EP2129632A2

EP2129632A2 - Process for fabricating a mask with submillimetre apertures for the production of a submillimetre grid, and submillimetre grid

Info

Publication number: EP2129632A2
Application number: EP08775743A
Authority: EP
Inventors: Emmanuel Valentin; Bernard Nghiem; Arnaud Huignard; Georges Zagdoun; Eddy Royer
Original assignee: Saint Gobain Glass France SAS; Compagnie de Saint Gobain SA
Current assignee: Saint Gobain Glass France SAS; Compagnie de Saint Gobain SA
Priority date: 2007-03-21
Filing date: 2008-03-21
Publication date: 2009-12-09
Also published as: WO2008132397A3; KR20100015787A; WO2008132397A2; KR101496980B1; CN101636361B; CN101636361A; US20100059365A1; JP2010524810A; JP5611602B2; FR2913972A1; FR2913972B1; TWI478886B; TW200902466A

Abstract

Process for fabricating a mask with submillimetre apertures on a surface portion of a substrate, characterized in that a "mask" layer is deposited using a solution of stabilized colloidal particles dispersed in a solvent; and the mask layer is dried until an irregular two-dimensional array of interstices is obtained, having an approximately straight edge, giving a mask with a random mesh of interstices in at least one direction. Submillimetre grid obtained by this process.

Description

Method for manufacturing a mask with submillimeter openings for producing a submillimetric grid, submillimetric grid

The subject of the present invention is a method for producing a mask with submillimeter openings with a view to producing a grid, possibly electroconductive, in particular for an electrochemical device, and / or electrically controllable of the glazing type and having optical properties and / or variable energy, or a photovoltaic device, or a light emitting device, or even a heating device, or possibly a flat lamp device.

Manufacturing techniques are known that make it possible to obtain metal grids of micron size. These have the advantage of achieving surface resistances less than 1 Ohm / square while maintaining a light transmission (TL) of the order of 75 to 85%. However, these grids have a certain number of disadvantages: their method of obtaining is based on a technique of etching a metal layer or by means of a photolithographic process associated with a chemical etching process by a liquid route, either by a laser ablation technique. Whatever the process, it induces a significant manufacturing cost incompatible with the applications envisaged, - the characteristic dimensions of these grids, generally of regular and periodic shape (square, rectangular), constitute networks of metallic strands of 20 to 30 μm wide spaced for example 300 microns, which are originally, when illuminated by a point light source, diffraction patterns. These manufacturing techniques of the prior art also have a resolution limit of the order of a few tens of microns, leaving the patterns aesthetically visible. US 7172822 discloses the uneven network conductor construction based on the use of a cracked silica gel sol mask. In the examples carried out, a soil based on water, alcohol and a silica precursor (TEOS) is deposited, the solvent is evaporated and annealed at 120 ^° C. for 30 minutes in order to form the cracked sol-gel mask. 0.4 μm thick.

Figure 3 of this document US7172822 discloses the morphology of the sol gel silica mask. It appears as fine fracture lines oriented in a preferred direction, with bifurcations characteristic of the fracture phenomenon of elastic material. These main fracture lines are linked episodically between them by the bifurcations.

The domains between the fracture lines are asymmetrical with two characteristic dimensions: one parallel to the crack propagation direction between 0.8 and 1 mm, the other perpendicular between 100 and 200 μm.

Moreover, masks that would be based on particles in solution are evoked in a vague way, without concrete examples of implementation. This method of manufacturing an electrode by cracking of the sol gel mask constitutes an advance for the manufacture of a network conductor by eliminating for example the use of photolithography (exposure of a resin to a radiation / beam and development), but can still be improved, especially to be compatible with industrial requirements (reliability, simplification and / or reduction of manufacturing steps, at a lower cost, etc.).

Furthermore, the electrical and / or optical properties of this irregular array electrode can be improved.

It may also be noted that the manufacturing process necessarily requires the deposition of an modifiable sub-layer (chemically or physically) at the interstices to either allow a preferred adhesion (of metal colloids for example) or allow the grafting of catalyst for a post-growth of metal, this sub-layer thus having a functional role in the growth process of the network.

In addition, the crack profile is in fact V fracture mechanics of the elastic material which involves using a post-mask process to grow the metal network from the colloidal particles at the base of V.

The present invention therefore aims at overcoming the drawbacks of the processes of the prior art by proposing a method of manufacturing a submillimeter and irregular network, in particular electroconductive, economical, reproducible, controlled, and whose optical properties and / or properties of electrical conductivity are at least comparable to those of the prior art.

For this purpose, the subject of the invention is firstly a method for manufacturing a mask with submillimeter openings on a surface portion of a substrate, especially with a glass function, comprising the following steps:

a mask layer is deposited on the substrate or on a sub-layer from a solution of colloidal particles stabilized and dispersed in a solvent,

the mask layer is dried until a two-dimensional network of interstices with a substantially straight edge is formed, forming the mask with a random interstice mesh, aperiodic in at least one direction. The average width A is submillimetric

The gap network has significantly more interconnections than the fissured silica gel ground mask. By the method according to the invention, thus forming a mesh of openings, which can be distributed over the entire surface, to obtain isotropic properties. The mask thus has a random, aperiodic structure on at least one direction, or even two (all) directions.

