Method for preparing coated glass substrates

Abstract

To provide a process for preparing a coated glass substrate for better sheet resistance in the glass substrate.SOLUTION: A chemical vapor deposition process for preparing a coated glass substrate 2 comprises at least the following steps in sequence: (a) providing a glass substrate 2 having a surface; (b) depositing a layer 3 based on SiCO and / or SiNO on the surface of the glass substrate; (c) exposing the layer 3 based on SiCO and / or SiNO to a gaseous mixture (i) comprising water; and (d) subsequently depositing layers 4, 5 based on a TCO over the layer 3 based on SiCO and / or SiNO.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for preparing a coated glass substrate.

Background Art

[0002] A photovoltaic (PV) cell or solar cell is a material junction device that converts sunlight into direct current (DC) power. When exposed to sunlight (which consists of energy from photons), the electric field at the p-n junction of the PV cell separates pairs of free electrons and holes, generating a photovoltaic power. The circuit from the n-side to the p-side allows the flow of electrons when the PV cell is connected to an electrical load, and during that time the area of the PV cell junction and other parameters determine the available current.

[0003] In the context of the present invention, the term "PV cell" is understood to include an assembly of components that generate a current between electrodes by the conversion of solar radiation, regardless of the dimensions, voltage and intensity of the current generated by the assembly, and whether or not this assembly of components has one or more internal electrical connections (in series and / or in parallel). Thus, the term "PV cell" in the meaning of the present invention is here equivalent to "photovoltaic device" or "photovoltaic panel", as well as "photovoltaic module", "solar cell" or "solar panel". A PV cell has a layer called a junction between an n-type material and a p-type material. Even in the absence of light, a small number of electrons move from the n-type to the p-type semiconductor across the junction, generating a low voltage. In the presence of light, photons expel a large number of electrons, which cross the junction

[0004] ​​​​​This process generates an electric current that can be used to supply power to electrical devices.

[0005] Conventional PV cells use silicon for the n-type and p-type layers. The latest generation of thin-film PV The cell is made of cadmium telluride (CdTe), amorphous or microcrystalline silicon instead. Alternatively, a thin layer of indium gallium diselenide (CIGS) is used.

[0006] The semiconductor junction is an amorphous silicon (a-Si) pin device, Or a heterojunction of CdTe and CIGS (for example, a thin sulfur that allows most sunlight to pass through). It is formed in various ways as a cadmium oxide layer. In its simplest form, a-Si cells experience a significant decrease in output (ranging from 15 to 35%) when exposed to sunlight. To increase stability, a thinner layer needs to be used, but this reduces light absorption. Cell efficiency decreases. As a result, the industry has been stacking PIN cells alternately at the top. We began developing tandem and triple junction devices.

[0007] Generally, a transparent conductive oxide (TCO) layer forms the front electrical contact of a thin-film photovoltaic cell. The metal layer forms the back contact. TCO is doped zinc oxide (e.g., ZnO:Al [ZAO] or ZnO:B), fluorine-doped tin oxide (SnO2:F) or These materials can be obtained based on indium and tin oxide materials (ITO). These materials can be obtained, for example, chemical Chemical deposition by methods such as vapor deposition ("CVD"), or by, for example, magnetrons It is physically deposited by vacuum deposition through puttering.

[0008] The TCO layer can be deposited as part of a stack of layers on a glass substrate. The contacting base layer generally allows for color suppression, and the sodium ions are located on any layer above it. It is provided to prevent migration. SnO2 and SiO2 are used in the base layer. However, SiCO has advantages in terms of durability and reduction of void defect levels. Silicon oxide is an alternative material. However, the SiCO-based layer is deposited in an inert atmosphere. If so, for example, inside the float bath, the TCO layer above is required for the photovoltaic cell. It may exhibit a sheet resistance higher than the sheet resistance that can be expected. Therefore, at least this problem Providing a process to mitigate the problem would be advantageous.

[0009] According to a first aspect of the present invention, a chemical vapor for preparing a coated glass substrate The process is provided. The process in question is at least, (a) The step of providing a glass substrate having a surface, (b) Steps to deposit a SiCO and / or SiNO-based layer on the surface of a glass substrate P and, (c) Expose the SiCO and / or SiNO-based layer to a gas mixture (i) containing water. The steps to take, (d) Next, a layer based on TCO is stacked on top of a layer based on SiCO and / or SiNO. The steps to be accumulated, It includes them in order.

