TCO coated glass for perovskite cell and production method of TCO coated glass

Abstract

The invention relates to the technical field of coated glass, in particular to TCO coated glass for a perovskite cell and a production method of the TCO coated glass, and the glass comprises a glass matrix layer, a sodium blocking layer, an induction seed layer, a first conductive functional layer, a middle passivation layer and a second conductive functional layer, a sodium blocking layer, an induction seed layer, a first conductive functional layer, a middle passivation layer and a second conductive functional layer are sequentially compounded on a glass substrate layer, colorless transparent glass or ultra-white glass is used as a substrate, and a TCO thin film with a novel structure is formed through online coating by utilizing a chemical vapor deposition process. The problems of internal defect increase, low light transmittance, large haze and the like caused by thickening of the film layer are solved, and the use requirement of the perovskite thin film battery is met.

Description

Technical Field

[0001] This invention relates to the field of coated glass technology, specifically to a TCO coated glass for perovskite batteries and its production method, which is produced by online chemical vapor deposition. Background Technology

[0002] As is well known, perovskite solar cells are a novel solar cell technology, belonging to the third generation of solar cells. They possess characteristics such as high conversion efficiency, low-temperature manufacturing and low energy consumption, short process cycle, good performance in low-light conditions, and strong power generation capacity, making them a research hotspot worldwide. Perovskite solar cells use glass as a substrate and consist of five thin-film materials: a transparent front electrode, a hole transport layer, a perovskite absorber layer, an electron transport layer, and a back electrode. The transparent front electrode is formed by depositing a transparent conductive oxide film, namely TCO glass, on transparent glass. It is a key raw material for perovskite solar cells, accounting for more than one-third of their manufacturing cost. The basic requirements for TCO glass in perovskite solar cells are high light transmittance and low resistance. Because the hole transport layer is very thin, it must be grown densely and uniformly without micropores; therefore, the TCO film layer must have low haze.

[0003] Currently, perovskite solar cells generally use fluorine-doped tin oxide produced by chemical vapor deposition (CVD) as the TCO film material, which has advantages such as high transmittance, low surface resistivity, good weather resistance, and high cost-effectiveness. Assuming the material resistivity remains constant, the surface resistivity of TCO glass is inversely proportional to the film thickness. To obtain lower surface resistivity, the film thickness needs to be increased. During CVD deposition of TCO thin films, the film grows continuously in a columnar shape. As the film thickness increases, grain growth and fission occur, grain boundary scattering increases, and the light absorption and haze of the film gradually increase, showing a trend of lower transmittance and greater haze with thicker film layers. Therefore, while achieving lower resistance through thicker film layers, the transmittance of TCO glass decreases and the haze gradually increases, making it difficult to simultaneously meet the requirements of low resistance, high transmittance, and low haze. Summary of the Invention

[0004] The purpose of this invention is to overcome the shortcomings of the prior art and provide a TCO-coated glass for perovskite thin-film batteries with high light transmittance, low resistance, and low haze, produced by online chemical vapor deposition, and a method thereof.

[0005] The technical solution adopted by this invention to solve its technical problem is: A TCO-coated glass for perovskite solar cells is characterized by comprising a glass substrate layer, a sodium-blocking layer, an inducing seed layer, a first conductive functional layer, an intermediate passivation layer, and a second conductive functional layer. The sodium-blocking layer, inducing seed layer, first conductive functional layer, intermediate passivation layer, and second conductive functional layer are sequentially laminated onto the glass substrate layer. The glass substrate layer is a colorless transparent glass layer or an ultra-white glass layer. The sodium-blocking layer is composed of silicon nitride with a thickness of 20 nm to 30 nm. The inducing seed layer is composed of titanium oxide with a thickness of 10 nm to 30 nm. The first conductive functional layer is composed of fluorine-doped tin oxide with a thickness of 300 nm to 500 nm. The intermediate passivation layer is composed of silicon oxide with a thickness of 10 nm to 20 nm. The second conductive functional layer is composed of fluorine-doped tin oxide with a thickness of 100 nm to 300 nm. The resulting TCO glass has a surface resistivity of 8.24-9.65 Ω / □, a photovoltaic transmittance of 82.8%-83.4%, and a haze of 1.32%-1.46%.

[0006] The function of the aforementioned sodium-blocking layer is to inhibit the leakage of alkali metal ions (including sodium and potassium ions) from the glass substrate and their diffusion into the conductive functional layer, thereby degrading the photoelectric properties of the film. Float-mount silicon nitride films, deposited online, exhibit high adhesion, good thermal stability, and strong ability to block alkali metal ions.

[0007] The role of the inducing seed layer is to form a thin rutile structure, which provides an inducing seed for the growth of the conductive functional layer. Both are rutile structures with the same lattice growth direction. Growth is stimulated through heterostructure to ensure the good quality of the growth and crystallization of the conductive functional layer.

[0008] The function of the first conductive functional layer is to utilize the semiconductor properties of fluorine-doped tin oxide to achieve conductivity and provide charge carriers for power transmission in perovskite solar cell devices.

