Device for covering thin film coating, and coating method using such device

0001This application is 35U.SC1 granted under serial number 61 / 466,501. 35U.SC119 (Filing date: March 23, 2011) of the provisional application under 11 (b) Claim the benefits under e). The entire provisional application is incorporated herein by reference.

0002The present invention relates to an apparatus for efficiently coating a thin film coating on a substrate. More details Specifically, the present invention may coat a particular thin film at a commercially feasible coating rate. It relates to a device having desired properties that are possible and not possible with conventional covering devices.

0003Two categories of thin films have been known in recent years. Distinguish between these two categories There are many methods, but for the purpose of this application, the main distinction methods are as follows: (1) Coating method I mean, online or offline) and (2) mainly by this way There is a type of film produced (hard coat (or pyrolysis) or soft coat).

0004Online coating is preferably a glass manufacturing process (typically a continuous floater) Raw by coating one or more thin film layers on a glass substrate, for example, during the lath manufacturing process) Made. Due to the characteristics of the float glass manufacturing process, the thin film coating process is commercially available To be feasible, the thin film coating process should be carried out at relatively high temperatures during very short chemical reactions It needs to be done in between and at a high coating rate.

0005If the online coating operation is successful, the resulting thin film will be most soft coated. It has relatively higher mechanical and chemical durability than the membrane.

0006In offline film coating, several known types of sputter coating processes One of them is often used. In such a sputter coating process Place the glass panel in one or more coating chambers and object of "target" material Exposing the glass panel to the atmosphere generated by a physical reaction or a chemical reaction, the glass panel The surface of the flannel is coated with this material. Sputtering process is fast in glass manufacturing process More complex film stacks by sputtering process as they are not controlled by degree It is possible to cover. These membrane stacks may depend on the properties of the pyrolyzed thin film. It can have excellent properties, but even in the case of such a sputtered film, it is significantly more expensive to manufacture. There is a possibility of a strike.

0007Devices for online coating are known, for example, from the following patent documents.

0008In U.S. Pat. No. 4,446,815, the vapor phase state from the three concentrated tuyere of the nozzle Reagent is ejected onto the substrate. The deflector member guides the gas between the deflector member and the substrate. Fits and extends over any side of the nozzle. The surface of the first deflector member has a substrate. It extends in the direction opposite to the direction of movement with respect to the slip, is parallel to the substrate, and extends the third tuyere. Forming an acute angle with the outer wall, the odor of the substrate with respect to the axial center surface of the first tuyere And offset laterally. In contrast, the surface of the second deflector member has a second tuyere. Form an obtuse-angled edge with the corresponding longitudinal wall of. Therefore, the first deflector member and the second The nozzle opening between the edges with the deflector member is effectively bent and the gas from this opening Is regularly deflected in the direction of movement of the substrate.

0009U.S. Pat. No. 4,934,020 describes atmospheric chemical vapor deposition using conveyors There is a description. This atmospheric chemical vapor deposition equipment uses a high-temperature muffle furnace and coating objects. Includes a conveyor belt for transport through the furnace. At least one chemical vapor deposition zone It is installed in the muffle furnace. An injector assembly is also provided. Injector Asen Buri covers the first reaction gas and the second reaction gas over the width of the conveyor belt. Inject evenly into the surface of the object to be coated. These gases are distributed Exit from the slot connected to Plenum. Purpose of minimizing the coating of chemicals on the surface Because of this, a polished cooling surface is used on the injector assembly.

0010Chemical vapor deposition of moving ribbons made of hot glass in U.S. Pat. No. 5,041,150 There is a description of the coating process. This coating is glass A first flow of the first reaction gas along a hot glass surface that is substantially parallel to the direction of movement of the Is established, and the second flow of the second reaction gas is turbulent and established at an angle with respect to the glass surface. This is done by avoiding the upstream flow of the second reaction gas in the first flow. While introducing the second flow into the first flow at the above angles, the first gas and the second The combination of gases is directed as turbulent on the surface of the hot glass.

0011In U.S. Pat. No. 5,122,391, dual electric children in a non-batch process Doping an indium oxide film with both tin and fluorine, which are said to form an adduct There is a description of the atmospheric pressure chemical vapor deposition system for this purpose. The coating system is a nitrogen purge Cons for continuous processing through one or more reaction chambers separated by a curtain It has a bear belt and a drive system. The board that passed through the system has several heaters Entering the muffle furnace heated by the reaction chamber, the reaction chamber delivers the source chemicals. Supplied from the stem. Source chemical delivery system is an oxidizer source, fluorine chemical source, Nitrogen source, rotor meter for the above sources, mass flow controller, tin chemical bubbler, high temperature lie Indium chemical bubbler, a pair of aquariums with heaters, and an associated bar Including bing.

0012Used in atmospheric pressure chemical vapor deposition equipment in US Pat. No. 5,136,975 The types of injectors listed are listed. This injector has multiple linear hole arrays Includes multiple plates provided. By stacking these plates, multiple so-called dregs A Kade hole array is obtained. These laminated plates work together to define a hole matrix Is said to be. A chute is placed below the hole matrix. On both sides of the shoot, A cooling plate is provided. The chute is a passage, a cooling plate and a chute type duct. Including the area between. The upper part of the hole matrix accepts multiple gaseous chemicals and forms them. The material is transported separately to the top of each cascade hole array. Then these vaporization The material is forced to move through a cascade hole array. In a cascade hole array And the gas is sent more and more evenly. After that, these gaseous chemicals individually pass through and And sent to the duct and to the area above the surface. In this area, these transformations The chemicals contact and react with each other to form a layer on the surface of the substrate.

