conductive electrode material is indium tin oxide (ITO). However, the square resistance of the ITO transparent conductive layer is relatively high, usually 100Ω / sq-200Ω / sq. If the ITO transparent conductive layer is thickened or doped with trace amounts of metals such as silver or combined with metal guide strips, the square resistance can be reduced to 10Ω / sq-30Ω / sq. However, at this time, the transmittance of the ITO transparent conductive layer will be greatly reduced, and the haze will also increase, sacrificing optical performance; and metals are usually easily corroded, resulting in reduced stability of the transparent conductive layer and the devices using it.

[0004] Therefore, how to make the transparent conductive electrode have good conductivity, light transmittance and stability has become a technical problem that needs to be solved urgently by those skilled in the art. Summary of the invention

[0005] To solve the above technical problems, the embodiments of the present application provide a transparent conductive electrode and a method for preparing the same, as well as a semiconductor device using the transparent conductive electrode, so that the transparent conductive electrode has good conductivity, light transmittance and stability.

[0006] To achieve the above objectives, the present application provides the following technical solutions:

[0007] A transparent conductive electrode, comprising:

[0008] a transparent substrate having a first surface;

[0009] A transparent conductive layer, located on the first surface of the transparent substrate;

[0010] a metal wire layer, located on a surface of the transparent conductive layer facing away from the transparent substrate, or embedded in at least a portion of the transparent conductive layer in a direction perpendicular to the first surface of the transparent substrate, the metal wire layer comprising a plurality of metal wires;

[0011] The transparent conductive layer exposes at least a portion of the metal wire layer, and a protective layer is disposed on the surface of the metal wire layer exposed by the transparent conductive layer. The material of the protective layer is the oxide of the metal in the metal wire layer.

[0012] Optionally, the plurality of metal lines include metal lines extending along a first direction and metal lines extending along a second direction, the first direction intersects with the second direction, and both the first direction and the second direction are parallel to the first surface of the transparent substrate.

[0013] Optionally, the transparent conductive layer exposing at least a portion of the metal wire layer comprises:

[0014] The transparent conductive layer exposes at least a portion of the surface of the metal wire in the metal wire layer that is away from the substrate;

[0015] The protection layer covers the surface of the metal wires in the metal wire layer exposed by the transparent conductive layer and facing away from the transparent substrate.

[0016] Optionally, the transparent conductive layer exposing at least a portion of the metal wire layer further comprises:

[0017] The transparent conductive layer also exposes at least part of the side surfaces of the metal wires in the metal wire layer;

[0018] The protection layer also covers the side surfaces of the metal wires in the metal wire layer that are exposed by the transparent conductive layer.

[0019] Optionally, the metal in the metal wire layer includes at least one of Al, Mg, Zn, Fe, Ti and Sn, and the protective layer correspondingly includes at least one of Al2O3, MgO, ZnO, Fe2O3, Fe3O4, TiO and SnO.

[0020] A method for preparing a transparent conductive electrode, comprising:

[0021] Providing a transparent substrate, wherein the transparent substrate has a first surface;

[0022] Forming a transparent conductive layer and a metal wire layer on the first surface of the transparent substrate, wherein the transparent conductive layer is located on the first surface of the transparent substrate, and the metal wire layer is located on the surface of the transparent conductive layer away from the transparent substrate, or is embedded in at least a portion of the transparent conductive layer in a direction perpendicular to the first surface of the transparent substrate, the metal wire layer includes a plurality of metal wires, and the transparent conductive layer exposes at least a portion of the metal wire layer;

[0023] The surface of the metal wire layer exposed by the transparent conductive layer is oxidized to form a protective layer on the surface of the metal wire layer exposed by the transparent conductive layer. The material of the protective layer is the oxide of the metal in the metal wire layer.

[0024] Optionally, forming a transparent conductive layer and a metal wire layer on the first surface of the transparent substrate specifically includes:

[0025] forming a transparent conductive layer on the first surface of the transparent substrate;

[0026] forming a metal wire layer on a surface of the transparent conductive layer facing away from the transparent substrate, wherein the metal wire layer comprises a plurality of metal wires, and the transparent conductive layer exposes the surface of the metal wires in the metal wire layer facing away from the transparent substrate and the side surfaces of the metal wires;

[0027] Performing oxidation treatment on the surface of the metal wire layer exposed by the transparent conductive layer to form a protective layer on the surface of the metal wire layer exposed by the transparent conductive layer comprises:

[0028] The surfaces of the metal wires in the metal wire layer exposed by the transparent conductive layer that are away from the transparent substrate and the sides of the metal wires are oxidized to form a protective layer on the surfaces of the metal wires in the metal wire layer exposed by the transparent conductive layer that are away from the transparent substrate and the sides of the metal wires.

[0029] Optionally, forming a transparent conductive layer and a metal wire layer on the first surface of the transparent substrate specifically includes:

[0030] forming a transparent conductive layer on the first surface of the transparent substrate;

[0031] forming a metal wire layer on a surface of the transparent conductive layer facing away from the transparent substrate, wherein the metal wire layer comprises a plurality of metal wires;

[0032] In a direction perpendicular to the first surface of the transparent substrate, pressing the metal wire layer into at least a portion of the transparent conductive layer, so that the transparent conductive layer at least exposes a surface of the metal wire in the metal wire layer that is away from the substrate;

[0033] Performing oxidation treatment on the surface of the metal wire layer exposed by the transparent conductive layer to form a protective layer on the surface of the metal wire layer exposed by the transparent conductive layer comprises:

[0034] The surface of the metal wire in the metal wire layer exposed by the transparent conductive layer which is away from the transparent substrate is subjected to oxidation treatment, and a protective layer is formed on the surface of the metal wire in the metal wire layer exposed by the transparent conductive layer which is away from the transparent substrate.

[0035] Optionally, forming a transparent conductive layer and a metal wire layer on the first surface of the transparent substrate specifically includes:

[0036] forming a metal wire layer on the first surface of the transparent substrate, wherein the metal wire layer comprises a plurality of metal wires;

[0037] forming a transparent conductive layer on other areas of the first surface of the transparent substrate except the area where the metal wire layer is located, so that the transparent conductive layer at least exposes a portion of the surface of the metal wire layer away from the transparent substrate;

[0038] Performing oxidation treatment on the surface of the metal wire layer exposed by the transparent conductive layer to form a protective layer on the surface of the metal wire layer exposed by the transparent conductive layer comprises:

[0039] The surface of the metal wire in the metal wire layer exposed by the transparent conductive layer which is away from the transparent substrate is subjected to oxidation treatment, and a protective layer is formed on the surface of the metal wire in the metal wire layer exposed by the transparent conductive layer which is away from the transparent substrate.

[0040] Optionally, the transparent conductive layer further exposes part of the side surfaces of the metal wires in the metal wire layer, and the surface of the metal wire layer exposed by the transparent conductive layer is oxidized, and the protective layer is formed on the surface of the metal wire layer exposed by the transparent conductive layer, and the like further comprises:

[0041] The side surfaces of the metal wires in the metal wire layer where the transparent conductive layer is exposed are subjected to oxidation treatment, so as to form a protective layer on the side surfaces of the metal wires in the metal wire layer where the transparent conductive layer is exposed.

[0042] Optionally, the process of performing oxidation treatment on the surface of the metal wire layer exposed by the transparent conductive layer includes:

[0043] In an air environment with an oxygen concentration of ≥20%, a relative humidity of ≤50% and a temperature of ≥20°C, the metal on the surface of the metal wire layer exposed by the transparent conductive layer reacts with oxygen for an oxidation time of ≥24h, thereby forming the protective layer on the surface of the metal wire layer exposed by the transparent conductive layer.

[0044] A semiconductor device comprises a transparent conductive electrode, wherein the transparent conductive electrode is any of the transparent conductive electrodes described above, or a transparent conductive electrode prepared by any of the methods described above.

