Transparent conductive glass and manufacturing method thereof

Abstract

The invention belongs to the technical field of electronic materials, and provides transparent conductive glass and a manufacturing method thereof.The transparent conductive glass comprises a glass substrate and a transparent conductive film arranged on the surface of the glass substrate; the transparent conductive film is arranged on the glass substrate, the metal grid is embedded in the glass substrate, and the metal grid and the transparent conductive film are contacted and electrically connected at the interface of the glass substrate and the transparent conductive film; according to the invention, the embedded metal grid is arranged and does not protrude to influence the surface smoothness, so that the resistance of the conductive glass can be effectively reduced by virtue of the excellent conductivity of metal, the connection between the conductive glass and the glass substrate and the transparent conductive film can be ensured to be tighter, and the light transmission and subsequent processing and utilization are not influenced.

Description

Technical Field

[0001] The invention belongs to the field of electronic materials and electronic technology, and relates to a transparent conductive glass and a manufacturing method thereof. Background Art

[0002] In the field of modern electronic technology and optoelectronic display, conductive glass plays a pivotal role as a key material. As a transparent electrode, it has been used in optoelectronic devices such as liquid crystal displays, organic light-emitting diode displays, touch screens, and various solar cells. The traditional manufacturing process of conductive glass is mainly to directly deposit a layer of transparent conductive oxide film (TCO, Transparent Conductive Oxide) on a glass substrate by physical or chemical methods to obtain the product, among which the most representative is indium tin oxide (ITO) thin film conductive glass.

[0003] The conductivity of traditional conductive glass is completely dependent on the TCO film deposited on the surface. However, the resistance of the TCO film is generally high, usually between tens and hundreds of ohms, which is increasingly unable to meet the actual needs of application scenarios with extremely low resistance values. To address this problem, an effective solution is to use metal materials to improve the conductivity of conductive glass. For example, silver nanowires can be sprayed on the surface of conductive glass. As a metal with excellent conductive properties, silver in its nanowire form can significantly improve the conductivity of the material while maintaining a certain degree of light transmittance.

[0004] However, the actual effect of this method is greatly affected by the thickness of the spraying. If the spraying is too thin, the connection between the silver nanowires is not tight enough, and it is difficult to form an effective conductive network, so the effect of reducing resistance is limited; on the contrary, if the spraying is too thick, although the resistance can be further reduced, the excessively thick silver nanowire layer will seriously block the light, resulting in a sharp drop in light transmittance. Moreover, the protruding part of the metal grid is too large, which seriously affects the flatness of the glass surface. The uneven surface not only affects the appearance, but also seriously interferes with the subsequent processing and utilization process, resulting in a decline in product quality or even the inability to complete production.

[0005] In summary, there is still a need to study and improve the scheme of optimizing conductive glass using metal materials in order to fully realize a significant improvement in conductive performance. Summary of the invention

[0006] In view of the problems existing in the prior art, the purpose of the present invention is to provide a transparent conductive glass and a method for manufacturing the same, wherein the transparent conductive glass comprises a glass substrate and a transparent conductive film arranged on the surface of the glass substrate; and further comprises a metal grid embedded in the glass substrate, wherein at the interface between the glass substrate and the transparent conductive film, the metal grid contacts the transparent conductive film and forms an electrical connection; the present invention arranges an embedded metal grid, which does not protrude and affect the surface flatness, and therefore, can effectively reduce the resistance of the conductive glass by relying on the excellent conductivity of the metal, and can ensure a tighter connection with the glass substrate and the transparent conductive film, and will not affect the light transmittance and subsequent processing and utilization.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a transparent conductive glass, comprising a glass substrate and a transparent conductive film arranged on the surface of the glass substrate; and also comprising a metal grid embedded in the glass substrate, wherein at the interface between the glass substrate and the transparent conductive film, the metal grid contacts the transparent conductive film and forms an electrical connection.

[0009] The present invention sets an embedded metal grid to ensure that it is only exposed on the surface of the glass to form contact and electrical connection with the transparent conductive film, that is, the surface of the glass is still flat, and the metal grid does not protrude, thereby ensuring the flatness of the transparent conductive film and the overall surface flatness of the conductive glass. Therefore, not only can the resistance of the conductive glass be greatly reduced, but also due to its embedded structural characteristics, it can ensure a tighter connection with the glass substrate and the transparent conductive film, and will not affect the light transmittance and subsequent processing and utilization.

