High-temperature-resistant transparent conductive oxide coated glass, method for preparing same, and use thereof

Abstract

This application relates to the field of coated glass technology, providing a high-temperature resistant transparent conductive oxide coated glass, its preparation method, and its application. The transparent conductive oxide coated glass includes a glass substrate, a shielding layer, an antireflective layer, a first conductive layer, and a second conductive layer stacked sequentially. The first and second conductive layers are fluorine-doped tin dioxide layers, with a crystallinity of ≥50% and a grain size of ≥50 nm. The transparent conductive oxide coated glass provided by this application has an antireflective layer that prevents sodium and potassium ions from the glass substrate from entering the conductive layer, improving the conductivity stability of the conductive layer at high temperatures. The antireflective layer improves the transmittance of the transparent conductive oxide coated glass. The first and second conductive layers ensure that the mean free path of free carriers at high temperatures is much smaller than the grain size, reducing the influence of grain boundary scattering on Hall mobility and further improving the photoelectric performance of the conductive layer at high temperatures.

Description

Technical Field

[0001] This application belongs to the field of coated glass technology, and particularly relates to a high-temperature resistant transparent conductive oxide coated glass, its preparation method and application. Background Technology

[0002] Thin-film solar cells are photovoltaic semiconductor films that directly generate electricity using sunlight, playing a crucial role in addressing the energy crisis. Cadmium telluride (CdTe) thin-film solar cells, in particular, have become commercially successful due to their high efficiency, ease of manufacturing, and low production cost. However, the semiconductor layer of thin-film solar cells has almost no lateral conductivity, requiring the use of transparent conductive oxide coated glass (TCO coated glass) as the front electrode to effectively collect the cell current. Therefore, TCO coated glass has become an indispensable component of thin-film solar cells. Currently, the near-space sublimation method is mainly used to produce CdTe thin-film solar cells. Since the evaporation source is placed in a container with the same area as the substrate (TCO coated glass), the substrate and evaporation source need to be placed close together to minimize the temperature difference between them, allowing the CdTe film growth to approach an ideal equilibrium state. This requires the TCO coated glass temperature to reach above 600°C. However, when the temperature of existing TCO coated glass reaches around 500°C, the film layer on the glass surface undergoes physical or chemical changes, reducing carrier concentration and mobility, thus affecting the photoelectric performance of the TCO coated glass.

[0003] Therefore, there is an urgent need to develop a high-temperature resistant transparent conductive oxide coated glass with good high-temperature stability. Summary of the Invention

[0004] The purpose of this application is to provide a high-temperature resistant transparent conductive oxide coated glass, its preparation method and application, which aims to solve the problem of poor high-temperature stability of existing TCO glass.

[0005] To achieve the above-mentioned objectives, the technical solution adopted in this application is as follows:

[0006] In a first aspect, this application provides a transparent conductive oxide coated glass, comprising a glass substrate, a shielding layer, an antireflective layer, a first conductive layer and a second conductive layer stacked sequentially, wherein the first conductive layer and the second conductive layer are fluorine-doped tin dioxide layers, the crystallinity of the first conductive layer and the second conductive layer is 50% or more, and the grain size is 50 nm or more.

[0007] In the embodiment, the crystallinity of the first conductive layer is 58% or more, and the grain size is 55 nm or more.

[0008] In this embodiment, the crystallinity of the first conductive layer is higher than that of the second conductive layer.

[0009] In one embodiment, the grain size of the first conductive layer is larger than the grain size of the second conductive layer.

[0010] In this embodiment, the refractive index of the second conductive layer is less than that of the first conductive layer.

[0011] In the embodiments, the crystallinity of the first conductive layer is 58% to 70%, and the grain size is 55 nm to 60 nm.

[0012] In the embodiments, the crystallinity of the second conductive layer is 50% to 58%, and the grain size is 50 nm to 55 nm.

[0013] In this embodiment, the refractive index of the first conductive layer is 1.82 to 1.9.

[0014] In this embodiment, the refractive index of the second conductive layer is 1.79 to 1.86.

[0015] In this embodiment, the thickness of the first conductive layer is 150 nm to 400 nm.

[0016] In this embodiment, the thickness of the second conductive layer is 200 nm to 400 nm.

[0017] In the embodiments, the refractive index of the shielding layer is 1.63 to 2.8.

[0018] In this embodiment, the thickness of the shielding layer is 40nm to 70nm.

[0019] In the embodiments, the shielding layer includes a tin dioxide layer, a titanium dioxide layer, and a SnSiO layer. x At least one of the P layers.

[0020] In an embodiment, the antireflection layer includes a first antireflection layer and a second antireflection layer, with the first antireflection layer disposed between the shielding layer and the second antireflection layer.

[0021] In this embodiment, the refractive index of the first antireflective layer is 1.45 to 1.52.

[0022] In this embodiment, the refractive index of the second antireflective layer is 1.42 to 1.5.

[0023] In this embodiment, the thickness of the first antireflection layer is 10 nm to 30 nm.

[0024] In this embodiment, the thickness of the second antireflection layer is 10 nm to 30 nm.

[0025] In this embodiment, the first antireflection layer and the second antireflection layer are silicon dioxide layers.

[0026] In this embodiment, the refractive index of the second antireflective layer is less than that of the first antireflective layer.

[0027] In this embodiment, the glass substrate is a float glass substrate with a transmittance of ≥89%.

[0028] In the embodiments, the transmittance of the transparent conductive oxide coated glass is 81% to 85%.

[0029] In this embodiment, the carrier concentration of the transparent conductive oxide coated glass is 2.6 × 10⁻⁶. 20 ~4.2×10 20 / cm - 3.

[0030] In the embodiments, the resistance of the transparent conductive oxide coated glass is 6 to 12 Ω / □.

[0031] In the embodiments, after passing the high-temperature heat resistance test, the transmittance of the transparent conductive oxide coated glass is 82%–86%; the carrier concentration of the transparent conductive oxide coated glass is 2.5 × 10⁻⁶. 20 ~4.1×10 20 / cm - 3; The resistance of the transparent conductive oxide coated glass is 6~12Ω / □; Among them, the high temperature heat resistance test is set to the transparent conductive oxide coated glass at a temperature of 600-700℃ and kept in air atmosphere for at least 2.5 hours.