[0045] Compared with the prior art, the above technical solution has the following advantages:

[0046] The transparent conductive electrode provided in the embodiment of the present application includes a transparent substrate and a transparent conductive layer and a metal wire layer located on the first surface of the transparent substrate. The transparent conductive layer is located on the first surface of the transparent substrate, and the metal wire layer is located on the surface of the transparent conductive layer away from the transparent substrate, or is embedded in at least a portion of the transparent conductive layer in a direction perpendicular to the first surface of the transparent substrate. The metal wire layer includes a plurality of metal wires, so that not only the transparent conductive layer can be conductive, but also each metal wire in the metal wire layer can be conductive, that is, the entire surface of the transparent conductive layer and the metal wire layer is conductive. Since the square resistance of the metal in the metal wire layer is smaller than the square resistance of the transparent conductive layer, the surface resistance of the entire surface of the transparent conductive layer and the metal wire layer is reduced, and the conductivity of the entire surface of the transparent conductive layer and the metal wire layer is improved. At the same time, since the hollow area between the metal wires in the metal wire layer is still a transparent conductive layer, the transparency of the entire surface of the transparent conductive layer and the metal wire layer is maintained to a large extent. In other words, the transparent conductive electrode provided in the embodiment of the present application takes into account both good conductivity and light transmittance.

[0047] Furthermore, considering that the transparent conductive layer (such as the ITO layer) is brittle, in the transparent conductive electrode provided in the embodiment of the present application, the transparent conductive layer is arranged to expose at least a portion of the metal wire layer, so that the transparent conductive layer is relatively flat and will not be broken due to the arrangement of the metal wire layer, thereby improving the stability of the transparent conductive electrode.

[0048] At the same time, in the transparent conductive electrode provided by the embodiment of the present application, a protective layer is provided on the surface of the metal wire layer exposed in the transparent conductive layer, so that the overall surface composed of the transparent conductive layer and the metal wire layer remains chemically / electrochemically inert and is not easily corroded by chemical substances, further improving the stability of the transparent conductive electrode. In particular, the material of the protective layer is the oxide of the metal in the metal wire layer, so that the formation process of the protective layer is simple, low-cost, green and pollution-free, and the transparent conductive electrode can withstand damage or cutting, because after damage or cutting, the exposed surface of the metal wire layer can still spontaneously form a protective layer with oxygen in the air, further improving the stability of the transparent conductive electrode. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0050] Figure 1 A schematic diagram of the overall structure of a transparent conductive electrode provided in an embodiment of the present application;

[0051] Figure 2 A schematic cross-sectional view of a transparent conductive electrode provided in an embodiment of the present application;

[0052] Figure 3 A schematic diagram of the overall structure of another transparent conductive electrode provided in an embodiment of the present application;

[0053] Figure 4 A schematic cross-sectional view of another transparent conductive electrode provided in an embodiment of the present application;

[0054] Figure 5 A schematic cross-sectional view of another transparent conductive electrode provided in an embodiment of the present application;

[0055] Figure 6 A schematic cross-sectional view of another transparent conductive electrode provided in an embodiment of the present application;

[0056] Figure 7 A schematic cross-sectional view of another transparent conductive electrode provided in an embodiment of the present application;

[0057] Figure 8 A schematic cross-sectional view of another transparent conductive electrode provided in an embodiment of the present application;

[0058] Figure 9a-9b A schematic diagram of each process step in a method for preparing a transparent conductive electrode provided in an embodiment of the present application;

[0059] Figure 10a-Figure 10d A schematic diagram of each process step in another method for preparing a transparent conductive electrode provided in an embodiment of the present application;

[0060] Figure 11a-Figure 11b A schematic diagram of each process step in another method for preparing a transparent conductive electrode provided in an embodiment of the present application;

[0061] Fig.12 A schematic diagram of the structure of a semiconductor device (electrochromic device) provided in an embodiment of the present application. DETAILED DESCRIPTION

[0062] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0063] As described in the background technology section, how to make a transparent conductive electrode have good conductivity, light transmittance and stability has become a technical problem that needs to be solved urgently by those skilled in the art.

[0064] In view of this, the present application provides a transparent conductive electrode. Figure 1 The overall structure diagram of a transparent conductive electrode provided in an embodiment of the present application is shown. Figure 2 A cross-sectional schematic diagram of a transparent conductive electrode provided in an embodiment of the present application is shown, combined with Figure 1 and Figure 2 As shown, the transparent conductive electrode comprises:

[0065] A transparent substrate 10, wherein the transparent substrate 10 has a first surface S1;

[0066] The transparent conductive layer 20 is located on the first surface S1 of the transparent substrate 10;

[0067] The metal wire layer 30 is located on the surface of the transparent conductive layer 20 facing away from the transparent substrate 10. The metal wire layer 30 includes a plurality of metal wires (eg Figure 1 M1 and M2).

[0068] In this embodiment, if Figure 2 As shown, the surface of the metal wire in the metal wire layer 30 facing away from the substrate 10 and the side of the metal wire are exposed on the surface of the transparent conductive layer 20 facing away from the transparent substrate 10. Accordingly, a protective layer 40 is arranged on the surface of the metal wire in the metal wire layer 30 facing away from the substrate 10 and on the side of the metal wire, and the material of the protective layer 40 is the oxide of the metal in the metal wire layer 30.

[0069] Optionally, the transparent substrate 10 may be a transparent glass substrate, a PET (polyethylene terephthalate) substrate, a PC (polycarbonate) substrate, a PEN (polyethylene naphthalate) substrate, a PI (polyimide) substrate, or the like.

[0070] Optionally, the transparent conductive layer 20 may be an ITO (indium tin oxide) layer, a FTO (fluorine-doped tin dioxide) layer, an AZO (aluminum zinc oxide) layer, a PSS-PEDOT (poly (3,4-ethylenedioxythiophene) / polystyrene sulfonate) layer, or a carbon nanotube.

[0071] In the transparent conductive electrode provided in this embodiment, not only the transparent conductive layer 20 can be conductive, but also the metal wires in the metal wire layer 30 can be conductive, that is, the entire surface of the transparent conductive layer 20 and the metal wire layer 30 is conductive, and because the square resistance of the metal in the metal wire layer 30 is smaller than the square resistance of the transparent conductive layer 20, the surface resistance of the entire surface of the transparent conductive layer 20 and the metal wire layer 30 is reduced, and the conductivity of the entire surface of the transparent conductive layer 20 and the metal wire layer 30 is improved. At the same time, because the hollow area between the metal wires in the metal wire layer 30 is still the transparent conductive layer 20, the entire surface of the transparent conductive layer 20 and the metal wire layer 30 maintains good transparency to a large extent. In other words, the transparent conductive electrode provided in this embodiment takes into account both good conductivity and light transmittance.

[0072] Optional, such as Figure 1 As shown, the plurality of metal wires in the metal wire layer 30 include metal wires M1 extending along a first direction X and metal wires M2 extending along a second direction Y. The first direction X intersects with the second direction Y, and the first direction X and the second direction Y are both parallel to the first surface S1 of the transparent substrate 10. For example, the first direction X and the second direction Y are perpendicular. Of course, the first direction X and the second direction Y may only intersect but not be perpendicular, so that the plurality of metal wires in the metal wire layer 30 form a grid-like arrangement, which is beneficial to further reduce the surface resistance of the whole composed of the transparent conductive layer 20 and the metal wire layer 30, and improve the conductivity of the whole composed of the transparent conductive layer 20 and the metal wire layer 30.

[0073] However, the present application does not limit the arrangement shape of the metal wires in the metal wire layer 30. The grid pattern formed by the metal wires in the metal wire layer 30 can also be a triangle, a quadrilateral, a pentagon, a hexagon, an octagon, a circle or an irregular shape, etc. The grid pattern can be set to different shapes according to actual needs to meet different requirements on the optical and electrical properties of the transparent conductive electrode. In addition, the metal wires in the metal wire layer 30 can also be arranged in parallel along the same direction.

[0074] For example, Figure 3 FIG. 2 shows a schematic diagram of the overall structure of another transparent conductive electrode provided in an embodiment of the present application. Figure 3 As shown, the metal wire layer 30 includes not only metal wires M1 extending along the first direction X and metal wires M2 extending along the second direction Y, but also metal wires M3 extending along the third direction J and metal wires M4 extending along the fourth direction K. These four metal wires form a grid arrangement in a cross shape within a square grid.

