Method for obtaining a substrate provided with a coating

C. 02823906 2013-07-04 1 W02012/120238 PCT/FR2012/050476 METHOD Of OBTAINING A SUBSTRATE With A COATING The invention relates to the thermal treatment of substrates with coatings using a laser radiation.

We know applications WO 2008/096089, WO 2010/139908 or WO 2010/142926 methods of heat treatment by laser radiation of coatings deposited on substrates, in particular glass.

The cured coatings include, for example, thin layers of silver, titanium oxide, or oxides, transparent électroconducteurs (100).

The laser radiation allows to heat quickly between the layers, and to improve their electronic conductivity or emissivity (for the layers of silver or TCO) or their photocatalytic activity (for layers of titanium oxide).

The rapid heating of the layers does not heat substantially in the substrate, which is not subject to strong constraints, thermo-mechanical, and can be immediately handled and stored without cooling stage slow and controlled, as is the case for treatments of annealing classics.

The invention aims to improve this process in order to be able to use lasers less powerful and therefore less expensive for the same processing speed, or be able to cure coatings more quickly for a same laser power, or even to be able, at the same processing speed and same laser power, further improving the properties of the cured coatings.

To this end, one aspect of the invention is a process for obtaining a substrate provided on at least one of its faces with a coating, comprising a step of depositing said coating and then a step of thermal treatment of said 2 coating using a laser beam, main, the said process being characterized in that at least a portion of the laser radiation the main transmitted through said substrate and/or reflected by said coating is redirected in the direction of the said substrate to form at least a laser radiation of secondary.

Another object of the invention is a process for obtaining a substrate provided on at least one of its faces with a coating, comprising a step of depositing said coating and then a step of thermal treatment of said coating using a laser radiation to the primary, in which at least a portion of the laser radiation the main transmitted through said substrate and/or reflected by said coating is redirected in the direction of the said substrate to form at least a laser radiation secondary, the angle formed by the radiation of principal and/or the secondary radiation and the normal to the substrate being nonnul.

The inventors have been able to highlight the fact that according to the nature of the coatings and the wavelength of the laser radiation, the major part of the laser radiation was transmise through the substrate or reflected by the coating, and therefore not used for the treatment of the coating.

Recovering at least a portion of this radiation is lost and redirecting the substrate, the treatment is significantly improved.

The choice to use the radiation of the main transmitted through the substrate (transmission mode ) or the radiation of the primary reflected by the stack (reflection mode ), or possibly use both, depends on the nature of the layer and the wavelength of the laser radiation.

Typically, we will choose the reflection mode if the wavelength of the laser reflection CA 2823906 2018-12-12 2a by the stack is greater than the square of the transmission through the substrate.

According to a first embodiment ( reflection mode ), a single secondary radiation is formed, from the portion of the laser radiation is primary reflected by the coating. This is typically the case when the coating includes at least one layer of silver, and that the wavelength of the laser is included in a domain ranging from 500 (in particular 700) to 2000 nm.

According to a second embodiment ( transmission mode ), a single secondary radiation is formed, from the portion of the laser radiation the main transmitted through the substrate.

CA 2823906 2018-12-12 C. 02823906 2013-07-04 3 W02012/120238 PCT/FR2012/050476 According to a third embodiment (which combines the modes of reflection and transmission ), we form two secondary radiation, one from the portion reflected back by the stack, the other from the part transmitted through the substrate.

The reflection mode will be preferentially used for coating highly reflective to the wavelength of the laser, typically, whose reflection is at least 20%.

The coating can be a thin layer of individual, or, more often, a stack of thin layers, at least one of which sees its properties improved by the heat treatment.

In the framework of the reflection mode , it is preferable that the reflection of the radiation of the primary coating due to the layer included in the coating and the properties of which are improved by the heat treatment.

This avoids having to design in a stack of layers of which the sole purpose is to reflect the radiation, but whose presence would ultimately be undesirable in the finished product.

We prefer instead to take advantage of the natural reflection of the layer to be processed. For example, when the stack contains a reflective layer (usually silver) on which they wish to improve the properties of crystallization, it is preferable to redirect to the stacking of the radiation of the primary reflected by the reflective layer itself, rather than by layers arranged under the reflective layer.

The substrate is preferably glass or organic polymeric substrate.

It is preferably transparent, colorless (it is then a clear glass or extra-clear) or colored, for example blue, grey, green or bronze.

The glass is preferably of the type silico-sodo-calcic, but C. 02823906 201_37-04 4 W02012/120238 PCT/FR2012/050476 it can also be glass type borosilicate or alumino-borosilicate glass.

The organic polymeric preferred are polycarbonate, polymethyl methacrylate, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or fluorinated polymers such as ethylene-tetrafluoroethylene (ETFE).

The substrate has advantageously at least one dimension greater than or equal to 1 m, or 2 m and even 3 m

The thickness of the substrate generally varies between 0.5 mm and 19 mm, preferably between 0.7 and 9 mm, in particular between 2 mm and 8 mm, or even between 4 and 6 mm.

The substrate can be planar or curved, or even flexible.

