Method for depositing and treating a silver based thin layer

0001The invention relates to the field of inorganic thin layers, in particular deposited on glass substrates. It relates more particularly to a process of at least partial crystallization of said thin layers and certain products obtained using this process.

0002Many thin layers are deposited on substrates, in particular flat or slightly curved glass, in order to give the materials obtained specific properties: optical properties, for example of reflection or absorption of radiation of a wavelength domain. data, properties of particular electrical conduction, or properties related to the ease of cleaning or the possibility for the material to self-clean.

0003These thin layers are most often based on inorganic compounds: oxides, nitrides, or metals. Their thickness generally varies from a few nanometers to a few hundred nanometers, hence their qualification as “thin”.

0004Mention may be made of thin layers based on metallic silver, which have properties of electrical conduction and reflection of infrared radiation, hence their use in glazing with solar control, in particular anti-solar glazing (aimed at reducing the quantity of (incoming solar energy) or low emissivity (aimed at reducing the amount of energy dissipated outside a building or a vehicle).

0005Silver-based layers have the particularity of seeing some of their properties improved when they are in an at least partially crystallized state. We generally seek to increase as much as possible the crystallization rate of these layers (the mass or volume proportion of crystallized material) and the size of the crystalline grains (or the size of coherent diffraction domains measured by X-ray diffraction methods), or even in certain cases to favor a particular crystallographic form.

0006It is known that silver layers having a high crystallization rate and consequently a low residual content of amorphous silver have a lower emissivity and resistivity than predominantly amorphous silver layers. The electrical conductivity and the low emissivity properties of these layers are thus improved.

0007A process commonly used on an industrial scale for the deposition of thin layers, in particular on a glass substrate, is the cathode sputtering process assisted by a magnetic field, called the “magnetron” process. In this process, a plasma is created under a high vacuum in the vicinity of a target comprising the chemical elements to be deposited. The active plasma species, by bombarding the target, tear off said elements, which are deposited on the substrate, forming the desired thin layer. This process is said to be “reactive” when the layer consists of a material resulting from a chemical reaction between the elements torn from the target and the gas contained in the plasma. The major advantage of this process lies in the possibility of depositing on a single line a very complex stack of layers by successively threading the substrate under different targets, this generally in a single device.

0008During the industrial implementation of the magnetron process, the substrate remains at room temperature or undergoes a moderate temperature rise (less than 80 ° C), particularly when the running speed of the substrate is high (which is generally sought for economic reasons). What may appear to be an advantage, however, constitutes a disadvantage in the case of the abovementioned layers, since the low temperatures involved generally do not allow sufficient crystal growth. This is particularly the case for thin thin layers and / or layers made of materials with a very high melting point. The layers obtained according to this process are therefore mainly or even completely amorphous or nano-crystallized (the average size of the crystalline grains being less than a few nanometers), and heat treatments appear to be necessary to obtain the desired crystallization rate or the desired grain size .

0009Possible heat treatments consist in reheating the substrate either during the deposition, or at the end of the deposition, at the outlet of the magnetron line. Most generally, temperatures of at least 200 ° C or 300 ° C are required. The crystallization is in fact all the better and the grain size is all the greater as the temperature of the substrate is close to the melting temperature of the material constituting the thin film.

0010Heating the substrate in industrial magnetron lines (during deposition) has however proved difficult to implement, in particular because heat transfers under vacuum, necessarily of a radiative nature, are difficult to control and involve a high cost in the case of large substrates, several meters wide. In the case of thin glass substrates, this type of treatment often involves high risks of breakage.

0011Heating the coated substrate after deposition, for example by placing the substrate in an oven or an oven or by subjecting the substrate to infrared radiation from conventional heating devices such as infrared lamps, also has disadvantages because these different processes contribute to indiscriminately heating the substrate and the thin layer. Heating the substrate to temperatures above 150 ° C is likely to generate breaks in the case of large substrates (several meters wide) because it is impossible to ensure an identical temperature over the entire width of the substrate. The heating of the substrates also slows down the whole process, because it is necessary to wait for their complete cooling before considering their cutting or their storage, which generally takes place by stacking the substrates on top of each other. Very controlled cooling is also essential to avoid the generation of stresses within the glass, and therefore the possibility of breakage. Since such highly controlled cooling is very expensive, annealing is generally not sufficiently controlled to eliminate thermal stresses within the glass, which generates an increased number of in-line breaks. Annealing also has the drawback of making cutting glass more difficult, the cracks having a less strong tendency to propagate linearly.

0012The heating of the substrates takes place in the case where the glazings are curved and / or toughened, since a reheating of the glass beyond its softening temperature (generally at more than 600 ° C. or even 700 ° C. for a few minutes) is performed. Quenching or bending therefore makes it possible to obtain the desired result of crystallization of the thin layers. However, it would be expensive to subject such glazing to all glazing for the sole purpose of improving the crystallization of the layers. In addition, tempered glazing can no longer be cut, and some stacks of thin layers do not withstand the high temperatures experienced during tempering of the glass. An example of this type of heat treatment is given in the document<patcit id="pcit0001" dnum="US20040005467A"><text>US 2004/0005467</text></patcit>.