[0010] The following are preferred technical solutions of the present invention, but are not intended to be limitations of the technical solutions provided by the present invention. Through the following technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved and realized.

[0011] As a preferred technical solution of the present invention, the thickness of the metal grid is 3 to 15 μm, such as 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, etc.; the thickness of the metal grid refers to its own thickness, not the height of the metal grid protruding from the glass substrate; the area duty ratio is 5% to 10%, such as 5%, 6%, 7%, 8%, 9% or 10%, etc. The area duty ratio refers to the ratio of the area occupied by the grid body to the total area occupied by the conductive glass.

[0012] As a preferred technical solution of the present invention, the material of the metal grid includes at least one of Au, Ag, Cu, Ni, Cr or Pb.

[0013] As a preferred technical solution of the present invention, the hollow shape in the metal grid includes at least one of a circle, a triangle, a square or a honeycomb.

[0014] As a preferred technical solution of the present invention, the transparent conductive film includes a metal oxide film, and the metal oxide film includes ITO and / or FTO.

[0015] As a preferred technical solution of the present invention, the resistance of the transparent conductive glass is 0.1-1Ω, for example, it can be 0.1Ω, 0.2Ω, 0.3Ω, 0.4Ω, 0.5Ω, 0.6Ω, 0.7Ω, 0.8Ω, 0.9Ω or 1Ω, etc., preferably 0.1-0.8Ω, and more preferably 0.1-0.5Ω, but it is not limited to the listed values, and other values ​​not listed within the above numerical range are also applicable.

[0016] In a second aspect, the present invention provides a method for manufacturing the transparent conductive glass according to the first aspect, the manufacturing method comprising:

[0017] S10. Providing a substrate, preparing a metal grid on a surface of one side of the substrate;

[0018] S20. Providing a glass matrix raw material, preparing a glass matrix on the surface of the substrate, and embedding the metal grid into the glass matrix;

[0019] S30. Separate the substrate from the surface of the glass substrate so that the metal grid embedded in the glass substrate is exposed to the surface of the glass substrate, prepare a transparent conductive film on the surface of the glass substrate, and make the metal grid contact with the transparent conductive film to form an electrical connection.

[0020] As a preferred technical solution of the present invention, in step S10, the substrate includes a silicon sheet or a metal sheet, and the metal sheet includes a copper sheet.

[0021] The manufacturing method of the present invention uses a substrate with a metal grid as a base for preparing a glass matrix, so that the molten glass wraps the metal grid on the surface of the substrate, thereby realizing the embedding of the metal grid after cooling to form a glass matrix. Due to the existence of the substrate, the embedding is not completely buried. When the substrate is removed from the surface of the glass matrix, the surface of the metal grid that was originally close to the substrate will be flush with the surface of the glass matrix and exposed to the outside world, so as to contact with the subsequent transparent conductive film and form an electrical connection. The steps and processes of the manufacturing method of the present invention, which first form the metal grid, then embed it, and finally prepare the transparent conductive film, can be more conducive to controlling the shape and size of the metal grid. Compared with directly preparing a protruding metal grid on the glass, the accuracy and stability are better, and the embedding and complete manufacturing of transparent conductive glass are also realized in a simpler and more convenient way.

[0022] Preferably, the method for preparing a metal grid on one side surface of the substrate includes: providing a substrate, coating a photoresist on one side surface of the substrate, and sequentially performing drying, exposure and development to form a pattern of the metal grid; depositing a metal layer to form a metal grid in the pattern; and cleaning to remove residual photoresist and expose the metal grid.

[0023] The present invention preferably adopts the photolithography method to prepare the pattern (referring to the grid body and the hollowing in the grid body), which can ensure the fineness of the pattern, can more conveniently control the duty cycle of the metal grid, ensure the overall light transmittance, and can also make special patterns according to needs, such as forming different control grid body thickness, shape, material and hollow shape at different positions.

[0024] Preferably, the drying temperature is 80-100°C, for example 80°C, 85°C, 90°C, 95°C or 100°C, and the drying time is 5-15min, for example 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min, but is not limited to the listed values, and other unlisted values ​​within the above numerical range are also applicable.