The glass substrate is preferably of the type float, that is to say, likely to have been obtained by a process consisting in pouring the molten glass on a bath of melting tin bath, float ).

In this case, the layer to process can as well be deposited on the face of tin on the face of atmosphere of the substrate.

Means faces atmosphere, and tin , the sides of the substrate having been respectively in contact with the atmosphere reigning in the bath float and in contact with the molten tin.

The front tin contains a small amount of superficial tin having diffused into the glass structure.

The glass substrate may also be obtained by rolling between two rolls, a technique to, in particular, to print patterns on the surface of the glass.

The coating treated includes preferably a thin layer selected from the layers of silver, the oxide layers of titanium and layers of transparent electroconductive.

The coating is advantageously a coating low-emitting, such that the emissivity is at most 20% or 10%, for example comprising at least a layer of silver.

These coatings typically exhibit strong reflection for the wavelengths of laser ranging C. 02823906 2013-07-04 W02012/120238 PCT/FR2012/050476 between 700 and 2000 nm so that the processing efficiency is greatly improved through the invention.

Preferably, the step of thermal treatment does not work with fusion, even partial, of layers 5 are present in the stack.

The heat treatment allows then to make an energy sufficient to promote the crystallization of the thin layer by a mechanism physico-chemical crystal growth around germs already present in the layer, while remaining in the solid phase.

This treatment does not work mechanism of crystallization by cooling from a molten material, on the one hand because it would require extremely high temperatures, and on the other hand, it would be liable to modify the thicknesses or the refractive indices of the layer, and thus their properties, for example, by altering their optical appearance.

The layered transparent electroconductive are typically based on mixed oxides of tin and indium (referred to as ITO ), based on mixed oxides of indium and zinc (called IZO ), based on zinc oxide doped with gallium or aluminum, based on titanium oxide doped with niobium, based stannate cadmium or zinc, oxide tin doped with fluorine and/or antimony.

These different layers have the distinction of being the transparent layers and nevertheless conductive or semiconductor, and are used in many systems in which these two properties are necessary: - screens (LCD), solar collectors, or photovoltaic devices électrochromes or light emitting diodes (including LED, OLED)...

Their thickness, generally driven by the resistance the square desired, is typically between 50 and 1000 nm, terminals included.

For the layers of ITO, is preferably used as the transmission mode (reuse of any part of the C. 02823906 201_37-04 6 W02012/120238 PCT/FR2012/050476 radiation main transmitted through the substrate), with a wavelength included in a domain ranging from 400 to 1200 nm, in particular from 800 to 1000 nm.

In the case of oxide layers of zinc or tin, we will use advantageously the transmission mode , with a wavelength included in a domain ranging from 400 nm to 12 micrometers, particularly from 1 to 12 micrometers.

The thin layers silver-based metal, but also on the basis of molybdenum or niobium metal, have properties of electrical conduction and reflection of infrared radiation, hence their use in glazings for solar control, especially anti-solar (designed to reduce the amount of solar energy incoming) or low-emissivity (in order to decrease the amount of energy dissipated to the outside of a building or a vehicle).

Their thickness, physical is typically between 4 and 20 nm (terminals included).

The stacks low-emissive, can frequently consist of several layers of silver, typically 2 or 3.

The or each silver layer is generally surrounded by layers of dielectric protecting them from corrosion and allows to adjust the appearance in reflection of the coating.

For the layers of silver whose thickness is at least 11 nm, is preferably used in the reflection mode ), with a wavelength ranging from 400 (in particular 700) to 2000 nm, or from 800 to 1200 nm (in particular 1000 nm).

In the case of layers of silver whose thickness is less than 11 nm and in the case of layers of niobium is preferably used in the transmission mode , with a wavelength ranging from 400 (in particular 700) to 2000 nm, or from 800 to 1200 nm (in particular 1000 nm).

The thin layers based on titanium oxide have the particularity of being self-cleaning, by facilitating the degradation of organic compounds under the action of C. 02823906 2013-07-04 7 W02012/120238 PCT/FR2012/050476 ultraviolet radiation and the removal of dirt, mineral (dust) under the action of runoff water.

Their thickness physical, is preferably between 2 and 50 nm, especially between 5 and 20 nm, terminals included.

For this type of layers, we will use preferentially the transmission mode , with a wavelength included in a domain ranging from 400 nm to 12 micrometers, in particular 500 to 1000 nm.

The different layers have the common feature to see some of their properties improved when they are in a state at least partially crystallized.

It generally seeks to increase the maximum rate of crystallization of these layers (the proportion of mass or volume of material crystallized) and the size of the crystalline grains (or the size of areas of coherent diffraction patterns measured by the methods of X-ray diffraction), and in certain cases even to promote a form crystallographic particular.

In the case of titanium oxide, it is known that titanium oxide crystallized in the form of anatase is much more efficient in term of degradation of the organic compounds as the titanium oxide, amorphous or crystallized in the form of rutile or brookite.

It is also known that the layers of silver with a rate of crystallization high and consequently a low residual content of silver, amorphous, exhibit an emissivity and a resistivity lower than that of layers of silver predominantly amorphous.

The electrical conductivity and the properties of low emissivity of these layers are thus improved.