[0032] Secondly, this application provides a method for preparing high-temperature resistant transparent conductive oxide coated glass, comprising the following steps:

[0033] Provide glass substrates and use online coating reaction equipment in the float glass tin bath forming area;

[0034] A shielding layer is prepared on the surface of a glass substrate;

[0035] An antireflective layer is prepared on the surface of the shielding layer that is away from the glass substrate;

[0036] A first conductive layer is prepared on the surface of the antireflection layer that is away from the shielding layer;

[0037] A second conductive layer is prepared on the surface of the first conductive layer that is away from the antireflective layer, resulting in high-temperature resistant transparent conductive oxide coated glass.

[0038] In an embodiment, the step of preparing a shielding layer on the surface of a glass substrate includes: using a titanium source and oxygen in a molar ratio of 1:(3.4 to 7.1) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of a glass substrate at a temperature of 690°C to 720°C to obtain a shielding layer.

[0039] In an embodiment, the step of preparing a shielding layer on the surface of a glass substrate includes: using tin, silicon, phosphorus, deionized water, and oxygen as gaseous raw materials in a molar ratio of 1:(0.96~1.32):(0.48~0.72):(0.94~1.29):(19.67~22.09), and nitrogen and helium as carrier gases, a chemical vapor phase reaction is carried out on the surface of a glass substrate at a temperature of 690℃~720℃ to obtain a shielding layer.

[0040] In an embodiment, the step of preparing a first conductive layer on the surface of the antireflection layer away from the shielding layer includes: using tin source, fluorine source, deionized water and oxygen in a molar ratio of 1:(0.41~1.16):(3.16~5.82):(8.19~13.45) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the antireflection layer away from the shielding layer at a substrate temperature of 660℃~680℃ to obtain the first conductive layer.

[0041] In an embodiment, the step of preparing a second conductive layer on the surface of the first conductive layer away from the antireflection layer includes: using tin source, fluorine source, deionized water and oxygen in a molar ratio of 1:(0.41~1.16):(3.16~5.82):(8.19~13.45) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the first conductive layer away from the antireflection layer at a substrate temperature of 650℃~670℃ to obtain the second conductive layer.

[0042] In an embodiment, the step of preparing an antireflection layer on the surface of the shielding layer away from the glass substrate includes: preparing a first antireflection layer on the surface of the shielding layer away from the glass substrate; and preparing a second antireflection layer on the surface of the first antireflection layer away from the shielding layer.

[0043] In an embodiment, the step of preparing the first antireflection layer on the surface of the shielding layer away from the glass substrate includes: using silane, ethylene and oxygen in a molar ratio of 1:(5.3~6.7):(3.2~4.8) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the shielding layer away from the glass substrate at a substrate temperature of 680℃~690℃ to obtain the first antireflection layer.

[0044] In an embodiment, the step of preparing a second antireflection layer on the surface of the first antireflection layer away from the shielding layer includes: using silane, ethylene and oxygen in a molar ratio of 1:(5.3~6.7):(3.2~4.8) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the first antireflection layer away from the shielding layer at a substrate temperature of 670℃~680℃ to obtain the second antireflection layer.

[0045] Thirdly, this application provides a solar cell, including high-temperature resistant transparent conductive oxide coated glass provided in this application or high-temperature resistant transparent conductive oxide coated glass prepared by the preparation method provided in this application.

[0046] Compared with the prior art, this application has the following beneficial effects:

[0047] The transparent conductive oxide coated glass provided in the first aspect of this application maintains the stability of the film structure and microstructure at high temperatures. It comprises a glass substrate, a shielding layer, an antireflective layer, a first conductive layer, and a second conductive layer stacked sequentially. The shielding layer can prevent sodium and potassium ions in the glass substrate from diffusing into the conductive layer during high-temperature processes, thereby improving the stability of the conductive layer at high temperatures. The antireflective layer can improve the transmittance of the TCO coated glass of this application, thereby improving the photoelectric conversion efficiency. The first and second conductive layers are fluorine-doped tin dioxide layers, which have good conductivity and can collect the current generated by the solar cell. Furthermore, the crystallinity of the first and second conductive layers is above 50%, and the grain size is above 50 nm. The crystal particles are densely packed, have good continuity, and high density, and do not undergo significant changes at high temperatures. This makes the mean free path of free carriers at high temperatures much smaller than the grain size, which can reduce the influence of grain boundary scattering on the Hall mobility of the conductive layer, thereby further improving the stability of the conductive layer at high temperatures. Therefore, the high-temperature resistant transparent conductive oxide coated glass of this application has stable photoelectric performance at high temperatures.

[0048] The method for preparing high-temperature resistant transparent conductive oxide coated glass provided in the second aspect of this application involves using an online coating reaction device in the tin bath forming area of ​​float glass to first prepare a shielding layer on the surface of the glass substrate, then prepare an anti-reflection layer on the surface of the shielding layer away from the glass substrate, then prepare a first conductive layer on the surface of the anti-reflection layer away from the shielding layer, and finally prepare a second conductive layer on the surface of the first conductive layer away from the anti-reflection layer. The resulting high-temperature resistant transparent conductive oxide coated glass exhibits stable photoelectric properties at high temperatures. Furthermore, this preparation method is simple, easy to operate, and suitable for industrial production.

[0049] The solar cell provided in the third aspect of this application can improve the photoelectric conversion efficiency of the solar cell because it contains the transparent conductive oxide coated glass provided in this application. Attached Figure Description

[0050] To more clearly illustrate the technical solutions in the embodiments of this application, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0051] Figure 1 This is a schematic diagram of the structure of a transparent conductive oxide coated glass provided in an embodiment of this application;

[0052] Figure 2 This is a schematic diagram of the structure of a transparent conductive oxide coated glass provided in another embodiment of this application;

[0053] Figure 3 These are XRD patterns of the transparent conductive oxide coated glass provided in Embodiment 1 and Comparative Example 1 of this application before and after high-temperature heating;

[0054] Figure 4 This is a SEM image of the transparent conductive oxide coated glass provided in Embodiment 1 of this application;

[0055] Figure 5 This is a SEM image of the transparent conductive oxide coated glass provided in Embodiment 1 of this application after high-temperature heating;

[0056] Figure 6 These are the transmittance and reflectance change curves of the transparent conductive oxide coated glass provided in Embodiment 1 and Comparative Example 1 of this application before and after high-temperature heating;

[0057] The following are the labeling elements in the figure:

[0058] 1—Glass substrate, 2—Shielding layer, 3—Antireflection layer, 31—First antireflection layer, 32—Second antireflection layer, 4—First conductive layer, 5—Second conductive layer. Detailed Implementation

[0059] To make the technical problems, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application.

[0060] In this application, the term "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.