[0010] Surprisingly, before depositing the TCO-based layer, SiCO and / or SiNO When the layer based on is treated with a water-containing gas mixture (i), the sheet resistance exhibited by the TCO-based layer It was found that resistance improved (i.e., decreased).

[0011] In the context of the present invention where a layer is said to be "based on" a particular material or a particular plurality of materials this means that the layer consists predominantly of the corresponding material or materials in question, which usually means containing at least about 50 at.% of the material or materials in question. .

[0012] In the following description of the present invention, unless otherwise specified, the disclosure of an upper limit or an alternative value of a lower limit of a parameter range is to be construed in conjunction with the indication that one of the aforementioned values is much more preferred than the other, and each intermediate value of the aforementioned parameter is between the more preferred and the less preferred of the aforementioned alternatives, and is itself more preferred than the less preferred value mentioned above, and also more preferred than each value between the less preferred value mentioned above and the intermediate value in question, and is to be construed as an implicit disclosure to this effect.

[0013] Throughout this specification, the terms "comprising" or "comprises" mean including the stated components but not excluding the presence of other components. The term "consisting essentially of" means including the stated components but excluding other components except for materials present as impurities, inevitable materials resulting from the processes used to provide the components, and additional components added for other purposes rather than to achieve the technical effects of the present invention. Usually, when referring to a composition, a composition consisting essentially of a set of components contains less than 5% by weight, usually less than 3% by weight, more typically 1 weight% or less, usually less than 3 weight%, more typically 1 Contains unspecified ingredients in amounts less than 1% by weight.

[0014] "consisting of" or "consists of" The term means including the specified components and excluding the other components.

[0015] Whenever appropriate, depending on the context, "to include" or "to provide" ("compris"). The use of the terms "es" or "comprising" means "essentially consisting of ~". (consisting essentially of or "consists It can also be interpreted as including the meaning of "essentially of", and also as "from The meaning is "consists of" or "consisting of". It could also be interpreted as including the taste.

[0016] References in this specification such as "the range of x to y" are intended to include the interpretation of "from x to y". It tastes good, and therefore includes values ​​x and y.

[0017] In the context of the present invention, the "thickness" of a layer is defined as the thickness of a layer at any predetermined position on the surface of the layer. From the aforementioned predetermined position on the surface of the layer in the direction of the minimum dimension, to the opposite surface of the layer It is represented by the distance traveled through the layers to the position.

[0018] In the context of the present invention, a transparent material or transparent substrate is capable of transmitting visible light. A material or substrate, and as a result, an object located on the other side or behind the aforementioned material Alternatively, the image can be clearly seen through the aforementioned material or substrate.

[0019] In the context of this invention, a "derivative" is a chemical substance that is structurally related to another chemical substance and then theoretically related to it. It is a chemical substance that can be derived.

[0020] Preferably, the layer is based on SiCO and / or SiNO, and is a layer based on SiCO. ru.

[0021] Preferably, a layer based on SiCO and / or SiNO is added in step (c) containing water. Exposure to a gas mixture (i), thereby converting oxide ions into SiCO and / or Si Incorporate into a NO-based layer. Preferably, step (c) is SiCO and / or S This process is carried out without depositing any further layers on top of the iNO-based layer.

[0022] Preferably, the gas mixture (i) also contains oxygen. Or, in addition, SiCO and / or the SiNO-based layer contains oxygen between steps (c) and (d). It may be exposed to mixture (iii).

[0023] Preferably, the gas mixture (i) is substantially water, oxygen, and optionally an inert gas It consists of, more preferably, water, oxygen, and optionally an inert gas. Preferably, the gas mixture (i) consists of water, oxygen, and an inert gas.

[0024] Preferably, the process consists substantially of the steps in the order described in the first embodiment. Preferably, the process consists of the steps in the order described in the first embodiment.

[0025] Preferably, the gas mixture (i) is at least 1.5:1 by volume, more preferably less Both are 3:1 volume, more preferably at least 4:1 volume, most preferably at least It also contains a water-to-oxygen ratio of 5.5:1 by volume, but preferably up to 50:1 by volume, more preferably The maximum is 10:1 volume, more preferably a maximum of 7:1 volume, most preferably a maximum This contains a water-to-oxygen ratio of 6:1 by volume.