0013The object of the invention is to propose a process which makes it possible to improve the crystallization properties of thin layers based on silver but which do not have the abovementioned drawbacks.

0014To this end, the invention relates to a method according to claim 1.

0015By "continuous thin layer" is meant in the sense of the present invention that the layer covers substantially the entire substrate or, in the case of a stack, the entire underlying layer. It is important that the continuous nature of the thin layer (and therefore its advantageous properties) is preserved by the treatment according to the invention.

0016By “layer point” is meant an area of ​​the layer undergoing treatment at a given time. According to the invention, the entire layer (therefore each point) is brought to a temperature of at least 300 ° C., but each point of the layer is not necessarily treated simultaneously. The layer can be treated at the same instant as a whole, each point of the layer being simultaneously brought to a temperature of at least 300 ° C. The layer can alternatively be treated so that the different points of the layer or of the sets of points are successively brought to a temperature of at least 300 ° C., this second mode being more often used in the case of a setting. in continuous use on an industrial scale.

0017The method according to the invention makes it possible to provide sufficient energy to promote the crystallization of the thin layer, by a physicochemical mechanism of crystal growth around germs already present in the layer, while remaining in the solid phase. The method according to the invention does not use a crystallization mechanism by cooling from a molten material, on the one hand because it would require bringing the thin layer to extremely high temperatures to obtain its fusion, and on the other hand because this would be likely to modify the thicknesses and / or the refractive indices of the layers, and therefore their properties. This would notably modify their optical appearance by generating inhomogeneities detectable to the eye.

0018The method according to the invention has the advantage of heating only the thin layer (or the thin layers in the case of a stack), without significant heating of the entire substrate. It is thus no longer necessary to carry out a slow and controlled cooling of the substrate before cutting or storing the glass. This process also makes it possible to integrate a heating device on existing continuous production lines, more particularly in the space between the outlet of the vacuum deposition chamber of the magnetron line and the device for storing the glass by stacking. It is also possible in certain cases to carry out the treatment according to the invention within the vacuum deposition enclosure itself.

0019In an industrial implementation integrated into a magnetron line, the process is generally continuous in the sense that the substrate is in movement, therefore undergoes a linear movement in a direction X. Each point of the thin layer is then preferably treated according to one of the following modes: either the heating means are fixed and a set of points forming a line can be treated simultaneously in a direction Y perpendicular to the direction X, or the heating means are movable in the direction Y and each point is treated successively. The method according to the invention can be implemented on a substrate placed both horizontally and vertically. It can also be implemented on a substrate provided with thin layers on its two faces, at least one layer of one of the faces or of each face being treated according to the invention. In the case where thin layers deposited on the two faces of the substrate are treated according to the invention, it is possible to treat said thin layers of each face either simultaneously or successively, by identical or distinct techniques, in particular depending on whether the nature of the treated layers is identical or distinct. The case where the treatment according to the invention is carried out simultaneously on the two faces of the substrate is therefore well understood within the scope of the invention.

0020It is not physically possible to heat the layer without heating the substrate, because the rise in temperature within the layer necessarily results, by thermal conduction mechanisms, in heating the zone of the substrate closest to the layer , and therefore a high thermal gradient in the thickness of the substrate. Such high thermal gradients, sometimes called thermal shocks, are known to systematically generate breakages in the case of soda-lime-silica glasses commonly used in the flat glass industry. These breaks, which originate from the differential thermal expansion between the different areas of the glass subjected to different temperatures, occur more easily in the case of soda-lime-silica glasses because their coefficient of expansion is quite high. They also occur more easily in the case of large substrates (at least 1 m, or even 2 or even 3 m wide) because it is more difficult to ensure high temperature uniformity for large substrates.

0021The inventors have however demonstrated that a heat treatment using only moderate and controlled heating of a limited area of ​​the substrate made it possible to overcome this problem of breakage, hitherto considered inevitable. It is therefore essential for the implementation of the present invention that the temperature of the face of the substrate opposite to the face carrying the treated thin layer is not greater than 150 ° C. This characteristic is obtained by choosing a heating mode specially adapted for heating the thin layer and not the substrate and by controlling the heating time or intensity and / or other parameters depending on the heating mode used, as described in more detail later in the text.