[0061] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0062] It should be understood that in the various embodiments of this application, the order of the above processes does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0063] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms “a,” “the,” and “the” used in the embodiments of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0064] The weights of the relevant components mentioned in the embodiments of this application can refer not only to the specific content of each component, but also to the proportional relationship between the weights of the components. Therefore, any scaling up or down of the content of the relevant components according to the embodiments of this application is within the scope disclosed in the embodiments of this application. Specifically, the mass described in the embodiments of this application can be a mass unit known in the chemical industry, such as μg, mg, g, or kg.

[0065] The terms "first" and "second" are used for descriptive purposes only, to distinguish objects, such as substances, from one another, and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. For example, without departing from the scope of the embodiments of this application, "first XX" may also be referred to as "second XX," and similarly, "second XX" may also be referred to as "first XX." Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of that feature.

[0066] The first aspect of this application provides a transparent conductive oxide-coated glass, such as... Figure 1 As shown, it includes a glass substrate 1, a shielding layer 2, an antireflection layer 3, a first conductive layer 4, and a second conductive layer 5 stacked sequentially. The first conductive layer 4 and the second conductive layer 5 are fluorine-doped tin dioxide layers. The crystallinity of the first conductive layer 4 and the second conductive layer 5 is more than 50%, and the grain size is more than 50 nm.

[0067] The transparent conductive oxide coated glass provided in this application comprises a glass substrate 1, a shielding layer 2, an antireflection layer 3, a first conductive layer 4, and a second conductive layer 5, which are sequentially stacked. This film structure can maintain stability at high temperatures. The shielding layer 2 can block the diffusion of sodium, potassium, and other ions from the glass substrate 1 into the conductive layer during high-temperature processes, thereby improving the stability of the conductive layer at high temperatures. The antireflection layer 3 can improve the light transmittance of the TCO coated glass of this application, thereby improving the light conversion efficiency. The first conductive layer 4 and the second conductive layer 5 are fluorine-doped tin dioxide layers, which have good conductivity and can collect the current generated by the solar cell. Furthermore, the crystallinity of the first conductive layer 4 and the second conductive layer 5 is above 50%, and the grain size is above 50 nm. The crystal particles are densely packed, have good continuity, and high density, and do not undergo significant changes at high temperatures, maintaining the stability of the microstructure. This makes the mean free path of free carriers at high temperatures much smaller than the grain size, which can reduce the influence of grain boundary scattering on the Hall mobility of the conductive layer, thereby further improving the stability of the conductive layer at high temperatures. Therefore, the transparent conductive oxide coated glass of this application has stable photoelectric performance at high temperatures.

[0068] In some embodiments, the crystallinity of the first conductive layer 4 is 58% or more, and the grain size is 55 nm or more.

[0069] In some embodiments, the crystallinity of the first conductive layer 4 is higher than that of the second conductive layer 5, the grain size of the first conductive layer 4 is larger than that of the second conductive layer 5, and the refractive index of the second conductive layer 5 is lower than that of the first conductive layer 4. In this way, the first conductive layer 4 and the second conductive layer 5 directly form a refractive index gradient, which can improve the transmittance of the transparent conductive oxide coated glass and thus have higher photoelectric conversion efficiency.

[0070] In some embodiments, the crystallinity of the first conductive layer 4 is 58% to 70%, and in exemplary examples, it can be typical but not limiting crystallinity such as 58%, 60%, 62%, 64%, 66%, 68%, and 70%. The grain size is 55 nm to 60 nm, and in exemplary examples, it can be typical but not limiting grain size such as 55 nm, 56 nm, 57 nm, 58 nm, 59 nm, and 60 nm. The crystallinity of the second conductive layer 5 is 50% to 58%, and in exemplary examples, it can be typical but not limiting crystallinity such as 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, and 58%. The grain size is 50 nm to 55 nm, and in exemplary examples, it can be typical but not limiting grain size such as 50 nm, 51 nm, 52 nm, 53 nm, 54 nm, and 55 nm. The inventors of this application discovered that the Hall mobility of the conductive layer is mainly affected by two scattering mechanisms: grain boundary scattering and ionic impurity scattering. When the mean free path of free carriers is much smaller than the grain size, grain boundary scattering has little effect on Hall mobility. However, when the mean free path of free carriers is comparable to the grain size, grain boundary scattering has a significant impact on Hall mobility. Therefore, within the grain size range of the first conductive layer 4 and the second conductive layer 5, the mean free path of free carriers at high temperatures can be made much smaller than the grain size, thus minimizing the impact of grain boundary scattering on the Hall mobility of the conductive layer and improving its conductivity stability at high temperatures. Furthermore, within the crystallinity range of the first conductive layer 4 and the second conductive layer 5, the absorption of photons by the conductive layer can be reduced, and photon reflection loss can be decreased, thereby improving the light transmittance of the transparent conductive oxide coated glass and resulting in higher photoelectric conversion efficiency.

[0071] In some embodiments, the refractive index of the first conductive layer 4 is 1.82 to 1.9. In exemplary examples, it can be a typical but not limiting refractive index such as 1.82, 1.83, 1.84, 1.85, 1.86, 1.87, 1.88, 1.89, or 1.9. The refractive index of the second conductive layer 5 is 1.79 to 1.86. In exemplary examples, it can be a typical but not limiting refractive index such as 1.79, 1.8, 1.81, 1.82, 1.83, 1.84, 1.85, or 1.86. Within the refractive index range of the first conductive layer 4 and the second conductive layer 5, the transparent conductive oxide coated glass can have high transmittance, thereby achieving high photoelectric conversion efficiency.

[0072] In some embodiments, the thickness of the first conductive layer 4 is 150 nm to 400 nm. In exemplary embodiments, typical but non-limiting thicknesses such as 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, and 400 nm are possible. The thickness of the second conductive layer 5 is 200 nm to 400 nm. In exemplary embodiments, typical but non-limiting thicknesses such as 200 nm, 250 nm, 300 nm, 350 nm, and 400 nm are possible. Within this thickness range of the first conductive layer 4 and the second conductive layer 5, the conductive layers can exhibit optimal conductivity.

[0073] In some embodiments, the refractive index of the shielding layer 2 is 1.63 to 2.8. In exemplary embodiments, it can be a typical but not limiting refractive index such as 1.63, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, etc., and the thickness is 40 nm to 70 nm. In exemplary embodiments, it can be a typical but not limiting thickness such as 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, etc. The shielding layer 2 with this range of refractive index and thickness not only imparts high transmittance to the transparent conductive oxide coated glass, but also better blocks the diffusion of sodium, potassium and other ions in the glass substrate 1 into the conductive layer at high temperatures, thereby improving the high-temperature stability of the transparent conductive oxide coated glass.