[0026] In a preferred embodiment, the gas mixture (i) consists of 25-65 volume% water and 2-20 asterisks. It contains a product percentage of oxygen. More preferably, the gas mixture (i) contains 40-50 volume percent of water and It contains 5-10% by volume of oxygen.

[0027] The gas mixture (i) is preferably an inert gas such as nitrogen or helium or similar. This also includes a mixture of the following. Preferably, the inert gas is nitrogen. Thus, this process is To provide one or more sources of inert gas from which separate supply lines may extend. It may contain. Preferably, the gas mixture (i) also contains at least 25% by volume of nitrogen, etc. 5% by volume of an inert gas, more preferably 40% to 50% by volume of an inert gas such as nitrogen. This also includes.

[0028] Preferably, in step (c), the water is at least 50 slm (standard liters / (minutes), more preferably at least 100 slm, even more preferably at least 150 It is delivered at a flow rate of slm, most preferably at least 190 slm, but preferably at a maximum 350 slm, more preferably up to 300 slm, and even more preferably up to 250 slm m, most preferably delivered at a flow rate of up to 210 slm.

[0029] Preferably, in step (c), if present, oxygen is at least 15 slm , more preferably at least 20 slm, even more preferably at least 25 slm, Most preferably delivered at a flow rate of at least 30 slm, but preferably up to 55 slm m, more preferably up to 50 slm, even more preferably up to 45 slm, most preferred The oxygen is delivered at a maximum of 40 slm. Preferably, oxygen is delivered at a minimum of 15 slm. More preferably at least 20 slm, even more preferably at least 25 slm, Preferably, the gas mixture (iii) is delivered at a flow rate of at least 30 slm, but is preferred Or at most 55 slm, more preferably at most 50 slm, and even more preferably at most It is delivered at 45 slm, most preferably up to 40 slm.

[0030] Preferably, in step (c), if present, an inert gas such as nitrogen is present in small amounts. At least 50 slm (standard liters / minute), more preferably at least 100 slm, further More preferably at least 150 slm, most preferably at least 190 slm sl It is delivered at a flow rate of m, preferably up to 350 slm, more preferably up to 300 sl m, more preferably up to 250 slm, and most preferably up to 210 slm, delivered It can be done.

[0031] This process may be carried out in conjunction with the manufacture of a glass substrate, preferably a transparent glass substrate. In one embodiment, the transparent glass substrate is made using a well-known float glass manufacturing process. It can be formed. In this embodiment, the transparent glass substrate may also be called a glass ribbon. A preferred method of chemical vapor deposition (CVD) is atmospheric pressure CVD (e.g., float glass process). It is an online CVD process performed inside. However, this process involves float gas In addition to the glass manufacturing process, or after the formation and cutting of glass ribbons, I want you to understand that it is possible.

[0032] Conveniently, this process can be done using a float bath, annealing rail, or rail gear. It can be done in either of the gaps. Rail gaps are float buses and annealing rails. It is defined as the area between the rails. At the rail gap, the surrounding atmosphere is that of a float bus. The atmosphere can change from a reducing atmosphere to an oxidizing (atmospheric) atmosphere within the annealing rail.

[0033] Preferably, step (b) is carried out in a non-oxidizing atmosphere. In the context of the present invention The term "non-oxidizing atmosphere" refers to an atmosphere that does not contain oxidizing agents such as oxygen, hydrogen peroxide, or halogens. This refers to the atmosphere contained within. Preferably, step (b) is performed in a float bath. More preferably, both steps (b) and (c) are performed on a float bus. More preferably, steps (b), (c), and (d) are all performed in a float bath. It can be done.

[0034] Preferably, step (b) involves rinsing the surface of the glass substrate with a silicon source, a carbon source, and an acid This is carried out by exposure to a gas mixture (ii) containing the elemental source.

[0035] Preferably, the silicon source is a silane such as monosilane, dimethylsilane, or disilane. It is preferably monosilane.

[0036] Preferably, the carbon source is an ethylenically unsaturated hydrocarbon compound (e.g., ethylene), acetylene. Teylene unsaturated compounds (e.g., acetylene) or aromatic compounds (e.g., toluene) These are unsaturated hydrocarbon compounds, but generally, under ambient conditions, gaseous unsaturated hydrocarbons are produced. It is most convenient to use. The unsaturated hydrocarbon is preferably an olefin, and 2-4 It is convenient that the olefin contains 1 carbon atom. Ethylene is particularly preferred.

