Preparation method of color-neutral controllable multi-interface structure conductive film glass

Abstract

The present application relates to a kind of color neutral controllable multi-interface structure conductive film glass preparation method, specifically, in the tin tank of float glass production line, multiple reactors are set, TiO2 barrier layer and SiCxOy chroma adjusting layer are deposited on the surface of continuous production hot glass using on-line chemical vapor deposition method;Multiple reactors with multiple gas inlet and multiple gas outlet structure are set in the A0 area of float glass production line annealing furnace, tin oxide conductive layer and antimony oxide color center modulation layer are plated on the surface of SiCxOy chroma adjusting layer using on-line chemical vapor deposition method, and multi-interface structure composite film layer is formed.This method can easily control the chroma, density of film layer, and large-area on-line preparation of low color saturation, neutral color, better optical performance and lower resistance conductive film glass.

Description

Technical Field

[0001] This invention relates to a method for preparing a multi-interface structure conductive film glass with controllable color neutrality, and more particularly to a method for producing transparent conductive film glass online on a float glass production line. Background Technology

[0002] Transparent conductive films mainly include oxides such as Sn, In, Sb, Zn, and Cd, as well as their composite multi-element oxide thin film materials. They share common optoelectronic properties such as wide bandgap, high light transmittance in the visible spectrum, and low resistivity, and can be widely used in various fields, such as solar cells, liquid crystal displays, and window coatings. These products generally require suitable optical performance, high light transmittance, strong film adhesion, and excellent conductivity.

[0003] The large-scale deposition of large-area transparent conductive films on flat glass has broad prospects. However, when conductive films are deposited directly on hot glass surfaces, sodium ions inside the glass migrate to the glass surface and form sodium chloride with chloride ions in the film, which damages the film structure, resulting in higher surface resistance and a cloudy surface. The interference coloring or decolorization of the film is extremely sensitive to the film thickness and the angle of illumination, resulting in high color saturation of the conductive film glass, which affects the visual aesthetics and makes it difficult to meet the requirements of optoelectronic devices for neutral colors of conductive film glass.

[0004] The invention patent with application number CN202211599506.X discloses a transparent conductive film glass for solar cells. The preparation method of the transparent conductive film glass for solar cells is an offline chemical vapor deposition method. This invention does not mention how to solve the matching problem with the conductive layer, including optical matching problems such as colorimetry.

[0005] The invention patent application CN202310075070.2 mentions a high-transmittance TCO glass and its preparation method. It utilizes an offline chemical vapor deposition process, where an anti-reflective film and a transparent conductive film are roll-coated onto two surfaces of the glass offline, followed by tempering. This method, an offline roll-coating method for producing conductive film glass, does not address the issue of achieving neutral color in the conductive film glass.

[0006] The invention patent with application number CN201811027660.3 discloses a Cdot@C3N4 modified TCO glass and its preparation method. The TCO glass is an AZO glass with silicon substrate. Carbon quantum dots are doped with C3N4 to improve electron transport performance to obtain Cdot@C3N4. TCO glass containing zinc oxide Cdot@C3N4 film is prepared by doping Cdot@C3N4 with zinc oxide. This invention does not involve how to use film matching to solve the problem of high color saturation.

[0007] The above-disclosed patents all involve offline production of conductive film glass, which has low production efficiency and cannot produce conductive film glass on a large scale online.

[0008] In addition, the invention patent with application number CN200910104849.2 discloses a method for online production of TCO thin film glass by float glass. The method includes two steps: first, a phosphorus-doped silicon oxide shielding layer is deposited on the hot glass surface, and then an aluminum-doped zinc oxide conductive layer is continuously deposited to form a simple composite conductive film. However, the invention does not mention the issue of color and chromaticity matching of the conductive film. Summary of the Invention

[0009] To address the shortcomings of the aforementioned technical problems, this invention provides a method for preparing multi-interface structure conductive film glass with controllable color neutrality, enabling large-scale, high-quality, continuous online production of transparent conductive film glass with low saturation, high transmittance, neutral color, and excellent conductivity.

[0010] The method for preparing a color-neutral, controllable multi-interface conductive film glass according to the present invention includes the following steps:

[0011] 1. In the tin bath of the float glass production line, multiple reactors are installed above the glass belt. A first precursor gas mixture consisting of titanium compounds, reaction promoters, and diluent gases is transported to the first reactor. Using online chemical vapor deposition, a first structural film layer, TiO2 barrier layer, is formed on the hot glass surface at a temperature of 680℃~720℃. The tail gas generated by the deposition reaction is discharged through the reactor's exhaust device and enters the tail gas treatment system for purification. Unreacted titanium compounds and other coating raw materials can be recycled.