Thanks to this particular process, it is possible to obtain cost, a mask consisting of random patterns (shape and / or size), aperiodic with appropriate characteristic dimensions:

the width (average) of the micron or even nanometric network A, in particular between a few hundred nanometers to a few tens of micrometers, in particular between 200 nm and 50 μm,

- size (average) pattern B millimeter or submillimeter, in particular between 5 to 500 microns, or even 100 to 250 microns,

- Adjustable ratio B / A depending in particular on the nature of the particles, in particular between 7 and 20 or even 40, - difference between the maximum width of openings and the minimum opening width of less than 4, or even less than or equal to 2, in a given region of the mask, even on the majority or the whole surface,

- difference between the maximum mesh size (pattern) and the minimum mesh size of less than 4, or even less than or equal to 2, in a given region of the mask, or even on the majority or even the entire surface,

the open mesh rate (non-emerging gap, "blind"), is less than 5%, or even less than or equal to 2%, in a given region of the mask, or even on the majority or the entire surface, therefore with a rupture limited network see almost zero, possibly reduced, and deleted by burning the network,

for a given mesh, the majority or even all the meshes, in a given region or on the whole surface, the difference between the greatest characteristic dimension of mesh and the smallest characteristic dimension of mesh is less than 2, to reinforce the isotropy,

for the majority or even all the segments of the network, the edges are of constant spacing, parallel, in particular at a scale of 10 μm (for example observed under an optical microscope with a magnification of 200). The width A may be for example between 1 and 20 microns, even between 1 and 10 microns, and B between 50 and 200 microns.

This makes it possible to carry out subsequently a grid defined by a middle strand width substantially the same as the width of the openings and a space (middle) between the strands substantially identical to the space between the openings (of a mesh). In particular, the sizes of the strands may preferably be between a few tens of microns to a few hundred nanometers. The ratio B / A can be chosen between 7 and 20, or even 30 to 40.

The meshes delimited by the openings are of various shapes, typically three, four, five sides, for example mainly four sides, and / or of various sizes, randomly distributed, aperiodic.

For the majority or all the meshes, the angle between two adjacent sides of a mesh can be between 60 ° and 1 10 °, in particular between 80 ° and 100 °.

In one configuration, a main network is obtained with gaps (possibly approximately parallel) and a secondary network of interstices (possibly approximately perpendicular to the parallel network), the location and distance of which are random. The secondary interstices have a width for example less than the main interstices. The drying causes a contraction of the mask layer and a friction of the nanoparticles at the surface inducing a tensile stress in the layer which, by relaxation, forms the interstices.

Unlike silica gel sol, the solution is naturally stable, with nanoparticles already formed, and preferably does not contain (or in negligible amount) polymer-precursor type reactive element.

Drying leads in one step to the removal of the solvent and the formation of the interstices. After drying, clusters of nanoparticles, clusters of variable size and separated by the interstices of variable size, are thus obtained. To obtain the openings over the entire depth, it is necessary at a time:

to choose particles of limited size (nanoparticles), to promote their dispersion, with preferably a characteristic (average) dimension between 10 and 300 nm, or even 50 and 150 nm,

to stabilize the particles in the solvent (in particular by treatment with surface charges, for example by a surfactant, by controlling the pH), in order to prevent them from aggregating with each other, precipitating them and / or They also fall by gravity. In addition, the concentration of particles is adjusted, preferably between 5% and even 10% and 60% by weight, more preferably between 20% and 40%. The addition of binder is avoided.

The solvent is preferably water-based or even entirely aqueous. In a first embodiment, the colloid solution comprises polymeric nanoparticles (and preferably with a water-based or even entirely aqueous solvent)

For example, acrylic copolymers, styrenes, polystyrenes, poly (meth) acrylates, polyesters or mixtures thereof are chosen. In a second embodiment, the solution comprises inorganic nanoparticles, preferably silica, alumina, iron oxide.

The particles having a given glass transition temperature Tg, the deposition and the drying can preferably be carried out at a temperature below said temperature Tg for a better control of the morphology of the grid mask,

The deposition and drying steps of the process may in particular be carried out (substantially) at room temperature, typically between 20 ° and 25 ° C. Annealing is not necessary. The difference between the given glass transition temperature Tg of the particles and the drying temperature is preferably greater than

10 ⁰ C or even 20 ⁰ C. The deposition and drying steps of the process can be carried out substantially at atmospheric pressure rather than vacuum drying for example.

A solution (aqueous or non-aqueous) of colloids can be deposited by a usual liquid route technique.

As wet track technique, known as spin coating (spin coating), curtain (curtain deposition), dip coating (dip coating), spray coating (spray coating), flow coating (runoff). The drying parameters (control parameter), such as the degree of humidity, the drying speed, can be modified to adjust B, A, and / or the B / A ratio.

The higher the humidity (all things being equal), the lower A is. The higher the temperature (all things being equal), the higher B is.