[0037] Oxygen sources include carbon dioxide, carbon monoxide, water vapor, sulfur dioxide, nitrogen oxides (nitrous oxide, Gaseous oxides such as nitric oxide or nitrogen dioxide, and olefin oxides, especially E It may be a ethylene oxide. Preferably, the oxygen source is carbon dioxide.

[0038] Further examples of oxygen sources include carbonyl compounds (especially ketones and aldehydes) and ethers. It is an organic oxygen-containing compound, including alcohols. Generally, at room temperature, it is at least 10 mm. It is most convenient to use compounds with a vapor pressure of , and therefore for this reason Any oxygen-containing organic compound used in this process typically has a carbon content of 8 or less, preferably 4 or less. Includes children.

[0039] The gas mixture (ii) is preferably an inert gas such as nitrogen or helium or the same This also includes mixtures of these. Preferably, the inert gas is nitrogen.

[0040] Preferably, the TCO-based layer is deposited directly onto the SiCO-based layer. Alternatively, The aforementioned TCO-based layers are indirectly deposited on SiCO and / or SiNO-based layers. It is possible. That is, the aforementioned TCO-based layer is based on SiCO and / or SiNO. It can be deposited on top of one or more layers previously deposited on the layer above. For example, based on the aforementioned TCO The deposits can be deposited on top of a tin oxide-based layer and / or a silica-based layer. Therefore, step (d) is performed before the layer based on TCO is deposited, SiCO and / Alternatively, this may further include depositing one or more layers on top of a SiNO-based layer.

[0041] Preferably, the TCO-based layer comprises one or more fluorine-doped tin oxide (SnO2:F) Zinc oxide (ZnO: Al, ZnO) doped with aluminum, gallium, or boron. :Ga, ZnO:B), tin-doped indium oxide (ITO), cadmium stannate Mu, ITO:ZnO, ITO:Ti, In2O3, In2O3-ZnO(IZO), In 2O3:Ti, In2O3:Mo, In2O3:Ga, In2O3:W, In2O3:Z r, In2O3:Nb, In 2-2x M x Sn x O3 (where M is Zn or Cu), ZnO: F, Zn 0.9 Mg 0.1 O:Ga, and (Zn,Mg)O:P, ITO:Fe, Sn O2:Co, In2O3:Ni, In2O3:(Sn,Ni), ZnO:Mn, and Z Contains nO:Co. Preferably, the aforementioned layer based on TCO is fluorine-doped tin oxide (S Based on nO2:F). Most preferably, the aforementioned layer based on TCO is fluorine-doped oxidation. It is tin (SnO2:F).

[0042] Preferably, step (d) is a layer based on SiCO and / or SiNO, One or more layers of SiCO and / or SiNO are deposited before the TCO-based layer is deposited. If it is deposited on top of the underlying layer, another layer will be exposed to the gas mixture (iv) This is how it is executed. For the deposition of SnO2:F, the gas mixture (iv) is preferably dimethyl Chilsutin dichloride (DMT), oxygen, vapor, and HF or trifluoroacetic acid, etc. Contains a fluorine source. More preferably, the gas mixture (iv) also contains an inert gas such as nitrogen. include.

[0043] This process preferably involves a transparent glass substrate of 450 ℃ from 800 ℃ When the temperature is within the range of 550, more preferably the transparent glass substrate is 550 ℃ From 770 ℃ This can be performed when the temperature is within this range. Depositing a CVD coating on a transparent glass substrate when it is at these preferred temperatures can result in a higher degree of crystallinity of the coating and improved toughness (resistance to heat treatment).

[0044] Preferably, step (b) is that the transparent glass substrate is at least 670 ℃ , more preferably at least 700 ℃ , more preferably at least 710 ℃ , most preferably at least 720 ℃ It is at a temperature, but preferably up to 770°C. ℃ , more preferably up to 750 ℃ More preferably, up to 740 ℃ , most preferably up to 730 ℃ It is carried out when the temperature is [temperature].