Similarly, the layers of transparent conductive described above, including those of zinc oxide-based doped layer or layers of indium oxide doped with tin have a C. 02823906 2013-07-04 8 W02012/120238 PCT/FR2012/050476 electrical conductivity much greater than their rate of crystallization is high.

Preferably, when the coating is conductive, its resistance square is decreased by at least 10%, even 15% or even 20% by the heat treatment.

This is a relative decrease, compared to the value of the resistance square before treatment.

The use of a laser radiation has the advantage of obtaining temperatures generally below 100 C, and even often below 50 C at the level of the face opposite to the first side of the substrate (that is to say at the level of the face not coated).

This feature is especially advantageous is due to the fact that the coefficient of heat exchange is very high, typically greater than 400 W/(m2.$). The power flux density of the laser radiation at the level of the stack to be treated is preferably greater than or equal to 20 or 30 kW/cm2.

This very high energy density allows to achieve at the level of the coating to the desired temperature extremely rapidly (generally in a time less than or equal to 1 second) and consequently to limit the duration of the treatment, the heat generated in there being no time to diffuse within the substrate.

Thus, each point of the coating is preferably subjected to the treatment according to the invention (and in particular brought to a temperature greater than or equal to 300 C) for a duration generally less than or equal to 1 second or even 0.5 seconds. Conversely, the infrared lamps conventionally used (without a device to focus the radiation) does not allow to achieve these high powers per unit area, the treatment time must be longer to reach the desired temperatures (often several seconds), and the substrate is then necessarily heated to high temperatures by C. 02823906 2013-07-04 9 W02012/120238 PCT/FR2012/050476 diffusion of the heat, even if the wavelength of the radiation is adapted to be absorbed by the coating and not the substrate.

Thanks to the very high coefficient of thermal exchange associated with the process according to the invention, the portion of the glass located 0.5 mm from the coating is not subjected to generally not at a temperature higher than 100 C.

The temperature of the face of the substrate opposite the face treated by the at least one laser radiation does not exceed preferably not 100 C, in particular 50 C and 30 C during the thermal treatment.

For simplicity of implementation increased, the lasers employed in the context of the invention may be fiber, which means that the laser radiation is injected into an optical fiber and then delivered close to the surface to be treated by a head of focus.

The laser can also be fiber, in the sense in which the environment of amplification is itself an optical fiber.

The laser beam can be punctual, in which case it is necessary to provide a system for moving the laser beam in the plane of the substrate.

Preferably, however, the laser radiation is the main is derived from at least one laser beam forming a line (called line laser in the following text) that simultaneously irradiates all or part of the width of the substrate.

This mode is preferred because it avoids the use of transport systems that are expensive, usually bulky, and maintenance tricky.

The laser beam in the line may in particular be obtained using systems of laser diodes of high power are associated with an optical focusing system.

The thickness of the line is preferably between 0.01 and 1 mm.

The length of the line is typically between 5 mm and 1 m.

The profile of the line may especially be a Gaussian curve or a niche.

C. 02823906 2013-07-04 W02012/120238 PCT/FR2012/050476 line laser irradiating simultaneously the whole or part of the width of the substrate can be composed of a single line (irradiating the entire width of the substrate), or several lines, possibly disjoint.

When 5 several lines are used, it is preferable that they be arranged so that the entire surface of the stack to be processed.

The or each line is preferably arranged perpendicular to the direction of travel of the substrate, or arranged obliquely.

The 10 different lines may treat the substrate simultaneously or staggered in time.

The important thing is that the surface to treat is.

In order to treat the entire surface of the layer, there is preferably implemented a relative displacement between the substrate and the or each laser line.

The substrate can thus be put in the move, including moving in translation in front of the line laser fixed, generally below but optionally above the laser line.

This embodiment is particularly important for a continuous treatment.

Alternatively, the substrate may be fixed and the laser can be mobile.

Preferably, the difference between the respective speeds of the substrate and of the laser is greater than or equal to 1 meter per minute, or even 4 and even 6, 8, 10, or 15 meters per minute, to ensure a high processing speed.

When the substrate is moving, especially in translation, it can be put into motion with the aid of any mechanical means for conveying, for example, using tape, rollers, trays, in translation.

The conveying system allows to control and regulate the speed of the movement.

If the substrate organic polymeric flexible, the displacement can be made to C. 02823906 2013-07-04 11 W02012/120238 PCT/FR2012/050476 using a system of advance of film in the form of a succession of rollers.

The laser can also be set in motion so as to adjust its distance from the substrate, which may be useful in particular when the substrate is convex, but not only.

In effect, it is preferable that the laser beam is focused on the coating process so that the latter is located at a distance less than or equal to 1 mm from the focal plane.

If the system of moving the substrate or the laser is not sufficiently precise as to the distance between the substrate and the focal plane, should preferably be able to adjust the distance between the laser and the substrate.

This adjustment may be automatic, in particular regulated through a measure of the distance upstream of the treatment.

When the laser line is moving, it is necessary to provide a system for moving the laser, located above or below the substrate.

The duration of treatment is regulated by the speed of movement of the laser line.