Other control parameters chosen from the coefficient of friction between the compacted colloids can be modified, in particular by nanotexturing of the substrate and the surface of the substrate, the size of the nanoparticles, and the initial concentration of particles, the nature of the solvent, the thickness depending on the deposition technique, to adjust B, A, and / or ratio B / A.

The thickness of the mask can be submicron up to several tens of microns. The greater the thickness of the mask layer, the larger A (respectively B) is.

The higher the concentration (all things being equal), the lower the B / A.

The edges of the mask are substantially straight, that is to say in a mean plane between 80 and 100 ° relative to the surface, or even between 85 ° and 95 °.

Thanks to the straight edges, the discontinuous layer is deposited (no or little deposit along the edges) and the coated mask can be removed. without damaging the grid. For the sake of simplicity, it is possible to favor directional grid material deposition techniques. The deposit can be made both through the interstices and on the mask.

The interstitial network can be cleaned using a plasma source at atmospheric pressure. In addition, it is possible to carry out:

after drying, a heat treatment (local or otherwise) at a temperature above Tg, in particular 3 times at 5 times Tg, and naturally below the melting temperature Tf, or a differential drying of the mask, for example by modifying locally the degree of humidity and / or the temperature.

This makes it possible to modify, locally or over the entire surface, the shape of the patterns and / or the size of the openings.

The pads consist of a mass of nanoparticles: under the action of temperature, these pads are likely to become denser. After densification the size of the pads (B) is decreased: their surface and the thickness are reduced. There is thus by this heat treatment modification in the characteristic dimensions of the mask: ratio between the opening of the stitches and the width of the stitches. The compaction of the mask, in the second advantage, causes an improvement in the adhesion thereof on the substrate which makes it more manipulable (it avoids chipping) while keeping the steps of lift-off possible (simple washing at the same time). water if the colloid was deposited from an aqueous solution). By compaction heat treatment of the colloid mask it is therefore possible to modify - locally or over the entire surface - its characteristic dimensions without resorting to a new mask (photolithography or etching). It is then possible to locally modify the shape of the meshes (width, height) and in the case of a conductive network to create zones with a conductivity gradient. It is possible to heat locally while keeping cold the rest. Preferably, the heating time is adjusted according to the temperature of the treatment. Typically the duration is less than 1 h, preferably 1 min to 20 min.

The modified zone or zones may be peripheral or central, of any form.

The surface for the deposition of the mask layer is film-forming, in particular hydrophilic if the solvent is aqueous. This is the surface of the substrate: glass, plastic (polycarbonate for example) or an optionally added underlayer: hydrophilic layer (silica layer, for example on plastic) and / or alkali barrier layer and / or or adhesion promoting layer of the gate material, and / or electroconductive layer (transparent), and / or decor layer, colored or opaque.

This underlayer is not necessarily a growth layer for electrolytic deposition of the gate material.

Between the mask layer there can be several sub-layers. The substrate according to the invention may thus comprise an underlayer (in particular as a base layer, the closest to the substrate), which is continuous and may be an alkaline barrier. It protects the grid material (pollution that can cause mechanical defects such as delamination) in the case of electroconductive deposition (to form an electrode in particular), and also preserves its electrical conductivity.

The basecoat is robust, easy and fast to deposit according to different techniques. It can be deposited, for example by a pyrolysis technique, especially in the gas phase (technique often referred to by the abbreviation of C. V. D, for "Chemical Vapor

Deposition "). This technique is interesting for the invention because appropriate settings of the deposition parameters make it possible to obtain a very dense layer for a reinforced barrier.

The primer may be optionally doped with aluminum and / boron to make its vacuum deposit more stable. The layer of background (monolayer or multilayer, possibly doped) may be of thickness between 10 and 150 nm, more preferably between 15 and 50 nm.

The bottom layer may preferably be: based on silicon oxide, silicon oxycarbide, layer of general formula SiOC,

based on silicon nitride, silicon oxynitride, silicon oxycarbonitride, layer of general formula SiNOC, in particular SiN, in particular SiaN ₄ . We can particularly prefer a bottom layer

(mainly) silicon nitride Si3N ₄ , doped or not. Silicon nitride is very fast to deposit and forms an excellent barrier to alkalis.

As a promoter layer for adhesion of the metal grid material (silver, gold), especially on glass, it is possible to choose a layer based on NiCr, Ti, Nb, Al or a single or mixed metal oxide, doped or not. , (ITO ...), layer for example with a thickness less than or equal to 5 nm.

If the substrate is hydrophobic, one can add a hydrophilic layer such as a silica layer.

The mask according to the invention therefore makes it possible to envisage, at a lower cost, other shapes, other grid sizes than regular grids with a geometric pattern and while keeping the irregular nature of the conducting network already known but which does not form a grid. wire rack. For the manufacture of a grid from the mask as defined above, the deposition, (in particular) through the interstices of said mask, of a so-called grid material to fill a fraction of the depth of the interstices.

The masking layer (which is optionally a first layer) is removed until the grid is revealed based on said gate material (one or more layers).

The arrangement of the strands can then be substantially the replica of that of the network of openings.

Preferably, the removal is carried out by liquid means, by an inert solvent for the grid, for example with water, acetone, alcohol,

(possibly hot and / or ultrasonically assisted). It is possible to clean the interstitial network prior to developing the deposition of the gate material.