0022A characteristic common to all the heating modes which can be used according to the invention lies in the fact that they make it possible to generate an extremely high power per unit area, which however cannot be quantified in an absolute manner since it depends on many factors among which the nature and thickness of the thin layer. This high power per unit area makes it possible to reach the desired temperature at the level of the layer extremely quickly (generally in a time less than or equal to 1 second) and therefore to limit the duration of the treatment accordingly, the heat generated then having no time to diffuse within the substrate. Each point of the thin layer is subjected to the treatment according to the invention (that is to say brought to a temperature greater than or equal to 300 ° C.) for a duration less than or equal to 1 second, or even 0.5 seconds. Conversely, the conventionally used infrared lamps do not allow these high powers to be achieved per unit area, the treatment time must be longer to reach the desired temperatures (often several seconds), and the substrate is then necessarily carried at high temperatures by diffusion of heat, even if the wavelength of the radiation is adapted to be absorbed only by the thin layer and not by the substrate.

0023In order to limit as much as possible the number of breaks for the largest substrates (for example 6 m long by 3 m wide), the temperature is preferably maintained throughout the treatment less than or equal to 100 ° C., in particular 50 ° C, at any point on the face of the substrate opposite the face on which the thin layer is deposited.

0024Another advantage of the invention resides in the fact that the process subjects the thin layer or the stack of thin layers to the equivalent of quenching. It happens that certain stacks of thin layers see their optical properties (colorimetric coordinates, light or energy transmission) modified when the glass is toughened. The method according to the invention then makes it possible to obtain an unhardened glass (therefore not having within it a stress profile specific to toughened glass, which makes it cuttable) but having substantially the same optical properties as if it had been soaked.

0025The crystallization rate obtained using the process according to the invention is preferably greater than or equal to 20% or 50%, in particular 70% and even 90%. This crystallization rate, defined as the mass of crystallized material over the total mass of material, can be evaluated by X-ray diffraction using the Rietveld method. Due to a mechanism of crystallization by growth of crystalline grains from germs or nuclei, the increase in the rate of crystallization is generally accompanied by an increase in the size of the crystallized grains or the coherent domains of diffraction measured by diffraction X-rays.

0026The substrate is preferably transparent, made of glass, in particular silica-soda-lime. It can also be made of plastic, such as polycarbonate or polymethyl methacrylate. It advantageously has at least one dimension greater than or equal to 1 m, even 2 m and even 3 m. The thickness of the substrate generally varies between 0.5 mm and 19 mm, the method according to the invention being particularly advantageous for the thinnest substrates, the thickness of which is less than or equal to 4 mm, or even 2 mm.

0027The thin layer is a silver-based layer. It is even preferably made of such a metal. The thickness of the thin layer is preferably between 2 and 500 nm.

0028These layers have the distinction of being generally transparent to UV-visible radiation (the absorption being less than 50% in the visible range). Their absorption spectrum being little different from that of the substrate (especially in the case where the latter is made of glass), it is all the more difficult to specifically heat the layer and not the substrate. Other layers such as silicon have a strong absorption in the visible and near infrared, which facilitates their selective heating, for example in the case of the transformation of amorphous silicon into polycrystalline silicon.

0029The thin layer treated according to the invention is included in a stack of thin layers, generally chosen from oxides, nitrides or metals. The method according to the invention can improve the crystallization properties of one or more thin layers of the stack.

0030The thin silver or silver-based layer is included in a stack of layers, in particular in order to avoid its oxidation. In the case of glazing with solar control or with low emissivity, the thin silver-based layer is placed between two thin dielectric layers based on oxide or nitride. Can also be placed under the silver layer a very thin layer intended to promote the wetting and nucleation of silver (for example zinc oxide ZnO) and on the silver layer a second very thin layer (sacrificial, for example titanium) intended to protect the silver layer in the case where the deposition of the subsequent layer is carried out in an oxidizing atmosphere or in the event of heat treatments leading to migration of oxygen within the stack. The stacks can also comprise several layers of silver, each of these layers being generally affected by the implementation of the method according to the invention. In the case where the stack comprises a layer of zinc oxide, the treatment of the silver layer is also generally accompanied by an increase in the rate of crystallization of the zinc oxide.

0031The thin layer before treatment according to the invention can be obtained by any type of process, in particular processes generating predominantly amorphous or nano-crystallized layers, such as the magnetron process, the chemical vapor deposition process assisted by plasma ( PECVD), the vacuum evaporation process, or the sol-gel process. It is however preferably a "dry" layer, not containing an aqueous or organic solvent, in opposition with a "wet" layer, for example obtained by the sol-gel process. It is even preferably obtained by sputtering, in particular assisted by magnetic field (magnetron process). In the case of a layer obtained by the sol-gel process, precursors in solution (sol) are deposited on the substrate, the layer obtained then having to be dried and annealed to remove all traces of solvent. In this case, the energy provided by the heating is then mainly used to remove this solvent, without necessarily affecting the crystallization properties of the layer, and it is therefore more difficult to improve said properties in a sufficiently short time so as not to also heat the substrate.