0013In U.S. Pat. No. 5,704,982, the flow of at least one precursor gas is transferred. On the nozzle for distribution by thermal decomposition / decomposition reaction on the surface of a moving glass substrate There is a description. This nozzle describes the nozzle body and the flow of at least one precursor gas. Independent of the main gas supply system for supplying into the body nozzle and the main gas supply system Includes auxiliary gas supply system. Auxiliary gas supply system is at least one precursor The gas is supplied to the nozzle body near the main gas of the nozzle body to localize the chemical composition of the main gas. Change to. The auxiliary gas flow into the nozzle body is controlled by a flow rate that changes over time.

0014In U.S. Pat. No. 6,022,414, a single body inje that delivers gas to the surface. There is a description about Kuta. This injector is an elongated member and at least one gas feeder. Including the surface. The elongated member includes an end face. At least one gas delivery surface is the length of the member It extends along the ridge and forms a plurality of elongated passages inside. In addition, there are multiple thin walls in the member. A distribution channel is provided. These distribution channels have elongated passages and gas delivery surfaces. Extends between. The gas is transported to the elongated passage and through the distribution channel to the gas delivery surface. Is sent and directed to the desired area. In this desired region, of these gases The mixing and reaction form a thin film on a substrate located below the injector. Moth The delivery surface includes a curved side region and a central concave region of the gas delivery surface.

0015U.S. Pat. No. 6,206,973 describes a chemical vapor deposition system. The system includes a hot muffle, a chamber, and a belt. Chamber is vaporization chemistry It has an injector assembly for introducing the reactants. The belt makes the board muff Move through the chamber and chamber. The belt has a coating on the belt (especially a chrome oxide cover). Has an antioxidant coating to reduce cover).

0016In US Pat. No. 6,521,048, inclusion of covering chamber and main chamber There is a description about the academic vapor deposition equipment. This covering chamber has at least one single indicator Includes an ejector and one or more emission channels. The main chamber supports the covering chamber Includes at least one gas inlet. These gas inlets allow at least one gas Infused into the main chamber. By removing these gases through the discharge channel A purge that flows inward is obtained, which serves to isolate the covering chamber. At least Reactive chemistry by forming one so-called semi-seal between the coating chamber and the substrate. Confine the material within each coverage area.

0017Injector for delivering gas to substrate in U.S. Pat. No. 6,890,386 And there is a description about the discharge assembly. These injectors and discharge assembly The lid includes at least two injectors and a mounting plate. These injeks Tas are placed adjacent to each other, spaced apart, and at least one excretion between them. Form an out channel. The mounting plate holds at least these two injectors together. Used to determine. Each of these at least two injectors is a mounting pre Attached individually to the mount or removed from the mounting plate to the mounting plate Has at least one drainage channel and at least one drainage slot for fluid communication Be kicked. The discharge assembly is a mounting device that removes exhaust gas from the injector. Connected to the rate.

0018The present invention relates to an apparatus for coating a thin film on a moving hot substrate. This device Has a main coating machine body. The main body of the main coating machine has a predetermined length, width and height (each , X, y and z), an upper surface z1 and a lower surface z2. Multiple entrances open By forming the mouth part in the z1 surface of the main coating machine body, the flow of gaseous chemical reactants is this. Allows them to pass through their entrance openings. Each of these inlet openings is a gaseous reactant Fluid communication with quality materials and / or sources of inert gas. Main coating machine book with multiple outlet openings By forming within the z2 surface of the body, multiple streams of gaseous reactants flow through these outlet openings. It is possible to pass through a predetermined flow path, and multiple flow paths are specified in the main coating machine body. Such a flow path is defined between each of the inlet openings and each of the outlet openings. Is done. A flow control device is placed within one or more of these channels.

0019A method of coating a thin film coating using the above-mentioned device is also a part of the present invention.

0020Those skilled in the art can read the detailed description below along with the accompanying drawings to the above and other aspects of the invention. Easily understand the benefits.

0021<figref num="1">It is a schematic diagram of the float glass manufacturing operation using the thin film coating apparatus of this invention.</figref><figref num="2">It is a front view of the coating apparatus by embodiment of this invention.</figref><figref num="3">It is an end view of the coating apparatus according to the embodiment of this invention.</figref><figref num="4">It is sectional drawing of the coating apparatus according to embodiment of this invention.</figref><figref num="5">It is sectional drawing of the coating apparatus according to embodiment of this invention.</figref><figref num="6">It is sectional drawing of the coating apparatus according to embodiment of this invention.</figref><figref num="7">It is sectional drawing of the coating apparatus according to embodiment of this invention.</figref><figref num="8">It is a perspective view of a part of the coating apparatus by embodiment of this invention.</figref><figref num="9">It is an enlarged view of a part of the coating apparatus shown in FIG. 8 according to the embodiment of the present invention.</figref><figref num="10">It is sectional drawing of a part of the coating apparatus shown in FIG. 9 by embodiment of this invention.</figref>

0022The present invention is a device for coating a thin film coating on a substrate (for example, a transparent glass substrate). Regarding the placement.