In preferred embodiments of the invention, one or more of the following may also be used: the deposition of the gate material fills both a fraction of the openings of the mask and also covering the surface of the mask,

the deposition of the gate material is a deposition at atmospheric pressure, in particular by plasma, vacuum deposition, sputtering, evaporation. One can thus choose one or more deposition techniques that can be carried out at room temperature, and / or simple (in particular simpler than a catalytic deposition necessarily using a catalyst) and / or giving dense deposits.

The material deposited in the interstices may be chosen from electrically conductive materials.

The gate material may be electrically conductive and is deposited on the gate material electrically conductive material by electrolysis.

The deposit is thus possibly supplemented by an electrolytic recharge by using an electrode made of Ag, Cu, Gold, or another metal of high conductivity that can be used.

If the substrate is insulating, electrolytic deposition can be carried out indifferently before or after removal of the mask.

By varying the ratio B / A (space between the strands (B) over the width of the strands (A) size of the strands) we obtain for the grid fuzziness values between 1 and 20%.

The invention also relates to a substrate carrying a grid irregular, that is to say a network of two-dimensional and meshed strands, with meshes (closed patterns), random, aperiodic.

This grid may in particular be formed from the mask already defined above. The grid may have one and / or the following characteristics:

a space (average) ratio between the strands (B) over the submillimetric width (average) of the strands (A) of between 7 and 40,

the grid patterns are random (aperiodic), of various shape and / or size,

- meshes delimited by the strands are three and / or four and / or five sides, for example mostly four sides,

the grid has an aperiodic (or random) structure in at least one direction, preferably in two directions, for most or all meshes, in a given region or over the entire surface, the gap between the largest dimension mesh characteristic and the smallest characteristic dimension of mesh less than 2,

for most or all meshes, the angle between two adjacent sides of a mesh may be between 60 ° and 110 °, in particular between 80 ° and 100 °,

the difference between the maximum width of strands and the minimum width of strands is less than 4, or even less than or equal to 2, in a given region of the grid, or even on the majority or the whole surface, the distance between the maximum mesh size (space between strands forming a mesh) and the minimum mesh size is less than 4, or even less than or equal to 2, in a given grid region, or even on the majority or even the entire surface,

the rate of non-closed mesh and / or cut strand segment ("blind"), is less than 5%, or even less than or equal to 2%, in a given grid region, or even on the majority or the entire surface area , or a limited network break, see almost zero, - Mostly, the edges of strands are constant spacing, including substantially linear, parallel to the scale of 10 microns (for example observed under an optical microscope with a magnification of 200).

The grid according to the invention may have isotropic electrical properties.

Unlike the networked conductor with a preferred direction, the irregular grid according to the invention can not diffract a point light.

The thickness of the strands may be substantially constant in the thickness, or be wider at the base.

The grid may comprise a main network with strands (possibly approximately parallel) and a secondary network of strands (possibly approximately perpendicular to the parallel network). The grid may be deposited on at least one surface portion of the substrate, in particular with a glass function, plastic or mineral, as already indicated.

The grid may be deposited on a sub-layer, hydrophilic and / or promoter adhesion and / or barrier and / or decor as already indicated. The electro-conductive grid may have a square resistance of between 0, 1 and 30 Ohm / square. Advantageously, the electro-conductive grid according to the invention may have a resistance per square which is less than or equal to 5 Ohm / square, or even less than or equal to 1 Ohm / square, or even 0.5 Ohm / square, in particular for an upper gate thickness or equal to 1 micron, and preferably less than 10 microns or even less than or equal to 5 microns.

The light transmission of the substrate coated with the grid greater than or equal to 50%, even more preferably greater than or equal to 70%, in particular is between 70% to 86%. The B / A ratio may be different, for example at least double, in a first gate region and in a second gate region. The first and second regions may be of a distinct or equal shape and / or of a distinct or equal size.

With an open ratio of the mesh / size of the variable strands, it is possible to create zones with: - a light transmission gradient,

- A gradient of electrical power (application to heating, defrosting, achieving homogeneous heat flow on non-rectangular surfaces.

The light transmission of the network depends on the ratio B / A between the average distance between the strands B on the average width of the strands A.

Preferably, the ratio B / A is between 5 and even more preferably of the order of 10 to easily retain transparency and facilitate manufacture. For example, B and A are respectively about 50 microns and 5 microns.

In particular, we choose an average width of strands A between

100 nra and 30 microns, preferably less than or equal to 10 microns, or even 5 microns to limit their visibility and greater than or equal to 1 micron to facilitate manufacture and to easily maintain high conductivity and transparency.

In particular, it is also possible to choose an average distance between strands B greater than A, between 5 μm and 300 μm, or even between 20 and 100 μm, to easily retain transparency.

The thickness of the strands may be between 100 nm and 5 μm, especially micron, more preferably 0.5 to 3 μm to easily maintain transparency and high conductivity.

The grid according to the invention may be over a large area, for example an area greater than or equal to 0.02 m ² or even greater than or equal to 0.5 m ² or 1 m ² . The substrate may be flat or curved, and further rigid, flexible or semi-flexible.