[0045] Preferably, step (c) is that the transparent glass substrate is at least 640 ℃ , more preferably at least 670 ℃ , more preferably at least 680 ℃ , most preferably at least 690 ℃ It is at a temperature, but preferably up to 760°C. ℃ , more preferably up to 740 ℃ More preferably, up to 730 ℃ , most preferably up to 700 ℃ It is carried out when the temperature is [temperature].

[0046] Preferably, step (d) is that the transparent glass substrate is at least 610 ℃ , more preferably at least 640 ℃ , more preferably at least 660 ℃ , most preferably at least 665 ℃ It is at a temperature, but preferably up to 710°C. ℃ More preferably, up to 690 ℃ More preferably, up to 680 ℃ , most preferably up to 675 ℃ It is carried out when the temperature is [temperature].

[0047] In certain embodiments, the CVD process involves the glass substrate being processed in steps (b), (c) and (d) is a dynamic process in motion. Preferably, the glass substrate is, for example, During steps (b), (c), and / or (d), at a predetermined speed of more than 3 m / min Move. More preferably, the glass substrate moves in steps (b), (c) and / or (d During this time, it moves at a speed of 3 m / min to 20 m / min.

[0048] As detailed above, preferably, the process is float glass manufacturing at substantially atmospheric pressure. It can be performed during the process. Alternatively, the process may involve low-pressure CVD or ultra-high-vacuum CVD. It can be performed using either aerosol CVD or direct liquid injection CVD. It can be performed in this way. Furthermore, CVD can be microwave plasma CVD, plasma CVD, Remote plasma CVD, atomic layer CVD, combustion CVD (flame thermal decomposition), hot wire CVD, Using metal-organic CVD, rapid thermal CVD, gas-phase epiquitosis, or photoinitiated CVD. This can be done. Glass substrates are typically stored from float glass manufacturing facilities to vacuum deposition facilities. For tubing or convenient transport, after step (d) (and before PVD coating deposition) ) is cut into sheets.

[0049] As will be understood by those skilled in the art, the use of any gas mixture used in this process Precursor compounds suitable for this purpose should be suitable for use in CVD processes. These compounds may be liquid or solid at some point, but are volatile, resulting in gaseous mixtures. It can be vaporized for use in a substance. In a gaseous state, it incorporates the precursor compound into the gas stream. It can be used in the process. For any specific combination of gas precursor compounds, The optimal concentration and flow rate for achieving the deposition rate and coating thickness may vary. ru.

[0050] In certain embodiments, the gas mixture is supplied through a coating apparatus and in step ( Before each of (b), (c), and (d), use one or more gas distribution beams It is discharged from the coating device. Preferably, each gas mixture is discharged through the coating device. It is formed before being supplied. For example, the precursor compound is connected to the inlet of the coating apparatus. They can be mixed in a supply line. In other embodiments, one or more gas mixtures are coated It can be formed within the apparatus.

[0051] One or more gas mixtures are directed toward and along the glass substrate. Obtain. The use of a coating apparatus involves applying one or more gas mixtures toward a glass substrate and It helps to direct along it. Preferably, one or more gas mixtures are in laminar flow to the glass group It is directed toward and along the board.

[0052] Preferably, the coating apparatus extends laterally across the glass substrate and applies a coating thereon It is provided at a fixed distance. The coating apparatus is preferably at least one predetermined position It is placed in the following location. When the process is used in conjunction with the float glass manufacturing process, the coating The rinsing device is preferably provided within its float bath section. However, the coating The annealing device is located within the annealing rail and / or the float bath and annealing rail. It may be provided within the gap between the two.

[0053] To prevent pre-reactions before the mixture reaches the surface of the glass substrate, one or more gas mixtures are used. It is desirable to keep the material at a temperature lower than the thermal decomposition temperature of the precursor compound. Coating apparatus Inside, the gas mixture is kept at a temperature lower than the temperature at which it reacts, on the surface of the glass substrate. It is delivered to a nearby location where the glass substrate is at a temperature higher than the reaction temperature. Step (b) The gas mixture of (d) reacts on or near the surface of the glass substrate, and on it The desired layer can be formed.