0023Preferably, during the manufacture of the glass substrate, a thin film coating is applied on the moving high temperature glass substrate. (For example, metal, metal oxide) is preferably coated by the float glass method. Suitably These thin films are coated by chemical vapor deposition, most preferably by atmospheric chemical vapor deposition. Will be done. One example is chemical vapor deposition of zinc oxide coatings (eg, US Patent Application No. 1). 61 / 466, 498). The entire disclosure of this document is incorporated for reference.

0024Of course, using a coating device to coat the selected thin film coating, It is possible to perform any suitable CVD and / or APCVD chemistry. Shi However, the coating device is when mixed and / or from a known coating device. Especially useful in delivering gas precursor compounds that react substantially before being discharged. To. Substantially when mixed and / or before being discharged from other known coating equipment Examples of gas precursor compounds known to react with each other include specific amine compounds. Zn (CH) including things₃)₂And H₂0, Zn (C₂H₅)₂And H₂0, TiCl₄And NH₃, And TiCl₄There is. As will be appreciated, the coats described herein. The above list of gas precursor compounds properly used with the ing device is comprehensive. Not intended. Also, this coating device is a gas precursor that "pre-reacts" with each other. It should be understood that it is not limited to the use of compounds. Therefore, when mixed with each other Gas precursor compounds that do not react substantially can be used with this coating device. is there. For example, a mixture of gas precursor compounds appropriately used with coating equipment. For example, Sn (CH) is one that does not substantially react when it is used.₃)₂Cl₂And H₂There is 0.

0025The apparatus of the present invention deviates from known chemical vapor deposition apparatus. For the design of known chemical vapor deposition equipment A temperature below the reaction temperature of the mixture by premixing various chemical components in a controlled manner. After generating a uniform premixture in, the surface of the glass substrate coated with the thin film or its React in the neighborhood. Because the temperature of the high temperature glass substrate is the premixed chemical reaction This is because it is higher than the temperature of the body.

0026In contrast, in the case of the coating device of the present invention, various reactants are phased within the coating device. Designed to hold apart from each other, and by the various methods described, uniform membranes The chemical reactants on the glass surface or so fast enough to produce at a commercially feasible rate. It is possible to mix and react in the vicinity of It has properties within the desired range to suit ting. The coated film using the coating device It also exhibits very uniform color and conductivity, if desired.

0027More specifically, the main body of the coating device of the present invention is made from a suitable material (preferably a metallic material). Can be generated from at least one block. These blocks are gaseous inside A material inlet opening is formed and is connected to the gaseous reactant outlet opening via multiple channels. Is done. These multiple channels keep various trickles separated from each other in the coating apparatus. Designed to hold. Preferably, these gaseous reactant outlet openings are slotted. (Ie, it has a length longer than the width of each outlet opening). Preferably, this These slots are arranged in parallel and spaced apart from each other. These gaseous fabrics The substance outlet openings may have the same dimensions as each other or may have different dimensions.

0028In embodiments, at least one of the channels can be substantially linear. other In the embodiment of, at least one of these channels is a substantially linear portion. Have (singular or plural). In a further embodiment, at least of these channels Also one is a bend that is connected to or connects to a substantially linear portion of these channels. Can have. In these embodiments, the flow path may have multiple bends. Further implementation In morphology, the channels are configured to have substantially the same shape, length and width. However , As shown in FIG. 8, the width of a specific flow path may be the same as or different from that of an adjacent flow path. It may be.

0029One or more gas flow control devices, gaseous reactant inlet opening and gaseous reactant out It can be placed in one or more of the flow paths to and from the mouth opening. Such a flow The regulatory device (s) is the gas from one or more of the gaseous reactant outlet openings. Laminar flow of body flow can be increased.

0030Separation distances between gaseous reactant outlet openings may be equal or some outlet openings The separation distance may be different between the mouth and the adjacent outlet opening.

0031It is desirable that a trickle of gaseous reactants react on or near the surface of the glass substrate. Less to keep these trickles separated and more reliably until the right time At least one gas discharge directioner directs the flow of gaseous reactants towards the surface of the glass substrate It can help to orient it as a prescriptive pattern. Uses a trickle of inert gas Until the desired timing of the reaction of the chemical reactant gas trickle is reached, this chemical reactant gas It is also possible to hold the trickle in a separated state.

0032The velocity at which the gaseous reactant flows from each gaseous reactant outlet opening is the gaseous reactant outlet. It can be used as a means to control the level of turbulent flow of collective discharge from the opening. Therefore, it has a great influence on the film coating speed and the uniformity of the film thickness. for that reason, The gas flow velocity can be adjusted according to the desired purpose by opening an outlet adjacent to a certain gaseous reactant outlet opening. It may be the same as the mouth or it may be separate.

0033Especially in the area of the gaseous reactant outlet opening, the device temperature will be within the specified range. It is preferable to control by a known method. One or more such desired temperature ranges May depend on the above factors (eg, the particular chemical reactant being processed by the instrument) ..

