Thin film deposition method.
Abstract
La invención se relaciona con un método para obtener un sustrato recubierto sobre al menos parte de su superficie con al menos una capa de óxido de metal M el espesor físico de la cual es de menos que o igual a 30 nm, no siendo la capa de óxido, parte de una pila de capas que comprende al menos una capa o película de plata. El método comprende los siguientes pasos: al menos una capa intermedia de un material elegido del metal M, un nitruro del metal M, un carburo del metal M y un óxido subestequiométrico en oxigeno del metal M, es depositada por deposición electrónica, no siendo la capa intermedia depositada por encima o por debajo de una capa a base de óxido de titanio, siendo el espesor físico de la capa intermedia de menos que o igual a 30 nm; y al menos parte de la superficie de la capa o película intermedia es oxidada usando un tratamiento con calor, durante el cual la capa intermedia está en contacto directo con una atmósfera oxidante, especialmente aire, no excediendo la temperatura del sustrato 150°C durante el tratamiento térmico.

Term
4 yearsleft in the term
Expires 30 September 2030.
- Priority
- Filed
- Granted
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12 claims: 9 independent, 3 dependent
- 1REIVINDICACIONES 1. Un proceso para obtener una hoja de vidrio recubierta sobre al menos parte de su superficie con al menos una película de óxido de un metal M cuyo espesor físico es 30 nm o menos, dicha película de óxido no siendo parte de una multicapa, comprendiendo al menos una película de plata, dicho proceso está caracterizado porque comprende los siguientes pasos:- depositar por pulverización catódica al menos una película intermedia de un material seleccionado del metal M, un nitruro del metal M, un carburo del metal M y un óxido subestequiométrico en oxígeno del metal M, dicha película intermedia no siendo depositada por encima o por debajo de una película a base de óxido de titanio, el espesor físico de dicha película intermedia siendo 30 nm o menos;y - oxidar al menos parte de la superficie de dicha película intermedia utilizando un tratamiento con calor, durante el cual dicha película intermedia está en contacto directo con una atmósfera oxidante, la temperatura de dicha hoja de vidrio durante dicho tratamiento con calor no excediendo 100°C.
- 2El proceso de conformidad con la reivindicación 1, caracterizado además porque el metal M se selecciona de titanio, estaño, circonio, zinc, tungsteno, INSTiruw';ij'K.··;/ DE Ln . j la película intermedia está hecha de titanio, la película de óxido obtenida después del tratamiento con calor siendo una película de óxido de titanio fotocatalítica.
- 34. El proceso de conformidad con una de las reivindicaciones precedentes, caracterizado además porque el espesor físico de la o de cada película de óxido del metal M es 20 nm o menos.
- 45. El proceso de conformidad con una de las reivindicaciones precedentes, caracterizado además porque la temperatura de la hoja de vidrio durante el tratamiento con calor no excede 50°C.
- 56. El proceso de conformidad con una de las reivindicaciones precedentes, caracterizado además porque el tratamiento con calor se lleva a cabo utilizando al menos una radiación láser o utilizando al menos una llama.
- 67. El proceso de conformidad con las IN3T;Y D. ;L/i ;··'?;-? reivindicaciones precedentes, caracterizado además porque la radiación láser tiene una longitud de onda entre 500 y 2000 nm.
- 78. El proceso de conformidad con cualquiera de la reivindicación 6 y 7, caracterizado porque la energía por unidad de área de la radiación láser en la película intermedia es mayor que o igual a 20 kW/cm 2 .
- 89. El proceso de conformidad con una de las reivindicaciones 6 a 8, caracterizado además porque la radiación láser proviene de al menos un haz de láser que forma una línea que irradia simultáneamente todo o parte del ancho de la hoja de vidrio.
- 910. El proceso de conformidad con las reivindicaciones precedentes, caracterizado además porque la hoja de vidrio recubierta con la película y el o cada láser lineal se mueven uno relativo al otro, de modo que la diferencia entre las velocidades respectivas de la hoja de vidrio y el láser es 4 metros por minuto o mayor.
- 1011. El proceso reivindicaciones 6 a 10, película intermedia está de conformidad con una de las caracterizado además porque la hecha de titanio, la película intermedia hecha de titanio metálico se dopeoita so lado de la hoja de vidrio y, sobre el otro lado de dicha hoja de vidrio, se deposita una multicapa de baja-E que comprende al menos una película de plata, después dicha película intermedia se trata con calor utilizando al menos una radiación láser de modo que la emisividad o resistividad de la multicapa de baja-E se reduzca por al menos 3%, y la película de óxido obtenida después del tratamiento con calor es una película de óxido de titanio fotocatalítico. '3 .3
- 1112. El proceso de conformidad con una de las reivindicaciones 1 a 8, caracterizado además porque solo parte de la superficie de la película intermedia se trata con calor para producir patrones, para propósitos estéticos o funcionales.
- 1213. Una hoja de vidrio que se obtiene mediante el proceso que se reclama en la reivindicación 1, la hoja de vidrio está caracterizada porque está recubierta sobre una parte de su área con una película de óxido de un metal M cuyo espesor físico es 30 nm o menos, y sobre otra parte de su área con una película de un material seleccionado de dicho metal M, un nitruro de dicho metal M y un carburo de dicho metal M.
Independent claims12
215 paragraphs in 23 sections, as filed
(54) Title: THIN FILM DEPOSITION METHOD.