[0054] Preferably, the surface of the glass substrate to be coated is the gas-side surface. Glass manufacturers typically prefer to deposit a coating on the gas side surface (float glass). (In contrast to the tin-side surface of the lath). This is because the deposition of the coating on the gas-side surface is the coating. This is because the characteristics of the glass can be improved. Preferably, the surface of the glass substrate is glass This is the main surface of the substrate. The glass substrate is preferably transparent. A transparent glass substrate is transparent. It may be a clear metal oxide-based glass ribbon or glass plate. Preferably, glass ribbon The ribbon or glass plate is a transparent float glass ribbon or glass plate, preferably It is a low-iron float glass ribbon or glass sheet. Transparent float glass is BSE This refers to glass with the composition defined in N572-1 and BSEN 572-2 (2004). Yes. In the case of clear float glass, the weight concentration of Fe2O3 is usually 0.11%. F Float glass with an e2O3 content of less than approximately 0.05% by weight is typically low-iron float glass. This is called [a specific type of glass]. Such glasses typically have the same base composition as other component oxides. Low-iron float glass is also soda-lime silica glass, just like clear float glass. Typically, low-iron float glass contains less than 0.02% by weight of Fe2O3. Alternatively, Glass ribbons or glass plates are borosilicate-based glass ribbons or glass plates, aluminum Potassium aluminosilicate-based glass ribbon or glass plate, or aluminum oxide base It is a crystalline glass ribbon or glass plate.

[0055] The coated glass substrate is preferably up to 21 ohms / sq, more Maximum 20 ohms / sq, more preferably maximum 19 ohms / sq, most preferably maximum It exhibits a sheet resistance of up to 18.5 ohms / sq, but preferably at least 5 ohms / sq. More preferably at least 10 ohms / sq, and even more preferably at least 14 ohms The sheet resistance is ohms / sq, most preferably at least 15 ohms / sq.

[0056] When the coated glass substrate was tested according to ASTM D1003-13 Preferably at least 0.5%, more preferably at least 0.8%, and even more preferably It exhibits a haze of at least 1%, most preferably at least 1.2%. However, preferably up to 5%, more preferably up to 3%, and even more preferably up to 2.5%. , most preferably exhibiting a haze of up to 2.3%. These preferred haze values ​​are photovoltaic This is beneficial for cell efficiency.

[0057] According to a second aspect of the present invention, prepared by performing the process of the first aspect Water and Oxygen will be provided as needed.

[0058] Any feature described above with respect to the first and second aspects of the present invention is also a feature of the present invention. It can be used in any aspect of the invention. Any invention described herein may be modified as necessary. This invention can be combined with any feature of any other invention described herein. Any feature applicable to one aspect can be used in any combination and in any number. Please understand. Furthermore, they can also be used in any combination with any other aspect of the present invention. It can be used in combination and in any number. This includes the dependency of other claims of the claims of this application. This includes, but is not limited to, dependent claims derived from claims used as claims. .

[0059] Reader's attention is to any information submitted concurrently with or prior to this application in connection with this application. This applies to all papers and documents made publicly available for public viewing in the specification. The contents of all such papers and documents are incorporated herein by reference.

[0060] All features disclosed herein (including the accompanying claims, abstract, and drawings) ), and / or all steps of any method or process disclosed in that manner at least some of such features and / or steps are mutually exclusive. Except for combinations, any combination is possible.

[0061] Each feature disclosed herein (including the accompanying claims, abstract, and drawings) Unless otherwise specified, replace with an alternative feature that serves the same, equivalent, or similar purpose. Therefore, unless otherwise specified, the disclosed features are equivalent or similar. This is just one example of a general series of features. [Brief explanation of the drawing]

[0062] Next, the present invention will be further described by the following specific embodiments, which are shown in the attached figures. The surface is given as an example, not as an limitation. [Figure 1] This is a schematic diagram of a cross-section of a coated glazing according to the present invention. [Figure 2] This is a schematic vertical cross-section of a facility for carrying out a float glass process, incorporating several CVD apparatus for preparing coated glazing according to the present invention. [Modes for carrying out the invention]

[0063] Figure 1 shows a cross-section of the coated glazing 1 according to a specific embodiment of the present invention. The coated glazing 1 is based on SiCO and is applied using CVD. Layer 3, Layer 4 based on fluorine-doped tin oxide (SnO2:F), and tin oxide (SnO2 It comprises a transparent float glass substrate 2 that is sequentially coated with layers 5 based on ).