[0074] In some embodiments, the material of the shielding layer 2 includes a tin dioxide layer, a titanium dioxide layer, and SnSiO2. x At least one of the P layers. In the example, the shielding layer 2 is a titanium dioxide layer. The titanium dioxide layer has higher uniformity and density, which can better block the diffusion of sodium, potassium and other ions in the glass substrate 1 into the conductive layer, thereby improving the high-temperature stability of the transparent conductive oxide coated glass.

[0075] In some embodiments, such as Figure 2 As shown, the antireflective layer 3 includes a first antireflective layer 31 and a second antireflective layer 32. The first antireflective layer 31 is disposed between the shielding layer 2 and the second antireflective layer 32, and the refractive index of the second antireflective layer 32 is less than that of the first antireflective layer 31. In this way, the first antireflective layer 31 and the second antireflective layer 32 directly form a refractive index gradient, which is beneficial to improving the transmittance and transparency of the transparent conductive oxide coated glass, thus resulting in higher photoelectric conversion efficiency.

[0076] In some embodiments, the refractive index of the first antireflective layer 31 is 1.45 to 1.52. In exemplary embodiments, it can be a typical but not limiting refractive index such as 1.45, 1.46, 1.47, 1.48, 1.49, 1.5, 1.51, or 1.52. The refractive index of the second antireflective layer 32 is 1.42 to 1.5. In exemplary embodiments, it can be a typical but not limiting refractive index such as 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, or 1.5. Within the refractive index range of the first antireflective layer 31 and the second antireflective layer 32, the transparent conductive oxide coated glass can have a higher transmittance, thereby having a higher photoelectric conversion efficiency.

[0077] In some embodiments, the thickness of the first antireflection layer 31 is 10nm to 30nm. In exemplary embodiments, it can be a typical but not limiting thickness such as 10nm, 15nm, 20nm, 25nm, or 30nm. The thickness of the second antireflection layer 32 is 10nm to 30nm. In exemplary embodiments, it can be a typical but not limiting thickness such as 10nm, 15nm, 20nm, 25nm, or 30nm. Within the thickness range of the first antireflection layer 31 and the second antireflection layer 32, the transparent conductive oxide coated glass can have a higher transmittance, thereby having a higher photoelectric conversion efficiency.

[0078] In some embodiments, the first antireflective layer 31 and the second antireflective layer 32 are silicon dioxide layers.

[0079] In some embodiments, the glass substrate is a float glass substrate with a transmittance ≥89% and a thickness of 2mm to 3.5mm. The float glass substrate can be any one of ordinary float glass, high-white float glass, or ultra-white float glass.

[0080] In some embodiments, the transmittance of the transparent conductive oxide coated glass is 81% to 85%.

[0081] In some embodiments, the carrier concentration of the transparent conductive oxide-coated glass is 2.6 × 10⁻⁶. 20 ~4.2×10 20 / cm - 3.

[0082] In some embodiments, the resistance of the transparent conductive oxide coated glass is 6 to 12 Ω / □.

[0083] In some embodiments, after the transparent conductive oxide coated glass passes the high-temperature heat resistance test, the transmittance of the transparent conductive oxide coated glass is 82% to 86%; wherein, the high-temperature heat resistance test is set to the transparent conductive oxide coated glass being kept in an air atmosphere at a temperature of 600-700°C for at least 2.5 hours.

[0084] In some embodiments, after passing a high-temperature heat resistance test, the carrier concentration of the transparent conductive oxide coated glass is 2.5 × 10⁻⁶. 20 ~4.1×10 20 / cm - 3; Among them, the high temperature heat resistance test is set as follows: transparent conductive oxide coated glass is kept in an air atmosphere at a temperature of 600-700℃ for at least 2.5 hours.

[0085] In some embodiments, after the transparent conductive oxide coated glass passes the high-temperature heat resistance test, the resistance of the transparent conductive oxide coated glass is 6 to 12 Ω / □; wherein, the high-temperature heat resistance test is set to the transparent conductive oxide coated glass being kept in an air atmosphere at a temperature of 600-700°C for at least 2.5 hours.

[0086] The high-temperature resistant transparent conductive oxide coated glass of this application embodiment can be prepared by the following preparation method.

[0087] The second aspect of this application provides a method for preparing high-temperature resistant transparent conductive oxide coated glass, comprising the following steps:

[0088] S01: Provide a glass substrate, and use an online coating reaction device in the float glass tin bath forming area;

[0089] S02: Prepare a shielding layer on the surface of a glass substrate;

[0090] S03: Prepare an anti-reflection layer on the surface of the shielding layer that is away from the glass substrate;

[0091] S04: Prepare a first conductive layer on the surface of the antireflection layer that is away from the shielding layer;

[0092] S05: Prepare a second conductive layer on the surface of the first conductive layer away from the antireflective layer to obtain high-temperature resistant transparent conductive oxide coated glass.

[0093] The method for preparing high-temperature resistant transparent conductive oxide coated glass provided in this application embodiment involves using an online coating reaction device in the tin bath forming area of ​​float glass. First, a shielding layer is prepared on the surface of the glass substrate. Then, an anti-reflection layer is prepared on the surface of the shielding layer away from the glass substrate. Next, a first conductive layer is prepared on the surface of the anti-reflection layer away from the shielding layer. Finally, a second conductive layer is prepared on the surface of the first conductive layer away from the anti-reflection layer. The resulting high-temperature resistant transparent conductive oxide coated glass has a stable film structure at high temperatures. Furthermore, this preparation method is simple, easy to operate, and suitable for industrial production.

[0094] In step S02, the step of preparing a shielding layer on the surface of the glass substrate includes: using a titanium source and oxygen in a molar ratio of 1:(3.4 to 7.1) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the glass substrate at a temperature of 690°C to 720°C to obtain the shielding layer. Specifically, the titanium source can be isopropyl titanate.

[0095] In some embodiments, the step of preparing a shielding layer on the surface of a glass substrate may further include: using a tin source, silicon source, phosphorus source, deionized water, and oxygen as gaseous raw materials in a molar ratio of 1:(0.96–1.32):(0.48–0.72):(0.94–1.29):(19.67–22.09), and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of a glass substrate at a temperature of 690°C–720°C to obtain the shielding layer. Specifically, the tin source may include at least one of trichloromonobutyltin, dichlorodimethyltin, tetramethyltin, and tin tetrachloride; the silicon source may be tetraethyl orthosilicate; and the phosphorus source may be triethyl phosphite. Preferred raw materials, ratios, and corresponding higher reaction temperatures can form a high-temperature resistant shielding layer.