[0009] The function of the intermediate passivation layer is to modify and passivate the surface of the first conductive layer, reduce surface defects, and provide a good interface for the growth of the second conductive layer.

[0010] The function of the second conductive functional layer is to utilize the semiconductor properties of fluorine-doped tin oxide to achieve conductivity, provide charge carriers for power transmission in perovskite solar cell devices, and connect with the film structure of the perovskite solar cell.

[0011] The aforementioned glass overcomes the problems of reduced light transmittance and increased haze caused by increased film thickness, and meets the requirements of high light transmittance, low resistance, and low haze for TCO glass.

[0012] A method for preparing TCO-coated glass for perovskite solar cells, characterized by the following steps: (1) Sodium barrier layer: A sodium barrier layer is deposited on the glass substrate; (2) Depositing an induction seed layer: Depositing an induction seed layer on the glass substrate layer that has been deposited with a sodium barrier layer in step (1); (3) Depositing the first conductive functional layer: depositing the first conductive functional layer on the glass substrate layer on which the sodium-blocking layer and the induction seed layer have been deposited in step (2); (4) Depositing an intermediate passivation layer: Depositing an intermediate passivation layer on the glass substrate layer on which the sodium barrier layer, the seed layer, and the first conductive functional layer have been deposited in step (3); (5) Depositing the second conductive functional layer: Depositing the second conductive functional layer on the glass substrate layer on which the sodium barrier layer, the seed layer, the first conductive functional layer and the intermediate passivation layer have been deposited in step (4); The sodium-blocking layer was deposited in the tin bath of the float glass production line using chemical vapor deposition. The seed layer, the first conductive functional layer, the intermediate passivation layer, and the second conductive functional layer were deposited in the A0 zone of the annealing furnace of the float glass production line using chemical vapor deposition.

[0013] The specific method for depositing a sodium-resistant layer according to the present invention is as follows: a mixed gas of silane and ammonia is used as the coating precursor, and nitrogen is used as the carrier gas. The mixture is introduced into the tin bath of the float glass production line at a temperature of 700~800°C through a reactor. A silicon nitride film layer is formed on a moving colorless transparent or ultra-white glass strip by chemical vapor deposition. Preferably, the molar ratio of the coating precursor is: 1~3% silane, 10~30% ammonia, and the remainder is nitrogen.

[0014] The specific method for depositing the seed layer described in this invention is as follows: a vaporized titanium-containing compound, with nitrogen as the vaporized carrier gas and air as the oxidant and carrier gas, is introduced into the annealing furnace A0 zone (580-620°C) of the float glass production line via a linear multi-channel reactor and uniformly sprayed onto a glass ribbon that has already been coated with a sodium-barrier layer. A titanium oxide film is then formed by chemical vapor deposition. Preferably, the titanium-containing compound is tetraisopropoxide titanium, tetraethyl titanate, or tetra(dimethylamino)titanium. Preferably, the molar ratio of the coating precursor is 1-3% titanium-containing compound, with the remainder being carrier gas.

[0015] The specific method for depositing the first conductive functional layer according to the present invention is as follows: using vaporized tin-containing compound, dopant, and catalyst as coating precursors (nitrogen as the vaporization carrier gas), and air as the oxidant and carrier gas, the mixture is introduced into the annealing furnace A0 zone (550-580°C) of the float glass production line via a linear multi-channel reactor and uniformly sprayed onto a glass ribbon that has already been coated with a sodium-blocking layer and an inducing seed layer. A fluorine-doped tin oxide film is formed by chemical vapor deposition. Preferably, the tin-containing compound is tetramethyltin, monobutyltin trichloride, or dimethyltin dichloride, the dopant is hydrofluoric acid or trifluoroacetic acid, and the catalyst is water vapor. Preferably, the molar ratio of the coating precursor is: 2-5% tin-containing compound, 0.1-0.5% dopant, 1-3% catalyst, and the remainder is carrier gas.

[0016] The specific method for depositing the intermediate passivation layer according to the present invention is as follows: using vaporized silicon-containing organic compounds and catalysts as coating precursors, using nitrogen as the vaporization carrier gas and air as the carrier gas, the mixture is introduced into the 530~550°C region of the A0 zone of the annealing furnace in the float glass production line through a linear multi-channel reactor, and uniformly sprayed onto the glass strip that has been coated with a sodium-blocking layer, an inducing seed layer and a first conductive functional layer, and a silicon oxide film is formed by chemical vapor deposition. Preferably, the silicon-containing organic compound is tetraethyl orthosilicate or octamethylcyclotetrasiloxane, and the catalyst is triethyl phosphate. Preferably, the molar ratio of the coating precursor is: 5~10% silicon-containing organic compound, 0.5~2% triethyl phosphate catalyst, and the remainder is carrier gas.