0032For simplicity, the heating of the layer is preferably done in air and / or at atmospheric pressure. Certain heating modes are, however, compatible with vacuum, and it may be advantageous to heat the layer within the vacuum deposition enclosure, for example before a subsequent deposition.

0033Different heating means make it possible to implement the method according to the invention, allowing the generation of a power per unit of very high surface area. The heating parameters such as the power of the heating means or the heating time are to be adapted on a case-by-case basis by a person skilled in the art as a function of various parameters such as the nature of the heating process, the thickness or the nature layer, size and thickness of substrates to be treated etc.

0034When the thin layer is electrically conductive (which is the case with silver), the heating of the thin layer can be carried out by induction.

0035Induction heating of metal parts is a well-known process for quickly and controlled reaching high temperatures in solid conductive parts (reinforcement of steels, melting of silicon zones, etc.). The main applications concern the fields of the food industry (heating tanks, cooking flat products on metal strips, cooking-extrusion) and the manufacturing of metals (melting, reheating before forming, heat treatment in the mass, surface heat treatment, coating treatment, welding, soldering).

0036An alternating current traversing a winding (called solenoid or whorl) generates inside this one a magnetic field oscillating at the same frequency. If an electrically conductive part is placed inside the coil (or solenoid), currents induced by the magnetic field develop there and heat the part by Joule effect.

0037Currents appear on the surface of the part to be heated. A characteristic depth called skin thickness can be defined, giving at first glance the thickness of the current layer. The thickness of the skin of the currents depends on the nature of the heated metal and decreases as the frequency of the current increases.

0038When heating an insulating substrate covered with a conductive layer, it is preferable to use high frequency polarization in order to concentrate the influence of the inductor on the surface part of the material. The frequency is preferably between 500 kHz and 5 MHz, in particular between 1 MHz and 3 MHz. An inductor specially adapted for treating flat surfaces is preferably used.

0039Induction is not preferred when the thin layer has a thickness of less than 20 nm, or even less than 10 nm. For these particularly thin layers, a very high frequency is necessary, and the volume of the layer being very small, the effectiveness of the treatment is compromised.

0040When the thin layer absorbs at least part of the infrared radiation, the heating of the thin layer can be carried out using radiation whose wavelength is included in said part of the infrared radiation absorbed by said layer. In order to minimize heat input to the substrate, the wavelength of the selected radiation is preferably not included in the part of the infrared radiation absorbed by the substrate. For the above reasons, radiation must be characterized by a high power per unit area. For this reason, the heating of the thin layer is preferably carried out using a laser emitting infrared radiation. Infrared lamp systems associated with a focusing device making it possible to reach high powers per unit area are also usable.

0041In the case of a silver-based layer, it is preferable to use a laser emitting a radiation whose wavelength is between 0.5 and 5 micrometers. A YAG laser (aluminum garnet and yttrium Y₂Al₁₅O₂) doped with neodymium, emitting, in continuous or pulsed mode, radiation of around 1 micrometer wavelength, has proved to be particularly well suited, in particular when the substrate does not absorb in this wavelength range , which is the case for clear glasses, whose content by weight of iron oxide is 0.1% or less.

0042For increased simplicity of 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 delivered near the surface to be treated by a focusing head. The laser can also be fiber, in the sense that the amplification medium is itself an optical fiber.

0043Lasers can only irradiate a small surface (typically of the order of a fraction of mm² a few hundred mm²), it is necessary, in order to treat the entire surface, to provide a system for moving the laser beam in the plane of the substrate or a system forming an online laser beam simultaneously irradiating the entire width of the substrate, and under which the latter comes scroll.

0044The heating of the thin layer can also be carried out by thermal spraying techniques, in particular by a plasma spraying technique (plasma spray).

0045A plasma is an ionized gas generally obtained by subjecting a gas called "plasmagenic" to an excitation such as a strong continuous or alternating electric field (for example an electric arc). Under the action of this excitation, electrons are torn from the atoms of the gas and the charges thus created migrate to the electrodes of opposite charge. These charges then excite other atoms of the gas by collision, creating by avalanche effect a homogeneous or microfilamentary discharge or even an arc. Plasmas can be “hot” (the gas is then fully ionized and the temperature of the plasma is around 10⁶° C), or "thermal" (the gas is almost fully ionized and the plasma temperature is around 10⁴° C, case for example of electric arcs). Plasmas contain many active species, that is to say capable of interacting with matter, including ions, electrons or free radicals. In the case of a plasma torch, a gas is blown through an electric arc, and the thermal plasma formed is blown towards the substrate to be treated. The plasma torch is commonly used to deposit thin layers on various substrates by adding precursors in the form of powders to the plasma.

0046In the context of the invention, the plasma torch is preferably associated with an automatic displacement system located perpendicular to the direction of travel of the coated substrate and allowing the treatment of the entire surface by successive round trip of the torch at above the substrate.