(54) Title: THIN FILM DEPOSITION METHOD.
(57) Summary
The invention relates to a method for obtaining a substrate coated on at least part of its surface with at least one layer of metal oxide M, the physical thickness of which is less than or equal to 30 nm, the layer not being oxide, part of a layer stack comprising at least one silver layer or film. The method comprises the following steps: at least an intermediate layer of a chosen material of metal M, a nitride of metal M, a carbide of metal M and a substoichiometric oxygen oxide of metal M, is deposited by electronic deposition, the intermediate layer deposited above or below a titanium oxide-based layer, the physical thickness of the intermediate layer being less than or equal to 30 nm; and at least part of the surface of the intermediate layer or film is oxidized using a heat treatment, during which the intermediate layer is in direct contact with an oxidizing atmosphere, especially air, not exceeding the temperature of the substrate 150 ° C during the heat treatment.
(57) Abstract
The invention relates to a method for obtaining a substrate coated on at least part of its surface, by at least one layer of an oxide of a metal M having a physical thickness of less than or equal to 30 nm, said oxide layer not being included in a stack of layers comprising at least one layer of silver. Said method comprises the following steps: at least one intermedíate layer of a material selected from the metal M, a nitride of the metal M, a Carbide of the metal M or an oxide sub-stoichiometric in oxygen of the metal M, is deposited by cathodic sputtering, said intermedíate layer not being deposited above or below a layer based on titanium oxide, the physical thickness of said intermedíate layer being less than or equal to 30 nm; and at least part of the surface of said intermedíate layer is oxidized by means of a heat treatment, during which said intermedíate layer is in direct contad with an oxidizing atmosphere, especially air, the temperature of said substrate not exceeding 150Á ° C during the heat treatment.
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Institute
Mexican Property
Industrial
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PATENT TITLE NO · 336914 _SE_
StCWtARÍA «» ECONOMY
Headlines):
Home:
Denomination:
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Inventor (s):
SAINT-GOBAIN GLASS FRANCE
18, avenue d'Alsace, F-92400, Courbevoie, FRANCE
THIN FILM DEPOSITION METHOD.
lnt.CI.8: C03C17 / 00; C03C17 / 245; C23C14 / 58
ANDRIY KHARCHENKO; ANNE DURANDEAU; NICOLAS NADAUD
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Industrial. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).
dad I lustrial.
bs imprc ogables. Keep the _______ j and the
JB, 12/26/1997, 1> 5/1999, 2); Articles 1 ·, 3 'iction V OF 14/12/1999, ref. Pones I and lll and 30 of the Statute) organic 29/07/2004, 04/08/2004 and 13/09 / 2φ; 1st, 3rd of the Opiety
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NAHANNY CANAL REYES
Issue Date: February 5, 2016
THE DIVISIONAL DIRECTOR OF PATENTS
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"Renal No 550, Floor 1,
Pueblo Ssnía María Tepepan, Xochimiico Delegation,
CP 16020, Mexico City Tel. (55) 53 34 07 00 www.impi.gob.mx
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MX / 2016/10133
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DELGA ^ oiS FILM DEPOSITION METHOD
—............. ..... - industrial lj
FIELD OF THE INVENTION
The invention relates to the field of inorganic thin films, especially deposited on substrates.
Thin films deposited on substrates are often based on metals, oxides, or even nitrides.
A widely used process on an industrial scale for thin film deposition, especially on a glass substrate, is sputtering, especially magnetically enhanced sputtering, called in this case magnetron sputtering. In this process, a plasma is created in a high vacuum near a target that includes the chemical elements to be deposited. The active species of the plasma, by bombardment of the target, give off elements, which are deposited on the substrate forming the desired thin film. This process is called a reactive process when the film is made of a material resulting from a chemical reaction between the elements released from the target and the gas contained in the plasma. The main advantage of this process lies in the possibility of depositing, on the
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INSTITUTO MSXIC 'DELAPROHEDAO INCUaTSUAL same line, a very complex multilayer did which substrate substrate runs in succession under several targets, generally in one and the same device.
It is known for example how to deposit titanium oxide films using a target made of oxygen-containing plasma titanium metal.
The oxygen contained in the plasma however has the disadvantage of oxidizing the surface of the metallic target, so that the sputtering rate is greatly reduced. Generally, the cathodic spray rate of oxide films has been found to be much slower than the deposition rate of metals or even nitrides or carbides.
BRIEF DESCRIPTION OF THE INVENTION
An object of the invention is to obtain, by sputtering, metal oxide films at high deposition rates.
For this purpose, an object of the invention is a process to obtain a substrate coated on at least part of its surface with at least an oxide film of a metal M, the physical thickness of which is 30 nm or less, the Oxide film is not part of a multilayer film comprising at least one silver film, the process comprising the following steps:
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- at least one int-prmpdia_r film (p nn chosen material of metal M, a nitride of metal M, a carbide of metal M and an oxygen substoichiometric oxide of metal M, is deposited by sputtering, the intermediate film is not deposited above or below a titanium oxide based film, the physical thickness of the intermediate film being 30 nm or less; and - at least part of the surface of the intermediate film is oxidized using a heat treatment, during which the intermediate film is in direct contact with an oxidizing atmosphere, especially air, not exceeding the temperature of the substrate during the heat treatment
150 ° C.