[0075] Optionally, the grid pattern formed by the metal wires in the metal wire layer 30 is evenly distributed. It can be understood that the more evenly the grid pattern formed by the metal wires in the metal wire layer 30 is distributed, the more evenly the conductivity of the metal wire layer 30 is, and the more evenly the conductivity of the whole composed of the transparent conductive layer 20 and the metal wire layer 30 is. Of course, the grid pattern formed by the metal wires in the metal wire layer 30 can also be unevenly distributed, which can be determined according to the actual requirements for the optical and electrical properties of the transparent conductive electrode.

[0076] Optionally, the shapes and sizes of the grid patterns formed by the metal wires in the metal wire layer 30 are the same, so that the more uniform the conductivity of the metal wire layer 30 is, the more uniform the conductivity of the entire transparent conductive layer 20 and the metal wire layer 30 is. Of course, the shapes and sizes of the grid patterns formed by the metal wires in the metal wire layer 30 may also be different, depending on the actual requirements for the optical and electrical properties of the transparent conductive electrode.

[0077] It can be understood that the denser the distribution of the grid pattern formed by the metal wires in the metal wire layer 30, the higher the conductivity of the metal wire layer 30, and the higher the conductivity of the whole composed of the transparent conductive layer 20 and the metal wire layer 30, but the transparency of the whole composed of the transparent conductive layer 20 and the metal wire layer 30 is relatively weakened. Therefore, the density of the grid pattern formed by the metal wires in the metal wire layer 30 can be set according to the actual requirements for the optical and electrical properties of the transparent conductive electrode.

[0078] Considering that the transparent conductive layer 20 (such as the ITO layer) is brittle, in the transparent conductive electrode provided in this embodiment, a metal wire layer 30 is arranged on the surface of the transparent conductive layer 20 away from the transparent substrate 10, so that the transparent conductive layer 20 is very flat and will not be broken due to the arrangement of the metal wire layer 30, thereby improving the stability of the transparent conductive electrode.

[0079] Furthermore, in the transparent conductive electrode provided in the present embodiment, a protective layer 40 is provided on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 and on the side surfaces of the metal wires, so that the overall surface composed of the transparent conductive layer 20 and the metal wire layer 30 remains chemically / electrochemically inert and is not easily corroded by chemical substances, thereby further improving the stability of the transparent conductive electrode.

[0080] In this embodiment, the material of the protective layer 40 is the oxide of the metal in the metal wire layer 30, that is, the metal in the metal wire layer 30 can be a metal or alloy that spontaneously forms a dense protective layer with oxygen in the air. Accordingly, the protective layer 40 can be a metal oxide layer spontaneously formed by the metal in the metal wire layer 30 and oxygen.

[0081] Optionally, the metal in the metal wire layer 30 may include at least one of Al, Mg, Zn, Fe, Ti and Sn, and the protective layer 40 correspondingly includes at least one of Al2O3, MgO, ZnO, Fe2O3, Fe3O4, TiO and SnO. Specifically, when the metal in the metal wire layer 30 is Al, the corresponding protective layer 40 is a dense Al2O3 layer; when the metal in the metal wire layer 30 is Mg, the corresponding protective layer 40 is a dense MgO layer; when the metal in the metal wire layer 30 is Zn, the corresponding protective layer 40 is a dense ZnO layer; when the metal in the metal wire layer 30 is Fe, the corresponding protective layer 40 is a dense Fe2O3 layer, or a Fe3O4 layer, or a mixed layer of Fe2O3 and Fe3O4; when the metal in the metal wire layer 30 is Ti, the corresponding protective layer 40 is a dense TiO layer; when the metal in the metal wire layer 30 is Sn, the corresponding protective layer 40 is a dense SnO layer; these dense metal oxide layers are formed on the metal surface, have high density and excellent chemical stability, and can be used to protect the metal from corrosion and oxidation.

[0082] In the actual process, after forming the transparent conductive layer 20 and the metal wire layer 30 on the first surface S1 of the transparent substrate 10, the obtained structure is placed in a certain environment, and the oxygen concentration, relative humidity, oxidation temperature and oxidation time in the environment are adjusted, so that a dense metal oxide protective layer 40 can be spontaneously formed on the surface of the metal wire layer 30 exposed by the transparent conductive layer 20. This process is simple, green and pollution-free, and has low cost. It should be noted that when the surface of the metal wire layer 30 exposed by the transparent conductive layer 20 is oxidized, gaseous reactants other than air components should not be introduced to avoid damaging the protective layer 40.

[0083] Therefore, the transparent conductive electrode provided in this embodiment can also withstand damage or cutting, because the exposed surface of the metal wire layer 30 after damage or cutting can still spontaneously form a protective layer with oxygen in the air, further improving the stability of the transparent conductive electrode.

[0084] It should be noted that the protective layer 40 disposed on the surface of the metal wire layer 30 exposed by the transparent conductive layer 20 is a dense metal oxide layer and is therefore inert to chemical substances, but the protective layer 40 is not necessarily an insulating layer. In other words, the protective layer 40 can be a good conductor of electrons, such as a Fe3O4 layer, a TiO layer, and a ZnO layer, or a poor conductor of electrons, such as an Al2O3 layer or a MgO layer, depending on the application requirements.

[0085] Figure 4 and Figure 5 Schematic cross-sectional views of two other transparent conductive electrodes provided in the embodiments of the present application are shown respectively. Figure 2The transparent conductive electrode shown is the same as Figure 4 and Figure 5 In the transparent conductive electrode shown, the transparent conductive layer 20 is also located on the first surface S1 of the transparent substrate 10. Figure 2 The transparent conductive electrode shown is different in that Figure 4 and Figure 5 In the transparent conductive electrode shown, the metal wire layer 30 is embedded in a portion of the transparent conductive layer 20 on the first surface S1 perpendicular to the transparent substrate 10. Figure 4 In the transparent conductive electrode shown, part of the metal wire layer 30 is embedded in the transparent conductive layer 20 on the first surface S1 perpendicular to the transparent substrate 10, and the transparent conductive layer 20 exposes the surface of the metal wires in the metal wire layer 30 away from the substrate 10 and part of the side surfaces of the metal wires. Accordingly, a protective layer 40 is provided on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20 away from the substrate 10 and part of the side surfaces of the metal wires. Figure 5 In the transparent conductive electrode shown, all metal wire layers 30 are embedded in the transparent conductive layer 20 on the first surface S1 perpendicular to the transparent substrate 10, and the transparent conductive layer 20 exposes the surface of the metal wires in the metal wire layer 30 facing away from the substrate 10. Accordingly, a protective layer 40 is arranged on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the substrate 10.

[0086] Figure 6 and Figure 7 Schematic cross-sectional views of two transparent conductive electrodes provided in the embodiments of the present application are shown respectively. Figure 2 The transparent conductive electrode shown is different in that Figure 6 and Figure 7 In the transparent conductive electrode shown, the transparent conductive layer 20 and the metal wire layer 30 are both located on the first surface S1 of the transparent substrate 10, and the metal wire layer 30 is embedded in the entire transparent conductive layer 20 perpendicular to the first surface S1 of the transparent substrate 10, or in other words, the metal wire layer 30 penetrates the transparent conductive layer 20 and contacts the first surface S1 of the transparent substrate 10. Figure 6 In the transparent conductive electrode shown, all metal wire layers 30 are embedded in the transparent conductive layer 20 on the first surface S1 perpendicular to the transparent substrate 10, and the transparent conductive layer 20 exposes the surface of the metal wires in the metal wire layer 30 away from the substrate 10. Accordingly, a protective layer 40 is provided on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20 away from the substrate 10. Figure 7In the transparent conductive electrode shown, part of the metal wire layer 30 is embedded in the transparent conductive layer 20 on the first surface S1 perpendicular to the transparent substrate 10, and the transparent conductive layer 20 exposes the surface of the metal wires in the metal wire layer 30 facing away from the substrate 10 and part of the side surfaces of the metal wires. Accordingly, a protective layer 40 is provided on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the substrate 10 and part of the side surfaces of the metal wires.