[0012] The composition of the gas mixture preceding the first structural film layer is as follows: 0.6 mol%–1.0 mol% titanium compound, 0.03 mol%–0.07 mol% reaction promoter, and the remainder is dilution gas, with a total gas volume of 6 m³. 3 / h~10m 3 / h.

[0013] The titanium compound mentioned is tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate, or titanium tetrachloride, preferably tetraethyl titanate; the reaction promoter mentioned is nitrous oxide, nitric oxide, preferably nitrous oxide; the diluent gas mentioned is nitrogen, air, or argon, preferably nitrogen.

[0014] 2. As the glass belt moves forward online, a second precursor gas mixture consisting of silane, ethylene, carbon dioxide, a reaction promoter, and an inert gas is fed into the second reactor. Using online chemical vapor deposition, a second structural film, SiC, is formed on the surface of the TiO2 barrier layer at a temperature of 630℃~680℃. x O y The color adjustment layer and the tail gas generated by the deposition reaction are discharged through the reactor's exhaust device and enter the tail gas treatment system for purification. Unreacted silane and other coating raw materials can be recycled and reused.

[0015] The preproton gas mixture for the second structural membrane layer consists of: silane 1 mol%–2 mol%, ethylene 0.05 mol%–0.1 mol%, carbon dioxide 0.05 mol%–0.1 mol%, reaction promoter 0.002 mol%–0.008 mol%, with the remainder being inert gases. The total gas volume is 10 m³. 3 / h~15m 3 / h.

[0016] The reaction promoter mentioned is nitrous oxide, preferably nitrous oxide.

[0017] The inert gases mentioned are nitrogen and argon, with nitrogen being preferred.

[0018] 3. The float glass with the first and second structural films deposited above continues to move forward in the tin bath, reaching the A0 zone of the float glass production line annealing furnace. A reactor with a multi-inlet and multi-outlet exhaust structure is installed upstream of the A0 zone of the annealing furnace. Within the temperature range of 580℃ to 610℃, this reactor is used to process the TiO2 barrier layer and SiC... x O y A third structural film layer, a fluorine-doped tin oxide conductive film layer, is deposited on the upper surface of the color adjustment layer. The exhaust gas generated by the deposition reaction is discharged through the exhaust device of the reactor and enters the exhaust gas treatment system for purification. Unreacted tin compounds and other coating raw materials can be recycled.

[0019] The composition of the gas mixture preceding the third structural film layer is as follows: 1.0 mol%–2.0 mol% tin compound, 0.5 mol%–1.0 mol% dopant, 0.3 mol%–0.6 mol% catalyst, 2 mol%–4 mol% carrier gas, and the remainder being dilution gas, with a total gas volume of 200 m³. 3 / h~300m 3 / h.

[0020] The tin compound mentioned can be dibutyltin, stannous octoate, dimethyltin, dioctyltin, tetraphenyltin, tributyltin, triphenyltin, trimethyltin, trimethyltin chloride, triethyltin, triethyltin chloride, triethyltin bromide, triethyltin iodide, triethyltin hydroxide, tributyltin chloride, triphenyltin chloride, triphenyltin acetate, tetraethyltin, tetrabutyltin, or tetraphenyltin. Triethyltin chloride is preferred.

[0021] The dopant mentioned is a fluorine compound, which can be trifluoroacetic acid, hydrogen fluoride, hexafluoropropylene, trifluoromethyl bromide, with hydrogen fluoride being preferred;

[0022] The catalyst mentioned is oxygen or water, preferably water;

[0023] The carrier gas is nitrogen or argon, preferably nitrogen; the diluent gas is air or nitrogen, preferably air.

[0024] 4. The glass ribbon with the three-layer structured film deposited continues to move forward. In the 550℃~580℃ temperature zone downstream of the A0 zone of the float glass production line annealing furnace, a second multi-inlet and multi-outlet reactor is used to deposit a fourth structured film, the antimony oxide color core modulation layer, on the upper surface of the glass ribbon with the three-layer structured film. The exhaust gas generated by the deposition reaction is discharged through the exhaust device of the reactor and enters the exhaust gas treatment system for purification. Unreacted antimony compounds and other coating raw materials can be recycled.