DETAILED DESCRIPTION OF THE INVENTION
According to the invention, the oxide is therefore obtained in two steps: first a deposition step of the corresponding metal, nitride or carbide, followed by an oxidation step using heat treatment. Against all expectations, localized heating of the intermediate film, when it is in contact with an oxidizing atmosphere, in particular air, has been shown to be capable of oxidizing thin films of relatively large thickness. Generally, at least 80% of the thickness of the intermediate film is oxidized, as all films in
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certain cases.
The oxidizing atmosphere is preferably air, especially at atmospheric pressure. If required, the oxygen content of the atmosphere can be increased to further promote oxidation of the intermediate film.
Heat treatment also has the distinction, in contrast to annealing or tempering treatments, of not heating the glass significantly. Thus it is not necessary for the substrate to undergo slow controlled cooling before the glass is cut or stored. The process also makes it possible to integrate a heater on existing continuous production lines, more particularly in the space located between the outlet of the vacuum deposition chamber of the magnetron line and the device for storing glass in the form of a stack. . It is also possible in certain cases to carry out the treatment according to the invention within the real vacuum deposition chamber.
The substrate is preferably a sheet of glass, glass-ceramic, or an organic polymer. This is preferably transparent, colorless (can then be clear or extra-clear glass) or colored, for example blue, green, gray or bronze. Glass is in:
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preferably soda-lime-silica glass, it can be a borosilicate glass or aluminum borosilicate. The preferred organic polymers are polycarbonate or polymethyl methacrylate or even polyethylene terephthalate (PET). The substrate advantageously has at least a dimension greater than or equal to 1 m, even 2 m or even 3 m. The thickness of the substrate generally varies between 0.5 mm and 19 mm, preferably between 0.7 and 9 mm, especially between 2 and 8 mm, even between 4 and 6 mm. The substrate can be flat or curved, or even flexible.
The glass substrate is preferably floating glass, that is to say capable of being obtained by a process consisting of pouring molten glass over a molten tin bath (the float bath). In this case, the film to be treated can also be deposited on the tin side as well as on the atmosphere side of the substrate. It should be understood that the terms sides of the atmosphere and tin mean the sides of the substrate which have respectively been in contact with the atmosphere above the float bath and in contact with the molten tin. The tin side contains a small surface amount of tin that has diffused into the glass structure. The glass substrate can also be obtained by laminating between two rollers, a technique which in particular allows them to be
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printed patterns on the glass surface ·: - · ..............
Metal M is preferably chosen from titanium, tin, zirconium, zinc, tungsten, tantalum, niobium, molybdenum, chromium, nickel, silicon, and aluminum. Those metals, or if their nitrides or carbides are required, have a higher near-infrared absorbance, so that most of the films formed from those metals heat up very quickly in the case of laser treatment or flame treatment, techniques that will be described in greater detail in the following text. Metal M can also be an alloy, especially a binary alloy of the above mentioned metals, for example a tin-zinc alloy or a nickel-chrome alloy.
According to a preferred embodiment, the intermediate film is made of titanium, the oxide film obtained after heat treatment, then being a photocatalytic film of titanium oxide. This process is particularly advantageous because, currently, photocatalytic films of titanium dioxide are obtained by a cathodic spraying step of titanium oxide, and therefore at particularly slow deposition rates, followed by a heat treatment step which is intended to crystallize the titanium oxide to make it photocatalytic. In the case of
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process according to the invention, -a metallic titanium film- is deposited at very high deposition rates and the heat treatment makes it possible, in a single step, to oxidize the titanium to titanium oxide and obtain a photocatalytic film and by therefore at least partially crystallized. The titanium oxide film is preferably at least partially crystallized from the anatase form, but the rutile phase may also optionally be present. Those photocatalytic films can also be obtained by oxidation of a film of titanium nitride, titanium carbide or substoichiometric titanium oxide in oxygen. The latter is denoted by TiO<sub>x</sub>. The value of x is preferably 1.8 or less, so that the intermediate film absorbs enough laser radiation.
Zirconium oxide can for example be obtained by oxidizing an intermediate film made of metallic zirconium or zirconium nitride. Zinc oxide can be obtained especially by oxidation of a film
<td colspan="3">intermediate zinc metal.</td><td colspan="2" rowspan="2">pure or combined with others</td>
<td></td><td>The metal</td><td>M can be</td>
<td>atoms.</td><td>By way</td><td>for example,</td><td>it is possible to modify</td><td>the</td>
<td>titanium</td><td colspan="3">using transition metals (eg W,</td><td>Mo,</td>
<td>V, Nb),</td><td>ions of</td><td>lanthanide or</td><td>noble metals (such as</td><td>by</td>
<td>example</td><td>platinum</td><td>or palladium)</td><td>or also with atoms</td><td>of</td>
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nitrogen or carbon. Once the t-11- ¿nir, has already ..... a í Hq ................
Oxidized to titanium oxide, these different modifiers will allow the material's photocatalytic activity to increase, or the forbidden band of titanium oxide to drift toward wavelengths that are either close to or within the visible range. Similarly, silicon can be modified with aluminum, because aluminum is often added to silicon targets to make them more conductive and thus make sputtering easier.
The physical thickness of the or each oxide film of metal M is preferably 20nm or less, especially 15nm, still 10nm. To achieve this the physical thickness of the intermediate film is preferably less than or equal to 20nm, still 15nm or even 10nm. The thickness of the intermediate film is however preferably greater than or equal to 2 nm, still 3 or 4 nm.