[0064] As described above, the present invention relates to the production of a glass substrate in a float glass process. In conjunction with the manufacturing process, it can be carried out using CVD. The float glass process is typically shown in Figure 2. This is carried out using float glass equipment such as the equipment 10 shown. However, this specification The float glass equipment 10 described is merely an example of such equipment. I want to be understood.

[0065] As shown in Figure 2, the float glass equipment 10 is such that molten glass 19 is removed from the melting furnace. It may include a water channel 20 that is delivered to the float bath section 11 where the substrate is formed. In this context, the glass substrate is called a glass ribbon 8. However, the glass substrate is a glass ribbon. Please understand that it is not limited. The glass ribbon 8 extends from the bus section 11 to the adjacent annealing It moves forward through the ang rail 12 and the cooling section 13. The float bath section 11 is filled with molten tin 1 The bottom 14, roof 16, opposite side wall (not shown), and end wall 17 include the bath 5. Includes: The roof 16, side walls and end walls 17 are all non-oxidative to prevent oxidation of the molten tin 15. Define an enclosure 18 where a sexual atmosphere is maintained.

[0066] During operation, the molten glass 19 moves along the water channel 20 below the adjustment tweel 21. Then, it flows downwards onto the surface of the tin bath 15 in a controlled amount. The molten glass 19 flows downwards onto the surface of the molten tin. On a surface, under the influence of gravity and surface tension, as well as under certain mechanical influences, it extends laterally. Then, it moves forward across the tin bath 15 and forms a glass ribbon 8. The glass ribbon 8 lifts Annie is removed from the bus section 11 on the outroll 22 and then placed on the aligned rolls. It is carried through the ring rail 12 and the cooling section 13. Coating deposition is preferably This is done in the float bath section 11, but deposition is carried out along the glass manufacturing line, for example, In the gap 28 between the annealing rail 11 and the annealing rail 12, or the annealing rail Further steps may be taken in Rule 12.

[0067] As shown in Figure 2, four CVD apparatuses 9, 9A, 9B, and 9C are located in the float bath section 11 This is shown inside. Thus, the required frequency and thickness of the coating layer, as well as the steps Depending on the amount of gas mixture (i) required in (c), CVD apparatus 9, 9A, 9B, 9 It may be desirable to use some or all of C. One or more additional codes. A CVD apparatus (not shown) may be provided. One or more CVD apparatuses may be alternative or additional. It can be placed within the rail gap 28. Any by-products can be placed via the coater extraction slot. Then, it is removed via a pollution control plant. For example, in one embodiment, a SiCO layer It is formed using CVD apparatus 9A, and a gas mixture of water, oxygen, and nitrogen is used in the CVD apparatus Equipment 9 is used for supplying the fluorine-doped tin oxide layer, and adjacent equipment 9B and 9C form the fluorine-doped tin oxide layer. It is used to achieve something.

[0068] To prevent oxidation of the molten tin 15 in the float bath, a suitable non-oxidizing atmosphere is provided. Generally, nitrogen or a nitrogen-dominant mixture of nitrogen and hydrogen is present in the float bath section 11. The atmosphere can be maintained. The atmospheric gas is supplied via a conduit 23 operably coupled to the distribution manifold 24. It is then sent. The non-oxidizing gas compensates for normal losses to prevent the intrusion of outside air and the surrounding area Leading at a speed sufficient to maintain a slight positive pressure approximately 0.001 to 0.01 above atmospheric pressure. It is included. For the purpose of explaining the present invention, the above pressure range is considered to correspond to normal atmospheric pressure. It can be done.

[0069] CVD is generally performed at virtually atmospheric pressure. Thus, the float bath section 11, - Between the annealing rail 12 and / or the float bus 11 and the annealing rail 12 The pressure within the gap 28 can be substantially atmospheric pressure. Float bath section 11 and enclosure The heat required to maintain the desired temperature range within 18 is provided by the radiant heater 25 within the enclosure 18. The cooling section 13 is not enclosed, and therefore the glass ribbon 8 is open to the ambient atmosphere. Therefore, the atmosphere inside rail 12 is normally the atmosphere. Next, glass ribbon 8 To cool the glass ribbon 8, ambient air is drawn into the cooling section 13. The fan 26 can direct the glass ribbon 8. It is carried through it Then, to gradually lower the temperature of the glass ribbon 8 according to a predetermined region, a heater ( (Not shown) can also be provided within the annealing rail 12. [Examples]

[0070] Using CV, all layers were deposited and exposed to water and water and oxygen. All examples shown in Table 1 below were fabricated on a float line using 3.2 mm soda-lime silica glass substrates. Comparative Examples 1-3 and Examples 4-7 were coated at an average line speed of 11 m / min. The SiCO base layer was deposited at 725 for all examples. ℃ The procedure was carried out at the glass temperature.