[0087] Figure 8 A cross-sectional schematic diagram of another transparent conductive electrode provided in an embodiment of the present application is shown. Figure 2 The transparent conductive electrode shown is different in that Figure 8 In the transparent conductive electrode shown in FIG. 1 , the transparent conductive layer 20 and the metal wire layer 30 are both located on the first surface S1 of the transparent substrate 10, and the metal wire layer 30 is embedded in the entire transparent conductive layer 20 perpendicular to the first surface S1 of the transparent substrate 10, or in other words, the metal wire layer 30 penetrates the transparent conductive layer 20 and contacts the first surface S1 of the transparent substrate 10, and Figure 8 In the transparent conductive electrode shown, the transparent conductive layer 20 covers the portion of the surface of the metal wire layer 30 where the metal wires are away from the transparent substrate 10, and exposes the portion of the surface of the metal wire layer 30 where the metal wires are away from the transparent substrate 10. Accordingly, a protective layer 40 is provided on the portion of the surface of the metal wire layer 30 where the metal wires are away from the transparent substrate 10 that is exposed by the transparent conductive layer 20.

[0088] By comparing the above-mentioned transparent conductive electrodes provided in the embodiments of the present application, it can be seen that: Figure 2 In the transparent conductive electrode shown, the metal wire layer 30 is located on the surface of the transparent conductive layer 20 facing away from the transparent substrate 10, which is recorded as the first type of transparent conductive electrode. Figure 4-Figure 8 In the transparent conductive electrode shown, the metal wire layer 30 is embedded in at least a portion of the transparent conductive layer 30 in a direction perpendicular to the first surface S1 of the transparent substrate 10, which is recorded as a second type of transparent conductive electrode. It can be understood that the second type of transparent conductive electrode can be thinner than the first type of transparent conductive electrode.

[0089] Table 1 below lists the performance parameters of the first type of transparent conductive electrode A, the second type of transparent conductive electrode B, and the existing transparent conductive electrode C in which only a transparent conductive layer is provided on a transparent substrate. It can be seen that, compared with the existing transparent conductive electrode C, the square resistance of the first type of transparent conductive electrode A and the second type of transparent conductive electrode B provided in the embodiment of the present application is greatly reduced, and the haze and visible light transmittance remain basically unchanged. In addition, the square resistance of the second type of transparent conductive electrode B is reduced more than that of the first type of transparent conductive electrode A by embedding the metal wire layer 30 in at least a portion of the transparent conductive layer 30 in a direction perpendicular to the first surface S1 of the transparent substrate 10.

[0090] Table 1 Performance parameters of the first type transparent conductive electrode A, the second type transparent conductive electrode B and the existing transparent conductive electrode C

[0091]

[0092] Among them, electrode A is Figure 2 The transparent conductive electrode shown, electrode B is Figure 8 The transparent conductive electrodes shown in the figure, and in the three electrodes A, B, and C, the transparent substrate 10 is a PEN substrate with a size of 10cm*10cm*120um, the transparent conductive layer 20 is an ITO layer with a thickness of 120nm, and in the A electrode and the B electrode, the metal in the metal wire layer is aluminum with a thickness of 100nm, the metal wire width is 10um, and the metal wire arrangement is as follows Figure 1 As shown, the interval between the metal wires is 100 um, and the surface of the exposed metal wire layer of the transparent conductive layer is oxidized by placing it in dry air for 24 hours at a temperature of 20°C.

[0093] It should be noted that for Figure 2 In the transparent conductive electrode shown, since the metal wire layer 30 is located on the surface of the transparent conductive layer 20 away from the transparent substrate 10, the transparent conductive layer 20 can be first formed on the first surface S1 of the transparent substrate 10, and then the metal wire layer 30 is formed on the surface of the transparent conductive layer 20 away from the transparent substrate 10, and then the protective layer 40 is formed on the surface of the metal wires in the metal wire layer 30 away from the transparent substrate 10 and on the side of the metal wires. It can be understood that this preparation method makes the transparent conductive layer 20 very flat, so that the stability of the transparent conductive electrode is very good.

[0094] for Figure 4-Figure 7 In the transparent conductive electrode shown, since the metal wire layer 30 is embedded in at least a portion of the transparent conductive layer 20 in a direction perpendicular to the first surface S1 of the transparent substrate 10, and the transparent conductive layer 20 at least exposes the surface of the metal wire layer 30 away from the transparent substrate 10, the transparent conductive layer 20 can be first formed on the first surface S1 of the transparent substrate 10, and then the transparent conductive layer 20 is etched to form grooves, and then metal wires are formed in the grooves to form the metal wire layer 30. However, since the transparent conductive layer 20 (such as the ITO layer) is relatively brittle, etching the transparent conductive layer 20 is likely to cause the transparent conductive layer 20 to break.

[0095] Based on this, preferably, metal wires can be formed on the first surface S1 of the transparent substrate 10 to form the metal wire layer 30, and then the transparent conductive layer 20 can be formed in other areas of the first surface S1 of the transparent substrate 10 except the area where the metal wire layer 30 is located, that is, the transparent conductive layer 20 is formed in the space area between the metal wires in the metal wire layer 30, and the thickness of the transparent conductive layer 20 can be greater than, less than or equal to the thickness of the metal wire layer 30, and then, the protective layer 40 is set on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20. It can be understood that this preparation method also makes the transparent conductive layer 20 relatively flat, so that the stability of the transparent conductive electrode is better.

[0096] In another preferred embodiment, a transparent conductive layer 20 may be first formed on the first surface S1 of the transparent substrate 10, and then a metal wire layer 30 may be formed on the surface of the transparent conductive layer 20 facing away from the transparent substrate 10, and then, in a direction perpendicular to the first surface S1 of the transparent substrate 10, the metal wire layer 30 may be fully or partially pressed into at least a portion of the transparent conductive layer 20, so that the transparent conductive layer 20 at least exposes the surface of the metal wires in the metal wire layer 30 facing away from the transparent substrate 10, and then, a protective layer 40 may be provided on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20. It is understandable that this preparation method also makes the transparent conductive layer 20 relatively flat, thereby making the stability of the transparent conductive electrode better.

[0097] for Figure 8 In the transparent conductive electrode shown, since the transparent conductive layer 20 and the metal wire layer 30 are both located on the first surface S1 of the transparent substrate 10, and the transparent conductive layer 20 covers the partial surface of the metal wire layer 30 where the metal wires are away from the transparent substrate 10, and exposes the partial surface of the metal wire layer 30 where the metal wires are away from the transparent substrate 10, therefore, metal wires can be first formed on the first surface S1 of the transparent substrate 10 to form the metal wire layer 30, and then the transparent conductive layer 20 can be formed in the space area between the metal wires in the metal wire layer 30. At this time, the thickness of the transparent conductive layer 20 can be greater than the thickness of the metal wire layer 30, and the transparent conductive layer 20 can cover the partial surface of the metal wire layer 30 where the metal wires are away from the transparent substrate 10, and then, a protective layer 40 is provided on the surface of the metal wire layer 30 where the metal wires are exposed in the transparent conductive layer 20 where the metal wires are away from the transparent substrate 10. It is understandable that this preparation method makes the thickness fluctuation of the transparent conductive layer 20 smaller, that is, the transparent conductive layer 20 is relatively flat and will not be broken due to the arrangement of the metal wire layer 30, thereby making the transparent conductive electrode more stable.

[0098] It is understandable that, considering the brittleness of the transparent conductive layer (such as the ITO layer), the above-mentioned preparation methods make the transparent conductive layer 20 relatively flat while inevitably exposing at least a portion of the metal wire layer 30 of the transparent conductive layer 20 .