0034With reference to the drawings, the coating device 10 coats one or more active gaseous chemical reactants 1 Designed to be maintained in a separate flow path in 0, and in certain embodiments, at least 1 After the two gaseous reactants have been ejected from the main body 12 of the coating device 10, the flow path geometry Designed to control over a period of time / distance. According to the method described later, the present invention The device is still at a speed at which a uniform film can be commercially achieved on the substrate coating surface 14 (eg). For example, 5 nm / sec or higher, preferably 50 nm / sec or higher, and even 350 nm / sec or higher. ) On or near the glass substrate coating surface 14 as fast as possible Allows mixing and reaction of, for example solar controllability, low emissivity or transparent conductivity It has desired properties suitable for thin film coatings.

0035The main body 12 of the coating device 10 of the present invention is made of a suitable material (eg, metal (high grade stainless steel). Can be produced from at least one block consisting of teal or steel alloy)), If it can withstand the environment of the glass float tank, use the main body 12 of the device 10. Other materials and methods may also be used in forming. As shown in Figure 4, various aspects of the main body Is traditionally designated as x16, y18, and z20, 22 (z1 and z2) .. One or more gaseous reactant inlet openings 24, top surface z120 by any suitable method Form inside. One or more gaseous reactant inlet openings have any desired geometry Get it. Preferably, a plurality of such gaseous reactant inlet openings 24 are z1 of apparatus 10. It is thus formed in surface 20. In a particular embodiment, for example, as shown in FIG. The so-called "cover block" 72 can be placed in one or more channels 28. this Such a cover block 72 is used to limit the flow into individual channels 28 in a desired manner. Can be done. Therefore, such a cover block 72 is used in one or more of one or more flow paths 28. It is preferable to place it in the vicinity of the above gaseous reactant inlet opening 24.

0036At least one gaseous reactant outlet opening 26 is covered, as described in more detail below. It is formed on the lower surface of the main body 12 of the covering device 10 or on or near the z2 surface 22. At least Also one separate flow path 28 extends through the main body 12 and at least one gaseous reactant The quality inlet opening 24 is fluidly connected to at least one gaseous reactant outlet opening 26. Preferably, a plurality of separate channels 28 (eg, 3, 5, 7 or 9 channels 28) are included in device 1. Multiple gaseous reactant inlet openings 24 extending through the main body 12 of 0 Connect to the reactant outlet opening 26. Such a flow path 28 may have any desired geometric structure. Can have growth.

0037In a particular embodiment of the covering device 10, the "baffle block" 74 is described, for example, in FIG. It can be located in one or more channels 28 as shown. Preferably there is a baffle block If so, this baffle block is placed between the cover block 72 and the flow regulator 30. It is arranged in the flow path 28. Preferably, the baffle block is placed in each flow path. Back Full block 74 is intended to increase the homogeneity of gaseous reactant trickles in channel 28. To do.

0038The gaseous reactant outlet opening 26 can have any desired shape, but is preferably a slot. It is preferable that the structure is such that the gaseous reactant outlet opening 26 is preferably a coating device. The "x" of the main body 12 of the covering device 10 rather than the "y" dimension of the main body 12 of the 10 Dimensionally larger). Preferably, a slotted gaseous reactant outlet opening 2 6 are arranged in parallel and spaced apart from each other. Any desired number of gaseous reactants Exit openings 26 are available, but 3, 5, 7 or 9 exit openings 26 are preferred Suitable. The separation distance between such outlet openings 26 is typically about 0.5 mm to 3 mm. Can be. A suitable separation distance between the gaseous reactant outlet openings 26 does not exceed about 1 mm. More preferably, such a separation distance is about 0.5 mm.

0039The gaseous reactant outlet opening 26 is formed in the z2 surface 22 of the main body 12 of the coating device 10. Alternatively, the covering device 10 may be up to a predetermined distance (eg, a distance of about 5.5 mm). It may be recessed in the main body 12. Dissolve by denting the gaseous reactant outlet opening 26 The gas discharge portion of the coating device 10 is removed from the heat from the tin melting tank and the high-temperature glass substrate coating surface 14. It has been found to be advantageous because it can protect to a certain level. Such a temperature is 10 It can be on the order of 50 ° F (566 ° C) to 1400 ° F (750 ° C). Preferably, moth The lath surface temperature ranges from 1100 ° F (600 ° C) to 1200 ° F (650 ° C).

0040The gaseous reactant outlet opening 26 is of size (particularly the y of the main body 12 of the coating device 10. "Dimensions) can be different. In some cases, a gaseous reactant outlet opening that discharges an inert gas. Discharge the active gaseous chemical reactant to the "y" dimension of part 26 (ie, the width of the outlet opening). It has been found to be advantageous to make it larger than the gaseous reactant outlet opening 26.

0041At least one gaseous reactant inlet opening 24 and at least one gaseous reactant out One or more gas flow control in one or more of the gas flow paths 28 extending between the mouth opening 26 The device 30 can be fixed. One or more such gas flow adjusting devices 30 Enhancing the laminar flow of one or more gas discharge fibrils from the above gaseous reactant outlet opening 26 Is intended. A "honeycomb" configuration, as shown in Figure 9, is one or more gas flow control devices. Suitable for S30. Other areas are of course possible, but suitable for honeycomb cells The area is about 1 square millimeter. Suitable vertical dimensions (thickness) of this honeycomb are suitable Can be about 5 mm to about 25 mm.