All the relative positions of the substrate and the laser are of course possible, as long as the surface of the substrate can be suitably Irradiated.

The substrate will be the most generally disposed in a horizontal manner, but it can also be arranged vertically, or according to any inclination possible.

When the substrate is disposed horizontally, the laser is generally disposed so as to irradiate the upper face of the substrate.

The laser may also irradiate the Lower face of the substrate.

In this case, it is necessary that the support system of the substrate, optionally the conveying system of the substrate when the latter is in motion, lets pass the radiation in the area to be irradiated. This is for example the case when using rollers for conveyor : the roller being C. 02823906 2013-07-04 12 W02012/120238 PCT/FR2012/050476 disjoint, it is possible to have the laser in a zone between two rolls in succession.

When the two faces of the substrate are to be treated, it is possible to use several lasers located on both sides of the substrate, whether the latter is in a horizontal position, vertical position, or according to any inclination.

These lasers can be identical or different, in particular their wavelengths may be different, especially adapted to each of the coatings process. For example, a prime coating (for example, low-emissive) located on a first side of the substrate can be processed by a first laser radiation emitting for example in the visible or near-infrared, while a second coating (e.g. a coating of photocatalytic) located on the second side of said substrate can be processed by a second laser, emitting for example in the far infrared.

The device of radiation, for example the laser line, can be integrated in a line of depositing layers of, for example, a line of deposit, by sputtering assisted by a magnetic field (a process magnetron), or a line of chemical vapor deposition (CVD), including plasma-assisted (PECVD), vacuum or atmospheric pressure (APPECVD).

The line comprises, in general, of devices for handling the substrates, a drop-off facility, control devices, optical devices and stacking.

The substrates parade, for example, on roller conveyors, successively in front of each device or each facility.

The device of radiation, for example the laser line, is preferably located just after the installation of the deposit of the coating, for example at the output of the drop-off facility.

The coated substrate may thus be treated in line after the deposit of the coating, C. 02823906 2013-07-04 13 W02012/120238 PCT/FR2012/050476 the output of the installation deposit and before the devices of optical control, or after the devices of optical control and before the devices for stacking the substrates.

The device of radiation can also be integrated into the installation repository.

For example, the laser can be introduced in one of the rooms of a facility to deposit by sputtering, especially in a room where the atmosphere is rarefied, in particular under a pressure of between 10-6 mbar and 10-2 mbar.

The laser may also be disposed outside of the installation deposit, but to treat a substrate located inside said installation.

It is sufficient to lay a transparent window at the wavelength of the radiation used, through which the laser beam would treat the layer.

It is thus possible to treat a layer (e.g. a layer of silver) prior to the subsequent deposit of another layer in the same installation.

The device of radiation, either outside or integrated into the installation repository, these processes online are preferable to a process that is in recovery in which it would be necessary to stack the glass substrates between the plating step and the heat treatment.

The processes in recovery may, however, have an interest in the case where the implementation of the heat treatment according to the invention is made in a different place from the one where is made the deposit, for example in a place where is achieved the transformation of glass.

The device of radiation can therefore be integrated with other lines than the line of deposition of the layers.

It may for example be integrated in a production line for glazing multiple (double or triple glazing), or to a line for manufacturing laminated glass.

In these different cases, the heat treatment according to the invention C. 02823906 2013-07-04 14 W02012/120238 PCT/FR2012/050476 is preferably carried out before the completion of the glazing, multiple or laminated.

The deposit of the stack on the substrate can be achieved through any type of process, in particular processes generating layers are mostly amorphous or nano-crystallized, such that the process of sputtering, in particular assisted by magnetic field (a process magnetron), the method of chemical deposit in vapour phase assisted by plasma (PECVD), the process of vacuum evaporation or the sol-gel process.

The stack is preferably deposited by sputtering, particularly assisted by a magnetic field (a process magnetron).

For simplicity, the laser treatment of the layer is preferably in air and/or atmospheric pressure.

However, it is possible to conduct the thermal treatment of the layer within the enclosure of vacuum deposition, for example before a subsequent deposit.

The wavelength of the laser radiation is preferably between 500 and 2000 nm, especially between 700 and 1100 nm.

This domain of wavelengths is particularly well suited to the case of layers of silver.

The absorption of the coating at the wavelength of the laser, defined in the usual way as being the complement to 100% of the reflection and the transmission, is advantageously of at least 20%, in particular 30%.

On the contrary, the glass (especially clear glass or extra-clear), and most plastics only absorb light in this wavelength so that the substrate is only slightly heated by the radiation.

One uses preferably laser diodes, emitting for example at a wavelength of the order of 808 nm, 880 nm, 915 or 940 nm or 980 nm.

In the form of systems of diodes, very high powers can C. 02823906 2013-07-04 W02012/120238 PCT/FR2012/050476 be obtained, allowing to reach powers surface at the level of the stack to handle higher than 20 kW/cm2, even 30 kW/cm2.

The laser secondary is preferably 5 formed in the reflective part of the laser radiation the main transmitted through the substrate and/or reflected by the at least one coating with the aid of at least one mirror or at least one prism, and possibly of at least one lens.