[0096] In step S03, the step of preparing an antireflection layer on the surface of the shielding layer away from the glass substrate includes: preparing a first antireflection layer on the surface of the shielding layer away from the glass substrate; and preparing a second antireflection layer on the surface of the first antireflection layer away from the shielding layer.

[0097] In some embodiments, the step of preparing a first antireflective layer on the surface of the shielding layer away from the glass substrate includes: using silane, ethylene, and oxygen in a molar ratio of 1:(5.3–6.7):(3.2–4.8) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the shielding layer away from the glass substrate at a substrate temperature of 680°C–690°C to obtain the first antireflective layer. Preferred raw materials, ratios, and corresponding higher reaction temperatures can form a high-temperature resistant first antireflective layer.

[0098] In some embodiments, the step of preparing a second antireflection layer on the surface of the first antireflection layer away from the shielding layer includes: using silane, ethylene, and oxygen in a molar ratio of 1:(5.3–6.7):(3.2–4.8) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the first antireflection layer away from the shielding layer at a substrate temperature of 670°C–680°C to obtain the second antireflection layer. Preferred raw materials, ratios, and corresponding higher reaction temperatures can form a high-temperature resistant second antireflection layer.

[0099] In some embodiments, the preparation methods of the first antireflection layer and the second antireflection layer are different, so that the first antireflection layer and the second antireflection layer form a refractive index gradient, which is beneficial to improving the transmittance and transparency of the transparent conductive oxide coated glass, and thus has higher photoelectric conversion efficiency.

[0100] In step S04, the step of preparing a first conductive layer on the surface of the antireflection layer away from the shielding layer includes: using a tin source, a fluorine source, deionized water, and oxygen in a molar ratio of 1:(0.41~1.16):(3.16~5.82):(8.19~13.45) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the antireflection layer away from the shielding layer at a substrate temperature of 660℃~680℃ to obtain the first conductive layer. Specifically, the tin source may include at least one of trichloromonobutyltin, dichlorodimethyltin, tetramethyltin, and tin tetrachloride; the fluorine source may include at least one of ammonium fluoride, trifluoroacetic acid, hydrofluoric acid, and tetrabutylammonium fluoride.

[0101] In step S05, the step of preparing a second conductive layer on the surface of the first conductive layer away from the antireflection layer includes: using a tin source, a fluorine source, deionized water, and oxygen in a molar ratio of 1:(0.41~1.16):(3.16~5.82):(8.19~13.45) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the first conductive layer away from the antireflection layer at a substrate temperature of 650℃~670℃ to obtain the second conductive layer. Specifically, the tin source may include at least one of trichloromonobutyltin, dichlorodimethyltin, tetramethyltin, and tin tetrachloride; the fluorine source may include at least one of ammonium fluoride, trifluoroacetic acid, hydrofluoric acid, and tetrabutylammonium fluoride.

[0102] In some embodiments, the glass substrate 1 used in the method for preparing high-temperature resistant transparent conductive oxide coated glass provided in this application, as well as the shielding layer 2, anti-reflection layer 3, first conductive layer 4 and second conductive layer 5 prepared on the glass substrate 1, can be selected from the film layer types, film layer thicknesses and film layer structures listed in the first aspect of this application, so as to obtain high-temperature resistant transparent conductive oxide coated glass.

[0103] A second aspect of this application provides a solar cell, including high-temperature resistant transparent conductive oxide coated glass provided in this application embodiment or high-temperature resistant transparent conductive oxide coated glass prepared by the preparation method provided in this application embodiment.

[0104] The solar cell provided in this application uses high-temperature resistant transparent conductive oxide coated glass provided or prepared in this application as the front electrode. After high temperature, the photoelectric performance of the front electrode remains stable, thus improving the conversion efficiency of the solar cell in this application.

[0105] The following description is based on specific embodiments.

[0106] Example 1

[0107] This embodiment provides a high-temperature resistant transparent conductive oxide coated glass and its preparation method.

[0108] like Figure 1 As shown, the high-temperature resistant transparent conductive oxide coated glass includes a glass substrate 1, a shielding layer 2, an antireflective layer 3, a first conductive layer 4, and a second conductive layer 5 stacked sequentially. The glass substrate 1 is a float glass substrate with a thickness of 4 mm. The shielding layer 2 is a titanium dioxide layer with a refractive index of 2.63 and a thickness of 43 nm. The first antireflective layer 31 and the second antireflective layer 32 are silicon dioxide layers. The first antireflective layer 31 has a refractive index of 1.48 and a thickness of 27 nm, and the second antireflective layer 32 has a refractive index of 1.46 and a thickness of 30 nm. The first conductive layer 4 and the second conductive layer 5 are fluorine-doped tin dioxide layers. The first conductive layer 4 has a crystallinity of 58%, a grain size of 55 nm, a refractive index of 1.9, and a thickness of 230 nm. The second conductive layer 5 has a crystallinity of 50%, a grain size of 50 nm, a refractive index of 1.86, and a thickness of 250 nm.

[0109] The preparation method of this high-temperature resistant transparent conductive oxide coated glass includes the following steps:

[0110] S1: In the float glass tin bath forming area with a drawing capacity of 520t / d, a coating reactor is installed above the float glass substrate;

[0111] S2: Using nitrogen and helium as carrier gases, and with a molar ratio of 1:5 for isopropyl titanate (evaporation temperature 150℃) and oxygen, isopropyl titanate and oxygen are introduced into the coating reactor. The flow rates of isopropyl titanate, oxygen, nitrogen and helium are controlled by flow meters to make the total gas volume 600 slpm. A chemical vapor phase reaction is carried out on the surface of float glass at 690℃ to form a titanium dioxide layer.

[0112] S3: Using nitrogen as the carrier gas, silane, ethylene and oxygen are introduced into the coating reactor according to the molar ratio of silane, ethylene and oxygen of 1:6:4. The flow rates of silane, ethylene, oxygen and nitrogen are controlled by flow meters to make the total gas volume 530 slpm. At a substrate temperature of 680℃, a chemical vapor phase reaction is carried out on the surface of the shielding layer 2 to form a silicon dioxide layer.