0047The blown gas is preferably nitrogen, air or argon, advantageously comprising a hydrogen content by volume of between 5 and 50%, in particular between 15 and 30%.

0048Heating the thin layer can also be achieved by subjecting said thin layer to the action of at least one flame.

0049This flame treatment is preferably carried out on a flame bench located perpendicular to the direction of travel of the substrate. The length of the flaming device is preferably at least equal to the width of the coated substrate, which easily allows processing on parade without requiring a displacement system. The gas used can be a mixture of an oxidizing gas, in particular chosen from air, oxygen or their mixtures, and a combustible gas, in particular chosen from natural gas, propane, butane, or even acetylene or hydrogen, or mixtures thereof. Oxygen is preferred as an oxidizing gas, in particular in combination with natural gas (methane) or propane, on the one hand because it makes it possible to reach higher temperatures and consequently to shorten the treatment and avoid the heats the substrate, and secondly because it avoids the creation of nitrogen oxides NO_x. To reach the desired temperatures at the level of the thin layer, the coated substrate is generally positioned within the visible flame, in particular at the level of the hottest zone of the flame, part of the visible flame then extending around the treated area.

0050Flaming is a technique commonly used for the surface treatment of polymers in order to improve their wettability properties and facilitate their coating with paints. In the use which is made of it, the principle is to subject the surface to be treated to the action of radicals created by combustion, without bringing said surface to a high temperature. Requirement<patcit id="pcit0002" dnum="US2006128563A"><text>US 2006/128563</text></patcit> describes the use of this technique to activate surfaces of titanium oxide layers in order to improve their hydrophilicity properties. The treatments described, quite similar to those practiced on polymeric substrates, consist in running a substrate at or slightly below (a few centimeters) from the tip of the visible flame. This type of treatment, which aims to create hydroxyl groups on the surface of the titanium oxide, is however not suitable for bringing the thin layer of titanium oxide to temperatures above 200 ° C. and increasing the Titanium oxide crystallization rate, because the temperatures at the tip of the visible flame are insufficient.

0051The heating of the thin layer can also be carried out using radiation in the microwave field (wavelengths ranging from 1 millimeter to 30 centimeters, or frequencies ranging from 1 to 300 GHz).

0052Heating of the thin layer can also be carried out by bringing said thin layer into contact with a solid or a hot liquid. It may for example be a heated roller movable in rotation in contact with which comes to pass the substrate coated with the thin layer to be heated. The roll can be cylindrical or include a multiplicity of facets, thereby increasing the contact surface between the roll and the substrate. The hot solid, preferably in the form of a roll, is preferably made of a flexible material in order to be able to conform to possible surface irregularities or deformations of the substrate. It preferably has a high thermal conductivity in order to obtain a good heat transfer to the surface of the substrate. The solid is preferably brought to temperatures of at least 500 ° C, even 600 ° C and even 700 ° C.

0053The induction and flame heating modes are preferred when it is not desired to use a mechanical device for moving above the substrate. As for the heating modes by infrared or induction radiation, they can be implemented within the vacuum deposition device of the magnetron line. The latter are also advantageous when it is not desired to consume large quantities of gas.

0054For the thin layer based on silver (or made of silver), said thin layer is preferably brought to a temperature of between 300 and 600 ° C., preferably between 350 and 550 ° C. The preferred techniques are heating using a laser emitting infrared radiation, by induction, by plasma torch or by flame.

0055It has been observed in the case of silver-based layers that heating too long or of too high intensity, in particular using a laser emitting in the infrared or by induction, could not only lead to a rise in temperature of the substrate, but also destroy the continuity of the layer by creating from an initially continuous layer a discontinuous layer comprising isolated silver nodules, producing a blur by direct observation or under strong illumination. This embodiment is obviously not desirable and is not included in the scope of the invention.

0056The invention also relates to a process for obtaining a material comprising a substrate and at least one thin layer, characterized in that said at least one thin layer is deposited on said substrate by sputtering assisted by magnetic field , and in that said at least one thin layer is subjected to a heat treatment according to the invention.

0057Another subject of the invention is the materials capable of being obtained by the method according to the invention.

0058The method according to the invention in fact makes it possible to obtain materials comprising a thin layer whose crystallization rate could only be obtained by heat treatments of quenching, bending or annealing, ie treatments affecting the entire substrate upon filing. The materials obtained according to the invention therefore differ from the materials known from the prior art by a different structure, in particular by the fact that in their thickness they do not have a stress profile characteristic of that of a toughened glass and / or that they do not give rise to the same diffusion of elements (alkalis, oxygen etc.) coming from the substrate or from the outside.