10 Preferably, the formation of the or of each laser radiation and the secondary puts it in the implementation of an optical assembly comprising optical elements selected from among the mirrors, the prisms and the lenses, preferably an assembly consisting of two mirrors and a 15 lens, or a prism and a lens.

In this way, the optical assembly is totally independent of the wavelength of the laser, unlike the case where the assembly includes elements such as beam splitters or blades to delay (the blades quarter-wave, half-wave...).

It is thus possible to use the same optical assembly for different lasers.

The laser secondary is preferably not polarized.

The optical assembly used to train and redirect the laser radiation to the secondary is thus considerably simplified, avoiding elements such as beam splitters or blades to delay (the blades one-quarter wavelength, which can only work to a wavelength-specific, and leads to loss of power.

The angle formed by the radiation of primary (and/or the secondary radiation) and the normal to the substrate is preferably non-zero, typically less than 45 , in particular between 8 and 13 , in order to prevent damage to the laser by the reflection of the radiation, primary or secondary.

C. 02823906 2013-07-04 16 W02012/120238 PCT/FR2012/050476 For the same reasons, it is preferable that the angle formed by the radiation and the normal to the substrate is different from the angle formed by the secondary radiation (transmission mode ) or reflected from the secondary radiation (in reflection mode ) and the normal to the substrate.

To improve the effectiveness of the treatment, the laser radiation secondary has preferably the same profile as the laser radiation the main.

In order to strengthen the effectiveness of the treatment, it is preferable that the laser radiation and secondary impacts the substrate at the same location as the laser main.

By the same place , it is meant that the two radiations are at a distance of at most 0.1 mm, or 0.05 mm (distance measured on the treated surface).

To optimize the effectiveness of the treatment, the depth of focus of the laser radiation and the secondary is advantageously the same as that of the laser radiation the main.

Different optical assemblies to implement the process according to the invention are illustrated by the Figures 1 to 3.

In a first mount (not shown), a portion of the radiation from the primary is reflected by the coating, and a single mirror is disposed so as to reflect this radiation toward the substrate.

Preferentially, the radiation primary and secondary radiation to impact the coating at the same place.

This assembly is very simple, includes only one mirror. The angle formed by the radiation and the normal to the substrate is preferably non-zero, so as to prevent damage to the laser by the reflection of the radiation main.

This angle is preferably less than 45 , typically between 2 and 20 , in particular between 8 and 13 .

This assembly is advantageously used for piles C. 02823906 2013-07-04 17 W02012/120238 PCT/FR2012/050476 highly reflective, such as stacks containing at least one layer of silver.

A second assembly, useful as, but not limited to, coatings, highly reflective, is shown in Figure 1.

It is to have a first mirror 8 that returns the radiation to the primary reflected to a second mirror 10, which forms by reflection, the secondary radiation 6, 7.

A lens may be used to adjust the secondary radiation 7 and the focus to the precise location where the radiation main 4 impacts the cladding 2 (again with a tolerance of at most 0.1 mm, or 0.05 mm).

More specifically, a laser 3 emits a radiation main 4 (typically a laser line) to the substrate 1 coated with its stack 2, the radiation 4 forming with the normal to the substrate 1 with an angle 01.

A portion of this radiation main 4 is reflected by the stack 2, in the form of a radiation 5, which also forms with the normal to the substrate with the same angle 01. The angle 01 is non-zero, in particular between 5 and 15 , or between 8 and 13 , so as to avoid that the radiation 5 vienna damage to the laser 3.

The portion reflected back 5 is then in turn reflected by a first mirror 8, and then by a second mirror 10, so as to form a secondary radiation 6, 7, which is focused using a lens 11 toward the coating 2.

The radiation 5 and 9 form with the normal to the first mirror 8 to an angle 92 of non-zero, typically between 5 and 15 , in particular between 8 and 13 .

This assembly is a little more complex than the first assembly, but is advantageous in that the part 12 of the secondary radiation reflected by the coating 2 may not damage the laser 3, the fact that the angle 94 between the secondary radiation 7 and the normal to the substrate 2 is C. 02823906 2013-07-04 18 W02012/120238 PCT/FR2012/050476 greater than the angle 01. The angle 64 is preferably between 10 and 20 , in particular between 13 and 18 .

By a simple adjustment of the orientation of the mirrors 8 and 10, and therefore of the angles 62 and 63, the secondary radiation 7 may impact the coating 2 in exactly the same place as the radiation main 4.

According to a variant of this second assembly, which is illustrated by Figure 2, the first and the second mirror are replaced by a prism 13, which has the advantage of greater ease of adjustment.

Figure 3 illustrates a third assembly, implementing the transmission mode of the process according to the invention, useful for the treatment of coatings little reflective.

In this embodiment, the part 14 of the radiation main 4 transmitted through the substrate 1 is reflected by a first mirror 15, and then by a second mirror 17, to form a secondary radiation 18, which after focusing using a lens 19, is going to impact the coating 2 in the same place as the primary reach 4. The use of two mirrors allows you to choose angles 95 and 96 (between the radiation 16 and the normal to the mirrors, respectively, 15 and 17) non-null, it is the angle 94 between the part transmitted of the secondary radiation 18 and the normal to the substrate 1 different from the angle 01.