[0071] A SiCO layer is deposited on a glass surface using a single coater having the following components. did. N2 carrier gas, C2H4, SiH4, and CO2. The SnO2 layer is deposited on the glass surface using a single coater having the following components: Ta. • N2 carrier gas, O2, dimethyltin dichloride, and H2O. The SnO2:F layer is applied to the glass surface using two coaters for each example, each having the following components. It was deposited there. • N2 carrier gas, O2, dimethyltin dichloride, HF, and H2O. Exposure of the SiCO layer to water or water and oxygen is prevented by a single coater having the following components. I used it and executed it. • N2 carrier gas, water, and O2 as needed.

[0072] The layer thickness is approximately SiCO (30-80 nm) and SnO2:F (320-370 nm). The haze value was SnO2 (50-100 nm). The haze value was obtained using the BYK-Gardner haze method. The sheet resistance was measured using a meter according to the ASTM D1003-13 standard. Measurements were taken using a commercially available four-point probe according to the four-point probe method.

[0073] [Table 1]

[0074] [Table 2]

[0075] As can be seen from the results in Table 2 above, when the SiCO layer is exposed to water, the final product sheet Resistance improves (decreases). Exposure to water also provides a higher haze that is beneficial to PV cells. do.

[0076] Exposure of the SiCO layer to both water and oxygen further reduces its sheet resistance. ru.

[0077] The values ​​of a* and b* shown in Table 2 are for achieving appropriate intermediate colors when using this method. It indicates that it is possible.

Claims

1. A method for preparing a coated glass substrate, The above method at least, (a) the step of providing a glass substrate having a surface, (b) A step of depositing a SiCO-based layer on the surface of the glass substrate, (c) Exposing the SiCO-based layer to a gas mixture (i) containing water and oxygen in a water-to-oxygen ratio of 3:1 to 10:1 by volume, (d) Next, the step of depositing a layer based on transparent conductive oxide (TCO) on the SiCO-based layer, It includes in order, In step (c), the water is delivered at a flow rate of at least 50 slm (standard liters / min), Furthermore, in step (c), the oxygen is delivered at a flow rate of at least 15 slm.

2. The method according to claim 1, wherein the SiCO-based layer is exposed to the gas mixture (i) in step (c), thereby incorporating oxide ions into the SiCO-based layer.

3. The method according to claim 1 or 2, wherein step (c) is carried out without depositing any further layers on the SiCO-based layer.

4. The method according to any one of claims 1 to 3, wherein the SiCO-based layer is exposed to an oxygen-containing gas mixture (iii) between steps (c) and (d).

5. The method according to any one of claims 1 to 4, wherein the gas mixture (i) comprises 25 to 65 volume percent of water and 2 to 20 volume percent of oxygen.

6. Step (b) is carried out in a non-oxidizing atmosphere, the method according to any one of claims 1 to 5.

7. The method according to any one of claims 1 to 6, wherein steps (b), (c), and (d) are all performed in a float bath.

8. The method according to any one of claims 1 to 7, wherein step (b) is carried out by exposing the surface of the glass substrate to a gas mixture (ii) comprising a silicon source, a carbon source and an oxygen source.

9. The method according to any one of claims 1 to 8, wherein the TCO-based layer is deposited directly on the SiCO-based layer.

10. The method according to any one of claims 1 to 9, wherein step (c) is performed when the glass substrate is at a temperature of 640°C to 760°C.

11. The method according to any one of claims 1 to 10, wherein the coated glass substrate exhibits a maximum sheet resistance of 21 ohms / sq.

12. The method according to any one of claims 1 to 11, wherein the coated glass substrate exhibits at least 0.5% haze (cloudiness) when tested according to ASTM D1003-13.

13. Use of water and oxygen to reduce the sheet resistance exhibited by a coated glass substrate prepared by performing the method according to any one of claims 1 to 12.

Images