[0025] Preferably, the development time is 8 to 16 seconds, for example 8 seconds, 9 seconds, 10 seconds, 11 seconds, 12 seconds, 13 seconds, 14 seconds, 15 seconds or 16 seconds, but is not limited to the listed values, and other values ​​not listed within the above range are also applicable.

[0026] Preferably, the developing solution comprises at least one of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution or a TMAH aqueous solution.

[0027] Preferably, the cleaning method includes soaking in the cleaning solution for 5 to 10 minutes, for example, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes or 10 minutes, but is not limited to the listed values, and other unlisted values ​​within the above numerical range are also applicable.

[0028] Preferably, the cleaning solution comprises an organic solvent, and the organic solvent comprises at least one of ethanol, isopropanol or acetone.

[0029] Preferably, the method of depositing the metal layer includes electroplating, and the electroplating current is 0.001-0.5A, for example, 0.001A, 0.005A, 0.008A, 0.01A, 0.03A, 0.05A, 0.08A, 0.1A, 0.15A, 0.2A, 0.25A, 0.3A, 0.35A, 0.4A, 0.45A or 0.5A, etc., and the time is 5-120min, for example, 5min, 10min, 30min, 50min, 80min, 100min or 120min, etc., but is not limited to the listed values, and other values ​​not listed within the above numerical range are also applicable.

[0030] The present invention preferably uses an electroplating method to prepare the metal grid, which can ensure the compactness of the metal and the adhesion with the surface of the substrate material, thereby ensuring the conductivity of the metal grid and the flatness of the surface of the conductive glass.

[0031] As a preferred technical solution of the present invention, in step S20, the method for preparing a glass matrix on the surface of the substrate includes any of the following methods.

[0032] Method 1: Sintering the glass matrix raw material into molten glass, applying the obtained molten glass onto the surface of the substrate, and cooling it to form a glass matrix.

[0033] Method 2: laying the glass matrix raw material on the surface of the substrate, and then sintering and cooling in sequence to form a glass matrix.

[0034] Preferably, the sintering temperature is 600-800°C, for example 600°C, 630°C, 650°C, 680°C, 700°C, 730°C, 750°C, 780°C or 800°C, but is not limited to the listed values, and other unlisted values ​​within the above numerical range are also applicable.

[0035] Preferably, in the first method, the substrate is preheated before the molten glass is applied to the surface of the substrate; preferably, the preheating temperature is less than or equal to the sintering temperature.

[0036] Preferably, the cooling time is 3 to 5 hours, for example 3 hours, 3.3 hours, 3.5 hours, 3.8 hours, 4 hours, 4.2 hours, 4.5 hours, 4.8 hours or 5 hours, etc., and the cooling target temperature is room temperature, but is not limited to the listed values, and other unlisted values ​​within the above numerical range are also applicable.

[0037] As a preferred technical solution of the present invention, in step S30, the method of separating the substrate from the surface of the glass base includes physical mechanical peeling.

[0038] Preferably, the method for preparing the transparent conductive film comprises a sputtering method.

[0039] Compared with the prior art solutions, the present invention has at least the following beneficial effects:

[0040] The present invention sets an embedded metal grid to ensure that it is only exposed on the surface of the glass to form contact and electrical connection with the transparent conductive film, that is, the surface of the glass is still flat, and the metal grid does not protrude, thereby ensuring the flatness of the transparent conductive film and the overall surface flatness of the conductive glass. Therefore, not only can the resistance of the conductive glass be greatly reduced, but also due to its embedded structural characteristics, it can ensure a tighter connection with the glass substrate and the transparent conductive film, and will not affect the light transmittance and subsequent processing and utilization.

[0041] The manufacturing method of the present invention first forms a metal grid, then embeds it into a glass substrate, and finally prepares a transparent conductive film. The steps and process can be more conducive to controlling the shape and size of the metal grid. Compared with directly preparing a protruding metal grid on the glass, it has better accuracy and stability. At the same time, it also realizes the complete manufacturing of embedding and transparent conductive glass in a simpler and more convenient way. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 Schematic diagram of the structure of the transparent conductive glass of Example 1.

[0043] Figure 2 It is a schematic flow chart of the method for manufacturing the transparent conductive glass of Example 1.

[0044] Figure 3 Schematic diagram of the metal grid in the transparent conductive glass of Example 1.