Such an assembly allows again to avoid damaging the laser 3 by direct reflection of the radiation transmitted 14.

According to a variant not represented, the substrate 1 may be provided on the face opposite to that bearing the coating 2, coating 2', identical or different, which can also be treated at the same time as the coating 2.

In order to further improve the final properties of the coating, the substrate can undergo a quenching step C. 02823906 2013-07-04 19 W02012/120238 PCT/FR2012/050476 after the step of heat treatment according to the invention.

Thermal tempering will generally be carried out after cutting the glass to the final dimensions desired.

When the coating process is a stacking low-emissive, it includes preferably, from the substrate, a first coating layer comprising at least a first dielectric layer, at least one silver layer, optionally a layer of on-blocker and a second coating layer comprising at least a second dielectric layer.

Preferably, the thickness of the or of each silver layer is between 6 and 20 nm.

The layer of on-blocker is intended to protect the silver layer during deposition of a subsequent layer (for example, if the latter is filed under oxidizing atmosphere or nitrurante) and during a possible heat treatment of type tempering or bending.

The layer of silver can also be deposited on and in contact with a layer of sub-blocker.

The stack may include a layer of surbloqueur and/or a layer of sub-blocker flanking the or each silver layer.

The layers of the blocker (sub-blocker and/or surbloqueur) are usually based on a metal chosen among nickel, chromium, titanium, niobium, or an alloy of these different metals.

Examples include alloys of nickel-titanium (including those comprising about 50% by weight of each metal) or nickel-chromium alloys (especially those comprising 80% by weight of nickel and 20% chromium).

The layer of surbloqueur can still be made up of several superimposed layers, for example, by moving away from the substrate, titanium and a nickel alloy (including an alloy C. 02823906 2013-07-04 W02012/120238 PCT/FR2012/050476 nickel-chromium), or the reverse.

The various metals or alloys mentioned can also be partially oxidized, in particular, present a sub-stoichiometry in oxygen (for example TiO. or NiCr0.).

5 These layers of blocker (sub-blocker and/or surbloqueur) are very fine, normally of a thickness of less than 1 nm, so as not to affect the light transmission of the stack, and are likely to be partially oxidized during the heat treatment according to 10 the invention. In general the layers of the blocker layers are sacrificial, that capture oxygen from the atmosphere or from the substrate, thus avoiding the oxidation of the silver layer.

The first and/or second dielectric layer 15 is typically in the oxide (especially tin oxide), or preferably a nitride, especially silicon nitride (in particular for the second dielectric layer, most distant from the substrate). In general, the silicon nitride may be doped with, for example, 20 of aluminum or boron, in order to facilitate its deposition by the techniques of sputtering.

The rate of doping (corresponding to the atomic percentage relative to the amount of silicon) generally do not exceed 2%.

These layers of dielectric have the function of protecting the silver layer from chemical attack or mechanical and also influence the optical properties, in particular in reflection, of the stack, thanks to phenomena interferential.

The first coating may include a dielectric layer, or several layers of dielectric, typically 2 to 4.

The second coating may include a dielectric layer, or several layers of dielectric, typically 2 to 3.

These layers of dielectric are preferably of a material selected from the nitride C. 02823906 2013-07-04 21 W02012/120238 PCT/FR2012/050476 of silicon, oxides of titanium, tin or zinc, or any of their mixtures or solid solutions, for example an oxide of tin and zinc, or an oxide of titanium and zinc.

In either the first coating or the second coating, the thickness of the dielectric layer, or the thickness overall physical of all of the layers of dielectric, is preferably between and 60 nm, especially between 20 and 50 nm.

The first coating includes preferably 10 immediately under the silver layer, or under any layer of sub-blocker, a layer of wetting, the function of which is to increase the wetting and attachment of the silver layer. Zinc oxide, especially aluminum-doped, proved to be particularly advantageous in this 15 regard.

The first coating may also contain, directly beneath the layer of wetting, a layer of smoothing, which is a mixed oxide partially or even completely amorphous (thus of very low roughness), the function of which is to foster the growth of the layer of wetting according to a crystallographic orientation preference, which promotes the crystallization of the silver by the phenomenon of epitaxy.

The finishing layer is preferably composed of a mixed oxide of at least two metals chosen from Sn, Zn, In, Ga, Sb.

An oxide, preferred is tin oxide and indium doped antimony.

In the first coating, the layer of wetting or the possible finishing layer is preferably deposited directly on the first dielectric layer.

The first dielectric layer is preferably deposited directly on the substrate.

To better adapt the optical properties of the stack (especially the appearance in reflection), the first dielectric layer may C. 02823906 2013-07-04 22 W02012/120238 PCT/FR2012/050476 alternatively be deposited on another layer of oxide or nitride, for example titanium oxide.

Within the second coating, the second dielectric layer can be deposited directly on the silver layer, or preferably on a one-on-pop-up blocker, or on other layers in the oxide or nitride, which are meant to adapt the optical properties of the stack.

For example, a layer of zinc oxide, notably doped with aluminum, or a layer of tin oxide, can be disposed between a blocker and the second dielectric layer, which is preferably silicon nitride.