[0025] The composition of the gas mixture preceding the fourth structural membrane layer is as follows: antimony compound 0.4 mol%–0.8 mol%, auxiliary solvent 0.04 mol%–0.08 mol%, carrier gas 3 mol%–5 mol%, and the remainder being dilution gas, with a total gas volume of 50 m³. 3 / h~100m 3 / h.

[0026] The antimony compound mentioned can be antimony ethanol, antimony butoxide, isopropyl antimony, ethyl antimony, methyl antimony, or antimony chloride, with antimony butoxide being preferred.

[0027] The auxiliary solvent mentioned is methanol or ethyl acetate, preferably ethyl acetate.

[0028] The carrier gas is nitrogen or argon, preferably nitrogen; the diluent gas is air or nitrogen, preferably air.

[0029] In this invention, the first structural film layer, TiO2, serves to firmly bond the glass to the film layer, while simultaneously preventing alkali metal ions (Na) in the glass substrate from entering. + K + The diffusion occurs at high temperatures to other film layers, preventing it from affecting the structure and photoelectric properties of each film.

[0030] Because TiO2 has a dense and smooth structure, it is suitable for SiC as a colorimetric adjustment layer. x O y The layer provides a good interface. SiC x O y The layer can effectively adjust the color of the film layer, and can make the multilayer film match well with each other, close to neutral color.

[0031] First TiO2 film layer and second SiC layer x O y The stacking of film layers results in a lower light absorption coefficient, a denser and smoother film, and a better interface for the third fluorine-doped conductive film, which is beneficial for the growth and crystallization of the conductive film. This also makes the conductive film easier to control, easier to adjust, and ensures long-term stability of the coating process.

[0032] Reaction promoters were added to both the first and second film layers. The reaction promoters facilitated the formation of the titanium dioxide film, controlled the activity of titanium dioxide, facilitated color adjustment between the first and second film layers, improved reaction efficiency, and enhanced the bonding and matching between the film layers.

[0033] The third layer is a fluorine-doped tin oxide film, which has excellent conductivity and high light transmittance, and is the functional layer material for achieving the conductive properties of glass.

[0034] The fourth layer is an antimony oxide film, which selectively absorbs sunlight and acts as a color center modulator. Due to the difference in refractive index between the thin film material and the glass substrate, interference coloring occurs, deviating from the neutral color. This interference coloring or achromatic effect is extremely sensitive to film thickness and illumination angle, resulting in high color saturation in the conductive film glass, affecting visual aesthetics and making it difficult to meet the neutral color requirements of optoelectronic devices. By adding a fourth color center modulator layer based on the matching and adjustment between the first, second, and third layers, its selective absorption of sunlight serves to absorb color centers and compensate for color differences, ensuring that the multi-interface structure film layer maintains a stable neutral color.

[0035] Meanwhile, the present invention discharges the high-temperature exhaust gas generated by the chemical vapor deposition reaction through the reactor's exhaust device, and then introduces it into the exhaust gas purification system through an induced draft fan, so as to recycle the coating raw materials that have not fully participated in the chemical reaction, which greatly improves the utilization rate of coating raw materials, and achieves both clean and environmentally friendly production.

[0036] The advantages of this invention are: a TiO2 barrier layer is used in the first layer, which increases the adhesion between the glass and the thin film; an antimony oxide color center modulation layer is used in the fourth layer, and the deposition and combination of the four layers makes the thin film neutral in color, while the conductive film has lower resistance and better conductivity. Detailed Implementation

[0037] The method of the present invention is further illustrated below with examples.

[0038] Example 1

[0039] Inside the tin bath of the float glass production line, two online coating reactors are installed above the glass belt. A first precursor gas mixture consisting of tetraethyl titanate, nitrous oxide, and nitrogen is fed into the first reactor. Using chemical vapor deposition, the first structural film layer, TiO2 barrier layer, is deposited on the hot glass surface at a temperature of 680°C. The high-temperature exhaust gas generated by the deposition reaction is discharged through the reactor's exhaust device and enters the exhaust gas treatment system for purification. Unreacted tetraethyl titanate and other coating raw materials can be recycled.

[0040] The gas mixture of the precursor layer for the first structural film consists of: tetraethyl titanate 0.6 mol%, nitrous oxide 0.03 mol%, and the remainder being nitrogen, with a total gas volume of 6 m³. 3 / h.