0059Such a material consists, for example, of a non-tempered glass substrate, coated with a stack of thin layers comprising at least one silver layer of thickness e (expressed in nm). The stack is characterized by a square resistance R_vs (expressed in ohm) corresponding to the formula: <maths id="math0001"><math display="block"><msub><mi mathvariant="normal">R</mi><mi mathvariant="normal">vs</mi></msub><mo>×</mo><msup><mi mathvariant="normal">e</mi><mn>2</mn></msup><mo>−</mo><mn>120</mn><mo>&lt;</mo><mn>25</mn><mo>×</mo><mi mathvariant="normal">e</mi><mo>.</mo></math><img file="EP2118031B2_D0001.tif" /></maths>

0060The resistance per square of a conductive thin film depends on its thickness according to the Fuchs-Sondheimer law which is expressed R_vs xe² = pxe + A. In this formula p denotes the intrinsic resistivity of the material forming the thin layer and A corresponds to the specular or diffuse reflection of the charge carriers at the interfaces. The invention makes it possible to obtain an improvement in the intrinsic resistivity p such that p is less than or equal to 25 and an improvement in the reflection of the carriers such that A is less than or equal to 120, preferably 110 and even 105.

0061The method according to the invention thus makes it possible to obtain layers having very low resistivities, which hitherto could only have been obtained by means of quenching. The glass not being tempered, however does not have in its thickness the stress profile characteristic of a toughened glass (presence of constraints of extension at the heart of the glass and of compression at the level of the two faces), and is not consequent cut-out.

0062The stack is preferably of the type previously described in the present text, or in the requests <patcit id="pcit0003" dnum="WO2007110552A"><text>WO2007 / 110552</text></patcit>, <patcit id="pcit0004" dnum="WO2007101964A"><text>WO2007 / 101964</text></patcit>, <patcit id="pcit0005" dnum="WO2007101963A"><text>WO2007 / 101963</text></patcit>, <patcit id="pcit0006" dnum="WO2007054656A"><text>WO2007 / 054656</text></patcit>, <patcit id="pcit0007" dnum="WO2007054655A"><text>WO2007 / 054655</text></patcit>, <patcit id="pcit0008" dnum="WO2007042688A"><text>WO2007 / 042688</text></patcit>, <patcit id="pcit0009" dnum="WO2007042687A"><text>WO2007 / 042687</text></patcit>, <patcit id="pcit0010" dnum="WO2005110939A"><text>WO2005 / 110939</text></patcit>, <patcit id="pcit0011" dnum="WO2005051858A"><text>WO2005 / 051858</text></patcit>, <patcit id="pcit0012" dnum="WO2005019126A"><text>WO2005 / 019126</text></patcit>, <patcit id="pcit0013" dnum="WO04043871A"><text>WO04 / 043871</text></patcit>, <patcit id="pcit0014" dnum="WO0024686A"><text>WO00 / 24686</text></patcit>, <patcit id="pcit0015" dnum="WO0029347A"><text>WO00 / 29347</text></patcit>, <patcit id="pcit0016" dnum="EP0995724A"><text>EP0995724</text></patcit>, <patcit id="pcit0017" dnum="EP0995725A"><text>EP0995725</text></patcit><patcit id="pcit0018" dnum="WO9945415A"><text>WO99 / ​​45415</text></patcit>, <patcit id="pcit0019" dnum="EP922681A"><text>EP922681</text></patcit>, <patcit id="pcit0020" dnum="EP894774A"><text>EP894774</text></patcit>, <patcit id="pcit0021" dnum="EP877006A"><text>EP877006</text></patcit>, <patcit id="pcit0022" dnum="EP745569A"><text>EP745569</text></patcit>, <patcit id="pcit0023" dnum="EP718250A"><text>EP718250</text></patcit>.

0063The substrates obtained according to the invention can be used in single, multiple or laminated glazings, mirrors, wall coverings in glass. In the case of multiple glazing comprising at least two sheets of glass separated by a gas plate, it is preferable that the thin layer is placed on the face in contact with said gas plate

0064The invention is illustrated with the aid of the following nonlimiting exemplary embodiments.

EXAMPLE 1

0065A silica-soda-lime glass substrate obtained by the float process and then cut so that its size is 3 m wide by 6 m long is coated in a known manner by the magnetron process with a stack of thin layers comprising a silver layer, said silver layer imparting low emissivity properties to glass.

0066This stack comprises in order (from the substrate to the outer surface) the following layers of oxides, metals or nitrides, the geometric thicknesses being indicated in parentheses:<ul id="ul0001" list-style="none" compact="compact"><li>Glass / SnO₂ (20 nm) / ZnO (15 nm) / Ag (8.5 nm) / Ni-Cr / ZnO (15 nm) / Si₃NOT₄ (25 nm).</li></ul>

0067Between the output of the magnetron line and the storage device, a device is inserted comprising:<ul id="ul0002" list-style="dash" compact="compact"><li>a YAG laser (aluminum garnet and yttrium Y₂Al₁₅O₂) doped with neodymium, emitting, in continuous or pulsed mode, radiation at 1.09 micrometer in wavelength focused on the silver layer, the width of the spot being approximately 0.3 to 0.5 mm, and</li><li>a system for rapidly moving the laser (of the order of 3 to 5 meters / second) in a direction perpendicular to the direction of travel of the substrate.</li></ul>

0068The temperature of the glass substrate during the treatment does not exceed 50 ° C, measured by pyrometry at the face of the substrate opposite the face carrying the coating of thin layers.