Zinc oxide, especially aluminum-doped, can improve the adhesion between the silver and the upper layers.

Thus, the stack treated according to the invention includes preferably at least a succession of ZnO / Ag / ZnO. The zinc oxide may be doped with aluminum.

A layer of sub-blocker can be disposed between the silver layer and the underlying layer.

Alternatively or additionally, a layer of on-blocker can be disposed between the silver layer and the layer overlying.

Finally, the second coating may be surmounted by an overlayer, sometimes called the overcoat in the art.

Last layer of the stack, in contact with the ambient air, it is designed to protect the stack against all mechanical damage (scratches etc.) or chemical.

This layer is generally very thin so as not to disturb the appearance in reflection of the stack (its thickness is typically between 1 and 5 nm).

It is preferably based on titanium oxide or a mixed oxide of tin and zinc, in particular doped with antimony, deposited in sub-stoichiometric.

The stack may comprise one or more layers of silver, including two or three layers of silver.

C. 02823906 2013-07-04 23 W02012/120238 PCT/FR2012/050476 When multiple layers of silver are present, the general architecture presented above may be repeated.

In this case, the second coating relating to a layer of money (and therefore located above this silver layer) generally coincides with the first coating on the layer of silver next.

The coated substrates obtained according to the invention can be used in glazing simple or multiple, laminated, mirrors, wall coverings of glass.

If the coating is a stack bottom-emissive, and in the case of a glazing multiple comprising at least two sheets of glass separated by a blade of a gas, it is preferable that the stack is disposed on the face in contact with said blade, gas, in particular, in the face of 2 with respect to the outside (that is to say, on the face of the substrate in contact with the outside of the building, which is opposite to the face facing toward the outside) or on side 3 (i.e. on the face of the second substrate starting from the outside of the building turned toward the outside).

If the coating layer is a photocatalytic, it is preferably arranged in front of 1, so in contact with the exterior of the building.

The coated substrates obtained according to the invention may also be used in cell or glass photovoltaic or solar panels, the coating treated according to the invention being for example an electrode based on Zn : Al or Ga in stacks based chalcopyrites (in particular of the type DIS - CuInSe2) or based on amorphous silicon and/or polycrystalline, or CdTe.

The coated substrates obtained according to the invention can still be used in display monitors of the type LCD (Liquid Crystal Display), OLED (Organic Light Emitting Diodes) or FED (Field Emission C. 02823906 2013-07-04 24 W02012/120238 PCT/FR2012/050476 Display), the coating treated according to the invention being for example a layer électroconductrice in ITO.

They can still be used in glazing électrochromes, the thin layer treated according to the invention being for example a layer électroconductrice transparent as taught in application FR-A-2 833 107, The invention is illustrated using examples of the embodiment are not limited to following.

EXAMPLE 1 On a substrate of clear glass 4 mm thick, marketed under the name SGG Planilux by the applicant, is deposited on a stacking bottom-emissive.

The stack is deposited, in known way, on a line of the sputtering process the magnetron) in which the substrate comes scroll under different targets.

Table 1 indicates the thickness of the physical layers, expressed in nm.

The first line corresponds to the layer the most distant from the substrate, in contact with the open air.

C. 02823906 2013-07-04 WO 2012/120238 PCT/FR2012/050476 ZnSnSbOx 2 Si3N4 :Al 43 ZnO :Al 5 Ti 0,5 Ag 15 ZnO :Al 5 TiO2 11 Si3N4 :Al 14 Table 1 table 2 below summarizes the parameters of the deposit 5 employees for the different layers.

Layer Target used Pressure Gas deposit Si3N4 Si:Al at 92:8 % wt of 1.5.10-3 mbar Ar / (Ar + N2) at 45 -`?, TiO2 TiOx with x 1.5.10-3 mbar Ar / (Ar + 02) in the order of 1.9 95 % ZnSnSbOx SnZn:Sb 34:65:1 2.10-3 mbar Ar / (Ar + 02) wt 58 % ZnO :Al, Zn:Al, 98:2 % wt 2.10-3 mbar Ar / (Ar + 02) to 52% Ti Ti 2.10-3 mbar Ar Ag Ag 2.10-3 mbar Ar at 100 % Table 2-C. 02823906 2013-07-04 26 W02012/120238 PCT/FR2012/050476 The samples are processed using a laser line emitting radiation of a wavelength of 980 nm, in relation to which the coated substrate comes scroll in translation.

The power linear is 40 W/mm, and the thickness of the beam is 63 micrometers.

The power flux density is therefore 63 kW/cm2.

The movement speed of the substrate is 5 m/min.

The coating has, at the wavelength of the laser, and a reflection of 65% and a transmission of 25%.

According to a first configuration, one has in regard to the coating of a mirror for reflecting the radiation main so as to form a secondary radiation that impacts the coating precisely at the same location as the primary reach.

Loss-of-resistance square after the heat treatment is then to 21% in relative.

According to a second configuration, one has in regard to the coating of two mirrors and a lens.