[0017] The specific method for depositing the second conductive functional layer according to the present invention is as follows: using vaporized tin-containing compound, dopant, and catalyst as coating precursors, nitrogen as the vaporization carrier gas, and air as the oxidant and carrier gas, the mixture is introduced into the 500~530°C zone of the annealing furnace in the float glass production line via a linear multi-channel reactor. It is uniformly sprayed onto a glass strip that has already been coated with a sodium-blocking layer, an inducing seed layer, a first conductive functional layer, and an intermediate passivation layer. A fluorine-doped tin oxide film is formed by chemical vapor deposition. Preferably, the tin-containing compound is tetramethyltin, monobutyltin trichloride, or dimethyltin dichloride; the dopant is hydrofluoric acid or trifluoroacetic acid; and the catalyst is water vapor. Preferably, the molar ratio of the coating precursor is: 0.5~3% tin-containing compound, 0.02~0.2% dopant, 1~3% catalyst, and the remainder is carrier gas.

[0018] The beneficial effects of this invention are as follows: Conventional TCO glass involves directly depositing a fluorine-doped tin oxide film on the surface of a sodium-blocking layer. Due to the inconsistency in their crystal structures, the growth quality of the tin oxide film is difficult to guarantee, and the greater the film thickness, the more defects appear. This invention provides a titanium oxide-induced seed layer. Based on the characteristic that both titanium oxide and tin oxide have rutile structures, a thin titanium oxide seed layer is used to provide an excitation interface for the growth of the tin oxide film, which is beneficial to improving the crystal integrity of the tin oxide film. This invention also provides a novel structure for a silicon oxide passivation layer, which can effectively passivate and modify the conductive functional layer, improve interface defects, and avoid the formation of larger grain boundary scattering due to homogeneous continuous growth, resulting in low transmittance and high haze. This invention uses colorless transparent glass or ultra-white glass as a substrate and utilizes chemical vapor deposition to form a novel TCO film structure through online deposition, overcoming the problems of increased internal defects, lower transmittance, and increased haze caused by thicker film layers, and better meeting the application requirements of perovskite thin-film batteries. Detailed Implementation

[0019] The present invention will be further described below: A TCO-coated glass for perovskite solar cells is characterized by comprising a glass substrate layer, a sodium-blocking layer, an inducing seed layer, a first conductive functional layer, an intermediate passivation layer, and a second conductive functional layer. The sodium-blocking layer, inducing seed layer, first conductive functional layer, intermediate passivation layer, and second conductive functional layer are sequentially laminated onto the glass substrate layer. The glass substrate layer is a colorless transparent glass layer or an ultra-white glass layer. The sodium-blocking layer is composed of silicon nitride with a thickness of 20 nm to 30 nm. The inducing seed layer is composed of titanium oxide with a thickness of 10 nm to 30 nm. The first conductive functional layer is composed of fluorine-doped tin oxide with a thickness of 300 nm to 500 nm. The intermediate passivation layer is composed of silicon oxide with a thickness of 10 nm to 20 nm. The second conductive functional layer is composed of fluorine-doped tin oxide with a thickness of 100 nm to 300 nm. The resulting TCO glass has a surface resistivity of 8.24-9.65 Ω / □, a photovoltaic transmittance of 82.8%-83.4%, and a haze of 1.32%-1.46%.

[0020] The function of the aforementioned sodium-blocking layer is to inhibit the leakage of alkali metal ions (including sodium and potassium ions) from the glass substrate and their diffusion into the conductive functional layer, thereby degrading the photoelectric properties of the film. Float-mount silicon nitride films, deposited online, exhibit high adhesion, good thermal stability, and strong ability to block alkali metal ions.

[0021] The role of the inducing seed layer is to form a thin rutile structure, which provides an inducing seed for the growth of the conductive functional layer. Both are rutile structures with the same lattice growth direction. Growth is stimulated through heterostructure to ensure the good quality of the growth and crystallization of the conductive functional layer.

[0022] The function of the first conductive functional layer is to utilize the semiconductor properties of fluorine-doped tin oxide to achieve conductivity and provide charge carriers for power transmission in perovskite solar cell devices.

[0023] The function of the intermediate passivation layer is to modify and passivate the surface of the first conductive layer, reduce surface defects, and provide a good interface for the growth of the second conductive layer.

[0024] The function of the second conductive functional layer is to utilize the semiconductor properties of fluorine-doped tin oxide to achieve conductivity, provide charge carriers for power transmission in perovskite solar cell devices, and connect with the film structure of the perovskite solar cell.

[0025] The aforementioned glass overcomes the problems of reduced light transmittance and increased haze caused by increased film thickness, and meets the requirements of high light transmittance, low resistance, and low haze for TCO glass.

[0026] A method for preparing TCO-coated glass for perovskite solar cells, characterized by the following steps: (1) Sodium barrier layer: A sodium barrier layer is deposited on the glass substrate; (2) Depositing an induction seed layer: Depositing an induction seed layer on the glass substrate layer that has been deposited with a sodium barrier layer in step (1); (3) Depositing the first conductive functional layer: depositing the first conductive functional layer on the glass substrate layer on which the sodium-blocking layer and the induction seed layer have been deposited in step (2); (4) Depositing an intermediate passivation layer: Depositing an intermediate passivation layer on the glass substrate layer on which the sodium barrier layer, the seed layer, and the first conductive functional layer have been deposited in step (3); (5) Depositing the second conductive functional layer: Depositing the second conductive functional layer on the glass substrate layer on which the sodium barrier layer, the seed layer, the first conductive functional layer and the intermediate passivation layer have been deposited in step (4); The sodium-blocking layer was deposited in the tin bath of the float glass production line using chemical vapor deposition. The seed layer, the first conductive functional layer, the intermediate passivation layer, and the second conductive functional layer were deposited in the A0 zone of the annealing furnace of the float glass production line using chemical vapor deposition.