This is because, for example, for very small thicknesses, the absorption of infrared radiation becomes too weak for sufficiently intense and rapid heating of the film.
The intermediate film can be treated over its entire area, so that after the process the entire surface of the substrate is covered with an oxide film.
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Intermediate film surface can be heat treated, especially for the purpose of producing patterns for aesthetic or functional purposes. As explained in more detail in the following text, the use of spot laser, combined with a system for moving the laser in the plane of the substrate, is particularly suitable for this modality.
Another object of the invention is therefore a substrate coated on one part of its area with an oxide film of an M metal, the physical thickness of which is 30 nm or less, and on another part of its area with a film. of a material chosen from metal M, a nitride from metal M, and a carbide from metal M. Preferably, the oxide film is not part of a multilayer comprising at least one silver film. The oxidized regions can represent for example between 0.1 and 99.9% of the area of the substrate, or between 10 and 90% of the area of the substrate. The oxidized and non-oxidized regions are of course located on the same side of the substrate. The oxidized regions can form any type of design or pattern chosen either for aesthetic reasons (drawing, logo, etc.) or for functional reasons.
Metallic or nitride films absorb or reflect in the visible range, while oxide layers are transparent. Oxidizing treatment.
iNSTiTu ¿c m>: - 'l DE lNDvii iii'.h involves only certain regions, thus allowing transparent and absorbent regions to be created in a predefined design. For example, specular films made of chrome or nickel chrome alloy can be locally treated to create transparent patterns.
Similarly, metal films conduct electricity, while oxide films are insulating. The treatment according to the invention can therefore allow conductive regions, hence electrodes, to be created in a predefined scheme, for example in the form of strips or even grids. In this way it is possible to create transparent printed circuits, for example by locally oxidizing conductive films made of aluminum or semiconductor films made of silicon.
Preferably, the temperature of the substrate during heat treatment does not exceed 100 ° C, especially 50 ° C. This may especially be the temperature on the side opposite the side on which the intermediate film was deposited. This temperature can for example be measured by pyrometry.
To do this, the oxidative heat treatment is carried out using a technique that heats the intermediate film very quickly, so that the substrate is not substantially heated.
In particular, heat treatment is preferably carried out using at least one laser radiation or using at least one flame (called flame treatment).
These techniques have the advantage of a very high heat transfer coefficient, typically greater than 400 W / (m<sup>2</sup>.K). The energy per unit area of the laser radiation in the intermediate film is preferably greater than or equal to 20 kW / cm<sup>2</sup> or 30 kW / cm<sup>2</sup>. This very high energy density allows the desired temperature in the intermediate film to be reached extremely quickly (generally a time of one second or less) and consequently allows the duration of the treatment to be correspondingly limited, thus not having the heat generated time to diffuse into the substrate.
In this way, each treated spot of the intermediate film is preferably subjected to the oxidative treatment for a time generally less than or equal to 1 second, even 0.5 seconds. In contrast, infrared lamps conventionally used for annealing treatments do not allow these high energies per unit area to be reached: the treatment time must be longer to reach the desired temperature (often several seconds), and
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the substrate is then necessarily ra i pnt-aHn temperatures by heat diffusion, even if the wavelength of radiation is selected to be absorbed only by the thin film and not by the substrate.
By virtue of the very high heat transfer coefficient associated with the process according to the invention, even the part of glass located 0.5 mm from the intermediate film is generally not subjected to temperatures greater than 100 ° C.
The process is generally a continuous process: the intermediate film and the heating means (for example laser beam or flame device) move relative to each other to treat the desired area and in general the entire area.
The laser radiation preferably has a wavelength of 500 and 2000 nm, especially between 530 and 1200 nm. This is because in the wavelength range the absorbance of metals, nitrides or carbides is maximized. Radiation is therefore specifically absorbed by the intermediate film and little by the underlying substrate, thereby allowing the intermediate film to be rapidly heated without heating the substrate.
Preferably the absorbance of the intermediate film at the wavelength of the laser radiation is
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MEXICAN INSTITUTE r »cia PttnPÍFt'JAD
20% or greater, especially 30%. As an example, the absorbance of a 10nm titanium or zirconium film reaches 40% at a wavelength of 808nm. In contrast, glass, especially clear or extra-clear glass, absorbs very weakly in this wavelength range so that most radiation contributes to heating only the film. Absorbance is defined as equal to 100% from which the transmittance and reflectance of the film are subtracted.
Preferably, laser diodes, which emit for example at a wavelength of about 808 nm,
880 nm, 940 nm, or even 980 nm or 1032 nm, are used. In the form of diode systems, very high energies can be obtained, possibly reaching energies per unit area, in the film to be treated, of more than 20 kW / cm<sup>2</sup>, still 30 kW / cm<sup>2</sup>.
For an even simpler implementation, the lasers used in the context of the invention can be fiberized, which means that the laser radiation is injected into an optical fiber and then released near the area to be treated with a focusing head. The laser can also be a fiber laser, in the sense that the amplifying medium is itself an optical fiber.