Its main faces can be rectangular, square or even of any other form (round, oval, polygonal ...). This substrate may be large, for example, top surface to 0.02 m ^2, or even 0.5 m ² or I m ² and with a lower electrode substantially occupying the surface (the structuring zones) The substrate may be substantially transparent, mineral or in plastic such as polycarbonate PC or polymethyl methacrylate PMMA or PET, polyvinyl butyral PVB, polyurethane PU, polytetrafluoroethylene PTFE etc.

The substrate is preferably glass, in particular of silicosodocalcic glass.

For the purposes of the invention, a substrate has a glass function when it is substantially transparent, and is based on minerals (a soda-lime glass, for example) or is based on plastic (like polycarbonate PC or polymethyl methacrylate PMMA),

The gate according to the invention can be used in particular as a lower electrode (closest to the substrate) for an organic electroluminescent device (OLED in English) in particular at the rear emission ("bottom emission" in English) or emission by the back and front.

A multiple glazing, laminated (interlayer laminating type EVA, PU, PVB ...) may incorporate a carrier substrate of the grid according to the invention.

According to yet another aspect of the invention, it aims to use a grid as previously described as

active layer (mono or multilayer electrode) in an electrochemical device, and / or electrically controllable and with variable optical and / or energy properties, for example a liquid crystal device or a photovoltaic device, or an organic electroluminescent device, a device for flat lamp,

active layer (heating) of a heating device, an electromagnetic shielding device, or any other device requiring a layer (optionally

(semi) transparent) electro-conductive.

The invention will now be described in more detail using non-limiting examples and figures:

FIGS. 1 to 2e represent examples of masks obtained by the method according to the invention,

FIG. 3 is an SEM view illustrating the profile of the crack

FIG. 4 represents a grid in plan view - FIGS. 5 and 6 show masks with different drying fronts,

FIGS. 7 and 8 represent partial views SEM of gate,

- Figures 9 and 10 show grids in plan view. On a glass-backed substrate portion, a spin coating emulsion of a single emulsion of acrylic-based copolymer-based particles stabilized in water at a mass concentration of 40% is deposited. of 5, 1, of viscosity equal to 15 mPa.s. The colloidal particles have a characteristic dimension of 80 to 100 nm and are marketed under the company DSM under the trademark Neocryl XK 52® and have a Tg equal to 1 15 ° C.

The layer incorporating the colloidal particles is then dried so as to evaporate the solvent and form the interstices. This drying can be carried out by any suitable method and preferably at a temperature below Tg (hot air drying, etc.), for example at room temperature.

During this drying step the system self-arranges and describes patterns, examples of which are shown in Figures 1 and 2 (views (400 microns x 500 microns)). A stable mask is obtained without resorting to annealing with a structure characterized by the width (average) of the strand subsequently referred to as A (in fact the size of the strand) and the (middle) space between the strands. This stabilized mask will subsequently be defined by the B / A ratio.

We obtain a two-dimensional network of interstices, mesh with little mesh breakage.

The influence of the drying temperature was evaluated. Drying at 100 ^° C. at 20% RH gives a mesh of 80 μm (FIG. 2a), while drying at 30 ^° C. at 20% RH gives a mesh of 130 μm (FIG. 2b).

The influence of the drying conditions, in particular the degree of humidity, was evaluated. The layer based on XK52 is this time deposited by flow coating, which gives a variation in thickness between the bottom and the top of the sample (from 10 μm to 20 μm) leading to a variation in mesh size. . The higher the humidity, the smaller B is.

This ratio B / A is also modified by adapting, for example, the coefficient of friction between the compacted colloids and the surface of the substrate, or the size of the nanoparticles, or even the rate of evaporation, or the initial concentration of particles, or the nature of the solvent, or the thickness depending on the deposition technique ...

In order to illustrate these various possibilities, a plan of experiments with two concentrations of the colloid solution (Co and 0.5 x Co) and different thicknesses deposited by adjusting the rate of rise of the DIP is given below. Note that one can change the ratio B / A by changing the concentration and / or the drying rate. The results are reported in the following table:

The colloid solution was coated at Co = 40% concentration using film pullers of different thicknesses. These experiments show that the size of the strands and the distance between the strands can be varied by adjusting the initial thickness of the colloid layer

The surface roughness of the substrate was finally modified by atmospheric plasma etching of the glass surface via a mask of Ag nodules. This roughness is of the order of magnitude of the size of the contact areas with the colloids which increases the coefficient of friction of these colloids with the substrate. The following table shows the effect of the change of coefficient of friction on the ratio B / A and the morphology of the mask. It appears that we obtain smaller mesh sizes with identical initial thickness and an increasing ratio B / A.

In another embodiment, the dimensional parameters of interstitial network obtained by spin coating of the same emulsion containing colloidal particles are given below. previously described. The different rotational speeds of the "spin coating" apparatus modify the structure of the mask.

The effect of propagation (see Figures 5 and 6) of a drying front on the morphology of the mask was studied. The presence of a drying front makes it possible to create an array of approximately parallel interstices whose direction is perpendicular to this drying front. There is also a secondary network of interstices approximately perpendicular to the parallel network whose location and distance between strands are random.