[0027] The specific method for depositing a sodium-resistant layer according to the present invention is as follows: a mixed gas of silane and ammonia is used as the coating precursor, and nitrogen is used as the carrier gas. The mixture is introduced into the tin bath of the float glass production line at a temperature of 700~800°C through a reactor. A silicon nitride film layer is formed on a moving colorless transparent or ultra-white glass strip by chemical vapor deposition. Preferably, the molar ratio of the coating precursor is: 1~3% silane, 10~30% ammonia, and the remainder is nitrogen.

[0028] The specific method for depositing the seed layer described in this invention is as follows: a vaporized titanium-containing compound, with nitrogen as the vaporized carrier gas and air as the oxidant and carrier gas, is introduced into the annealing furnace A0 zone (580-620°C) of the float glass production line via a linear multi-channel reactor and uniformly sprayed onto a glass ribbon that has already been coated with a sodium-barrier layer. A titanium oxide film is then formed by chemical vapor deposition. Preferably, the titanium-containing compound is tetraisopropoxide titanium, tetraethyl titanate, or tetra(dimethylamino)titanium. Preferably, the molar ratio of the coating precursor is 1-3% titanium-containing compound, with the remainder being carrier gas.

[0029] The specific method for depositing the first conductive functional layer according to the present invention is as follows: using vaporized tin-containing compound, dopant, and catalyst as coating precursors, nitrogen as the vaporized carrier gas, and air as the oxidant and carrier gas, the mixture is introduced into the 550~580°C region of the annealing furnace in the float glass production line via a linear multi-channel reactor. It is uniformly sprayed onto the glass ribbon that has been coated with a sodium-blocking layer and an inducing seed layer, and a fluorine-doped tin oxide film is formed by chemical vapor deposition. Preferably, the tin-containing compound is tetramethyltin, monobutyltin trichloride, or dimethyltin dichloride, the dopant is hydrofluoric acid or trifluoroacetic acid, and the catalyst is water vapor. Preferably, the molar ratio of the coating precursor is: 2~5% tin-containing compound, 0.1~0.5% dopant, 1~3% catalyst, and the remainder is carrier gas.

[0030] The specific method for depositing the intermediate passivation layer according to the present invention is as follows: using vaporized silicon-containing organic compounds and catalysts as coating precursors, using nitrogen as the vaporization carrier gas and air as the carrier gas, the mixture is introduced into the 530~550°C region of the A0 zone of the annealing furnace in the float glass production line through a linear multi-channel reactor, and uniformly sprayed onto the glass strip that has been coated with a sodium-blocking layer, an inducing seed layer and a first conductive functional layer, and a silicon oxide film is formed by chemical vapor deposition. Preferably, the silicon-containing organic compound is tetraethyl orthosilicate or octamethylcyclotetrasiloxane, and the catalyst is triethyl phosphate. Preferably, the molar ratio of the coating precursor is: 5~10% silicon-containing organic compound, 0.5~2% triethyl phosphate catalyst, and the remainder is carrier gas.

[0031] The specific method for depositing the second conductive functional layer according to the present invention is as follows: using vaporized tin-containing compound, dopant, and catalyst as coating precursors (nitrogen as the vaporization carrier gas), and air as the oxidant and carrier gas, the mixture is introduced into the 500-530°C zone of the annealing furnace in the float glass production line via a linear multi-channel reactor. It is uniformly sprayed onto a glass strip that has already been coated with a sodium-blocking layer, an inducing seed layer, a first conductive functional layer, and an intermediate passivation layer. A fluorine-doped tin oxide film is formed by chemical vapor deposition. Preferably, the tin-containing compound is tetramethyltin, monobutyltin trichloride, or dimethyltin dichloride, the dopant is hydrofluoric acid or trifluoroacetic acid, and the catalyst is water vapor. Preferably, the molar ratio of the coating precursor is: 0.5-3% tin-containing compound, 0.02-0.2% dopant, 1-3% catalyst, and the remainder is carrier gas.

[0032] The beneficial effects of this invention are as follows: Conventional TCO glass involves directly depositing a fluorine-doped tin oxide film on the surface of a sodium-blocking layer. Due to the inconsistency in their crystal structures, the growth quality of the tin oxide film is difficult to guarantee, and the greater the film thickness, the more defects appear. This invention provides a titanium oxide-induced seed layer. Based on the characteristic that both titanium oxide and tin oxide have rutile structures, a thin titanium oxide seed layer is used to provide an excitation interface for the growth of the tin oxide film, which is beneficial to improving the crystal integrity of the tin oxide film. This invention also provides a novel structure for a silicon oxide passivation layer, which can effectively passivate and modify the conductive functional layer, improve interface defects, and avoid the formation of larger grain boundary scattering due to homogeneous continuous growth, resulting in low transmittance and high haze. This invention uses colorless transparent glass or ultra-white glass as a substrate and utilizes chemical vapor deposition to form a novel TCO film structure through online deposition, overcoming the problems of increased internal defects, lower transmittance, and increased haze caused by thicker film layers, and better meeting the application requirements of perovskite thin-film batteries.