The laser beam can be a point laser beam, in which case it is necessary to provide a system to move itj?
h
INSTITUTC L't LA i the laser beam in the plane of the substrate. mg d aT-j-da-dr ^ particularly preferred when only part of the intermediate film surface is to be heat treated to produce patterns for aesthetic or functional purposes. The spot laser beam can move in an XY plane and create all kinds of patterns or designs transforming the absorbent and / or reflective and / or electrically conductive regions into transparent and / or electrically insulating regions.
Laser radiation preferably comes from at least one line-forming laser beam (also called a linear laser in the following text) that simultaneously irradiates all or some of the width of the substrate. This modality is preferred in the case where it is desired to treat the entire surface of the substrate, since it avoids the use of expensive movement systems, which are generally bulky and difficult to maintain. The linear laser beam can be specially obtained using high energy laser diode systems combined with optical focusing devices. The thickness of the line is preferably between 0.01 and 1 mm. The length of the line is typically between 5mm and 1m. The profile of the line can be especially that of a Gaussian curve or a hat.
The linear laser, which simultaneously radiates
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INSTITUTE
D2 LA Τί · INL all or part of the width of the substrate, can ootar eiompngst'q<sup>1 </sup>single line (thereby irradiating the entire width of the substrate) or a plurality of optionally separate lines. When a plurality of lines are used, it is preferable that they be positioned so that the entire area of the multilayer is treated. The or each line is preferably positioned perpendicular to, or obliquely positioned in, the direction of travel of the substrate. The different lines can treat the substrate simultaneously, or in a delayed way. The important point is that the entire area to be treated is treated.
To treat the entire area of the film, the film-coated substrate and the or each linear laser are preferably moved relative to one another. The substrate can thus be moved, especially, so that it travels translationally oriented towards the stationary linear laser, generally below, optionally above the linear laser. This modality is especially particular for continuous treatment. Alternatively, the substrate can be stationary and the laser can then move. Preferably the difference between the respective speeds of the substrate and the laser are greater than or equal to one meter per minute, still 4 meters per minute and still 6, 8, 10 or 15 meters per minute, thus ensuring high speed. of treatment.
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IMPI
MEXICAN INSTITUTE OF THE INDUSTRIAL FROPl'ÓDAD
When the substrate moves, in a translational way, it can be moved using any mechanical means of transport, for example bands, rollers, or trays that run translationally. The transport system allows the travel speed to be controlled and regulated. If the substrate is made of a flexible organic polymer, it can be moved using a film advance system in the form of a succession of rollers.
The laser can also be moved to adjust the distance to the substrate, which can be useful in particular when the substrate is curved, but not only. In fact, it is preferable that the laser beam is focused on the coating to be treated, so that the latter is located less than 1 mm from the focal plane. If the system for moving the substrate or laser is not precise enough in relation to the distance between the substrate and the focal plane, it is preferable to be able to adjust the distance between the laser and the substrate. This setting can be automatic, specially regulated using a distance measurement upstream of the treatment.
In order for the linear laser to be set in motion, it is necessary to provide a system for moving the laser, located above or below the substrate. The duration of the treatment is regulated by the speed of
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linear laser offset. ..................
Of course, all the relative positions of the substrate and the laser are possible as long as the substrate area can be adequately irradiated. More generally, the substrate will be placed horizontally, but it can also be placed vertically, or at any possible inclination. When the substrate is placed horizontally, the laser will generally be placed to irradiate the top side of the substrate. The laser can also irradiate the underside of the substrate. In this case, the support system for the substrate is necessary, and optionally the substrate transport system when the substrate is in motion, to allow the radiation to pass into the region to be irradiated. This is the case for example when transport rollers are used: with the rollers being separated, it is possible to place the laser in a region located between two successive rollers.
When both sides of the substrate are to be treated, it is possible to employ a number of lasers located on either side of the substrate, whether the latter is in a horizontal, vertical, or any tilt position.
The laser, especially the linear laser, can be integrated into a film deposition line, by
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IMPI example, a magnetically enhanced CAT-Olilta spray line · (magnetron). In general, the line includes devices to handle the substrate, a deposition unit, optical control devices, and stacking devices. For example, the substrate runs on transport rollers, in succession at the front of each device or each unit.
The laser is preferably located just after the film deposition unit, for example at the exit of the deposition unit. The coated substrate can thus be treated online after the film has been deposited, at the outlet of the deposition unit and before the optical control devices, or after the optical control devices and before the devices of stacking the substrate.
The laser can also be integrated into the deposition unit. For example, the laser can be introduced into one of the chambers of a sputtering unit. The laser can also be placed outside the deposition unit, but in such a way that a substrate located inside the unit can be treated. To achieve this, all that is required is to provide a transparent window at the wavelength of the radiation used, through which the laser beam would pass to treat the film. In this way it is possible to treat an η * lt.
IMPI
DELA PRO? Ier MEXICAN INSTITUTE; AD INDUETjuAL
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film before the subsequent deposition of another film in the same unit. In order not to prevent oxidation of the intermediate film, it is possible to treat the multilayer in a special chamber, in which the oxidizing atmosphere is controlled.
If the laser is outside or integrated into the deposition unit, those flow processes are preferable to a batch process in which it would be necessary to stack the glass substrates between the deposition step and the heat treatment.
However, batch processes may however be of interest in the case where the heat treatment according to the invention is carried out in a location other than deposition, for example in a place where the glass is converted. The radiation device can therefore be integrated into lines other than the film deposition line. For example, it can be integrated into a multiple glass manufacturing line (especially double or triple glass) or a laminated glass manufacturing line. In those different cases, the heat treatment according to the invention is preferably carried out before the multiple or laminated glass is assembled.