0069Table 1 below indicates the variation following the processing of the following properties:<ul id="ul0003" list-style="dash" compact="compact"><li>the light transmission under illuminant D65, calculated from an experimental spectrum, taking as reference the standard illuminant D65 and the reference observer "CIE 1964", for double glazing whose glass sheets have a thickness of 4 mm and the gas slide (mixture of 90% argon and 10% air) has a thickness of 16 mm, transmission denoted “TL” and expressed in percent,</li><li>the square resistance, noted R_vs and expressed in ohms,</li><li>normal emissivity at a temperature of 283 K calculated according to standard EN 12898 from a spectrum in reflection in the spectral range 5 - 50 micrometers, denoted ε_not, and expressed in percent.</li></ul>

0070These last two properties (square resistance and emissivity), which illustrate the electrical conductivity and low-emissivity performances of the layer, reflect the crystallization rate and the size of the crystals of the silver layer because silver layers better crystals have both higher electrical conductivity and better emissivity properties.<tables id="tabl0001" num="0001"><table frame="all"><title><b>Table 1</b></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="14mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="14mm" /><colspec colnum="4" colname="col4" colwidth="14mm" /><colspec colnum="5" colname="col5" colwidth="14mm" /><colspec colnum="6" colname="col6" colwidth="14mm" /><thead><row><entry namest="col1" nameend="col2" align="center" valign="top">TL (%)</entry><entry namest="col3" nameend="col4" align="center" valign="top">R_vs (Ω)</entry><entry namest="col5" nameend="col6" align="center" valign="top">ε_not (%)</entry></row><row><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry></row></thead><tbody><row><entry>77,0</entry><entry>78,3</entry><entry>5,0</entry><entry>4,5</entry><entry>5,5</entry><entry>5,0</entry></row></tbody></tgroup></table></tables>

0071The variations due to the treatment in terms of square resistance and normal emissivity are of the order of 10%. These results show that the treatment of the stack (and in particular the treatment of the silver layer) using the infrared laser has resulted in an improvement in the crystallization of the silver layer, characterized in particular by a stronger crystallization rate and larger crystal size. We can also note a significant increase in the light transmission of the glazing obtained.

EXAMPLE 2

0072In this example, a coated substrate identical to that of Example 1 is used, therefore coated with a stack comprising a layer of silver.

0073The heating process is induction, carried out using an inductor whose geometry is specifically adapted to the treatment of flat surfaces. The frequency is 2 MHz, the power can vary around a few kW.

0074The temperature of the glass substrate during the treatment, which lasts only a few seconds, does not exceed 150 ° C.

0075Table 2 below indicates the variation of the properties described in the case of Example 2.<tables id="tabl0002" num="0002"><table frame="all"><title><b>Table 2</b></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="14mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="14mm" /><colspec colnum="4" colname="col4" colwidth="14mm" /><colspec colnum="5" colname="col5" colwidth="14mm" /><colspec colnum="6" colname="col6" colwidth="14mm" /><thead><row><entry namest="col1" nameend="col2" align="center" valign="top">TL (%)</entry><entry namest="col3" nameend="col4" align="center" valign="top">R_vs (Ω)</entry><entry namest="col5" nameend="col6" align="center" valign="top">ε_not (%)</entry></row><row><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry></row></thead><tbody><row><entry>76,9</entry><entry>77,5</entry><entry>5,0</entry><entry>4,6</entry><entry>5,5</entry><entry>5,1</entry></row></tbody></tgroup></table></tables>

0076The variations in square resistance and emissivity, which are fairly comparable with those induced by infrared laser treatment, again show an increase in the crystallization rate of the silver layer.

EXAMPLE 3

0077A substrate identical to that treated according to Examples 1 and 2 undergoes in the context of this example a heating carried out using a plasma torch. Plasma gas is a mixture of argon or nitrogen with hydrogen in a 4: 1 ratio.

0078The plasma torch, with a power of 25 to 40 kW, is mounted on a rapid displacement device (of the order of 1 to 4 meters / second) in a direction perpendicular to the direction of travel of the substrate. The width of the area affected by the plasma torch is approximately 3 to 10 mm.

0079The temperature of the glass substrate during processing does not exceed 90 ° C.