[0033] Example 1 (1) Sodium resist layer In the tin bath of a float glass production line, a reactor is located above the glass strip. A mixed gas consisting of silane, ammonia, and nitrogen as a carrier gas is sprayed onto the surface of the moving ultra-clear glass strip through the reactor's inlet channel. The gas flows, decomposes, and reacts along the glass strip surface, completing chemical vapor deposition. Residual gas is discharged from the reactor through the exhaust channel. The glass strip is 3.2 mm thick, with a surface temperature of 720°C. The molar ratio of silane gas is 1.3%, the molar ratio of ammonia gas is 15%, and the remainder is nitrogen. The resulting sodium-barrier layer has a thickness of 23 nm.

[0034] (2) Plating an induction seed layer A glass ribbon coated with a sodium-barrier layer is drawn into zone A0 of the annealing furnace in the float glass production line. Above it is a linear, multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. Vaporized tetraisopropoxide (TiO2) is used as the coating precursor (nitrogen is used as the vaporization carrier gas). Air is used as the carrier gas, and the vaporization reaches the glass ribbon surface through the reactor inlet channel for decomposition and chemical reaction. Residual gas is discharged from the reactor through the exhaust channel. The glass ribbon surface temperature is 585°C, the molar ratio of TiO2 is 1.2%, and the remainder is carrier gas. The resulting induced seed layer thickness is 12 nm.

[0035] (3) Deposit the first conductive functional layer In zone A0 of the annealing furnace of the float glass production line, glass ribbons coated with a sodium-blocking layer and an inducing seed layer advance to the downstream area. Above them is a linear multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. A mixture of vaporized monobutyltin trichloride, water, and trifluoroacetic acid is used as the coating precursor (nitrogen is used as the vaporization carrier gas). Air is used as the carrier gas. The mixture reaches the surface of the glass ribbon through the reactor inlet channel for decomposition and chemical reaction. The residual gas is discharged from the reactor through the exhaust channel. The surface temperature of the glass ribbon is 555°C. The molar ratio of monobutyltin trichloride is 2.2%, the molar ratio of water is 1.4%, the molar ratio of trifluoroacetic acid is 0.12%, and the remainder is the carrier gas. The thickness of the resulting conductive functional layer is 310 nm.

[0036] (4) Plating an intermediate passivation layer In zone A0 of the annealing furnace of the float glass production line, glass ribbons coated with a sodium-blocking layer, an inducing seed layer, and a first conductive functional layer advance to the downstream area. Above them is a linear multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. A mixture of vaporized tetraethyl orthosilicate and triethyl phosphate is used as the coating precursor (nitrogen is used as the vaporization carrier gas). Air is used as the carrier gas. The mixture reaches the glass ribbon surface through the reactor inlet channel for decomposition and chemical reaction. The residual gas is discharged from the reactor through the exhaust channel. The glass ribbon surface temperature is 530°C, the molar ratio of tetraethyl orthosilicate is 5.5%, the molar ratio of triethyl phosphate is 0.6%, and the remainder is the carrier gas. The resulting intermediate passivation layer has a thickness of 11 nm.

[0037] (5) Deposit a second conductive functional layer In zone A0 of the annealing furnace of the float glass production line, glass ribbons coated with a sodium-blocking layer, an induction seed layer, a first conductive functional layer, and an intermediate passivation layer advance to the downstream area. Above them is a linear multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. A mixture of vaporized monobutyltin trichloride, water, and trifluoroacetic acid is used as the coating precursor (nitrogen is used as the vaporization carrier gas). Air is used as the carrier gas. The mixture reaches the surface of the glass ribbon through the reactor inlet channel for decomposition and chemical reaction. The residual gas is discharged from the reactor through the exhaust channel. The surface temperature of the glass ribbon is 510°C. The molar ratio of monobutyltin trichloride is 2.1%, the molar ratio of water is 2.5%, the molar ratio of trifluoroacetic acid is 0.18%, and the remainder is the carrier gas. The thickness of the resulting conductive functional layer is 275 nm.

[0038] The TCO glass, composed of an ultra-white glass substrate, a sodium-blocking layer, an induction seed layer, a first conductive functional layer, an intermediate passivation layer, and a second conductive functional layer, has a surface resistivity of 8.24 Ω / □, a photovoltaic transmittance of 82.8%, and a haze of 1.44%.

[0039] Example 2 (1) Sodium resist layer In the tin bath of a float glass production line, a reactor is located above the glass strip. A mixed gas consisting of silane, ammonia, and nitrogen carrier gas is used as a coating precursor. This gas is sprayed onto the surface of the moving ultra-clear glass strip through the reactor's inlet channel, where it flows, decomposes, and reacts along the glass strip surface, completing chemical vapor deposition. Residual gas is discharged from the reactor through the exhaust channel. The glass strip is 3.2 mm thick, with a surface temperature of 780°C. The molar ratio of silane gas is 2.7%, the molar ratio of ammonia gas is 28%, and the remainder is nitrogen. The resulting sodium-barrier layer has a thickness of 28 nm.