[0099] In summary, the transparent conductive electrode provided in the embodiment of the present application includes a transparent substrate 10 and a transparent conductive layer 20 and a metal wire layer 30 located on a first surface S1 of the transparent substrate 10. The transparent conductive layer 20 is located on the first surface S1 of the transparent substrate 10, and the metal wire layer 30 is located on the surface of the transparent conductive layer 20 away from the transparent substrate 10 (such as Figure 2 Alternatively, the transparent conductive layer 20 may be embedded in at least a portion of the transparent conductive layer 20 in a direction perpendicular to the first surface S1 of the transparent substrate 10 (as shown in FIG. Figure 4-Figure 8 As shown in the figure, the metal wire layer 30 includes a plurality of metal wires, so that not only the transparent conductive layer 20 can be conductive, but also each metal wire in the metal wire layer 30 can be conductive, that is, the entire surface of the transparent conductive layer 20 and the metal wire layer 30 is conductive. Since the square resistance of the metal in the metal wire layer 30 is smaller than that of the transparent conductive layer 20, the surface resistance of the entire surface of the transparent conductive layer 20 and the metal wire layer 30 is reduced, and the conductivity of the entire surface of the transparent conductive layer 20 and the metal wire layer 30 is improved. At the same time, since the hollow area between each metal wire in the metal wire layer 30 is still a transparent conductive layer, the entire surface of the transparent conductive layer 20 and the metal wire layer 30 maintains good transparency to a large extent. In other words, the transparent conductive electrode provided in the embodiment of the present application takes into account both good conductivity and light transmittance.

[0100] Furthermore, considering that the transparent conductive layer 20 (such as the ITO layer) is brittle, in the transparent conductive electrode provided in the embodiment of the present application, the transparent conductive layer 20 is arranged to expose at least a portion of the metal wire layer 30, so that the transparent conductive layer 20 is relatively flat and will not be broken due to the arrangement of the metal wire layer 30, thereby improving the stability of the transparent conductive electrode.

[0101] At the same time, in the transparent conductive electrode provided by the embodiment of the present application, a protective layer 40 is provided on the surface of the metal wire layer 30 exposed in the transparent conductive layer 20, so that the overall surface composed of the transparent conductive layer 20 and the metal wire layer 30 remains chemically / electrochemically inert and is not easily corroded by chemical substances, further improving the stability of the transparent conductive electrode. In particular, the material of the protective layer 40 is the oxide of the metal in the metal wire layer 30, so that the formation process of the protective layer is simple, low in cost, green and pollution-free, and the transparent conductive electrode can withstand damage or cutting, because after damage or cutting, the exposed surface of the metal wire layer can still spontaneously form a protective layer with oxygen in the air, further improving the stability of the transparent conductive electrode.

[0102] On this basis, optionally, the transparent conductive layer 20 exposes at least a portion of the metal wire layer 30, including the transparent conductive layer 20 exposing at least a portion of the surface of the metal wire in the metal wire layer 30 away from the transparent substrate 10, specifically as follows: Figure 2 , Figure 4-Figure 8As shown, the transparent conductive layer 20 exposes at least a portion of the surface of the metal wire layer 30 away from the transparent substrate 10 . At this time, the protective layer 40 covers the exposed surface of the metal wire layer 30 of the transparent conductive layer 20 away from the transparent substrate 10 .

[0103] Further optionally, the transparent conductive layer 20 exposing at least a portion of the metal wire layer 30 further includes the transparent conductive layer 20 also exposing at least a portion of the side surfaces of the metal wires in the metal wire layer 30, specifically as follows: Figure 2 , Figure 4 and Figure 7 As shown, the transparent conductive layer 20 exposes the surface of the metal wire layer 30 where the metal wires are away from the transparent substrate 10 and at least part of the side surfaces of the metal wires. At this time, the protective layer 40 also covers the side surfaces of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20, that is, the protective layer 40 covers the surface of the metal wire layer 30 where the metal wires are away from the transparent substrate 10 and the side surfaces of the metal wires.

[0104] It should be noted that, since the metal wire layer 30 is located on the surface of the transparent conductive layer 20 or embedded in at least a portion of the transparent conductive layer 20, the metal wire layer 30 and the transparent conductive layer 20 are in close contact, so that current can flow freely between the two. In addition, since the exposed surface of the metal wire layer 30 of the transparent conductive layer 20 spontaneously forms a dense metal oxide protective layer 40 with oxygen in the air, the exposed surface of the metal wire layer 30 of the transparent conductive layer 20 is also in close contact with the protective layer 40 to protect the exposed surface of the metal wire layer 30 of the transparent conductive layer 20 from corrosion.

[0105] Optionally, the thickness of the transparent substrate 10 can be 1μm-1000μm, including endpoint values; the thickness of the transparent conductive layer 20 can be 0.01μm-10μm, including endpoint values; the thickness of the metal wire layer 30 can be 0.1μm-100μm, including endpoint values, and the line width of the metal wire in the metal wire layer 30 can be 1μm-100μm, including endpoint values.

[0106] Accordingly, the present invention also provides a method for preparing a transparent conductive electrode, referring to Figure 2 , Figure 4-Figure 8 As shown, the preparation method comprises:

[0107] S100: providing a transparent substrate 10, wherein the transparent substrate 10 has a first surface S1;

[0108] S200: forming a transparent conductive layer 20 and a metal wire layer 30 on the first surface S1 of the transparent substrate 10, wherein the transparent conductive layer 20 is located on the first surface of the transparent substrate 10, and the metal wire layer 30 is located on the surface of the transparent conductive layer 20 away from the transparent substrate 10 (eg Figure 2Alternatively, the transparent conductive layer 20 may be embedded in at least a portion of the transparent conductive layer 20 in a direction perpendicular to the first surface S1 of the transparent substrate 10 (as shown in FIG. Figure 4-Figure 8 As shown), the metal line layer 30 includes a plurality of metal lines (such as Figure 1 The metal wires M1-M2 in Figure 3 The transparent conductive layer 20 exposes at least a portion of the metal wire layer 30;

[0109] S300 : performing oxidation treatment on the surface of the metal wire layer 30 exposed in the transparent conductive layer 20 , and forming a protective layer 40 on the surface of the metal wire layer 30 exposed in the transparent conductive layer 20 . The material of the protective layer 40 is the oxide of the metal in the metal wire layer 30 .

[0110] Optionally, in step S200, forming the transparent conductive layer 20 and the metal wire layer 30 on the first surface S1 of the transparent substrate 10 specifically includes:

[0111] S210: Figure 9a As shown, a transparent conductive layer 20 is formed on the first surface S1 of the transparent substrate 10;

[0112] S211: Figure 9b As shown, a metal wire layer 30 is formed on the surface of the transparent conductive layer 20 facing away from the transparent substrate 10 , and the metal wire layer 30 includes a plurality of metal wires. The transparent conductive layer 20 exposes the surface of the metal wire layer 30 facing away from the transparent substrate 10 and the side surfaces of the metal wires.

[0113] Then, in step S300, the surface of the metal wire layer 30 exposed by the transparent conductive layer 20 is oxidized to form a protective layer 40 on the surface of the metal wire layer 30 exposed by the transparent conductive layer 20, which includes:

[0114] S310: Figure 2 As shown, the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20 away from the transparent substrate 10 and the side of the metal wires are oxidized, and a protective layer 40 is formed on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20 away from the transparent substrate 10 and the side of the metal wires. Figure 2 The transparent conductive electrode shown.

[0115] Alternatively, in step S200, forming the transparent conductive layer 20 and the metal wire layer 30 on the first surface S1 of the transparent substrate 10 specifically includes:

[0116] S220: Figure 9a As shown, a transparent conductive layer 20 is formed on the first surface S1 of the transparent substrate 10;

[0117] S221: Figure 9bAs shown, a metal wire layer 30 is formed on the surface of the transparent conductive layer 20 facing away from the transparent substrate 10, and the metal wire layer 30 includes a plurality of metal wires;

[0118] S222: Figure 10a-Figure 10d As shown, in a direction perpendicular to the first surface S1 of the transparent substrate 10 , the metal wire layer 30 is pressed into at least a portion of the transparent conductive layer 20 , so that the transparent conductive layer 20 at least exposes the surface of the metal wires in the metal wire layer 30 facing away from the substrate.