[0045] In the figure: 1-glass substrate, 2-transparent conductive film, 3-metal grid, 4-metal layer, 5-hollowing, 6-photoresist, 7-substrate. DETAILED DESCRIPTION

[0046] The technical solution of the present invention is further illustrated below through specific implementation methods.

[0047] It should be clear to those skilled in the art that the embodiments are only intended to help understand the present invention and should not be considered as specific limitations of the present invention.

[0048] Example 1

[0049] This embodiment provides a transparent conductive glass such as Figure 1 As shown, the transparent conductive glass comprises a glass substrate 1, and a transparent conductive film 2 arranged on the surface of the glass substrate 1; and further comprises a metal grid 3 embedded in the glass substrate 1, and at the interface between the glass substrate 1 and the transparent conductive film 2, the metal grid 3 contacts the transparent conductive film 2 and forms an electrical connection; the area ratio of the metal grid 3 is 6%, the thickness is 5 μm, and the material of the metal grid 3 is Ni; the shape of the hollow 5 in the metal grid 3 is a honeycomb shape, as shown in FIG. Figure 3 As shown; the transparent conductive film is a metal oxide film ITO.

[0050] like Figure 2 As shown, the manufacturing method of the transparent conductive film 2 includes:

[0051] S10. Provide a substrate 7, which is a cleaned conductive silicon wafer, spin-coat a positive photoresist 6 on one side of the substrate 7, dry it at 100°C for 10 minutes, expose it through a mask under parallel light to photoetch a grid body with a width of 2 μm, and the shape of the hollow 5 in the grid body is a honeycomb shape. Soak it in a developer sodium hydroxide aqueous solution for 10 seconds to develop, and obtain a pattern of a metal grid 3; soak it in an electrolyte, control the current at 0.08A, and control the time at 8 minutes to deposit a metal layer 4 to form a metal grid 3 in the pattern; then soak it in a cleaning solution ethanol for 5 to 10 minutes to clean it, remove the residual photoresist 6, and expose the metal grid 3;

[0052] S20. providing a glass substrate 1 raw material, sintering the glass substrate 1 raw material at 700° C. into molten glass, preheating the substrate 7 to 500° C., applying the obtained molten glass to the surface of the substrate 7, controlling the temperature to slowly drop to room temperature for cooling for 4 hours, forming a glass substrate 1, and embedding the metal grid 3 in the glass substrate 1;

[0053] S30. Directly physically and mechanically peel off the substrate 7 from the surface of the glass substrate 1, so that the metal grid 3 embedded in the glass substrate 1 is exposed to the surface of the glass substrate 1, and sputter a transparent conductive film ITO on the surface of the glass substrate 1, so that the metal grid 3 is in contact with the transparent conductive film 2 and forms an electrical connection.

[0054] Example 2

[0055] The present embodiment provides a transparent conductive glass, which includes a glass substrate 1 and a transparent conductive film 2 arranged on the surface of the glass substrate 1; it also includes a metal grid 3 embedded in the glass substrate 1, and at the interface between the glass substrate 1 and the transparent conductive film 2, the metal grid 3 is in contact with the transparent conductive film 2 and forms an electrical connection; the area ratio of the metal grid 3 is 9%, the thickness is 8μm, and the material of the metal grid 3 is Ag; the shape of the hollow 5 in the metal grid 3 is a honeycomb shape; the transparent conductive film is a metal oxide film ITO.

[0056] The manufacturing method of the transparent conductive film 2 includes:

[0057] S10. Provide a substrate 7, the substrate 7 is a polished copper sheet, spin-coat a positive photoresist 6 on one side of the substrate 7, dry it at 90°C for 15 minutes, expose it through a mask under parallel light to photoetch a grid body with a width of 3 μm, the shape of the hollow 5 of the grid body is square, soak it in a developer sodium hydroxide aqueous solution for 10 seconds to develop, and obtain a pattern of a metal grid 3; soak it in an electrolyte, control the current at 0.4A, control the time at 10 minutes, deposit a metal layer 4, and form a metal grid 3 in the pattern; then soak it in a cleaning solution ethanol for 10 minutes to clean it, remove the residual photoresist 6, and expose the metal grid 3;

[0058] S20. Provide a glass substrate 1 raw material, lay the glass substrate 1 raw material on the surface of the substrate 7, sinter the whole at 800° C., and then control the temperature to slowly drop to room temperature for cooling for 5 hours to form a glass substrate 1, so that the metal grid 3 is embedded in the glass substrate 1;

[0059] S30. Directly physically and mechanically peel off the substrate 7 from the surface of the glass substrate 1, so that the metal grid 3 embedded in the glass substrate 1 is exposed to the surface of the glass substrate 1, and sputter a transparent conductive film ITO on the surface of the glass substrate 1, so that the metal grid 3 is in contact with the transparent conductive film 2 and forms an electrical connection.