0080Table 3 below presents the variations due to heating in terms of light transmission, square resistance and normal emissivity.<tables id="tabl0003" num="0003"><table frame="all"><title><b>Table 3</b></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="14mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="14mm" /><colspec colnum="4" colname="col4" colwidth="14mm" /><colspec colnum="5" colname="col5" colwidth="14mm" /><colspec colnum="6" colname="col6" colwidth="14mm" /><thead><row><entry namest="col1" nameend="col2" align="center" valign="top">TL (%)</entry><entry namest="col3" nameend="col4" align="center" valign="top">R_vs (Ω)</entry><entry namest="col5" nameend="col6" align="center" valign="top">ε_not (%)</entry></row><row><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry></row></thead><tbody><row><entry>77,0</entry><entry>78,5</entry><entry>5,0</entry><entry>4,4</entry><entry>5,5</entry><entry>4,9</entry></row></tbody></tgroup></table></tables>

0081Table 4 below details the same properties, but for a stack in which the silver layer has a thickness of 15 nm.<tables id="tabl0004" num="0004"><table frame="all"><title><b>Table 4</b></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="14mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="14mm" /><colspec colnum="4" colname="col4" colwidth="14mm" /><colspec colnum="5" colname="col5" colwidth="14mm" /><colspec colnum="6" colname="col6" colwidth="14mm" /><thead><row><entry namest="col1" nameend="col2" align="center" valign="top">TL (%)</entry><entry namest="col3" nameend="col4" align="center" valign="top">R_vs (Ω)</entry><entry namest="col5" nameend="col6" align="center" valign="top">ε_not (%)</entry></row><row><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry></row></thead><tbody><row><entry>71,0</entry><entry>72,0</entry><entry>2,2</entry><entry>2,0</entry><entry>2,4</entry><entry>2,2</entry></row></tbody></tgroup></table></tables>

0082As in the case of Examples 2 and 3, heating induces an improvement in properties, a sign of better crystallization of the silver layer.

EXAMPLE 4

0083The same coated substrate as that treated in Examples 1, 2 and 3 undergoes in the context of this example heating using flames. The fuel is propane, the oxidizer being air. Oxygen also provides good results.

0084The coated substrate, after deposition within the magnetron deposition enclosure, is moved at constant speed under a fixed flame bench whose width is greater than or equal to the width of the substrate, the latter traveling at a speed of between 2 and 10 meters / minute under the bench. The layer to be treated is placed at the hottest area of ​​the flame.

0085The temperature of the glass substrate during processing does not, however, exceed 100 ° C.

0086Table 5 below also shows a favorable development in the crystallization of the silver layer.<tables id="tabl0005" num="0005"><table frame="all"><title><b>Table 5</b></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="14mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="14mm" /><colspec colnum="4" colname="col4" colwidth="14mm" /><colspec colnum="5" colname="col5" colwidth="14mm" /><colspec colnum="6" colname="col6" colwidth="14mm" /><thead><row><entry namest="col1" nameend="col2" align="center" valign="top">TL (%)</entry><entry namest="col3" nameend="col4" align="center" valign="top">R_vs (Ω)</entry><entry namest="col5" nameend="col6" align="center" valign="top">ε_not (%)</entry></row><row><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry></row></thead><tbody><row><entry>77,0</entry><entry>78,2</entry><entry>5,1</entry><entry>4,5</entry><entry>5,6</entry><entry>5,0</entry></row></tbody></tgroup></table></tables>

EXAMPLE 5 (comparative)

0087A substrate coated with a stack comprising a silver layer already described in Examples 1, 2, 3 and 4, but in which the thickness of the silver layer is 9 nm, is moved after deposition in a series lamps emitting infrared radiation and indiscriminately heating the layer as the substrate.

0088The lamp power was about 150 kW / m² and the wavelength of the emitted radiation between 1 and 3 micrometers.

0089Table 6 below shows that heating with the lamps significantly improves the crystallization of the silver layers.

0090The temperature of the substrate at the level of the face opposite the face carrying the layer stack, however, exceeded 300 ° C. during the treatment, causing breakage of the majority of the treated glass sheets.<tables id="tabl0006" num="0006"><table frame="all"><title><b>Table 6</b></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="14mm" /><colspec colnum="2" colname="col2" colwidth="14mm" /><colspec colnum="3" colname="col3" colwidth="14mm" /><colspec colnum="4" colname="col4" colwidth="14mm" /><colspec colnum="5" colname="col5" colwidth="14mm" /><colspec colnum="6" colname="col6" colwidth="14mm" /><thead><row><entry namest="col1" nameend="col2" align="center" valign="top">TL (%)</entry><entry namest="col3" nameend="col4" align="center" valign="top">R_vs (Ω)</entry><entry namest="col5" nameend="col6" align="center" valign="top">ε_not (%)</entry></row><row><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry><entry valign="top">before</entry><entry valign="top">after</entry></row></thead><tbody><row><entry>77,2</entry><entry>78,5</entry><entry>4,6</entry><entry>3,8</entry><entry>5,1</entry><entry>4,3</entry></row></tbody></tgroup></table></tables>