[0040] (2) Plating an induction seed layer A glass ribbon coated with a sodium-barrier layer is drawn into zone A0 of the annealing furnace in the float glass production line. Above it is a linear, multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. Vaporized tetraethyl titanate is used as a coating precursor (nitrogen is used as the vaporization carrier gas), with air as the carrier gas. The gas reaches the glass ribbon surface through the reactor inlet channel for decomposition and chemical reaction. Residual gas is discharged from the reactor through the exhaust channel. The glass ribbon surface temperature is 610°C, the molar ratio of tetraethyl titanate is 2.7%, and the remainder is carrier gas. The resulting induced seed layer thickness is 25 nm.

[0041] (3) Deposit the first conductive functional layer In zone A0 of the annealing furnace of the float glass production line, glass ribbons coated with a sodium-blocking layer and an inducing seed layer advance to the downstream area. Above them is a linear multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. A mixture of vaporized tetramethyltin, water, and trifluoroacetic acid is used as the coating precursor (nitrogen is used as the vaporization carrier gas). Air is used as the carrier gas. The mixture reaches the surface of the glass ribbon through the reactor inlet channel for decomposition and chemical reaction. The residual gas is discharged from the reactor through the exhaust channel. The surface temperature of the glass ribbon is 570°C, the molar ratio of tetramethyltin is 2.6%, the molar ratio of water is 1.2%, the molar ratio of trifluoroacetic acid is 0.15%, and the remainder is the carrier gas. The thickness of the resulting conductive functional layer is 320 nm.

[0042] (4) Plating an intermediate passivation layer In zone A0 of the annealing furnace of the float glass production line, glass ribbons coated with a sodium-blocking layer, an inducing seed layer, and a first conductive functional layer advance to the downstream area. Above them is a linear multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. A mixture of vaporized octamethylcyclotetrasiloxane and triethyl phosphate is used as the coating precursor (nitrogen is used as the vaporization carrier gas). Air is used as the carrier gas. The mixture reaches the surface of the glass ribbon through the reactor inlet channel for decomposition and chemical reaction. The residual gas is discharged from the reactor through the exhaust channel. The surface temperature of the glass ribbon is 545°C, the molar ratio of octamethylcyclotetrasiloxane is 8%, the molar ratio of triethyl phosphate is 1.2%, and the remainder is the carrier gas. The thickness of the resulting intermediate passivation layer is 14 nm.

[0043] (5) Deposit a second conductive functional layer In zone A0 of the annealing furnace of a float glass production line, glass ribbons coated with a sodium-blocking layer, an induction seed layer, a first conductive functional layer, and an intermediate passivation layer advance to the downstream area. Above them is a linear multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. A mixture of vaporized tetramethyltin, water, and trifluoroacetic acid is used as the coating precursor (nitrogen is used as the vaporization carrier gas). Air is used as the carrier gas. The mixture reaches the surface of the glass ribbon through the reactor inlet channel for decomposition and chemical reaction. Residual gas is discharged from the reactor through the exhaust channel. The surface temperature of the glass ribbon is 525°C, the molar ratio of tetramethyltin is 1.1%, the molar ratio of water is 1.5%, the molar ratio of trifluoroacetic acid is 0.08%, and the remainder is the carrier gas. The thickness of the resulting conductive functional layer is 185 nm.

[0044] The TCO glass, composed of an ultra-white glass substrate, a sodium-blocking layer, an inducing seed layer, a first conductive functional layer, an intermediate passivation layer, and a second conductive functional layer, has a surface resistivity of 9.65 Ω / □, a photovoltaic transmittance of 83.4%, and a haze of 1.32%.

[0045] Example 3 (1) Sodium resist layer Inside the tin bath of a float glass production line, a reactor is located above the glass strip. A mixed gas consisting of silane, ammonia, and nitrogen carrier gas is used as a coating precursor. This gas is sprayed onto the surface of the moving ultra-clear glass strip through the reactor's inlet channel, where it flows, decomposes, and reacts along the glass strip surface, completing chemical vapor deposition. Residual gas is discharged from the reactor through the exhaust channel. The glass strip is 3.2 mm thick, with a surface temperature of 760°C. The molar ratio of silane gas is 1.8%, the molar ratio of ammonia gas is 20%, and the remainder is nitrogen. The resulting sodium-barrier layer has a thickness of 25 nm.

[0046] (2) Plating an induction seed layer A glass ribbon coated with a sodium-barrier layer is drawn into zone A0 of the annealing furnace in the float glass production line. Above it is a linear, multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. Vaporized tetra(dimethylamino)titanium is used as the coating precursor (nitrogen is used as the vaporization carrier gas), with air as the carrier gas. The gas reaches the glass ribbon surface through the reactor inlet channel for decomposition and chemical reaction. Residual gas is discharged from the reactor through the exhaust channel. The glass ribbon surface temperature is 600°C, the molar ratio of tetra(dimethylamino)titanium is 1.8%, and the remainder is carrier gas. The resulting induced seed layer thickness is 16 nm.