[0119] Specifically, Fig.10a As shown, the metal wire layer 30 is pressed into a portion of the transparent conductive layer 20, and the transparent conductive layer 20 exposes the surface of the metal wires in the metal wire layer 30 away from the transparent substrate 10, and exposes a portion of the side surfaces of the metal wires in the metal wire layer 30;

[0120] like Fig.10b As shown, the metal wire layer 30 is pressed into a portion of the transparent conductive layer 20, and the transparent conductive layer 20 exposes the surface of the metal wire layer 30 where the metal wires are away from the transparent substrate 10;

[0121] like Fig.10c As shown, the metal wire layer 30 is pressed into the entire transparent conductive layer 20, and the transparent conductive layer 20 exposes the surface of the metal wire layer 30 where the metal wires are away from the transparent substrate 10;

[0122] exist Fig.10d As shown, the metal wire layer 30 is pressed into the entire transparent conductive layer 20 , and the transparent conductive layer 20 exposes the surface of the metal wires in the metal wire layer 30 facing away from the transparent substrate 10 , and exposes part of the side surfaces of the metal wires in the metal wire layer 30 .

[0123] On this basis, in step S300, the surface of the metal wire layer 30 exposed by the transparent conductive layer 20 is oxidized to form a protective layer 40 on the surface of the metal wire layer 30 exposed by the transparent conductive layer 20, including:

[0124] S320 : performing oxidation treatment on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 , and forming a protective layer 40 on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 .

[0125] Specifically, the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 is oxidized, and a protective layer 40 is formed on the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10, thereby obtaining Figure 5 The transparent conductive electrode shown.

[0126] Similarly, the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 is oxidized, and a protective layer 40 is formed on the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10, thereby obtaining Figure 6 The transparent conductive electrode shown.

[0127] If the transparent conductive layer 20 also exposes part of the side surface of the metal wire in the metal wire layer 30, such as Fig.10a and Fig.10d As shown, the surface of the metal wire layer 30 exposed by the transparent conductive layer 20 is oxidized, and the protective layer 40 is formed on the surface of the metal wire layer 30 exposed by the transparent conductive layer 20, and the method further includes:

[0128] S321: performing oxidation treatment on the side surfaces of the metal wires in the metal wire layer 30 exposed in the transparent conductive layer 20, and forming a protective layer 40 on the side surfaces of the metal wires in the metal wire layer 30 exposed in the transparent conductive layer 20, that is, performing oxidation treatment on the surface of the metal wires in the metal wire layer 30 exposed in the transparent conductive layer 20 which are away from the transparent substrate 10 and the side surfaces of the metal wires, and forming a protective layer 40 on the surface of the metal wires in the metal wire layer 30 exposed in the transparent conductive layer 20 which are away from the transparent substrate 10 and the side surfaces of the metal wires.

[0129] Specifically, the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 and the side of the metal wire are oxidized, and a protective layer 40 is formed on the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 and the side of the metal wire, so as to obtain Figure 4 The transparent conductive electrode shown.

[0130] The surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 and the side of the metal wire are oxidized, and a protective layer 40 is formed on the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 and the side of the metal wire, thereby obtaining Figure 7 The transparent conductive electrode shown.

[0131] Alternatively, in step S200, forming the transparent conductive layer 20 and the metal wire layer 30 on the first surface S1 of the transparent substrate 10 specifically includes:

[0132] S230: Fig.11a As shown, a metal wire layer 30 is formed on the first surface S1 of the transparent substrate 10, and the metal wire layer 30 includes a plurality of metal wires;

[0133] S231: Figure 10c-10d , Fig.11bAs shown, a transparent conductive layer 20 is formed on the first surface S1 of the transparent substrate 10 except the area where the metal wire layer 30 is located, and the transparent conductive layer 20 at least exposes a portion of the surface of the metal wire layer 30 where the metal wires are away from the transparent substrate 10 .

[0134] Specifically, Fig.10c As shown, after the transparent conductive layer 20 is formed on the first surface S1 of the transparent substrate 10 except the area where the metal wire layer 30 is located, the transparent conductive layer 20 exposes the surface of the metal wire layer 30 away from the transparent substrate 10 .

[0135] like Fig.10d As shown, after the transparent conductive layer 20 is formed on the first surface S1 of the transparent substrate 10 except the area where the metal wire layer 30 is located, the transparent conductive layer 20 exposes the surface of the metal wires in the metal wire layer 30 away from the transparent substrate 10 and exposes part of the side surfaces of the metal wires in the metal wire layer 30.

[0136] like Fig.11b As shown, after a transparent conductive layer 20 is formed in other areas of the first surface S1 of the transparent substrate 10 except the area where the metal wire layer 30 is located, the transparent conductive layer 20 covers the portion of the surface where the metal wires in the metal wire layer 30 are away from the transparent substrate 10, and exposes the portion of the surface where the metal wires in the metal wire layer 30 are away from the transparent substrate 10.

[0137] On this basis, in step S300, the surface of the metal wire layer 30 exposed by the transparent conductive layer 20 is oxidized to form a protective layer 40 on the surface of the metal wire layer 30 exposed by the transparent conductive layer 20, including:

[0138] S320 : performing oxidation treatment on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 , and forming a protective layer 40 on the surface of the metal wires in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 .

[0139] Specifically, the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 is oxidized, and a protective layer 40 is formed on the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10, thereby obtaining Figure 6 The transparent conductive electrode shown.

[0140] The surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 is oxidized, and a protective layer 40 is formed on the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10, thereby obtaining Figure 8 The transparent conductive electrode shown.

[0141] If the transparent conductive layer 20 also exposes part of the side surface of the metal wire in the metal wire layer 30, such as Fig.10d As shown, the surface of the metal wire layer 30 exposed by the transparent conductive layer 20 is oxidized, and the protective layer 40 is formed on the surface of the metal wire layer 30 exposed by the transparent conductive layer 20, and the method further includes:

[0142] S321: performing oxidation treatment on the side surfaces of the metal wires in the metal wire layer 30 exposed in the transparent conductive layer 20, and forming a protective layer 40 on the side surfaces of the metal wires in the metal wire layer 30 exposed in the transparent conductive layer 20, that is, performing oxidation treatment on the surface of the metal wires in the metal wire layer 30 exposed in the transparent conductive layer 20 which are away from the transparent substrate 10 and the side surfaces of the metal wires, and forming a protective layer 40 on the surface of the metal wires in the metal wire layer 30 exposed in the transparent conductive layer 20 which are away from the transparent substrate 10 and the side surfaces of the metal wires.

[0143] Specifically, the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 and the side of the metal wire are oxidized, and a protective layer 40 is formed on the surface of the metal wire in the exposed metal wire layer 30 of the transparent conductive layer 20 facing away from the transparent substrate 10 and the side of the metal wire, so as to obtain Figure 7 The transparent conductive electrode shown.

[0144] It is understandable that, considering the brittleness of the transparent conductive layer (such as the ITO layer), in the above-mentioned methods of forming the transparent conductive layer 20 and the metal wire layer 30 on the first surface S1 of the transparent substrate 10, the thickness fluctuation of the transparent conductive layer 20 is small, that is, the transparent conductive layer 20 is relatively flat and will not be broken due to the setting of the metal wire layer 30, so that the stability of the transparent conductive electrode is better. At the same time, the transparent conductive layer 20 must expose at least a portion of the metal wire layer 30.

[0145] If no treatment is performed on the surface of the exposed metal wire layer 30 of the transparent conductive layer 20, the obtained transparent conductive electrode will be quickly corroded by the chemical substances in the semiconductor device, causing the semiconductor device to fail. Therefore, in step S300, the surface of the exposed metal wire layer 30 of the transparent conductive layer 20 is oxidized to form a dense metal oxide protective layer 40 on the surface of the exposed metal wire layer 30 of the transparent conductive layer 20.

[0146] The metal in the metal wire layer 30 may be a metal or alloy that spontaneously forms a dense protective layer with oxygen in the air. Accordingly, the protective layer 40 may be a metal oxide layer that spontaneously forms a dense protective layer with oxygen in the air.