The laser can be replaced with any device that emits infrared radiation and focuses on
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IN & UiT!
the substrate, for example using mirrors or l'entys, to obtain sufficient energy per unit area.
Flame treatment is preferably carried out by at least one flame treatment device located perpendicular to the direction of the substrate displacement, or along any relatively oblique direction. A number of elementary devices can be combined to form a single device. The total length of the flame treatment device is preferably at least equal to the width of the coated substrate, thereby easily allowing treatment during movement without requiring a movement system.
In general, at least one burner is used. The or each burner may be an external combustion burner, in that the fuel and oxidant are mixed at the burner nozzle or at a nozzle extension. In this case, the substrate is subjected to the action of a flame. The burner can also be an internal combustion burner, in that the fuel and oxidant are mixed within the burner: the substrate is then subjected to the action of hot gases. All intermediate cases are of course possible, in the sense that only part of the combustion can take place inside the burner, and the other
<img file="MX336914B_D0027.tif" />
<img file="MX336914B_D0028.tif" />
part out. Certain burners, in particular, hot air burners, which use air as the oxidant, have premix chambers in which all or some of the combustion takes place. In this case, the substrate can be subjected to the action of a flame and / or hot gases. Oxy-fuel burners, which use pure oxygen, generally do not contain a premix chamber. Hot gases can also be produced using a plasma torch: the heat is not produced by a combustion reaction, but by ionization between the electrodes of the torch.
The gas used may be a mixture of an oxidizing gas, especially chosen from air, oxygen, or mixtures thereof, and a fuel gas, especially chosen from natural gas, propane, butane, even acetylene or hydrogen, or mixtures thereof. Oxygen is preferred as the oxidizing gas, particularly in combination with natural gas (methane or propane), or on the other hand because it allows higher temperatures to be reached and consequently shortens the treatment, preventing the substrate from overheating, and on the other hand because it prevents the production of nitrous oxides NO<sub>X</sub>.
To achieve the desired temperatures in the intermediate film, the coated substrate is generally placed within the visible flame, especially in the
<img file="MX336914B_D0029.tif" />
hottest area of the flame, and a part of the flame visible around the treated region.
The temperature of the hot gases is preferably between 1300 and 2200 ° C, especially between 1300 and 1700 ° C in the case of hot air burners. The speed of the hot gases is preferably between 5 and 100 meters per second.
The oxide film obtained according to the invention may then be the only film deposited on the substrate, or it may belong to a multilayer. In the latter case, the film may especially be the last film on the multilayer.
When the oxide film is a titanium oxide photocatalytic film, the latter is normally the last film of the multilayer deposited on the substrate, in other words, the film furthest from the multilayer removed from the substrate. This is because it is important that the photocatalytic film is in contact with the atmosphere and its contaminants. However, it is possible to deposit on the photocatalytic film a very thin film, generally discontinuous or porous. This may for example be a film based on noble metals that is intended to increase the photocatalytic activity of the material. This can also be a
<img file="MX336914B_D0030.tif" />
IM
Delgada thin hydrophilic film, for example made of siiípp, as taught in patent applications WO 05/040058 or WO 07/045805. A sublayer, which is intended to prevent migration of alkali metal ions from the substrate to the titanium oxide film, can be placed between the substrate and the photocatalytic film. By way of example, this may especially be a film based on an oxide, nitride, oxynitride, or even silicon or aluminum oxycarbon, or even based on tin or zirconium oxide. However, since the heat treatment according to the invention is of short duration and does not heat the glass at high temperatures, the migration of the alkalis is greatly reduced, so that the alkali metal migration barrier film does not is absolutely necessary. A sublayer may however be useful in the case where the substrate may have or undergo post heat treatment, such as tempering or flexing. It is also possible to provide, underneath the titanium oxide-based film, a sublayer that promotes growth of the titanium oxide crystal, especially in the anatase form. This can be especially a ZrO sublayer<sub>2</sub> as described in patent application WO 02/40417, or even a sublayer that promotes heteroepitaxial growth of titanium oxide in the anatase form, as described for example,
<img file="MX336914B_D0031.tif" />
in patent application WO 05/040058, especially a film made of BaTiO<sub>3</sub> or SrTiO3. Titanium oxide film can also be the latest low E and / or solar control multilayer film. The film in this case allows the appearance of condensation (fog and / or frost) on the external surface of the glass to be limited, particularly when the substrate is integrated into a double or triple glass, especially inclined glass (for example in a ceiling or terraces). The presence of a low E film on the outer side of the glass limits heat exchange with the outside at night, and therefore maintains the temperature of the glass surface above the dew point. The appearance of fog or frost is therefore greatly reduced or even completely avoided.
When the oxide film is a zirconium oxide film, it can be used for its corrosion and scratch resistance properties.
A tungsten oxide based film can be used to produce a blue wall covering.
The substrate obtained according to the invention is preferably incorporated into a glass unit. The crystal can be a single crystal or a multiple crystal (especially double or triple), in the sense that it can comprise a plurality of glass sheets housed in a
IMP
MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY
<img file="MX336914B_D0032.tif" />
space full of gas. The crystal can be Irtmin ^ and / ^. tempered and / or reinforced and / or curved.