At this stage of the implementation of the method, a mask is obtained. A morphological study of the mask showed that the interstices present a right crack profile. We can refer to Figure 3 which is a transverse view of the mask obtained by SEM.

The crack profile shown in FIG. 3 has a certain advantage for: depositing, in particular in a single step, a large thickness of material,

- Keep a pattern, particularly thick, consistent with the mask after removing it.

The mask thus obtained can be used as modified or modified by different post treatments. For example, according to this configuration, there is no no colloidal particles in the bottom of cracks, so there will be a maximum adhesion of the material that is expected to provide so as to fill the crack (this will be described in detail later in the text) with the substrate glass function. The inventors have furthermore discovered that the use of a plasma source as a cleaning source for organic particles situated at the bottom of the crack subsequently makes it possible to improve the adhesion of the material used for the grid.

As an exemplary embodiment, a cleaning using a plasma source at atmospheric pressure, plasma blown based on a mixture of oxygen and helium allows both the improvement of the adhesion of the material deposited at the bottom of the interstices and widening of the interstices. It will be possible to use a plasma source of "ATOMFLOW" brand marketed by the company Surfx. In another embodiment, a single emulsion of colloidal particles based on acrylic copolymer stabilized in water is deposited in a mass concentration of 50%, a pH of 3, of viscosity equal to 200 mPa.s. The colloidal particles have a characteristic dimension of about 18 nm and are marketed under the company DSM under the trademark Neocryl XK 38® and have a Tg equal to 71 ^° C. The resulting network is shown in Figure 2c.

The influence of annealing on the network parameters was evaluated as compiled in the following table

By compaction, the width of the double or even triple strands as shown in FIG. 2d (sample treated at 100 ^° C. for 15 minutes).

It is possible to modify locally, for example in the center of the mask, with a focused IR lamp. We can thus obtain a grid with a gradient of TL.

In another embodiment, a 40% silica colloid solution, with a characteristic dimension of about 10 to 20 nm, is deposited, for example the LUDOX® AS 40 product sold by Sigma Aldrich. The B / A ratio is about 30 or so, as shown in FIG.

Typically, it is possible to deposit, for example, between 15% and 50% of silica colloids in an organic solvent (in particular aqueous).

From the mask according to the invention, a grid is produced. To do this, we proceed to deposit, through the mask, a material to fill the interstices. The material chosen is preferably from electrically conductive materials such as aluminum, silver, copper, nickel, chromium, the alloys of these metals, conductive oxides chosen in particular from HTO, IZO, ZnO: Al; ZnO: Ga ZnO: B; SnO2: F; SnO2: Sb; nitrides such as titanium nitride, carbides such as silicon carbide ... This deposition phase may be carried out for example by magnetron sputtering or by gas phase deposition. The material is deposited inside the network of interstices so as to fill the cracks, the filling taking place in a thickness for example of the order of 1/2 mask height.

In order to reveal the grid structure from the mask, a "lift off" operation is performed. This operation is facilitated by the fact that the cohesion of the colloids results from weak forces VanderWaals type (no binder, or bonding resulting by annealing). The colloidal mask is then immersed in a solution containing water and acetone (the cleaning solution is chosen according to the nature of the colloidal particles) and then rinsed so as to remove all the parts coated with colloids. We can accelerate the phenomenon through the use of ultrasound to degrade the mask of colloidal particles and reveal the complementary parts (the network of interstices filled by the material) that will conform the grid.

FIG. 4 shows a photograph obtained by SEM of a grid thus obtained.

The electrical and optical characteristics obtained for aluminum-based grids are given below.

V. rotation (rpm) 200 400 700 1000 thickness Al (nm) 300 1000 300 1000 300 1000 300 1000

Paid (Ω / D) 2.1 0.65 2, 4 0. 7 3 0.9 3, 1 0.95

% TL 79.8 79.3 81, 9 82, 1 83, 2 83, 1 84, 9 83.9

% RL 14.7 15.0 14, 6 14, 2 13, 1 12.4 1 1, 7 1 1, 6

Thanks to this particular grid structure, it is possible to obtain, at lower cost, an electrode compatible with the systems electrically controllable while having high electrical conductivity properties.

Figures 7 and 8 show SEM views from above (in perspective) and detail of the strands of an aluminum grid. It is observed that the strands have relatively smooth and parallel edges.

The electrode incorporating the gate according to the invention has an electrical resistivity of between 0.1 and 30 Ohm / square and a TL of 70 to 86%, which makes its use as a transparent electrode perfectly satisfactory. Preferably, in particular to reach this level of resistivity, the metal gate has a total thickness of between 100 nm and 5 μm.

In these ranges of thicknesses, the electrode remains transparent, that is to say that it has a low light absorption in the visible even in the presence of the grid (its network is almost invisible given its dimensions).

The grid has an aperiodic or random structure in at least one direction to avoid diffractive phenomena and induces a shadowing of 15 to 25% of the light. For example, a network as shown in FIG. 4, having metal wires 700 nm wide spaced apart by 10 μm, gives a bare light transmission substrate 92% an 80% light transmission.