[0041] As the glass ribbon moves forward online, a second precursor gas mixture consisting of silane, ethylene, carbon dioxide, nitrous oxide, and nitrogen is fed into the second reactor. Using chemical vapor deposition, a second structural film, SiC, is deposited on the surface of a TiO2 barrier layer at 630°C. x O y The color adjustment layer and the tail gas generated by the deposition reaction are discharged through the reactor's exhaust device and then enter the tail gas treatment system for purification. Unreacted silane and other coating raw materials can be recycled.

[0042] The pre-film gas mixture for the second structure consists of: 1.0 mol% silane, 0.05 mol% ethylene, 0.05 mol% carbon dioxide, 0.002 mol% nitrous oxide, with the remainder being nitrogen. The total gas volume is 10 m³. 3 / h.

[0043] The float glass with the first and second structural films deposited described above continues to move forward in the tin bath, reaching the A0 zone of the annealing furnace in the float glass production line. A reactor with a multi-inlet and multi-outlet exhaust structure (multi-inlet, multi-outlet structure) is installed upstream of the A0 zone of the annealing furnace. At a temperature range of 580°C, this reactor is used to process the TiO2 barrier layer and SiC... x O y A third structural film layer, a fluorine-doped conductive film layer, is deposited on the upper surface of the color adjustment layer. The exhaust gas generated by the deposition reaction is discharged through the reactor's exhaust device and then enters the exhaust gas treatment system for purification. Unreacted coating raw materials such as triethyltin chloride can be recycled.

[0044] The composition of the gas mixture preceding the third structural membrane layer is: 1.0 mol% triethyltin chloride, 0.5 mol% hydrogen fluoride, 0.3 mol% water, 2 mol% nitrogen, with the remainder being air, and a total gas volume of 200 m³. 3 / h.

[0045] The glass ribbon, having deposited the first, second, and third structural film layers, continues to move forward. In the 550°C temperature zone downstream of the A0 zone of the float glass production line annealing furnace, a separate multi-inlet, multi-outlet reactor is used to deposit the fourth structural film layer, an antimony oxide color core modulation layer, on the upper surface of the third structural film layer. The high-temperature exhaust gas generated by the deposition reaction is discharged through the reactor's exhaust device and then enters the exhaust gas treatment system for purification. Unreacted antimony butoxide and other coating raw materials can be recycled.

[0046] The composition of the gas mixture preceding the fourth structural membrane layer is: 0.4 mol% antimony butoxide, 0.04 mol% ethyl acetate, 3 mol% nitrogen, and the remainder is air, with a total gas volume of 50 m³. 3 / h.

[0047] This method was used to deposit a conductive film glass product with a neutral color and low resistance multi-interface structure on the surface of float glass. Measurements showed that the total thickness of the composite film was 500 nm, the optical coefficient a* value was -1.5, the optical coefficient b* value was 1.5, and the surface resistance of the conductive layer was 7 Ω / □.

[0048] Example 2

[0049] Similar to Example 1, in the tin bath of the float glass production line, a first precursor gas mixture consisting of tetraethyl titanate, nitrous oxide, and nitrogen is transported to the first reactor. Using chemical vapor deposition, a TiO2 barrier layer is deposited on the hot glass surface at a temperature of 710°C. The high-temperature exhaust gas generated by the deposition reaction is discharged through the reactor's exhaust device and then enters the exhaust gas treatment system for purification. Unreacted tetraethyl titanate and other coating raw materials can be recycled.

[0050] The gas mixture composition of the precursor gas for the first structural film layer is: tetraethyl titanate 0.8 mol%, nitrous oxide 0.05 mol%, with the remainder being nitrogen, and the total gas volume is 8 m³. 3 / h.

[0051] As the glass ribbon moves forward online, a pre-film gas mixture consisting of silane, ethylene, carbon dioxide, nitrous oxide, and nitrogen is fed into the second reactor. Using chemical vapor deposition, a SiC layer is deposited on the surface of the TiO2 barrier layer at 665°C. x O yColor adjustment layer. The exhaust gas generated by the deposition reaction is discharged through the reactor's exhaust device. After purification, the unreacted silane and other coating materials can be recycled.

[0052] The pre-film gas mixture for the second structure consists of: 1.5 mol% silane, 0.08 mol% ethylene, 0.08 mol% carbon dioxide, 0.005 mol% nitrous oxide, with the remainder being nitrogen. The total gas volume is 13 m³. 3 / h.