0042Until the timing when it is desirable to react the gaseous reactant fibrils and the inert gas fibrils In order to further reliably separate the two, on or near the glass substrate coating surface 14 At least one gas discharge directional device 32 defines one or more parts of the flow path. In a particular embodiment as shown in FIG. 6, at least one gas discharge directional device 32 , Any of the gaseous reactant outlet openings 26, over a distance beyond the outlet opening 26 It can extend on the sides, which allows the flow of gaseous reactants to flow through the coated surface of the glass substrate 14 Direct as a defined pattern towards. Rhinoceros in the zone where gaseous reactants are mixed The positions and positions and the mechanisms for performing such mixing are described in some embodiments of the present invention. Can be different. For example, mixing by diffusion of gaseous reactants is a flow regulator or its In the vicinity, on the z2 surface of the coating device 10 or its vicinity, and on the substrate coating surface 14 or its vicinity Can be done at. At least one gas discharge directioner opens the gaseous reactant outlet In an embodiment extending beyond the mouth 26, at least one gas discharge directional device 32 A thin protrusion (preferably a thin metal material) with one or more gaseous reactant outlet openings 2 High temperature of about 5.5 mm, preferably moving from the main body 12 of the covering device 10 in the vicinity of 6 Extends within the coated surface 14 of the moving glass substrate. One or more gaseous chemicals Failure from one or more inert gaseous reactant outlet openings 26 adjacent to the response outlet opening 26 It is desirable to react the gas chemical reactant fibrils with a trickle of active gas. It is also possible to hold the gaseous chemical reactant fibrils in a separated state until the end.

0043The velocity of the flow of the gaseous reactant from each gaseous reactant outlet opening 26 is the gaseous reactant Used as a means to control the level of collective discharge turbulence from the outlet opening 26 Therefore, it has a great influence on the film coating speed and the uniformity of the film thickness. So Therefore, the gas flow velocity is adjacent to a gaseous reactant outlet opening 26, depending on the desired purpose. It may be the same as or separate from the tangent outlet opening 26. But, Preferably, the gas flow velocities are substantially equal between the gas outlet openings 26.

0044The apparatus of the present invention also advantageously includes one or more gas discharge openings 36. One or more gas discharge open The mouth 36 extends through the main body 12 of the covering device 10 and is in the form of a used or unused gaseous. Allows continuous removal of reactants. Such used or unused gaseous Due to the reactants, unwanted contaminants can be generated on the coating surface of the substrate 14. this Occurs on or near the coated surface of a hot glass substrate using such gas emission extraction It is also possible to influence the amount of gas flow turbulence and reactant mixture, which allows , The possibility of improving the thin film coating speed can be obtained.

0045By any known method, especially in the vicinity of at least one gaseous reactant outlet opening 26 And in the region containing at least one gaseous reactant outlet opening 26, the coating It is preferable to control the temperature of the device 10 so as to be within a predetermined range. For example, temperature control The method preferably comprises oil cooling and water cooling, but air cooling is also possible.

0046For example, in FIGS. 4 to 7, a typical cooling material passage 76 is shown. If you are a person skilled in the art, like this Various thermal and electronic devices are required to carry out various temperature control systems Understand that there are many cases. The desired temperature control range of device 10 depends on one or more factors. Can differ (eg, certain chemical reactants being processed by coating device 10) In terms of type, it is preferable to control the temperature of the device within the range of ± 50 ° F (± 10 ° C). Other interests As a point, such a temperature control system is such a gas discharge portion of the coating device 10 (eg, gas). Maintains thermal stability and structural integrity of the components associated with the discharge orientation device 32) I know I will have it. Avoiding chemical pre-reactions is also the purpose of this temperature control system Is.

0047As described above in the present specification, the main body 12 of the apparatus 10 of the present invention is preferably made of a metallic material. Can be formed from at least one block of. Is the main body of the device multiple metal blocks? It is advantageous to assemble it. List the benefits of using multiple metal blocks Easy assembly and maintenance, for example, temperature control of individual areas of the covering device 10. There are improvements in the structure and thermal stability of the coating device 10.

0048The device 10 of the present invention has been described. Here, the thin film coaty using the coating device 10. A method of coating the shavings will be described. It has been described elsewhere in this specification. In the floating glass manufacturing process, more specifically, in the floating glass manufacturing process In the float bath portion, at least one thin film coating device 10 according to the present invention is used in a molten tin tank. At a predetermined distance above the coated surface 14 of the continuously moving glass substrate supported above Deploy.

0049A separate supply line extends from at least one source of the gaseous chemical reactant and is similarly non-existent. Extends from at least one source of active gas. At least one source of these inert gases is Preferably, it is located outside the float tank and opens the gas inlet in the main body 12 of the covering device 10. Separate the mouth 24. At least one gaseous chemical reactant and at least one inactive Initiate a flow of sex gas at a given flow rate and at least one gas through the supply line Transport to the entrance opening 24. At least at least one gas inlet opening 24 Also one gaseous chemical reactant and at least one inert gas are the main components of the coating device 10. It flows at a predetermined speed through a separate flow path 28 extending through the body 12.

0050Preferably, at least one gaseous reactant in a predetermined location within each gas flow path 28. And at least one inert gas contacts the flow control device 30. Flow control device The chair 30 is intended to improve the laminar flow of each separate gas flow path 28. Preferably less At least one flow control device 30 has a "honeycomb" configuration as shown in FIG. Other configurations are possible. Honeycomb cell dimensions may vary in size and shape I. It is shown in FIG. 10 depending on the range in which it is desired to change the laminar flow of a particular gas trickle. The vertical dimension or "thickness" of such a flow control device 30 can also vary.