Another advantage of this embodiment method is that it is possible to modulate the blur value in reflection of the grids.

For example, for inter-strand spacing (dimension B) of less than 15 μm, the fuzziness value is of the order of 4 to 5%.

For a spacing of 100 μm, the blur value is less than 1%, with B / A being constant. For a strand spacing (B) of the order of 5 μm and a strand size of 0.3 μm, a blur of the order of 20% is obtained. Beyond a fuzziness value of 5%, this phenomenon can be used as a means light extraction at the interfaces or means for trapping light.

Prior to the deposition of the mask material, it is possible to deposit, in particular by vacuum deposition, a promoter-adhesion sub-layer of the gate material.

For example, nickel is deposited and aluminum as the gate material. This grid is shown in Figure 9.

For example, ITO, NiCr or Ti is deposited and as silver gate material. To increase the thickness of the metal layer and thus reduce the electrical resistance of the gate we deposited, by electrolysis (soluble anode method), a copper overcoat on the silver gate.

The glass coated with the adhesion promoting sublayer and the magnetron sputtering silver grid constitutes the cathode of the experimental device; the anode consists of a copper plate. Its role in dissolving, to maintain constant throughout the deposition process concentration of Cu ²⁺ ions and thus the deposition rate. The electrolysis solution (bath) consists of an aqueous solution of copper sulphate (CUSO 4 -5H 2 O = 70 g / ^l ) to which 50 ml of sulfuric acid (10 N H 2 SO 4) are added. The temperature of the solution during the electrolysis is 23 ± 20 ^° C.

The deposition conditions are as follows: voltage <1, 5 V and current £ 1 A.

The anode and cathode, spaced 3 to 5 cm apart and of the same size, are positioned parallel to obtain perpendicular line lines

The copper layers are homogeneous on the silver grids. The thickness of the deposit increases with the duration of the electrolysis and the current density as well as the morphology of the deposit. The results are reported in the table below and in Figure 10.

The SEM observations (performed on these grids show that the mesh size is 30 μm ± 10 μm and the size of the strands is between 2 and 5 μm.

As mentioned above, the invention can be applied to different types of electrochemical or electrically controllable systems in which the grid can be integrated as an active layer (as an electrode for example). It is more particularly interested in electrochromic systems, especially the "all solid" ones (the "all solid" being defined, within the meaning of the invention for stacks of layers for which all the layers are of inorganic nature) or the "all solid" polymer "(the" all polymer "being defined, within the meaning of the invention for stacks of layers for which all the layers are of organic nature), or for mixed electrochromic or hybrid (the layers of the stack are of organic nature and inorganic nature) or to liquid crystal or viologen systems, or electroluminescent systems, flat lamps. The metal grid thus produced may also constitute a heating element in a windshield, or an electromagnetic shield.

The invention also relates to the incorporation of grid as obtained from the development of the mask previously described in windows, operating in transmission. The term "glazing" is to be understood in the broad sense and encompasses all material essentially transparent, glass function, glass and / or polymeric material (such as polycarbonate PC or polymethyl methacrylate PMMA). The carrier substrates and / or counter-substrates, that is to say the substrates surrounding the active system, can be rigid, flexible or semi-flexible.

The invention also relates to the various applications that can be found in these devices, glazing or mirrors: it may be to make glazing for building, including external glazing, internal partitions or glass doors). It can also be windows, roofs or internal partitions of means of transport such as trains, planes, cars, boats, construction equipment. It can also be display or display screens, such as projection screens, television or computer screens, touch screens, illuminating surfaces, heated windows.

Claims

1. A method of manufacturing a mask with submillimeter openings on a surface portion of a substrate, in particular with glass function, by deposition and drying of a mask layer characterized in that:

a mask layer is deposited from a solution of colloidal particles stabilized and dispersed in a solvent,

the mask layer is dried until a two-dimensional network of interstices with a substantially straight edge is formed, forming the mask with a random interstice mesh in at least one direction.

2. Method according to claim 1, characterized in that, the particles having a given glass transition temperature Tg, the deposition and drying are carried out at a temperature below said temperature Tg.

3. Method according to the preceding claim, characterized in that the deposition and drying are carried out at room temperature, the difference between the glass transition temperature Tg given particles and the drying temperature is preferably greater than 10 ⁰ C .

4. Method according to one of the preceding claims, characterized in that the deposition and drying are carried out is carried out substantially at atmospheric pressure.

5. Method according to one of the preceding claims, characterized in that the colloid solution comprises polymeric nanoparticles, preferably acrylic copolymers, styrenes, polystyrenes, poly (meth) acrylates, polyesters or their mixtures.

6. Method according to one of the preceding claims, characterized in that the solution comprises mineral nanoparticles, preferably silica, alumina, iron oxide.

7. Method according to any one of the preceding claims, characterized in that the solution is aqueous.

8. Process according to any one of the preceding claims, characterized in that by modifying the control parameters chosen from the coefficient of friction between the compacted colloids (and the surface of the substrate, in particular by nanotexturation of the substrate, the size of the nanoparticles, the evaporation rate, the initial concentration of particles, the nature of the solvent, the thickness depending on the deposition technique, the degree of humidity, AB and / or the B / A ratio are adjusted.