The side of the substrate opposite to the side on which the oxide film is deposited, or if one side of another multiple crystal substrate is required, may be coated with another functional film or a multilayer comprising functional films. This can be especially a photocatalytic film. There may also be films or multilayers which have a thermal function, especially solar control or low E functions, for example multilayers comprising a silver film protected by dielectric films. There may also be a mirror film, especially based on silver. Finally, there may be a lacquer or varnish that is intended to opaque the glass to form a covering panel (also called a wall covering) for a curtain wall. The wall covering is placed on the curtain wall near the transparent glass and allows curtain walls made entirely of glass to be obtained, and aesthetically uniform.
Other films or multilayers located on the side of the substrate opposite the side on which the oxide film is deposited can see its improved properties using the heat treatment according to the invention.
MEXICAN INSTITUTE OF PROPERTY
INDUSTRIAL ^ 6 " <sup>r</sup>’<sup>s</sup>
There may especially be properties associated with better crystallization of functional films, for example silver films. Thus, it has been observed, particularly in the case of glass substrates over 6 mm thick, that the oxidative heat treatment according to the invention can also reduce the emissivity and / or resistivity of low-E multilayers that they contain at least one silver film.
According to a preferred embodiment of the invention, an intermediate film made of metallic titanium is therefore deposited on the side of the substrate and, on the other side of the substrate, a low E multilayer comprising at least one silver film is deposited The intermediate film is then treated using at least laser radiation, so that the emissivity or resistivity of the low E multilayer is reduced by at least 3%. The improvements in emissivity or resistivity are at least 3%, still 5% and even 10%.
Thus, using a single heat treatment it is possible to improve the emissivity properties of a low E multilayer and obtain a photocatalytic film. This is made possible by the fact that laser radiation is only partially absorbed by the intermediate film and the substrate, so that the multilayer lowers
E located on the other side receives part of the energy
<img file="MX336914B_D0033.tif" />
<img file="MX336914B_D0034.tif" />
MEXICAN INSTITUTE OF PROPERTY
INDUSTRIAL radiation, which is used to improve the crystallization properties of the or each silver film. The product obtained has a self-cleaning photocatalytic function on one side, which will therefore be directed quickly towards the outside of the building, and a thermal insulation function on the other hand, which will therefore be directed quickly towards the interior of the building. .
The invention is illustrated using the following exemplary non-limiting embodiments:
EXAMPLE 1
In this example, a 5 or 10 nm thick intermediate film of metallic titanium was deposited on a clear soda-lime-silica glass substrate.
The intermediate film was deposited by sputtering titanium white with argon plasma.
The specimens were treated in air using a linear laser that emitted radiation at a wavelength of
808 nm, along which the coated substrate would travel translationally at speeds ranging from 3 to 20 meters per minute.
Photocatalytic activity was measured as follows, verifying the degradation of stearic acid:
<img file="MX336914B_D0035.tif" />
<img file="MX336914B_D0036.tif" />
MEXICAN INSTITUTE OF THE f-ROTF.DAD
INDUSTRIAL 5'1Γ5 ”cm specimens were cut<sup>2</sup>; the specimens were cleaned for 45 minutes under UV radiation and under a flow of oxygen;
the infrared spectrum was measured by FTIR during wave numbers between 4000 and 400 cm<sup>-1</sup>, to form a reference spectrum;
Stearic acid was deposited: 60 microlites of a stearic acid solution, dissolved at 10 g / 1 stearic acid in ethanol, were deposited by coating by centrifugation on the specimen;
the infrared spectrum was measured by FTIR and the area of the wide bands of CH2-CH3 bonds was measured between 3000 and 2700 cm '<sup>1</sup>;
UVA radiation exposure: the energy received per specimen, approximately 35 W / m<sup>2</sup> to simulate outdoor exposure, it was controlled by a photoelectric cell within the wavelength range of 315 to 400 nm; and the photodegradation of the stearic acid film was verified by measuring the area of the extensive bands of CH2-CH3 bonds, between 3000 and 2700 cm<sup>-1</sup>, after successive exposure times of 30 minutes twice and then one hour.
photocatalytic activity was defined by the slope, expressed in cm<sup>_1</sup>.min<sup>_1</sup>, from the straight line that
<img file="MX336914B_D0037.tif" />
represents the area of the extensive bands da. ^ aa.1 flCfíS-CHa-CH ^ between 3000 and 2700 cm<sup>-1</sup>, as a function of the time of
<td>exposure to</td><td>the</td><td>UV, for a while</td><td>of</td><td>between 0 and 30</td>
<td>minutes.</td><td></td><td></td><td></td><td></td>
<td>The</td><td colspan="2">photocatalytic activity</td><td>of</td><td>the movies</td>
<td>obtained was</td><td>of</td><td>about 4 to 5 x</td><td> 10’<sup>3</sup></td><td>cm<sup>-1</sup>.min '<sup>1</sup> for</td>
travel speeds ranging from 4 to 15 meters per minute. The photocatalytic activities were similar to those obtained for a 10 nm thick film of T1O2 deposited by sputtering and then annealed using conventional means. The titanium film would therefore have been well oxidized and would have crystallized in an active phase, especially the anatase phase.
Photocatalytic activity was reduced at the highest travel speeds (20 meters per minute), evidence of imperfect oxidation.
EXAMPLE 2
In this example, a 5nm thick intermediate film of metallic titanium was deposited on clear soda-lime-silica glass substrate.