[0053] The float glass with the first and second structural films deposited described above continues to move forward in the tin bath, reaching the A0 zone of the annealing furnace in the float glass production line. A reactor with a multi-inlet and multi-outlet exhaust structure is installed upstream of the A0 zone of the annealing furnace. At a temperature range of 600°C, this reactor is used to process the TiO2 barrier layer and SiC... x O y A third structural film, a fluorine-doped conductive film, is deposited on the upper surface of the color adjustment layer. The exhaust gas generated during the deposition reaction is discharged through the reactor's exhaust device and then enters the exhaust gas treatment system for purification. Unreacted coating materials, such as triethyltin chloride, can be recycled.

[0054] The composition of the gas mixture preceding the third structural membrane layer is: 1.5 mol% triethyltin chloride, 0.8 mol% hydrogen fluoride, 0.5 mol% water, 3.0 mol% nitrogen, and the remainder is air, with a total gas volume of 260 m³. 3 / h.

[0055] The glass ribbon, having deposited the first, second, and third structural films, continues to move forward. In the 565°C temperature zone downstream of the A0 area of ​​the float glass production line annealing furnace, a separate reactor with a multi-inlet and multi-outlet exhaust structure is used to deposit the fourth structural film—an antimony oxide color center modulation layer—on the upper surface of the third structural film. After purification, the unreacted antimony butoxide and other coating raw materials produced by the deposition reaction can be recycled.

[0056] The composition of the gas mixture preceding the fourth structural membrane layer is: 0.6 mol% antimony butoxide, 0.06 mol% ethyl acetate, 4 mol% nitrogen, and the remainder is air, with a total gas volume of 80 m³. 3 / h.

[0057] This method was used to deposit a conductive film glass product with a neutral color and low resistance multi-interface structure on the surface of float glass. Measurements showed that the total thickness of the composite film was 540 nm, the optical coefficient a* value was -1.05, the optical coefficient b* value was 1.25, and the surface resistance of the conductive layer was 8.23 ​​Ω / □.

[0058] Example 3

[0059] In the tin bath of the float glass production line, a first precursor gas mixture consisting of tetraethyl titanate, nitrous oxide, and nitrogen is transported to the first online coating reactor. Using chemical vapor deposition, a TiO2 barrier layer is formed on the hot glass surface at a temperature of 720°C. The tail gas generated by the deposition reaction is discharged through the reactor's exhaust device and then enters the tail gas treatment system for purification. Unreacted tetraethyl titanate and other coating raw materials can be recycled.

[0060] The gas mixture of the precursor layer for the first structural film consists of: 1.0 mol% tetraethyl titanate, 0.07 mol% nitrous oxide, and the remainder being nitrogen gas, with a total gas volume of 10 m³. 3 / h.

[0061] As the glass ribbon moves forward online, a pre-film gas mixture consisting of silane, ethylene, carbon dioxide, nitrous oxide, and nitrogen is fed into a second online coating reactor. Using chemical vapor deposition, a SiC layer is deposited on the surface of the TiO2 barrier layer at a temperature of 680℃. x O y The color adjustment layer and the tail gas generated by the deposition reaction are discharged through the reactor's exhaust device. The unreacted coating materials such as silane can be recycled after purification.

[0062] The pre-film gas mixture for the second structure consists of: 2.0 mol% silane, 0.1 mol% ethylene, 0.1 mol% carbon dioxide, 0.008 mol% nitrous oxide, with the remainder being nitrogen. The total gas volume is 15 m³. 3 / h.

[0063] The float glass with the first and second structural films deposited described above continues to move forward in the tin bath, reaching the A0 zone of the annealing furnace in the float glass production line. A reactor with a multi-inlet and multi-outlet exhaust structure is installed upstream of the A0 zone of the annealing furnace. At a temperature range of 610°C, this reactor is used to process the TiO2 barrier layer and SiC... x O y A third structural film, a fluorine-doped conductive film, is deposited on the upper surface of the color adjustment layer. The exhaust gas generated by the deposition reaction is discharged through the reactor's exhaust device and then enters the exhaust gas treatment system for purification. Unreacted coating materials, such as triethyltin chloride, can be recycled.

[0064] The composition of the gas mixture preceding the third structural membrane layer is: 2 mol% triethyltin chloride, 1 mol% hydrogen fluoride, 0.6 mol% water, 4 mol% nitrogen, and the remainder is air, with a total gas volume of 300 m³. 3 / h.