[0147] Optionally, the metal in the metal wire layer 30 may include at least one of Al, Mg, Zn, Fe, Ti and Sn, and the protective layer 40 correspondingly includes at least one of Al2O3, MgO, ZnO, Fe2O3, Fe3O4, TiO and SnO. Specifically, when the metal in the metal wire layer 30 is Al, the corresponding protective layer 40 is a dense Al2O3 layer; when the metal in the metal wire layer 30 is Mg, the corresponding protective layer 40 is a dense MgO layer; when the metal in the metal wire layer 30 is Zn, the corresponding protective layer 40 is a dense ZnO layer; when the metal in the metal wire layer 30 is Fe, the corresponding protective layer 40 is a dense Fe2O3 layer, or a Fe3O4 layer, or a mixed layer of Fe2O3 and Fe3O4; when the metal in the metal wire layer 30 is Ti, the corresponding protective layer 40 is a dense TiO layer; when the metal in the metal wire layer 30 is Sn, the corresponding protective layer 40 is a dense SnO layer; these dense metal oxide layers are formed on the metal surface, have high density and excellent chemical stability, and can be used to protect the metal from corrosion and oxidation.

[0148] Specifically, the dense metal oxide layer is formed by the reaction of the metal surface with oxygen or water. In this process, the atoms on the metal surface combine with oxygen or oxygen atoms in water to form metal oxides. These metal oxides will continue to accumulate on the metal surface to form a dense metal oxide layer.

[0149] In the actual process, after forming the transparent conductive layer 20 and the metal wire layer 30 on the first surface S1 of the transparent substrate 10, the obtained structure is placed in a certain environment, and the oxygen concentration, relative humidity, oxidation temperature and oxidation time in the environment are adjusted, so that a dense metal oxide protective layer 40 can be spontaneously formed on the surface of the metal wire layer 30 exposed by the transparent conductive layer 20. This process is simple, green and pollution-free, and has low cost. It should be noted that when the surface of the metal wire layer 30 exposed by the transparent conductive layer 20 is oxidized, gaseous reactants other than air components should not be introduced to avoid damaging the protective layer 40.

[0150] Table 2 lists the performance parameters of seven transparent conductive electrodes (D electrode to K electrode) prepared under different conditions (oxygen concentration, relative humidity, oxidation temperature and oxidation time) for use in electrochromic devices. Figure 2 As shown, the transparent substrate 10 is a PEN substrate with a thickness of 120 μm, the transparent conductive layer 20 is an ITO layer with a thickness of 120 nm, the metal in the metal wire layer is aluminum with a thickness of 100 nm, the metal wire width is 10 μm, and the metal wire arrangement is as follows Figure 1 As shown, the spacing between metal wires is 100um. The structure of the electrochromic device using transparent conductive electrodes is as follows Fig.12 As shown, the electrochromic device includes a first conductive electrode 100, a second conductive electrode 200 and an electrochromic layer 300 located between the first conductive electrode 100 and the second conductive electrode 200, wherein the first conductive electrode 100 and the second conductive electrode 200 are both Figure 2 The transparent conductive electrode shown has a size of 20cm*20cm*350um, and the composition of the electrochromic layer 300 is 100mM diethyl viologen chloride and 50mM ferrocene, and the solvent is propylene carbonate. In specific operation, the coloring voltage is 1V, the coloring process time is set to 20s, the fading voltage is 0V, and the fading process time is set to 25s. One coloring process and one fading process add up to one cycle, and the cycle test temperature is 20°C.

[0151] Table 2 Performance parameters of seven transparent conductive electrodes (D electrode to J electrode) prepared under different conditions and applied to electrochromic devices

[0152]

[0153] It can be seen from Table 2 that by comparing the electrochromic devices corresponding to the three electrodes D, E and F, it can be known that under the same oxygen concentration, relative humidity and oxidation temperature, as the oxidation time increases, such as the oxidation time ≥ 24h, the protective layer 40 on the surface of the exposed metal wire layer 30 of the transparent conductive layer 20 becomes denser, so that the transparent state transmittance and the colored state transmittance of the electrochromic device change less compared with the initial state after 10,000 cycles of coloring and fading, that is, the electrochromic device is more stable.

[0154] By comparing the electrochromic devices corresponding to the three electrodes F, G and H, it can be seen that under the conditions of the same oxygen concentration, oxidation time and oxidation temperature, as the relative humidity decreases, such as the relative humidity ≤50%, the protective layer 40 on the surface of the exposed metal wire layer 30 of the transparent conductive layer 20 becomes denser, so that the transparent state transmittance and the colored state transmittance of the electrochromic device change less compared with the initial state after 10,000 cycles of coloring and fading, that is, the electrochromic device becomes more stable.

[0155] By comparing the electrochromic devices corresponding to the F electrode and the I electrode, or by comparing the electrochromic devices corresponding to the J electrode and the K electrode, it can be seen that under the conditions of the same oxygen concentration, oxidation time and relative humidity, as the oxidation temperature increases, such as the oxidation temperature ≥ 20°C, the protective layer 40 on the surface of the exposed metal wire layer 30 of the transparent conductive layer 20 becomes denser, so that the transparent state transmittance and the colored state transmittance of the electrochromic device change less compared with the initial state after 10,000 cycles of coloring and fading, that is, the electrochromic device becomes more stable.

[0156] By comparing the electrochromic devices corresponding to the G electrode and the J electrode, it can be seen that under the same oxidation time, relative humidity and oxidation temperature, as the oxygen concentration increases, such as the oxygen concentration ≥ 20%, the protective layer 40 on the surface of the exposed metal wire layer 30 of the transparent conductive layer 20 becomes denser, so that the transparent state transmittance and the colored state transmittance of the electrochromic device change less compared with the initial state after 10,000 cycles of coloring and fading, that is, the electrochromic device is more stable.

[0157] The above is only presented by taking the electrochromic device as an example. It can be understood that when the protective layer 40 on the surface of the exposed metal wire layer 30 of the transparent conductive layer 20 in the transparent conductive electrode is denser, the semiconductor device using the transparent conductive electrode is more stable.

[0158] Based on the above analysis, optionally, in one embodiment of the present application, the process of oxidizing the surface of the metal wire layer 30 exposed by the transparent conductive layer 20 includes:

[0159] In an air environment with an oxygen concentration of ≥20%, a relative humidity of ≥50% and a temperature of ≥20°C, the metal on the surface of the exposed metal wire layer 30 of the transparent conductive layer 20 reacts with oxygen for an oxidation time of ≥24h, thereby forming a protective layer 40 on the surface of the exposed metal wire layer 30 of the transparent conductive layer 20, so that the protective layer 40 is very dense, thereby making the prepared transparent conductive electrode more stable, and thus making the semiconductor device using the transparent conductive electrode more stable.

[0160] Since the oxygen concentration in the air is 21%, the surface of the metal wire layer 30 exposed by the transparent conductive layer 20 can be oxidized in the air environment.

[0161] Among them, relative humidity refers to the percentage of water vapor pressure in the air to the saturated water vapor pressure at the same temperature.

[0162] In the above-mentioned embodiments, the process method for forming the transparent conductive layer 20 includes coating or sputtering, and the process method for forming the metal wire layer 30 includes evaporation, electroplating, attachment, etc.

[0163] The present application also provides a semiconductor device, including a transparent conductive electrode, which is a transparent conductive electrode provided by any of the above embodiments, or a transparent conductive electrode prepared by the method provided by any of the above embodiments. Optionally, the semiconductor device can be a semiconductor device such as an electrochromic device, a solar cell device, etc.

[0164] Fig.12 A cross-sectional schematic diagram of an electrochromic device provided in an embodiment of the present application is shown, such as Fig.12As shown, the electrochromic device includes a first conductive electrode 100, a second conductive electrode 200 and an electrochromic layer 300 located between the first conductive electrode 100 and the second conductive electrode 200. The first conductive electrode 100 and the second conductive electrode 200 are both transparent conductive electrodes provided by any of the above embodiments. Since the transparent conductive layer 20 and the metal wire layer 30 in the first conductive electrode 100 and the second conductive electrode 200 can both conduct electricity, and the square resistance of the metal wires in the metal wire layer 30 is very small, and the space area of ​​the metal wires in the metal wire layer 30 can transmit light, the first conductive electrode 100 and the second conductive electrode 200 have good conductivity and light transmittance. Therefore, the electrochromic device has a fast color change speed and more uniform color change. At the same time, in the first conductive electrode 100 and the second conductive electrode 200, the surface of the exposed metal wire layer 30 is provided with a protective layer 40, and the protective layer 40 is a dense metal oxide layer, so that the overall surface composed of the transparent conductive layer 20 and the metal wire layer 30 maintains good chemical / electrochemical inertness, which can protect the first conductive electrode 100 and the second conductive electrode 200 from corrosion by the electrochromic layer 300, and the device stability is high. Fig.12 As shown, in the electrochromic device, an encapsulation layer 400 is further disposed around the electrochromic layer.