[0047] (3) Deposit the first conductive functional layer In zone A0 of the annealing furnace of the float glass production line, glass ribbons coated with a sodium-blocking layer and an inducing seed layer advance to the downstream area. Above them is a linear multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. A mixture of vaporized dimethyl tin chloride, water, and hydrofluoric acid is used as the coating precursor (nitrogen is used as the vaporization carrier gas). Air is used as the carrier gas. The mixture reaches the surface of the glass ribbon through the reactor inlet channel for decomposition and chemical reaction. The residual gas is discharged from the reactor through the exhaust channel. The surface temperature of the glass ribbon is 570°C. The molar ratio of dimethyl tin chloride is 3.5%, the molar ratio of water is 2.4%, the molar ratio of hydrofluoric acid is 0.4%, and the remainder is the carrier gas. The thickness of the resulting conductive functional layer is 460 nm.

[0048] (4) Plating an intermediate passivation layer In zone A0 of the annealing furnace of the float glass production line, glass ribbons coated with a sodium-blocking layer, an inducing seed layer, and a first conductive functional layer advance to the downstream area. Above them is a linear multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. A mixture of vaporized tetraethyl orthosilicate and triethyl phosphate is used as the coating precursor (nitrogen is used as the vaporization carrier gas). Air is used as the carrier gas. The mixture reaches the surface of the glass ribbon through the reactor inlet channel for decomposition and chemical reaction. The residual gas is discharged from the reactor through the exhaust channel. The surface temperature of the glass ribbon is 540°C, the molar ratio of tetraethyl orthosilicate is 9%, the molar ratio of triethyl phosphate is 1.6%, and the remainder is the carrier gas. The thickness of the resulting intermediate passivation layer is 18 nm.

[0049] (5) Deposit a second conductive functional layer In zone A0 of the annealing furnace of the float glass production line, glass ribbons coated with a sodium-blocking layer, an induction seed layer, a first conductive functional layer, and an intermediate passivation layer advance to the downstream area. Above them is a linear multi-channel reactor with multiple inlets and outlets. The inlet chamber is connected to an inlet distributor connected to the inlet pipe and contains an airflow damper. The exhaust chamber is connected to an exhaust integrator connected to the exhaust pipe and contains a buffer and a negative pressure regulating device. A mixture of vaporized dimethyl tin chloride, water, and hydrofluoric acid is used as the coating precursor (nitrogen is used as the vaporization carrier gas). Air is used as the carrier gas. The mixture reaches the surface of the glass ribbon through the reactor inlet channel for decomposition and chemical reaction. The residual gas is discharged from the reactor through the exhaust channel. The surface temperature of the glass ribbon is 520°C. The molar ratio of dimethyl tin chloride is 0.6%, the molar ratio of water is 1.2%, the molar ratio of hydrofluoric acid is 0.04%, and the remainder is the carrier gas. The thickness of the resulting conductive functional layer is 105 nm.

[0050] The TCO glass, composed of an ultra-white glass substrate, a sodium-blocking layer, an induction seed layer, a first conductive functional layer, an intermediate passivation layer, and a second conductive functional layer, has a surface resistance of 8.58 Ω / □, a photovoltaic transmittance of 83.1%, and a haze of 1.46%.

[0051] As can be seen from the above embodiments, the prepared product has high light transmittance, low resistance, and low haze.

Claims

1. A TCO-coated glass for perovskite solar cells, characterized in that... The glass comprises a glass substrate layer, a sodium-blocking layer, an inducing seed layer, a first conductive functional layer, an intermediate passivation layer, and a second conductive functional layer. The sodium-blocking layer, inducing seed layer, first conductive functional layer, intermediate passivation layer, and second conductive functional layer are sequentially laminated onto the glass substrate layer. The glass substrate layer is a colorless transparent glass layer or an ultra-white glass layer. The sodium-blocking layer is composed of silicon nitride with a thickness of 20nm~30nm. The inducing seed layer is composed of titanium oxide with a thickness of 10nm~30nm. The first conductive functional layer is composed of fluorine-doped tin oxide with a thickness of 300nm~500nm. The intermediate passivation layer is composed of silicon oxide with a thickness of 10nm~20nm. The second conductive functional layer is composed of fluorine-doped tin oxide with a thickness of 100nm~300nm. The resulting TCO glass has a surface resistivity of 8.24-9.65Ω / □, a photovoltaic transmittance of 82.8%-83.4%, and a haze of 1.32%-1.46%.