[0113] Using nitrogen as the carrier gas, silane, ethylene and oxygen are introduced into the coating reactor according to the molar ratio of silane, ethylene and oxygen of 1:6.1:4.1. The flow rates of silane, ethylene, oxygen and nitrogen are controlled by flow meters to make the total gas volume 550 slpm. A chemical vapor phase reaction is carried out on the surface of the first antireflection layer 31 at 670℃ to form the silicon dioxide layer of the second antireflection layer 32.

[0114] S4: Using nitrogen and helium as carrier gases, monobutyltin trichloride, trifluoroacetic acid, deionized water and oxygen are introduced into the coating reactor according to the molar ratio of monobutyltin trichloride, trifluoroacetic acid, deionized water and oxygen of 1:0.8:4.5:10.5. The flow rates of monobutyltin trichloride, trifluoroacetic acid, deionized water and oxygen are controlled by flow meters to make the total gas volume 710 slpm. At a substrate temperature of 660℃, a chemical vapor phase reaction is carried out on the surface of the antireflection layer to form a fluorine-doped tin dioxide layer.

[0115] S5: Using nitrogen and helium as carrier gases, monobutyltin trichloride, trifluoroacetic acid, deionized water and oxygen are introduced into the coating reactor according to the molar ratio of monobutyltin trichloride, trifluoroacetic acid, deionized water and oxygen as 1:0.8:4.5:10.5. The flow rates of monobutyltin trichloride, trifluoroacetic acid, deionized water and oxygen are controlled by flow meters to make the total gas volume 710 slpm. At a substrate temperature of 650℃, a chemical vapor phase reaction is carried out on the surface of the first conductive layer 4 to form a fluorine-doped tin dioxide layer, and high-temperature resistant transparent conductive oxide coated glass is obtained.

[0116] Example 2

[0117] This embodiment provides a high-temperature resistant transparent conductive oxide coated glass and its preparation method.

[0118] like Figure 1 As shown, the difference between this high-temperature resistant transparent conductive oxide coated glass and Example 1 is that the first conductive layer 4 has a crystallinity of 70%, a grain size of 60 nm, a refractive index of 1.82, and a thickness of 230 nm, while the second conductive layer 5 has a crystallinity of 58%, a grain size of 55 nm, a refractive index of 1.7, and a thickness of 250 nm.

[0119] The difference between the steps of this high-temperature resistant transparent conductive oxide coated glass and those of Example 1 is that the substrate temperature in step S4 is 680°C and the substrate temperature in step S5 is 670°C.

[0120] Example 3

[0121] This embodiment provides a high-temperature resistant transparent conductive oxide coated glass and its preparation method.

[0122] like Figure 1As shown, the difference between this high-temperature resistant transparent conductive oxide coated glass and Example 1 is that the first conductive layer 4 has a crystallinity of 63%, a grain size of 57 nm, a refractive index of 1.87, and a thickness of 230 nm, while the second conductive layer 5 has a crystallinity of 54%, a grain size of 52 nm, a refractive index of 1.81, and a thickness of 250 nm.

[0123] The difference between the steps of this high-temperature resistant transparent conductive oxide coated glass and those of Example 1 is that the substrate temperature in step S4 is 670°C and the substrate temperature in step S5 is 660°C.

[0124] Example 4

[0125] This embodiment provides a high-temperature resistant transparent conductive oxide coated glass and its preparation method.

[0126] like Figure 2 As shown, the difference between this high-temperature resistant transparent conductive oxide coated glass and Example 1 is that: the antireflective layer is a silicon dioxide layer with a refractive index of 1.48 and a thickness of 27 nm; the first conductive layer 4 and the second conductive layer 5 are fluorine-doped tin dioxide layers; the crystallinity of the first conductive layer 4 is 63%, the grain size is 57 nm, the refractive index is 1.87, and the thickness is 230 nm; the crystallinity of the second conductive layer 5 is 54%, the grain size is 52 nm, the refractive index is 1.81, and the thickness is 250 nm.

[0127] The difference between the steps of this high-temperature resistant transparent conductive oxide coated glass and those of Example 1 is that in step S3, nitrogen is used as the carrier gas, and silane, ethylene and oxygen are introduced into the coating reactor according to the molar ratio of silane, ethylene and oxygen of 1:6:4. The flow rates of silane, ethylene, oxygen and nitrogen are controlled by flow meters to make the total gas volume 530 slpm. A chemical vapor phase reaction is carried out on the surface of the shielding layer 2 at 680°C to form a silicon dioxide layer.

[0128] The substrate temperature in step S4 is 670°C, and the substrate temperature in step S5 is 660°C.

[0129] Comparative Example 1

[0130] This comparative example provides a transparent conductive oxide coated glass.

[0131] The transparent conductive oxide coated glass includes a glass substrate, a shielding layer, an antireflective layer, a first conductive layer, and a second conductive layer stacked sequentially. The glass substrate is a float glass substrate with a thickness of 4 mm. The shielding layer is a tin dioxide layer with a refractive index of 1.89 and a thickness of 43 nm. The antireflective layer is a silicon dioxide layer with a refractive index of 1.49 and a thickness of 27 nm. The first conductive layer and the second conductive layer are both fluorine-doped tin dioxide layers with a crystallinity of 48%, a grain size of 44 nm, a refractive index of 1.81, and a thickness of 250 nm.

[0132] The method for preparing this transparent conductive oxide coated glass includes the following steps:

[0133] S1: In the float glass tin bath forming area with a drawing capacity of 520t / d, a coating reactor is installed above the float glass substrate;

[0134] S2: Using nitrogen and helium as carrier gases, monobutyltin trichloride (evaporation temperature 180℃), deionized water (evaporation temperature 150℃) and oxygen are introduced into the coating reactor at a molar ratio of 1:6:4. The flow rates of monobutyltin trichloride, deionized water, oxygen, nitrogen and helium are controlled by flow meters to make the total gas volume 650 slpm. A chemical vapor phase reaction is carried out on the surface of a float glass substrate at 680℃ to form a tin dioxide layer.

[0135] S3: Using nitrogen as the carrier gas, silane, ethylene and oxygen are introduced into the coating reactor according to the molar ratio of silane, ethylene and oxygen of 1:6:4. The flow rates of silane, ethylene, oxygen and nitrogen are controlled by flow meters to make the total gas volume 530 slpm. At a substrate temperature of 660℃, a chemical vapor phase reaction is carried out on the surface of the shielding layer to form a silicon dioxide layer.