[0060] Example 3

[0061] This embodiment provides a transparent conductive glass. The manufacturing method of the transparent conductive glass is adjusted so that the duty cycle of the metal grid 3 is adjusted from 6% to 3%. Except for the above, other conditions are exactly the same as those in Embodiment 1.

[0062] Example 4

[0063] This embodiment provides a transparent conductive glass. The manufacturing method of the transparent conductive glass is adjusted so that the duty cycle of the metal grid 3 is adjusted from 6% to 13%. Except for the above, other conditions are exactly the same as those in Embodiment 1.

[0064] Example 5

[0065] This embodiment provides a transparent conductive glass, and the electroplating parameters in the manufacturing method of the transparent conductive glass are adjusted so that the thickness of the formed metal grid 3 is adjusted from 5 μm to 2 μm. Except for the above, other conditions are exactly the same as those in Example 1.

[0066] Example 6

[0067] This embodiment provides a transparent conductive glass, and the electroplating parameters in the manufacturing method of the transparent conductive glass are adjusted so that the thickness of the formed metal grid 3 is adjusted from 5 μm to 0.5 μm. Except for the above, other conditions are exactly the same as those in Example 1.

[0068] Example 7

[0069] This embodiment provides a transparent conductive glass, and the electroplating parameters in the manufacturing method of the transparent conductive glass are adjusted so that the thickness of the formed metal grid 3 is adjusted from 5 μm to 7 μm. Except for the above, other conditions are exactly the same as those in Example 1.

[0070] Example 8

[0071] This embodiment provides a transparent conductive glass, and the electroplating parameters in the manufacturing method of the transparent conductive glass are adjusted so that the thickness of the formed metal grid 3 is adjusted from 8 μm to 15 μm. Except for the above, other conditions are exactly the same as those in Example 2.

[0072] Comparative Example 1

[0073] This comparative example provides a transparent conductive glass, which includes a glass substrate 1, a protruding metal grid 3 arranged on the surface of the glass substrate 1, and a transparent conductive film 2 covering the metal grid 3 and the glass substrate 1; the manufacturing method of the transparent conductive glass includes directly sintering to prepare the glass substrate 1, then using a photolithography method to prepare the metal grid 3 on the surface of the glass substrate 1, and finally sputtering to form the transparent conductive film 2. Except for the above, other conditions are exactly the same as those in Example 1.

[0074] Comparative Example 2

[0075] This comparative example provides a transparent conductive glass, which includes a glass substrate 1 and a transparent conductive film 2 arranged on the surface of the glass substrate 1. Except for the above, other conditions are exactly the same as those in Example 1.

[0076] Characterization and testing

[0077] Ⅰ. The transparent conductive glass obtained in the embodiment and the comparative example was tested, and the test items included sheet resistance, light transmittance and surface undulation. Sheet resistance, the full name of which is sheet resistance, refers to the resistance between two opposite sides of a square thin film conductive material. It is an important indicator for measuring the conductive performance of the conductive film and is tested using a coated sheet resistance tester. Light transmittance is the ability of light to pass through a medium. It is the percentage of the luminous flux passing through a transparent or translucent body to its incident luminous flux. It is tested using a spectrophotometer, in which the blank control is ordinary white glass. The surface undulation is tested using a step meter to test the height of the peak produced after the addition of a metal grid. The results are recorded in Table 1.