9. Process according to any one of the preceding claims, characterized in that after drying, the mask is heated at least locally to a temperature above Tg and below the melting temperature Tf.

10. Process according to any one of the preceding claims, characterized in that a differential drying is carried out.

1. Process according to any one of the preceding claims, characterized in that it is deposited directly on the substrate, preferably made of glass.

12. Method according to any one of the preceding claims, before the deposition of the mask layer, is deposited on the substrate on a sub-layer selected from a hydrophilic layer, a barrier layer, a layer of adhesion of a material of grid, a layer decor.

13. Use of the carrier substrate of the mask according to one of the preceding claims for producing an irregular submillimeter grid, in particular electroconductive.

14. A method of manufacturing an irregular submillimeter grid characterized in that is deposited, through the interstices of the mask obtained by the method defined according to one of claims 1 to 12, a gate material up to fill a fraction of the depth of the interstices.

15. A method of manufacturing a grid according to claim 14, characterized in that one carries out a removal of the mask layer, until revealing the grid based on said grid material.

16. A method of manufacturing a grid according to claim 15, characterized in that one carries out a removal of the mask layer, by liquid, in particular by a solvent.

17. A method of manufacturing a grid according to one of claims 14 to 16, characterized in that one carries out a cleaning of the network of interstices prior to the development of the deposition of the gate material.

18. A method of manufacturing a grid according to one of claims 14 to 17, characterized in that one proceeds to the cleaning of the interstice network using a plasma source at atmospheric pressure.

19. A method of manufacturing a gate according to one of claims 14 to 18, characterized in that the deposition of the gate material is deposited at atmospheric pressure, plasma, or vacuum, by sputtering, by evaporation.

20. A method of manufacturing a grid according to one of claims 14 to 19, characterized in that the gate material deposited in the interstices is selected from electrically conductive materials.

21. A method of manufacturing a grid according to one of claims 14 to 20 characterized in that the gate material is electrically conductive, is deposited on the gate material, a electrically conductive material by electrolysis.

22. Substrate carrying an irregular submillimetric grid obtained by the manufacturing method according to one of claims 14 to 21.

23. Substrate carrying a random submillimetric irregular grid in at least one direction, comprising a main network with first submillimeter-width strands and a secondary network of second strands of smaller width than the first strands.

24. substrate carrying an irregular grid according to one of claims 22 or 23 characterized in that the grid has a ratio spacing between the strands (B) on the submillimeter width of the strands (A) between 7 and 40.

25. Carrier substrate of a grid according to one of claims 22 to 24, characterized in that the patterns of the grid are random, aperiodic, of varying shape and / or size.

26. The carrier substrate of a grid according to one of claims 22 to 25 characterized in that the gate has an aperiodic or random structure in at least one direction, preferably in two directions.

27. Grid carrier substrate according to one of claims 22 to 26, characterized in that for the majority of the meshes, the difference between the greatest mesh characteristic dimension and the smallest mesh characteristic dimension is less than or equal to 2. .

28. Grid-carrying substrate according to one of claims 22 to 27, characterized in that the difference between the maximum width of strands and the minimum width of strands is less than 4, in a given region of the grid, and / or in the difference between the maximum mesh size and the minimum mesh size is less than 4, in a given grid region.

29. Grid carrier substrate according to one of claims 22 to 28 characterized for the majority of meshes, the breaking rate of mesh and / or cut strands, is less than 5%, or even less than or equal to 2% .

30. carrier substrate of a grid according to any one of claims 22 to 29, characterized in that the electroconductive grid has a square resistance of between 0.1 and 30 Ohm / square.

31. substrate carrying a grid according to any one of claims 22 to 30, characterized in that the grid is deposited directly or not, on at least a portion of the surface of the substrate including glass function, plastic or mineral material .

32. Substrate carrying a grid according to any one of Claims 22 to 31, characterized in that the gate is deposited on a sub-layer, preferably a hydrophilic layer, in particular a silica layer, and / or a promoter layer for adhesion of the gate material, in particular NiCr, Ti, ITO , Al, Nb and / or a barrier layer including Si3N4, SiO2 and / or a decorative layer.

33. The carrier substrate of a grid according to one of claims 22 to 32, characterized in that the light transmission of the substrate coated with the grid is between 70% to 86%.

34. Grid carrier substrate according to one of claims 22 to 33, characterized in that the ratio B / A is different in a first gate region and a second gate region.

35. Substrate carrying a grid according to one of claims 22 to 34, characterized in that it comprises a light transmission gradient and / or electric power.

36. Multiple glazing, laminated with the grid substrate according to one of claims 22 to 35

37. Use of an electroconductive grid according to any one of claims 22 to 36 as an active layer, in particular an electrode or a heating layer, in an electrochemical device, and / or electrically controllable and with variable optical and / or energy properties, in particular liquid crystal, or a photovoltaic device, or a light-emitting device, in particular organic, or even a heating device, or possibly a flat-lamp device, an electromagnetic shielding device, or any other device requiring a conductive layer, in particular transparent .