The intermediate film was deposited by sputtering a titanium target with an argon plasma.
<img file="MX336914B_D0038.tif" />
<img file="MX336914B_D0039.tif" />
and
The coated substrate was treated.
<img file="MX336914B_D0040.tif" />
INSTITUTE m ^; í: í '/. FROM THE Pk ~ Wf
INOU-n A using, as an oxidant, a mixture of air (1500 L / min) and oxygen (163 L / min) and, as fuel, natural gas (214 L / min). The distance between the substrate and the burner nozzle was 12 nm.
Treatment at a speed of 3 meters per minute allowed a catalytic activity of 5x10 to be obtained<sup>-3</sup> cm<sup>-1</sup>.min<sup>-1</sup>.
EXAMPLE 3
Depending on the test, a 5nm or 10nm thick zirconium metal intermediate film was deposited on a clear soda-lime-silica glass substrate.
The intermediate film was deposited by sputtering a zirconia blank with an argon plasma.
The specimens were treated in air using a linear laser that emitted radiation at a wavelength of
980 nm, along which the coated substrate moved translationally, at speeds of several meters per minute.
The treatment oxidized the zirconia film to zirconium oxide, making the film perfectly transparent.
EXAMPLE 4
<img file="MX336914B_D0041.tif" />
The substrates used in the case of Example 3 were also flame treated, in the same manner as in Example 2.
The metallic zirconia film was thereby oxidized to zirconium oxide, making the film perfectly transparent.
EXAMPLE 5
Depending on the test, a 5 nm or 10 nm thick intermediate film of metallic zirconium nitride was deposited on a clear lime-silica soda glass substrate.
An identical flame treatment to that described in Example 2 allowed a perfectly transparent zirconium oxide film to be obtained.
<img file="MX336914B_D0042.tif" />
<img file="MX336914B_D0043.tif" />
Contents23
43 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13 Sheet 14 Sheet 15 Sheet 16 Sheet 17 Sheet 18 Sheet 19 Sheet 20 Sheet 21 Sheet 22 Sheet 23 Sheet 24 Sheet 25 Sheet 26 Sheet 27 Sheet 28 Sheet 29 Sheet 30 Sheet 31 Sheet 32 Sheet 33 Sheet 34 Sheet 35 Sheet 36 Sheet 37 Sheet 38 Sheet 39 Sheet 40 Sheet 41 Sheet 42 Sheet 43
30 members in 19 offices
Priority claims9
| Document | Office | Kind | Date |
|---|---|---|---|
| 0956866 | France | A | |
| 0956866 | France | A | |
| 0956866 | France | – | |
| 2010052073 | France | W | |
| 2010052073 | France | W | |
| 0956866 | – | – | – |
| FR1052073 | – | – | – |
| FR20090056866 | – | – | – |
| WO2010FR52073 | – | – | – |
Members30
| Document | Office | Kind | |
|---|---|---|---|
| CA2774937A1 | Canada | A1 | |
| WO2011039488A1 | World Intellectual Property Organization (WIPO) | A1 | |
| FR2950878A1 | France | A1 | |
| FR2950878B1 | France | B1 | |
| MX2012003610A | Mexico | A | |
| AU2010302459A1 | Australia | A1 | |
| US2012171439A1 | United States of America | A1 | |
| CN102574731A | China | A | |
| EP2483214A1 | European Patent Office (EPO) | A1 | |
| KR20120091043A | Republic of Korea | A | |
| EA201270487A1 | Eurasian Patent Organization (EAPO) | A1 | |
| JP2013506758A | Japan | A | |
| AU2010302459B2 | Australia | B2 | |
| DE202010018173U1 | Germany | U1 | |
| EP2483214B1 | European Patent Office (EPO) | B1 | |
| DK2483214T3 | Denmark | T3 | |
| PT2483214E | Portugal | E | |
| ES2530270T3 | Spain | T3 | |
| JP5681194B2 | Japan | B2 | |
| US9011649B2 | United States of America | B2 | |
| PL2483214T3 | Poland | T3 | |
| EG27080A | Egypt | A | |
| IN2079DEN2012A | India | A | |
| EA022598B1 | Eurasian Patent Organization (EAPO) | B1 | |
| MX336914BThis record | Mexico | B | |
| CN102574731B | China | B | |
| KR101746245B1 | Republic of Korea | B1 | |
| CA2774937C | Canada | C | |
| BR112012006868B1 | Brazil | B1 | |
| BR112012006868B8 | Brazil | B8 |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| Grant or registrationFG | FG |
Numbers
- Publication
- 336914
- Publication, DOCDB
- 336914
- Publication, EPODOC
- MX336914
- Application
- 2012003610
- Application, DOCDB
- 2012003610
- Application, EPODOC
- MX202012003610
Titles
- Spanish
- METODO DE DEPOSICION DE PELICULA DELGADA.
Classification
- CPC, 15
- C03C17/002
- C03C17/245
- C03C2217/71
- C03C2218/154
- C03C2218/322
- C23C14/185
- C23C14/5813
- C23C14/5853
- Y10T428/24917
- Y10S977/755
- Y10S977/891
- C23C14/14
- C23C14/541
- C23C14/0641
- C23C14/0635
- IPC, 4
- C03C17 00
- C03C17 245
- C23C14 58
- B01J35 00