[0078] Table 1

[0079] Group Square resistance(Ω) Light transmittance (%) Surface relief (μm) Example 1 1 90 0.05 Example 2 0.5 90 0.07 Example 3 3 92 0.05 Example 4 0.3 80 0.06 Example 5 3 92 0.03 Example 6 6 93 0.01 Example 7 0.5 80 0.10 Example 8 0.1 75 0.50 Comparative Example 1 1 90 5.00 Comparative Example 2 6 93 0.00

[0080] It can be seen from Table 1 that:

[0081] (1) The current commercial ITO conductive glass (Comparative Example 2) generally has a square resistance of about 6Ω and a light transmittance of about 93%. Compared with Examples 1 and 2, the present invention can significantly reduce the resistance (less than 1Ω) while ensuring that the light transmittance and surface undulation of the conductive glass are not affected;

[0082] (2) By comparing Example 1 with Comparative Example 1, it can be seen that embedding the metal grid in the glass can avoid excessive surface undulations caused by the metal wire protruding from the surface, and is not easily affected by accidental wear and tear, resulting in a decrease in conductivity or even loss of conductivity. The flat surface has great advantages for subsequent fine processing on the conductive glass surface;

[0083] (3) By comparing Example 1 with Examples 3-4, it can be seen that a reasonable metal grid duty cycle can ensure that the light transmittance of the material is not affected while improving the conductivity;

[0084] (4) By comparing Example 1 with Examples 5-8, it can be seen that the thickness of the metal grid directly affects the conductivity of the conductive glass. Only when the metal grid reaches a certain thickness can the conductivity of the conductive glass be improved. However, an excessively thick metal grid will affect the light transmittance and surface undulation of the conductive glass. The thickness can be adjusted according to actual needs.

[0085] II. The transparent conductive glass provided in Example 1 and Comparative Example 2 is used to prepare a perovskite solar cell, wherein the solar cell comprises a transparent conductive glass, a hole transport layer, a perovskite layer, an electron transport layer, and a top electrode, and the effective area is 1 cm 2 , wherein the transparent conductive glass is exactly the same as that in Example 1;

[0086] The method for manufacturing the perovskite solar cell comprises:

[0087] 1) The transparent conductive glass was sequentially soaked in water, acetone, ultrapure water, and isopropanol for 10 minutes and then placed in a 60°C oven for drying;

[0088] 2) PTAA (triphenylamine polymer) was dissolved in toluene at 2.5 mg / mL, mixed thoroughly, and then a proper amount of the solution was dropped on the surface of the conductive glass. The solution was spin-coated at 6000 rpm for 30 seconds and then heated at 100°C for 10 minutes to obtain a hole transport layer (HTL);

[0089] 3) Weigh CsI, FAI, MAI, PbI2, and PbBr2 and add them to a mixed solution of DMF:DMSO in a volume ratio of 4:1 in a certain proportion to prepare a perovskite precursor solution with a concentration of 1.8 mol / mL. After fully mixing, apply the precursor solution on the hole transport layer under a nitrogen environment at a spin coating speed of 1500 rpm for 10 s and then at 5000 rpm for 30 s. At 35 s after the start, add 60 μL of CB (chlorobenzene) dropwise, and then heat at 120° C. for 20 min to obtain a perovskite layer;

[0090] 4) 20 nm of C was deposited on the perovskite layer by vacuum evaporation. 60 and 7.5nm BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) as an electron transport layer, and then 100nm Cu is deposited as the top electrode to obtain a perovskite solar cell.

[0091] Then, the photoelectric conversion efficiency (PCE) of each cell was tested. PCE is an important indicator for measuring the performance of solar cells. Under standard test conditions, including the setting of parameters such as light intensity (usually 1000 watts / square meter), spectral distribution (as close to the solar spectrum as possible) and temperature (usually 25°C), the current-voltage (JV) curve of the perovskite solar cell was measured to calculate its PCE value. The results are recorded in Table 2.

[0092] Table 2

[0093] Transparent conductive glass <![CDATA[V OC (V)]]> <![CDATA[J SC (mA cm -2 )]]> FF(%) PEC(%) Example 1 1.05 24.24 72.65 18.77 Comparative Example 2 1.02 22.71 70.03 16.21

[0094] It can be seen from Table 2 that:

[0095] By comparing the transparent conductive glass of Example 1 with that of Comparative Example 2, it can be seen that the photoelectric conversion efficiency of the perovskite solar cell is significantly increased after the conductivity is increased.