[0065] The glass ribbon, having deposited the first, second, and third structural films, continues to move forward. In the 580°C temperature zone downstream of the A0 section of the float glass production line annealing furnace, a separate multi-inlet, multi-outlet reactor is used to deposit the fourth structural film, an antimony oxide color center modulation layer, on the upper surface of the third structural film. After purification, the unreacted residual gas containing coating materials (such as antimony butoxide) can be recycled.

[0066] The composition of the gas mixture preceding the fourth structural membrane layer is: 0.8 mol% antimony butoxide, 0.08 mol% ethyl acetate, 5 mol% nitrogen, with the remainder being air, and a total gas volume of 100 m³. 3 / h.

[0067] This method was used to deposit a conductive film glass product with a neutral color and low resistance multi-interface structure on the surface of float glass. Measurements showed that the total thickness of the composite film was 700 nm, the optical coefficient a* was 1.0, the optical coefficient b* was -1.0, and the surface resistance of the conductive layer was 10 Ω / □.

[0068] Example 4

[0069] In the tin bath of the float glass production line, a first precursor gas mixture consisting of titanium tetrachloride, nitric oxide, and nitrogen is transported to the first online coating reactor. Using chemical vapor deposition, a TiO2 barrier layer is formed on the hot glass surface at a temperature of 690°C. The tail gas generated by the deposition reaction is discharged through the reactor's exhaust device and then enters the tail gas treatment system for purification. Unreacted titanium tetrachloride and other residual coating raw materials can be recycled.

[0070] The composition of the gas mixture preceding the first structural film layer is: 0.6 mol% titanium tetrachloride, 0.04 mol% nitric oxide, with the remainder being nitrogen gas, and the total gas volume is 6 m³. 3 / h.

[0071] As the glass ribbon moves forward online, a pre-film gas mixture consisting of silane, ethylene, carbon dioxide, nitric oxide, and nitrogen is fed into the second online deposition reactor. Using chemical vapor deposition, a SiC layer is deposited on the surface of the TiO2 barrier layer at 670°C. x O y Color adjustment layer. After purification treatment, the exhaust gas generated by the deposition reaction can be recycled for residual coating materials such as unreacted silane.

[0072] The pre-proton gas mixture of the second structural membrane layer consists of: 1.4 mol% silane, 0.06 mol% ethylene, 0.07 mol% carbon dioxide, 0.006 mol% nitric oxide, with the remainder being nitrogen. The total gas volume is 12 m³. 3 / h.

[0073] The float glass with the first and second structural films deposited described above continues to move forward in the tin bath, reaching the A0 zone of the float glass production line annealing furnace. A multi-inlet, multi-outlet reactor is installed upstream of the A0 zone of the annealing furnace. At a temperature range of 640°C, this reactor is used to process the TiO2 barrier layer and SiC... x O y A third structural film layer, a fluorine-doped conductive film layer, is deposited on the upper surface of the color adjustment layer. The tail gas generated by the deposition reaction is discharged through the exhaust device of the reactor. After purification, the residual coating materials such as incompletely reacted tin triphenylacetate can be recycled.

[0074] The composition of the gas mixture preceding the third structural membrane layer is as follows: 1.8 mol% triphenyltin acetate, 1.0 mol% hydrogen fluoride, 0.6 mol% water, 3.0 mol% nitrogen, and the remainder is air, with a total gas volume of 270 m³. 3 / h.

[0075] The glass ribbon, having deposited the first, second, and third structural films, continues to move forward. In the 565°C temperature zone downstream of zone A0 of the float glass production line's annealing furnace, a second multi-inlet, multi-outlet reactor is used to deposit the fourth structural film—an antimony oxide color core modulation layer—on the upper surface of the third structural film. The exhaust gas generated during the deposition reaction is discharged through the reactor's exhaust system. After purification, unreacted antimony chloride and other residual coating materials can be recycled.

[0076] The composition of the gas mixture preceding the fourth structural membrane layer is: antimony chloride 0.8 mol%, methanol 0.06 mol%, nitrogen 3 mol%, with the remainder being air, and a total gas volume of 85 m³. 3 / h.

[0077] This method was used to deposit a conductive film glass product with a neutral color and low resistance multi-interface structure on the surface of float glass. Measurements showed that the total thickness of the composite film was 545 nm, the optical coefficient a* value was -1.10, the optical coefficient b* value was 1.22, and the surface resistance of the conductive layer was 7.68 Ω / □.