[0165] The various parts in this manual are described in a combination of parallel and progressive ways. Each part focuses on the differences from other parts, and the same or similar parts between the various parts can be referenced to each other.

[0166] With respect to the above description of the disclosed embodiments, the features described in the embodiments in this specification may be replaced or combined with each other, so that professionals in the field can implement or use the present application. Various modifications to these embodiments will be apparent to professionals in the field, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A transparent conductive electrode, characterized in that: include: a transparent substrate having a first surface; A transparent conductive layer, located on the first surface of the transparent substrate; a metal wire layer, located on a surface of the transparent conductive layer facing away from the transparent substrate, or embedded in at least a portion of the transparent conductive layer in a direction perpendicular to the first surface of the transparent substrate, the metal wire layer comprising a plurality of metal wires; The transparent conductive layer exposes at least a portion of the metal wire layer, and a protective layer is disposed on the surface of the metal wire layer exposed by the transparent conductive layer. The material of the protective layer is the oxide of the metal in the metal wire layer.

2. The transparent conductive electrode according to claim 1, characterized in that: The plurality of metal lines include metal lines extending along a first direction and metal lines extending along a second direction, the first direction intersects with the second direction, and both the first direction and the second direction are parallel to the first surface of the transparent substrate.

3. The transparent conductive electrode according to claim 1, characterized in that: The transparent conductive layer exposing at least a portion of the metal line layer comprises: The transparent conductive layer exposes at least a portion of the surface of the metal wire in the metal wire layer that is away from the substrate; The protection layer covers the surface of the metal wires in the metal wire layer exposed by the transparent conductive layer and facing away from the transparent substrate.

4. The transparent conductive electrode according to claim 3, characterized in that: The transparent conductive layer exposing at least a portion of the metal line layer further comprises: The transparent conductive layer also exposes at least part of the side surfaces of the metal wires in the metal wire layer; The protection layer also covers the side surfaces of the metal wires in the metal wire layer that are exposed by the transparent conductive layer.

5. The transparent conductive electrode according to any one of claims 1 to 4, characterized in that: The metal in the metal wire layer includes at least one of Al, Mg, Zn, Fe, Ti and Sn, and the protective layer correspondingly includes at least one of Al2O3, MgO, ZnO, Fe2O3, Fe3O4, TiO and SnO.

6. A method for preparing a transparent conductive electrode, characterized in that: include: Providing a transparent substrate, wherein the transparent substrate has a first surface; Forming a transparent conductive layer and a metal wire layer on the first surface of the transparent substrate, wherein the transparent conductive layer is located on the first surface of the transparent substrate, and the metal wire layer is located on the surface of the transparent conductive layer away from the transparent substrate, or is embedded in at least a portion of the transparent conductive layer in a direction perpendicular to the first surface of the transparent substrate, the metal wire layer includes a plurality of metal wires, and the transparent conductive layer exposes at least a portion of the metal wire layer; The surface of the metal wire layer exposed by the transparent conductive layer is oxidized to form a protective layer on the surface of the metal wire layer exposed by the transparent conductive layer. The material of the protective layer is the oxide of the metal in the metal wire layer.

7. The method for preparing a transparent conductive electrode according to claim 6, characterized in that: Forming a transparent conductive layer and a metal wire layer on the first surface of the transparent substrate specifically includes: forming a transparent conductive layer on the first surface of the transparent substrate; forming a metal wire layer on a surface of the transparent conductive layer facing away from the transparent substrate, wherein the metal wire layer comprises a plurality of metal wires, and the transparent conductive layer exposes the surface of the metal wires in the metal wire layer facing away from the transparent substrate and the side surfaces of the metal wires; Performing oxidation treatment on the surface of the metal wire layer exposed by the transparent conductive layer to form a protective layer on the surface of the metal wire layer exposed by the transparent conductive layer comprises: The surfaces of the metal wires in the metal wire layer exposed by the transparent conductive layer that are away from the transparent substrate and the sides of the metal wires are oxidized to form a protective layer on the surfaces of the metal wires in the metal wire layer exposed by the transparent conductive layer that are away from the transparent substrate and the sides of the metal wires.

8. The method for preparing a transparent conductive electrode according to claim 6, characterized in that: Forming a transparent conductive layer and a metal wire layer on the first surface of the transparent substrate specifically includes: forming a transparent conductive layer on the first surface of the transparent substrate; forming a metal wire layer on a surface of the transparent conductive layer facing away from the transparent substrate, wherein the metal wire layer comprises a plurality of metal wires; In a direction perpendicular to the first surface of the transparent substrate, pressing the metal wire layer into at least a portion of the transparent conductive layer, so that the transparent conductive layer at least exposes a surface of the metal wire in the metal wire layer that is away from the substrate; Performing oxidation treatment on the surface of the metal wire layer exposed by the transparent conductive layer to form a protective layer on the surface of the metal wire layer exposed by the transparent conductive layer comprises: The surface of the metal wire in the metal wire layer exposed by the transparent conductive layer which is away from the transparent substrate is subjected to oxidation treatment, and a protective layer is formed on the surface of the metal wire in the metal wire layer exposed by the transparent conductive layer which is away from the transparent substrate.

9. The method for preparing a transparent conductive electrode according to claim 6, characterized in that: Forming a transparent conductive layer and a metal wire layer on the first surface of the transparent substrate specifically includes: forming a metal wire layer on the first surface of the transparent substrate, wherein the metal wire layer comprises a plurality of metal wires; forming a transparent conductive layer on other areas of the first surface of the transparent substrate except the area where the metal wire layer is located, so that the transparent conductive layer at least exposes a portion of the surface of the metal wire layer away from the transparent substrate; Performing oxidation treatment on the surface of the metal wire layer exposed by the transparent conductive layer to form a protective layer on the surface of the metal wire layer exposed by the transparent conductive layer comprises: The surface of the metal wire in the metal wire layer exposed by the transparent conductive layer which is away from the transparent substrate is subjected to oxidation treatment, and a protective layer is formed on the surface of the metal wire in the metal wire layer exposed by the transparent conductive layer which is away from the transparent substrate.

10. The method for preparing a transparent conductive electrode according to claim 8 or 9, characterized in that: The transparent conductive layer also exposes part of the side surfaces of the metal wires in the metal wire layer, and the surface of the metal wire layer exposed by the transparent conductive layer is oxidized, and a protective layer is formed on the surface of the metal wire layer exposed by the transparent conductive layer, and the like further comprises: The side surfaces of the metal wires in the metal wire layer where the transparent conductive layer is exposed are subjected to oxidation treatment, so as to form a protective layer on the side surfaces of the metal wires in the metal wire layer where the transparent conductive layer is exposed.

11. The method for preparing a transparent conductive electrode according to claim 6, characterized in that: The process of oxidizing the surface of the metal wire layer exposed by the transparent conductive layer includes: In an air environment with an oxygen concentration of ≥20%, a relative humidity of ≤50% and a temperature of ≥20°C, the metal on the surface of the metal wire layer exposed by the transparent conductive layer reacts with oxygen for an oxidation time of ≥24h, thereby forming the protective layer on the surface of the metal wire layer exposed by the transparent conductive layer.

12. A semiconductor device, characterized in that: The invention comprises a transparent conductive electrode, wherein the transparent conductive electrode is the transparent conductive electrode according to any one of claims 1 to 5, or a transparent conductive electrode prepared by the method according to any one of claims 6 to 11.

Images