[0096] In summary, the present invention sets an embedded metal grid to ensure that it is only exposed on the surface of the glass to form contact and electrical connection with the transparent conductive film, that is, the surface of the glass is still flat, and the metal grid does not protrude, thereby ensuring the flatness of the transparent conductive film and the overall surface flatness of the conductive glass. Therefore, not only can the resistance of the conductive glass be greatly reduced, but also due to its embedded structural characteristics, it can ensure a tighter connection with the glass substrate and the transparent conductive film, and will not affect the light transmittance and subsequent processing and utilization.

[0097] The present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must rely on the above detailed structural features to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the components selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0098] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0099] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0100] In addition, various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

Claims

1. A transparent conductive glass, characterized in that: It includes a glass substrate and a transparent conductive film arranged on the surface of the glass substrate; it also includes a metal grid embedded in the glass substrate, and at the interface between the glass substrate and the transparent conductive film, the metal grid contacts the transparent conductive film and forms an electrical connection.

2. The transparent conductive glass according to claim 1, characterized in that: The area ratio of the metal grid is 5% to 10%; the thickness of the metal grid is 3 to 15 μm.

3. The transparent conductive glass according to claim 1 or 2, characterized in that: The material of the metal grid includes at least one of Au, Ag, Cu, Ni, Cr or Pb.

4. The transparent conductive glass according to any one of claims 1 to 3, characterized in that: The hollow shape in the metal grid includes at least one of a circle, a triangle, a square or a honeycomb.

5. The transparent conductive glass according to any one of claims 1 to 4, characterized in that: The transparent conductive film includes a metal oxide film, and the metal oxide film includes ITO and / or FTO.

6. The transparent conductive glass according to any one of claims 1 to 5, characterized in that: The resistance of the transparent conductive glass is 0.1-1Ω.

7. A method for manufacturing the transparent conductive glass according to any one of claims 1 to 6, characterized in that: The manufacturing method comprises: S10. Providing a substrate, preparing a metal grid on a surface of one side of the substrate; S20. Providing a glass matrix raw material, preparing a glass matrix on the surface of the substrate, and embedding the metal grid into the glass matrix; S30. Separate the substrate from the surface of the glass substrate so that the metal grid embedded in the glass substrate is exposed to the surface of the glass substrate, prepare a transparent conductive film on the surface of the glass substrate, and make the metal grid contact with the transparent conductive film to form an electrical connection.

8. The method for manufacturing transparent conductive glass according to claim 7, characterized in that: In step S10, the substrate includes a silicon sheet or a metal sheet, and the metal sheet includes a copper sheet; Preferably, the method for preparing a metal grid on one side surface of the substrate comprises: providing a substrate, coating a photoresist on one side surface of the substrate, sequentially performing drying, exposure and development to form a pattern of the metal grid; depositing a metal layer to form a metal grid in the pattern; performing cleaning to remove residual photoresist and expose the metal grid; Preferably, the drying temperature is 80-100°C and the drying time is 5-15 minutes; Preferably, the development time is 8 to 16 seconds; Preferably, the developing solution comprises at least one of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution or a TMAH aqueous solution; Preferably, the cleaning method comprises soaking in a cleaning solution for 5 to 10 minutes; Preferably, the cleaning solution comprises an organic solvent, and the organic solvent comprises at least one of ethanol, isopropanol or acetone; Preferably, the method for depositing the metal layer comprises electroplating, the electroplating current is 0.001-0.5A, and the time is 5-120min.

9. The method for manufacturing transparent conductive glass according to claim 7 or 8, characterized in that: In step S20, the method for preparing a glass matrix on the surface of the substrate includes any of the following methods: Method 1: sintering the glass matrix raw material into molten glass, applying the obtained molten glass onto the surface of the substrate, and cooling it to form a glass matrix; Method 2: laying the glass matrix raw material on the surface of the substrate, and then sintering and cooling in sequence to form a glass matrix; Preferably, the sintering temperature is 600-800°C; Preferably, in the first method, before applying the molten glass onto the surface of the substrate, the substrate is preheated; Preferably, the cooling time is 3 to 5 hours, and the cooling target temperature is room temperature.

10. The method for manufacturing a transparent conductive glass according to any one of claims 7 to 9, characterized in that: In step S30, the method of separating the substrate from the surface of the glass substrate includes a physical mechanical peeling method; Preferably, the method for preparing the transparent conductive film comprises a sputtering method.

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