[0078] Example 5

[0079] In the tin bath of the float glass production line, a first precursor gas mixture consisting of tetraisopropyl titanate, nitrous oxide, and nitrogen is transported to the first online coating reactor. Using chemical vapor deposition, a TiO2 barrier layer is deposited on the hot glass surface at a temperature of 695°C. The tail gas generated by the deposition reaction is discharged through the reactor's exhaust device. After purification, the unreacted tetraisopropyl titanate and other residual coating materials can be recycled.

[0080] The gas mixture of the precursor layer for the first structural film consists of: tetraisopropyl titanate 0.8 mol%, nitric oxide 0.045 mol%, with the remainder being nitrogen, and the total gas volume is 7 m³. 3 / h.

[0081] As the glass ribbon moves forward online, a pre-film gas mixture consisting of silane, ethylene, carbon dioxide, nitric oxide, and nitrogen is fed into the second online deposition reactor. Using chemical vapor deposition, a SiC layer is deposited on the surface of the TiO2 barrier layer at a temperature of 675°C. x O y The color adjustment layer and the tail gas generated by the deposition reaction are discharged through the reactor's exhaust device. The unreacted silane and other coating raw materials can be recycled after purification.

[0082] The composition of the gas mixture preceding the second structural membrane layer is: 1.46 mol% silane, 0.065 mol% ethylene, 0.067 mol% carbon dioxide, 0.006 mol% nitric oxide, with the remainder being nitrogen. The total gas volume is 11 m³. 3 / h.

[0083] The float glass with the first and second structural films deposited described above continues to move forward in the tin bath, reaching the A0 zone of the annealing furnace in the float glass production line. A reactor with a multi-inlet and multi-outlet exhaust structure is installed upstream of the A0 zone of the annealing furnace. At a temperature range of 645°C, this reactor is used to process the TiO2 barrier layer and SiC... x O y A third structural film, a fluorine-doped conductive film, is deposited on the upper surface of the color adjustment layer. The exhaust gas generated by the deposition reaction is discharged through the reactor's exhaust device, and the unreacted coating materials, such as tributyltin, can be recycled after purification.

[0084] The composition of the gas mixture preceding the third structural membrane layer is: 2.0 mol% tributyltin, 1.0 mol% trifluoroacetic acid, 0.5 mol% water, 3.0 mol% nitrogen, and the remainder is air, with a total gas volume of 280 m³. 3 / h.

[0085] The glass ribbon, having deposited the first, second, and third structural films, continues to move forward. In the 565°C temperature zone downstream of the A0 area of ​​the float glass production line annealing furnace, a second reactor with a multi-inlet and multi-outlet exhaust structure is used to deposit the fourth structural film, an antimony oxide color core modulation layer, on the upper surface of the third structural film. The exhaust gas generated during the deposition reaction is discharged through the reactor's exhaust system. Unreacted coating materials, such as antimony ethanol, can be recycled after purification.

[0086] The composition of the gas mixture preceding the fourth structural membrane layer is: 0.85 mol% antimony ethanol, 0.06 mol% methanol, 3 mol% nitrogen, and the remainder is air, with a total gas volume of 90 m³. 3 / h.

[0087] This method was used to deposit a conductive film glass product with a neutral color and low resistance multi-interface structure on the surface of float glass. Measurements showed that the total thickness of the composite film was 560 nm, the optical coefficient a* value was -1.0, the optical coefficient b* value was 1.2, and the surface resistance of the conductive layer was 8.21 Ω / □.

[0088] It should be noted that the above embodiments only illustrate some implementation methods of the present invention and are not intended to limit the present invention in any way. Even for those skilled in the art or patent practitioners, several modifications and improvements can be made based on the concept of the present invention, but all of them will fall within the protection scope of the present invention.