0051Within a separate gas flow path 28, preferably after passing through at least one flow control device 30 The gas flowing through the gas approaches each separate gas outlet opening 26. Each separate gas outlet opening 26 Preferably has a slotted configuration. At least one stream in a particular embodiment The adjusting device is in close proximity to the gas outlet opening 26.

0052Alternatively, after being discharged from a separate gas outlet opening 26, to a particular embodiment of the covering device. The separate flows of the gaseous chemical reactant and the inert gas are set forth herein above. Smell that is still separated by at least one gas discharge directional device 32 Further direct to the coated surface of the substrate 14. For the reasons mentioned above, the temperature of the coating device 10 (In particular, the temperature in the vicinity of the gaseous reactant outlet opening 26) is ± 50 ° F (± 10 ° C). It has been found to be preferable to control within the range.

0053Separate gas flow at or near the coated surface 14 of a moving hot glass substrate The trickle is mixed in the desired mixing zone and chemically reacted in a predetermined manner. Such an anti As a result, a thin film is commercially feasible on the coated surface of the moving high temperature glass substrate 14. It is coated at the coating rate.

0054As mentioned above, the method of the invention is performed in connection with the formation of a continuous glass ribbon substrate. Often. Active gaseous reactants combine on or near the surface of the glass 14 It is intended to be done. In the gas mixture, the carrier gas or diluent (eg, nitrogen, empty) Qi or helium) is also often included. The temperature at which this gas mixture is sent to the mixing zone is Below the temperature at which this gas mixture reacts to form a thin film coating, the substrate surface 14 , The temperature is higher than this reaction temperature. According to the present invention, the production of thin film coatings is commercially available. Achievable coating rate (preferably 5 nm / sec or higher, more preferably 50 nm / sec or higher). It will be possible to do it at 350 nm / sec or more). High coating speed, glass manufacturing professional It is important when coating a thin film on a glass substrate in Seth. Because the glass ribbon The speed at which the line travels is in the range of hundreds of inches / minute, with only a few thin films of a particular thickness. This is because it is necessary to cover in one minute second. For any particular combination of reactants Test or computer model for optimum concentration and flow rate to achieve high coating rate Can be determined by Fields with higher concentrations of reactants and higher gas flow rates In this case, the efficiency for converting the reactants to the thin film as a whole is likely to be low. It is understood that the optimum conditions for commercial operation may differ from the conditions under which the maximum coating rate is obtained. Is done.

0055Float glass production introduction can be used as a means to carry out the method of the present invention. Wear. The float glass introductions described herein are exemplary of such introductions. It is not limited to the invention.

0056More specifically, the float glass introduction as shown in FIG. 1 includes a tube portion. Along this pipe Then, the molten glass from the melting furnace is delivered to the float tank portion 42, and the continuous glass ribbon 51 is released. It is formed according to a well-known float process. The temperature inside the float tank is typically 10 It is 50 ° F (566 ° C) to 1400 ° F (750 ° C). Preferably the temperature is 1100 ° It is F (600 ° C) to 1200 ° F (650 ° C). The glass ribbon 51 is from the tank 42 Advance through the adjacent annealing furnace 44 and cooling section 46. Continuous glass ribbon 51 It is preferably a substrate, on which a thin film is formed by the apparatus 10 of the present invention. flow The tank portion 42 is a side wall (not shown) facing the lower portion 48 accommodating the tank of molten tin 50. Includes root 52 and end wall 54. The roof portion 52, the side wall and the end wall 54 cooperate with each other to form a housing 56. To specify. Non-oxidizing atmosphere in the housing 56 to avoid oxidation of molten tin 50 Is retained.

0057During operation, the molten glass flows in a controlled amount along the lower tube of the twill weave. , Flows downward on the surface of the tin tank 50. Gravity and surface tension on molten tin surface 50 The molten glass diffuses laterally under the influence of force and certain mechanical influences, and the tin tank 4 2 Move forward to form the glass ribbon 51. The glass ribbon 51 is a lift-out roll Removed from tin tank 42 on 64 and then smelled on aligned rolls It is transported through the annealing furnace 44 and the cooling unit 46. The coating of the thin film of the present invention is preferably Is performed in the float tank section 42, but further along the glass production line (eg, In the gap 45 between the float tank 42 and the annealing furnace 44 or in the annealing furnace 44) It is also possible to cover it.

0058Suitable non-oxidizing atmosphere (generally nitrogen or nitrogen-based nitrogen and water A mixture of elements) is maintained in the float tank housing 56 to form the tin tank 50. Avoid oxidation of molten tin. Through a conduit 66 operably connected to the distribution manifold 68 , Send atmosphere gas. When introducing non-oxidizing gas, compensate for normal loss and maintain some positive pressure Leading the environmental atmospheric pressure on the order of about 0.001 to about 0.01 atm at a speed sufficient to hold Ingress, thereby avoiding ingress of external atmosphere. The pressure described above for the purposes of the present invention. The force range is considered to constitute normal atmospheric pressure. In tin tank 42 and housing 56 The heat to maintain the desired temperature regime is provided by the radiant heater in the housing 56. Will be done. The atmosphere in the furnace 44 is typically the atmosphere. Because the cooling part 46 is enclosed This is because the glass ribbon 51 inside it is exposed to the atmosphere. Fa in the cooling section The outside air can be applied to the glass ribbon with the 70. In the annealing furnace 44 A heater is provided to gradually adjust the temperature of the glass ribbon 51 carried inside according to a predetermined system. May be reduced to.