The radiation of the primary, which is reflected by the 20 coating is in turn reflected by the first mirror, and then by a second mirror to a lens disposed so as to re-focus the secondary radiation to the precise location where the radiation main impact on the coating.

Loss-of-resistance square after heat treatment is from 21% to 23% in relative.

Without reuse of the portion reflected back to the primary reach, the loss-of-resistance-square is 18%.

The better efficacy of the treatment associated with this gain in loss-of-resistance square allows you to increase the processing speed of from about 30% to loss equal.

C. 02823906 2013-07-04 27 W02012/120238 PCT/FR2012/050476 EXAMPLE 2 On a substrate of clear glass 4 mm thick, marketed under the name SGG Planilux by the applicant, is deposited on a stacking bottom-emissive.

The stack is deposited, in known way, on a line of the sputtering process the magnetron) in which the substrate comes scroll under different targets.

Table 3 below shows the thickness of the physical layers of the stack, expressed in nm.

The first line corresponds to the layer the most distant from the substrate, in contact with the open air.

ZnSnSb0. 3 Si2N4 :Al 45 ZnO :Al 4 TiOx 2 Ag 6,7 ZnO :Al 5 TiO2 12 Si2N4 :Al 23 Table 3 The parameters of the deposit used for the different layers are those of table 2.

The samples are processed using a laser line emitting radiation of a wavelength of 980 nm, in relation to which the coated substrate comes scroll in translation.

The power linear is 40 W/mm and C. 02823906 2013-07-04 28 W02012/120238 PCT/FR2012/050476 the thickness of the beam is 63 micrometers.

The power flux density is therefore 63 kW/cm'.

The movement speed of the substrate is 7.5 m/min.

The coating has, at the wavelength of the laser, a reflection of 9% and a transmission of 73%.

It has next to the coating of a mirror for reflecting the radiation main so as to form a secondary radiation that impacts the coating precisely at the same location as the primary reach.

Loss-of-resistance square after heat treatment is 21.3% in relative.

Without reuse of the portion reflected back to the primary reach, the loss-of-resistance-square is 18%.

The better efficacy of the treatment associated with this gain in loss-of-resistance square allows you to increase the processing speed of from about 30% to loss equal.

EXAMPLE 3 Is deposited on a substrate of clear glass 4 mm thick, marketed under the name SGG Planilux by the applicant a layer of zinc oxide doped with aluminum with a thickness of 190 nm. The stack is deposited in a manner known, on a line of the sputtering process the magnetron).

The samples are processed using a CO2 laser, emitting in the form of a laser line radiation main of which the wavelength is 10.6 micrometers.

The laser power is 300 W and the line width is of the order of 0.5 mm.

C. 02823906 2013-07-04 29 W02012/120238 PCT/FR2012/050476 the wavelength of the laser, the coating shows a reflection of 18.5% and a transmission of 74.4%.

In a comparative trial, only the primary reach is used to treat the coating.

For a speed of displacement of the substrate under the laser of 1.6 m/s, the gain in resistivity is 57%, the final value being 7.7.10-4 Ç2.cm.

In a test implementing the process according to the invention, are available under the substrate an optical assembly consisting of 2 mirrors and a lens, as depicted in Figure 3, in order to reflect to the substrate the portion transmitted from the radiation main (transmission mode ).

The secondary radiation thus formed affects the substrate in precisely the same place as the primary reach.

The use of the process according to the invention allows to achieve the same gain of resistivity, but with a scroll speed of the substrate of 1.73 m/s, which is an 8% gain in productivity.

EXAMPLE 4 On a substrate of clear glass 4 mm thick, marketed under the name SGG Planilux by the applicant, is deposited on a silica layer of 20 nm thickness and then a thin layer of titanium oxide of 10 nm thickness, and finally a thin layer of titanium of 5 nm thickness. The stack is deposited, in known way, on a line of the sputtering process the magnetron) in which the substrate comes scroll under different targets (in the case of targets of silicon doped with aluminium and titanium).

CA02823M620104 W02012/120238 PCT/FR2012/050476 Between the output of the line magnetron, and the storage device, a transmitting device laser based on laser diodes emitting at a wavelength of 808 nm, produces a laser radiation to a primary focus on 5 the layer of titanium, according to a line corresponding to the width of the substrate.

In a comparative trial, only the primary reach is used to treat the coating.

For a speed of displacement of the substrate under the laser 10 4 m/minute, the photocatalytic activity, measured according to the test described in the application W02011039488 (by monitoring the degradation of stearic acid) is 22.10-4 power linear laser is 37.5 W/mm.

In a test implementing the process according to 15 the invention, are available under the substrate an optical assembly consisting of a prism and a lens, as depicted in Figure 2, in order to reflect to the substrate the portion reflected back to the radiation main (reflection mode ).

The secondary radiation thus formed had an impact on the substrate 20 in precisely the same place as the primary reach.

The use of the process according to the invention allows to achieve the same level of photocatalytic activity, with the same laser power, but with a speed of displacement greater than 4.2 m/min, i.e. a gain of 25 in productivity of 4%.

Conversely, for a same movement speed as for the comparative test (4 m/min), the same level of photocatalytic activity has been obtained, but for a laser power lower, only 36,8 W/mm.