[0136] S4: Using nitrogen and helium as carrier gases, monobutyltin trichloride, trifluoroacetic acid, deionized water and oxygen are introduced into the coating reactor according to the molar ratio of monobutyltin trichloride, trifluoroacetic acid, deionized water and oxygen as 1:0.8:4.5:10.5. The flow rates of monobutyltin trichloride, trifluoroacetic acid, deionized water and oxygen are controlled by flow meters to make the total gas volume 710 slpm. At a substrate temperature of 550℃, a chemical vapor phase reaction is carried out on the surface of the antireflection layer to form a fluorine-doped tin dioxide layer.

[0137] S5: Using nitrogen and helium as carrier gases, monobutyltin trichloride, trifluoroacetic acid, deionized water and oxygen are introduced into the coating reactor according to a molar ratio of 1:0.8:4.5:10.5. The flow rates of monobutyltin trichloride, trifluoroacetic acid, deionized water and oxygen are controlled by flow meters to make the total gas volume 710 slpm. At a substrate temperature of 550℃, a chemical vapor phase reaction is carried out on the surface of the antireflection layer to form a fluorine-doped tin dioxide layer, resulting in transparent conductive oxide coated glass.

[0138] Analysis of relevant performance tests before and after high-temperature heat resistance test:

[0139] (1) The high-temperature resistant transparent conductive oxide coated glass provided in Example 1 of this application and the transparent conductive oxide coated glass provided in Comparative Example 1 were placed in an air atmosphere (oxygen content of about 20%), heated to 650°C and kept at a constant temperature for 4 hours. Then, XRD tests were performed on the coated glass before and after the high-temperature heat treatment. The test results are as follows: Figure 3 As shown:

[0140] from Figure 3 It can be seen that the first conductive layer 4 and the second conductive layer 5 of the transparent conductive oxide coated glass provided in Embodiment 1 and Comparative Example 1 of this application are mainly grown along the (110) preferred orientation. Furthermore, the (110) strength of the high-temperature resistant transparent conductive oxide coated glass of Embodiment 1 of this application is significantly higher than that of Comparative Example 1, the crystallinity is more than 50%, and the main crystal orientations are (110), (101), (200), and (211). Moreover, the crystallinity and main crystal orientation remain unchanged after high-temperature heat treatment. This indicates that the first conductive layer 4 and the second conductive layer 5 of the transparent conductive oxide coated glass provided in the embodiments of this application have higher crystallinity and maintain the corresponding crystallinity and main crystal orientation at high temperature.

[0141] (2) The transparent conductive oxide coated glass provided in Example 1 of this application was subjected to field emission scanning electron microscopy (SEM) tests before and after high-temperature heat treatment. The test results are as follows: Figure 4 (before high-temperature heat treatment) and Figure 5 As shown (after high-temperature heat treatment):

[0142] from Figure 4 and Figure 5 It can be seen that the high-temperature resistant transparent conductive oxide coated glass provided in Embodiment 1 of this application has a grain size of more than 50nm on the surface of the thin film before high-temperature heat treatment. The grains are densely packed, have good continuity and high density. After high-temperature heat treatment, the grain outline is sharper and clearer. Moreover, the grain size of the conductive layer of the high-temperature resistant transparent conductive oxide coated glass does not change much after high-temperature heat treatment. This indicates that the high-temperature resistant transparent conductive oxide coated glass provided in Embodiment 1 of this application has better microstructure stability at high temperatures.

[0143] (3) The high-temperature resistant transparent conductive oxide coated glass provided in Example 1 of this application and the transparent conductive oxide coated glass provided in Comparative Example 1 were subjected to optical performance tests before and after high-temperature heat treatment, respectively. The test results are as follows: Figure 6 As shown:

[0144] from Figure 6 It can be seen that the transparent conductive oxide coated glass provided in Comparative Example 1 exhibits reduced absorption of photons at the carrier ion concentration in the near-infrared range of 780nm-2500nm before and after heat treatment, leading to an increase in the thin film transmittance. However, the high-temperature resistant transparent conductive oxide coated glass provided in Example 1 of this application maintains essentially unchanged transmittance and reflectance in the near-infrared range of 780nm-2500nm before and after heat treatment. Furthermore, Comparative Example 1 shows a greater increase in transmittance in the near-infrared region. This is due to the penetration of oxygen from the air into the thin film surface, resulting in a decrease in the oxygen hole concentration in the thin film, or the reduction in fluorine ion doping concentration in the thin film due to high-temperature heat treatment, thereby decreasing the carrier concentration in the thin film. Therefore, it is demonstrated that the high-temperature resistant transparent conductive oxide coated glass provided in this application has stable optical properties at high temperatures.

[0145] (4) The high-temperature resistant transparent conductive oxide coated glass provided in Examples 1-4 of this application and the transparent conductive oxide coated glass provided in Comparative Example 1 were subjected to Hall effect measurements before and after high-temperature heat treatment. The test results are shown in Table 1:

[0146] Table 1

[0147]

[0148] As shown in Table 1, the high-temperature resistant transparent conductive oxide coated glasses provided in Examples 1-4 of this application exhibit relatively small changes in resistivity, mobility, carrier concentration, and resistance before and after high-temperature heating, with the carrier concentration change rate in Example 1 decreasing to 1%. However, the transparent conductive oxide coated glass provided in Comparative Example 1 shows significant changes in resistivity, mobility, carrier concentration, and resistance before and after high-temperature heating, with the carrier concentration change rate in Example 1 decreasing by 6.9%. It is evident that the transparent conductive oxide coated glasses provided in the embodiments of this application possess more stable conductivity at high temperatures, indicating that the crystallinity of the first conductive layer 4 and the second conductive layer 5 in this application is above 50%, and the grain size is above 50 nm. This allows the mean free path of free carriers in the first conductive layer 4 and the second conductive layer 5 at high temperatures to be much smaller than the grain size, reducing the influence of grain boundary scattering on the Hall mobility of the conductive layer, thereby improving the conductivity stability of the first conductive layer 4 and the second conductive layer 5 at high temperatures.

[0149] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A high-temperature resistant transparent conductive oxide-coated glass, characterized in that, The material comprises a glass substrate, a shielding layer, an antireflection layer, a first conductive layer, and a second conductive layer, which are stacked sequentially. The first conductive layer and the second conductive layer are fluorine-doped tin dioxide layers. The crystallinity of the first conductive layer and the second conductive layer is greater than 50%, and the grain size is greater than 50 nm. The first conductive layer has a crystallinity of 58% or higher and a grain size of 55 nm or higher; The crystallinity of the first conductive layer is higher than that of the second conductive layer; The grain size of the first conductive layer is larger than the grain size of the second conductive layer; The refractive index of the second conductive layer is less than that of the first conductive layer.