<p num="0059"> This coating device is a belt conveyor furnace (more specifically, a substrate heating zone, a coating zone). Coat on a glass substrate transported through a three-zone furnace with a cooling zone) Used to cover the ing. Seo with a pre-coated silica barrier layer on the surface -A sheet of da lime silica glass and a sheet of soda lime silica glass come out of the furnace Load it on the transport belt, set the glass temperature to 650 ° C, and then enter the coating zone. I made it enter. Then, the high temperature glass substrate was passed under the coating device. This covering device , It was placed about 4 mm above the surface of the glass substrate. The dimensions are 100 x 300 mm and the thickness Covered at a line speed of 0.5-3 m / min on a glass sheet with a width of 3 mm Was done. The coating device was maintained at a temperature of 150 ° C. Avoiding interference with the coating process Therefore, virtually all of the input used / unused gas is discharged from the coating zone. I put it out. In the following examples, the "slot" is defined as the same as the gas flow path 28. Should be released and exit the coating through the corresponding gaseous reactant outlet opening 26 go.</p><p num="0060"> Example 1-5 Coating of zinc oxide with an additive compound using a slot coating machine</p><p num="0061"> Slot 1 is provided on the left side of the coating machine, slot 5 is provided on the right side of the coating machine, and each slot is provided. The precursor of was input as follows.</p><p num="0062"> Slot 1 and Slot 5-These two slots allow N₂And H2₀(Steaming The mixture was transported. For brevity, use a single evaporator, steam and N₂Mixed A mixture was produced and the mixture was evenly divided and delivered to, for example, slots 1 and 5. Stiff To avoid shrinkage, all reactant delivery lines were maintained at temperatures above the dew point. Steam and N₂The mixture was produced by injecting water into a heated evaporator. N₂Add transport gas to the evaporator to steam and N₂Transport the mixture to slots 1 and 5 did. Inject 10 ml / min of water into the evaporator and add to the evaporator N₂The amount of N₂+ Steam The total flow rate is equal to 20slm, of which 10slm goes to slots 1 and 5 respectively. I set it to move.</p><p num="0063"> Slot 2 and Slot 4-Weighed 10 slmN₂The flow of coal gas, each slot Flowed downwards in steps 2 and 4.</p><p num="0064"> Slot 3-The gaseous reactants flowing in Slot 3 are dimethylzinc (DMZ) and It was modified to include a mixture of additive compounds (ie, acetylacetonate). Two A bubbler was used to produce a mixture of these two chemicals. Maintained at a temperature of 36 ° C A DMZ precursor mixture was produced by using a reference bubbler. Bubba the flow of He The gas DMZ of 0.077 mol / min was evaporated by passing it through the water. Second The acetylacetoneate bubbler was maintained at a temperature of 60 ° C. N₂Put the gas in the second bubbler It was passed through to produce acetylacetoneate. Smell these two chemicals in the pipe Premix and add more N₂Add 10sl of total gas flow in slot 3 Generated with m.</p><p num="0065"> Under these conditions, the glass sheet is placed under the coating machine at a line speed of 1.8 m / min. I moved it with. A zinc oxide film with a thickness of 450 nm was coated at a coating rate of 68 nm / sec. The obtained coated glass has a haze of 4.8% and a visible light transmittance of 76%. it was high.</p><p num="0066"> Example 2-5 Ga-doped zinc oxide coating with additive compounds using a slot coating machine</p><p num="0067"> Using the experimental conditions described above in connection with Example 1, N₂+ H₂Slot 0 gas mixture Sent through 1 and slot 5. Pour water into the evaporator at 24 ml / min, 0.5 sl m N₂Was added. Mixture of DMZ, acetylacetoneate and dopant compound ( That is, a gaseous reaction that passes through slot 3 to contain trimethylgallium (TMG)). Changed the flow of substances. Produce a mixture of these three chemicals using three bubblers It was done. DMZ bubbler and acetylacetoneate bubbler as described in Example 1. Operated to. The DMZ is passed through the first bubbler by He and the DMZ is 0.077. Evaporated at mol / min. The second trimethylgallium bubbler was maintained at a temperature of 10 ° C. N₂The gas was passed through a second bubbler to create a gallium flow. Before these three After premixing the vehicle in the pipe, an additional N₂Add, 10slm slot The entire gas flow through G3 was generated. Under these conditions, apply the glass sheet under the coating machine. At a line speed of 3.0 m / min, the thickness is 200-230 nm and Resistance is 1x10^-3Coating speed 50-60 with conductive zinc oxide coating that is ohm cm Covered at nm / sec. By changing the composition of the DMZ / dopant mixture, the resistance is increased. It is understood that it is possible to produce higher or lower membranes. For example, gas phase For membranes coated with 0.002 mol / min TMG, the resistance is 1.3 x 10^-2Oh Of coated glass with TMG of 0.004 mol / min of gas phase, while cm cm If the resistance is 4.3 x 10^-3It was ohm cm. Also, these coated glasses Has a high visible light transmittance of 60 to 70%, a low IR radiation absorption of 13 to 20%, and The is low at 0.6-1.1%. For comparison, use the same amount as the above TMG and acetyl For membranes without lucetate added, the resistance is 3.9 x 10^-1Ohm cm and 9 .3 × 10^-2It was much higher than ohm cm.