Claims

1. A method for preparing a multi-interface structure conductive film glass with controllable color neutrality, comprising the following steps: (1) In the tin bath of the float glass production line, multiple online coating reactors are set up above the glass belt. A precursor gas mixture consisting of titanium compounds, reaction promoters, and dilution gases is fed into the first online coating reactor. Using online chemical vapor deposition, a TiO2 barrier layer is formed on the hot glass surface at a temperature of 680℃~720℃. The precursor gas mixture consists of 0.6mol%~1.0mol% titanium compounds, 0.03mol%~0.07mol% reaction promoters, and the remainder is dilution gas. The total gas volume is 6m³. 3 / h~10m 3 / h, (2) A precursor gas mixture consisting of silane, ethylene, carbon dioxide, reaction promoter, and inert gas is fed into a second online coating reactor. Using online chemical vapor deposition, a SiC layer is formed on the surface of the TiO2 barrier layer at a temperature of 630℃~680℃. x O y The color conditioning layer consists of a precursor gas mixture comprising: 1 mol%–2 mol% silane, 0.05 mol%–0.1 mol% ethylene, 0.05 mol%–0.1 mol% carbon dioxide, 0.002 mol%–0.008 mol% reaction promoter, with the remainder being inert gases. The total gas volume is 10 m³. 3 / h~15m 3 / h, (3) In the temperature zone of 580℃~610℃ upstream of zone A0 of the annealing furnace, a first multi-inlet, multi-outlet reactor is set up, and online chemical vapor deposition is used to deposit SiC on the above-mentioned SiC. x O y A fluorine-doped tin oxide conductive film is deposited on the surface of the color adjustment layer. The pre-plasma mixture for this film consists of: 1.0 mol%–2.0 mol% tin compound, 0.5 mol%–1.0 mol% dopant, 0.3 mol%–0.6 mol% catalyst, 2 mol%–4 mol% carrier gas, and the remainder being dilution gas, with a total gas volume of 200 m³. 3 / h~300m 3 / h, (4) In the temperature zone of 550℃~580℃ downstream of zone A0 of the annealing furnace, a second multi-inlet, multi-outlet reactor is set up. An antimony oxide color core modulation layer is deposited on the surface of the aforementioned fluorine-doped tin oxide conductive film using online chemical vapor deposition. The composition of the gas mixture preceding the film layer is: 0.4mol%~0.8mol% antimony compound, 0.04mol%~0.08mol% auxiliary solvent, 3mol%~5mol% carrier gas, and the remainder being dilution gas. The total gas volume is 50m³. 3 / h~100m 3 / h, (5) The tail gas generated by the chemical vapor deposition reaction is discharged through the exhaust device of the reactor and then enters the tail gas treatment system for purification. The unreacted coating raw materials can be recycled again.

2. The method for preparing a multi-interface structure conductive film glass with controllable color neutrality according to claim 1, characterized in that... The titanium compound is tetraethyl titanate, tetrabutyl titanate, tetraisopropyl titanate, or titanium tetrachloride.

3. The method for preparing a multi-interface structure conductive film glass with controllable color neutrality according to claim 1, characterized in that... The reaction promoter is nitrous oxide or nitric oxide.

4. The method for preparing a multi-interface structure conductive film glass with controllable color neutrality according to claim 1, characterized in that... Both the inert gas and the carrier gas are nitrogen or argon.

5. The method for preparing a multi-interface structure conductive film glass with controllable color neutrality according to claim 1, characterized in that... The tin compound is dibutyltin, stannous octoate, dimethyltin, dioctyltin, tetraphenyltin, tributyltin, triphenyltin, trimethyltin, trimethyltin chloride, triethyltin, triethyltin chloride, triethyltin bromide, triethyltin iodide, triethyltin hydroxide, tributyltin chloride, triphenyltin chloride, triphenyltin acetate, tetraethyltin, tetrabutyltin, or tetraphenyltin.

6. The method for preparing a multi-interface structure conductive film glass with controllable color neutrality according to claim 1, characterized in that... The dopant is a fluorine compound, including one or more of trifluoroacetic acid, hydrogen fluoride, hexafluoropropylene, and trifluoromethyl bromide.

7. The method for preparing a color-neutral and controllable multi-interface structure conductive film glass according to claim 1, wherein the antimony compound is antimony ethanol, antimony butoxide, isopropyl antimony, ethyl antimony, methyl antimony, or antimony chloride.

8. The method for preparing a multi-interface structure conductive film glass with controllable color neutrality according to claim 1, characterized in that... The catalyst is oxygen or water.

9. The method for preparing a multi-interface structure conductive film glass with controllable color neutrality according to claim 1, characterized in that... The diluting gas is nitrogen or air.

10. The method for preparing a multi-interface structure conductive film glass with controllable color neutrality according to claim 1, characterized in that... The multi-interface structure conductive film has a thickness of 500nm to 700nm, an optical coefficient a* value of -1.5 to 1.0, an optical coefficient b* value of -1.0 to 1.5, and a surface resistance of 7Ω / □ to 10Ω / □.