2. The high-temperature resistant transparent conductive oxide coated glass as described in claim 1, characterized in that, The first conductive layer has a crystallinity of 58%~70% and a grain size of 55nm~60nm; and / or, The second conductive layer has a crystallinity of 50%~58% and a grain size of 50nm~55nm; and / or, The refractive index of the first conductive layer is 1.82~1.9; and / or, The refractive index of the second conductive layer is 1.79~1.86; and / or, The thickness of the first conductive layer is 150nm~400nm; and / or, The thickness of the second conductive layer is 200nm~400nm.

3. The high-temperature resistant transparent conductive oxide coated glass as described in claim 1, characterized in that, The refractive index of the shielding layer is 1.63~2.8; and / or, The thickness of the shielding layer is 40nm~70nm; and / or, The shielding layer includes at least one of tin dioxide layer, titanium dioxide layer, and SnSiOx:P layer.

4. The high-temperature resistant transparent conductive oxide coated glass as described in claim 1, characterized in that, The antireflection layer includes a first antireflection layer and a second antireflection layer, with the first antireflection layer disposed between the shielding layer and the second antireflection layer.

5. The high-temperature resistant transparent conductive oxide coated glass as described in claim 4, characterized in that, The refractive index of the first antireflective layer is 1.45~1.52; and / or, The refractive index of the second antireflective layer is 1.42~1.5; and / or, The thickness of the first antireflective layer is 10nm~30nm; and / or, The thickness of the second antireflective layer is 10nm~30nm.

6. The high-temperature resistant transparent conductive oxide coated glass as described in claim 4, characterized in that, The first antireflective layer and the second antireflective layer are silicon dioxide layers; and / or, The refractive index of the second antireflective layer is less than that of the first antireflective layer.

7. The high-temperature resistant transparent conductive oxide coated glass as described in claim 1, characterized in that, The glass substrate is a float glass substrate, and the transmittance of the float glass substrate is ≥89%.

8. The high-temperature resistant transparent conductive oxide coated glass as described in claim 1, characterized in that, The transmittance of the transparent conductive oxide coated glass is 81%~85%; and / or, The carrier concentration of the transparent conductive oxide coated glass is 2.6×10²⁰ ~ 4.2×10²⁰ / cm². -3 ; and / or, The resistance of the transparent conductive oxide coated glass is 6~12Ω / □.

9. The high-temperature resistant transparent conductive oxide coated glass as described in claim 1, characterized in that, After passing a high-temperature heat resistance test, the transmittance of the transparent conductive oxide coated glass is 82%~86%; and / or, The carrier concentration of the transparent conductive oxide coated glass is 2.5×10²⁰ ~ 4.1×10²⁰ / cm². -3 ; and / or, The resistance of the transparent conductive oxide coated glass is 6~12Ω / □; The high-temperature heat resistance test is set to be conducted on the transparent conductive oxide coated glass at a temperature of 600-700℃ in an air atmosphere for at least 2.5 hours.

10. A method for preparing high-temperature resistant transparent conductive oxide coated glass as described in any one of claims 1 to 9, characterized in that, Includes the following steps: Provide glass substrates and use online coating reaction equipment in the float glass tin bath forming area; A shielding layer is prepared on the surface of the glass substrate; An antireflective layer is prepared on the surface of the shielding layer opposite to the glass substrate; A first conductive layer is prepared on the surface of the antireflective layer opposite to the shielding layer; A second conductive layer is prepared on the surface of the first conductive layer that is away from the antireflective layer, to obtain high-temperature resistant transparent conductive oxide coated glass.

11. The preparation method according to claim 10, characterized in that, The step of preparing a shielding layer on the surface of the glass substrate includes: using titanium source and oxygen in a molar ratio of 1:(3.4~7.1) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the glass substrate at a temperature of 690℃~720℃ to obtain the shielding layer; or, Using tin, silicon, phosphorus, deionized water, and oxygen as gaseous raw materials in a molar ratio of 1:(0.96~1.32):(0.48~0.72):(0.94~1.29):(19.67~22.09), and nitrogen and helium as carrier gases, a chemical vapor phase reaction is carried out on the surface of the glass substrate at a temperature of 690℃~720℃ to obtain a shielding layer.

12. The preparation method according to claim 10, characterized in that, The step of preparing a first conductive layer on the surface of the antireflective layer away from the shielding layer includes: using tin source, fluorine source, deionized water and oxygen in a molar ratio of 1:(0.41~1.16):(3.16~5.82):(8.19~13.45) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the antireflective layer away from the shielding layer at a substrate temperature of 660℃~680℃ to obtain the first conductive layer; and / or, The step of preparing a second conductive layer on the surface of the first conductive layer away from the antireflection layer includes: using tin source, fluorine source, deionized water and oxygen in a molar ratio of 1:(0.41~1.16):(3.16~5.82):(8.19~13.45) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the first conductive layer away from the antireflection layer at a substrate temperature of 650℃~670℃ to obtain the second conductive layer.

13. The preparation method according to claim 10, characterized in that, The step of preparing an antireflection layer on the surface of the shielding layer opposite to the glass substrate includes: A first antireflective layer is prepared on the surface of the shielding layer opposite to the glass substrate; A second antireflection layer is prepared on the surface of the first antireflection layer that is opposite to the shielding layer.

14. The preparation method according to claim 13, characterized in that, The step of preparing a first antireflective layer on the surface of the shielding layer away from the glass substrate includes: using silane, ethylene, and oxygen in a molar ratio of 1:(5.3~6.7):(3.2~4.8) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the shielding layer away from the glass substrate at a substrate temperature of 680℃~690℃ to obtain the first antireflective layer; and / or, The step of preparing a second antireflection layer on the surface of the first antireflection layer away from the shielding layer includes: using silane, ethylene and oxygen in a molar ratio of 1:(5.3~6.7):(3.2~4.8) as gaseous raw materials, and nitrogen and helium as carrier gases, performing a chemical vapor phase reaction on the surface of the first antireflection layer away from the shielding layer at a substrate temperature of 670℃~680℃ to obtain the second antireflection layer.

15. A solar cell, characterized in that, This includes the high-temperature resistant transparent conductive oxide coated glass according to any one of claims 1 to 9, or the high-temperature resistant transparent conductive oxide coated glass prepared by the preparation method according to any one of claims 10 to 14.

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