</p><p num="0068"> Example 3-7 Ga-doped zinc oxide coating with additive compounds using a slot coating machine</p><p num="0069"> In Example (3-1), the same notation as in Example 1, Example 2, and Example 3 is used. Used for the slots of the lot coating machine, slot 1 and slot 7 are on the left end of the coating machine, respectively. And placed on the right end.</p><p num="0070"> Slot 1 and Slot 7-These two slots are used in this embodiment to N₂+ H₂A mixture of 0 was carried (in vapor form). As in Example 1, a single evaporator was used. Steam and N₂Was produced and evenly distributed between slot 1 and slot 7. .. Again, all precursor delivery lines were kept above dew point. Evaporate water at 6 ml / min It was injected into the vessel. Again, N₂The steam and N₂Used as a carrier gas for the mixture of .. 10 slm steam and N flowing down slot 1 and slot 7, respectively₂Mixed The total flow rate of the mixture was again 20 slm.</p><p num="0071"> Slots 2, 3 and 5, 6-N₂Weighed flow of transport gas in slot 2 with 5 slm , 3 and 5 and 6 respectively, flow down and flow down slot 4 A reliable separation was made between the mixture and the chemical mixture flowing down through slots 1 and 7.</p><p num="0072"> Slot 4-This slot is also used here for dimethylzinc (DMZ), acetylace. A precursor mixture of tonate and trimethylgallium (TMG) was transported. Standard bubbler Is also used here at 36 ° C to generate a gaseous DMZ, which is passed through the bubbler by He. The DMZ was allowed to evaporate at 0.077 mol / min. Second reference bubbler at 60 ° C It is also used here to produce gaseous acetylacetone and through a bubbler N₂Sent by .. A third reference bubbler is also used here at a temperature of 10 ° C to generate a gaseous TMG and bubbler. TMG was evaporated at 0.005 mol / min by sending by He through. Three conversions Premix the chemicals in the pipe and then N₂And the gas flow through slot 4 The total was generated with 10slm. Under these conditions, place the glass sheet under the coating machine. A conductive acid with a thickness of 280 to 1420 nm, which is moved at a line speed of 0.5 to 3.0 m / min. The zinc chemical coating was coated at a coating rate of 60 to 70 nm / sec. Of the resulting coating Resistance is &lt;1 × 10^-3It was ohm cm. List other properties of this coated glass And there is a high visible light transmittance&gt; 71% and a low haze &lt;2.0%. Again, DMZ / By changing the composition of the dopant mixture, a film with higher or lower resistance is produced. It is understood that it is possible to do so.</p><p num="0073"> Example (3-2) Slot 1 and Slot 7-Weighed 10 slm N₂Transport gas Flow down in these slots into slot 2 and slot 6 Improved flow mixing in.</p><p num="0074"> Slot 2 and Slot 6-These two slots are used in this embodiment. N as in Example 4-1₂+ H₂A mixture of 0 was carried (in the form of vapor). For a single evaporator Steam and N₂A mixture of was produced and evenly distributed between slots 2 and 6. Again, all precursor delivery lines were kept above dew point. Evaporate 6 ml / min of water Infused into. Again, N₂The steam and N₂Was used as the transport gas for the mixture. here Even the total flow rate is 20slm, 10slm steam and N₂Mixtures in slot 2 and And 6 each flowed downward.</p><p num="0075"> Slot 3 and Slot 5-Weighed 10 slm N₂Transport gas in these slots The chemical mixture that flows downward in each slot 4 and the slot 4 It was reliably separated from the chemical mixture flowing downwards at T2 and 6.</p><p num="0076"> Slot 4-This slot is also used here for dimethylzinc (DMZ), acetylace. A precursor mixture of tonate and trimethylgallium (TMG) was transported. Standard bubbler Is also used here at 36 ° C to generate a gaseous DMZ, which is passed through the bubbler by He. The DMZ was allowed to evaporate at 0.077 mol / min. Second reference bubbler at 60 ° C It is also used here to produce gaseous acetylacetone and through a bubbler N₂Sent by .. A third reference bubbler is also used here at a temperature of 10 ° C to generate a gaseous TMG and bubbler. TMG was evaporated at 0.005 mol / min by sending by He through. These 3 Premix the two chemicals in the pipe and then N₂With the addition of 13.5slm Gas flow was made through slot 4.</p><p num="0077"> Under these conditions, the glass sheet is applied under the coating machine at a line speed of 3.0 m / min. Moved, 570 nm thick and resistance 8.5 x 10^-4Conductive oxidation that is ohm cm The zinc coating was coated at a coating rate of 141 nm / sec. Obtained coated glass The Tvis of the product was about 62% and the haze was about 7.7%.</p><p num="0078"> In addition to acetylacetoneate, other additions deemed appropriate in the context of the present invention. Trifluoroacetylacetone and hexafluoroacetylacetone, to name a few Tonate.</p><p num="0079"> In accordance with the provisions of the Patent Act, the present invention is considered to indicate a suitable embodiment thereof. Has been explained. However, it specifies the invention without departing from the intent and scope of the invention. It should be noted that it is possible to carry out in a manner other than those shown and described in.</p>