2. A method for preparing TCO-coated glass for perovskite solar cells, characterized in that... The preparation method involves the following steps: (1) Sodium barrier layer: A sodium barrier layer is deposited on the glass substrate; (2) Depositing an induction seed layer: Depositing an induction seed layer on the glass substrate layer that has been deposited with a sodium barrier layer in step (1); (3) Depositing the first conductive functional layer: depositing the first conductive functional layer on the glass substrate layer on which the sodium-blocking layer and the induction seed layer have been deposited in step (2); (4) Depositing an intermediate passivation layer: Depositing an intermediate passivation layer on the glass substrate layer on which the sodium barrier layer, the seed layer, and the first conductive functional layer have been deposited in step (3); (5) Depositing the second conductive functional layer: Depositing the second conductive functional layer on the glass substrate layer on which the sodium barrier layer, the seed layer, the first conductive functional layer and the intermediate passivation layer have been deposited in step (4); The sodium-blocking layer was deposited in the tin bath of the float glass production line using chemical vapor deposition. The seed layer, the first conductive functional layer, the intermediate passivation layer, and the second conductive functional layer were deposited in the A0 zone of the annealing furnace of the float glass production line using chemical vapor deposition.

3. The method for preparing TCO-coated glass for perovskite solar cells according to claim 2, characterized in that... The specific method for depositing the sodium-resistant layer is as follows: a mixture of silane and ammonia gas is used as the coating precursor, and nitrogen gas is used as the carrier gas. The mixture is introduced into the tin bath of the float glass production line at a temperature of 700~800°C through a reactor. A silicon nitride film is formed on a moving colorless transparent or ultra-white glass strip by chemical vapor deposition. Preferably, the molar ratio of the coating precursor is: 1~3% silane, 10~30% ammonia, and the remainder is nitrogen.

4. The method for preparing TCO-coated glass for perovskite solar cells according to claim 2, characterized in that... The specific method for depositing the seed layer is as follows: a vaporized titanium-containing compound, with nitrogen as the vaporized carrier gas and air as the oxidant and carrier gas, is introduced into the annealing furnace A0 zone (580-620°C) of the float glass production line via a linear multi-channel reactor and uniformly sprayed onto a glass strip already coated with a sodium-barrier layer. A titanium oxide film is formed by chemical vapor deposition. Preferably, the titanium-containing compound is tetraisopropoxide titanium, tetraethyl titanate, or tetra(dimethylamino)titanium. Preferably, the molar ratio of the coating precursor is 1-3% titanium-containing compound, with the remainder being carrier gas.

5. The method for preparing TCO-coated glass for perovskite solar cells according to claim 2, characterized in that... The specific method for depositing the first conductive functional layer is as follows: using vaporized tin-containing compound, dopant, and catalyst as coating precursors, nitrogen as the vaporized carrier gas, and air as the oxidant and carrier gas, the mixture is introduced into the annealing furnace A0 zone (550-580°C) of the float glass production line via a linear multi-channel reactor. It is uniformly sprayed onto a glass ribbon already coated with a sodium-blocking layer and an inducing seed layer, and a fluorine-doped tin oxide film is formed through chemical vapor deposition. Preferably, the tin-containing compound is tetramethyltin, monobutyltin trichloride, or dimethyltin dichloride; the dopant is hydrofluoric acid or trifluoroacetic acid; and the catalyst is water vapor. Preferably, the molar ratio of the coating precursor is: 2-5% tin-containing compound, 0.1-0.5% dopant, 1-3% catalyst, and the remainder is carrier gas.

6. The method for preparing TCO-coated glass for perovskite solar cells according to claim 2, characterized in that... The specific method for depositing the intermediate passivation layer is as follows: using vaporized silicon-containing organic compounds and catalysts as coating precursors, nitrogen as the vaporization carrier gas, and air as the carrier gas, the mixture is introduced into the annealing furnace A0 zone (530-550°C) of the float glass production line via a linear multi-channel reactor. The mixture is uniformly sprayed onto a glass strip that has already been coated with a sodium-blocking layer, an inducing seed layer, and a first conductive functional layer. A silicon oxide film is formed by chemical vapor deposition. Preferably, the silicon-containing organic compound is tetraethyl orthosilicate or octamethylcyclotetrasiloxane, and the catalyst is triethyl phosphate. Preferably, the molar ratio of the coating precursor is: 5-10% silicon-containing organic compound, 0.5-2% triethyl phosphate catalyst, and the remainder is carrier gas.

7. The method for preparing TCO-coated glass for perovskite solar cells according to claim 2, characterized in that... The specific method for depositing the second conductive functional layer is as follows: using vaporized tin-containing compound, dopant, and catalyst as coating precursors (nitrogen as the vaporization carrier gas), and air as the oxidant and carrier gas, the mixture is introduced into the annealing furnace A0 zone (500-530°C) of the float glass production line via a linear multi-channel reactor. It is uniformly sprayed onto a glass strip that has already been coated with a sodium-blocking layer, an inducing seed layer, a first conductive functional layer, and an intermediate passivation layer. A fluorine-doped tin oxide film is formed through chemical vapor deposition. Preferably, the tin-containing compound is tetramethyltin, monobutyltin trichloride, or dimethyltin dichloride; the dopant is hydrofluoric acid or trifluoroacetic acid; and the catalyst is water vapor. Preferably, the molar ratio of the coating precursor is: 0.5-3% tin-containing compound, 0.02-0.2% dopant, 1-3% catalyst, and the remainder is carrier gas.