FR2938375A1 - Flexible, transparent and self-supporting multi-layer film for e.g. organic LED device, has organic and inorganic layers whose thicknesses are chosen such that total thickness of film is greater than or equal to ten micrometers - Google Patents

Abstract

The film (1') has an outer layer (4), and inorganic layers (12, 22, 32) respectively formed on organic polymeric layers (11, 21, 31). One of the organic layers form a film face that is delaminated with respect to a rigid silicon/glass substrate (2). The face is made of transparent polymer having reduced adhesion with the substrate. The organic and inorganic layers have thicknesses respectively ranging between 2 and 20 micrometers and between 20 and 200 micrometers, and chosen such that total thickness of the film is greater than or equal to 10 micrometers to allow the delamination of the face. The outer layer is made of transparent conductive oxide such as indium tin oxide and zinc oxide, or a compound chosen from graphene monolayer composite, carbon nanotube and transparent conductive oxide/metal/transparent conductive oxide structure composites. An independent claim is also included for a method for fabricating a flexible, transparent and self-supporting multi-layer film.

Description

MULTILAYER SOFT, TRANSPARENT, AUTOPORTE AND BARRIER EFFECT FILM, METHOD FOR MANUFACTURING SAME, AND OPTOELECTRONIC DEVICE INCORPORATING SAME.

The present invention relates to a flexible multilayer film, transparent, self-supporting and gas barrier effect, its manufacturing method and an organic or organic / inorganic hybrid type optoelectronic device incorporating this film. The invention applies in particular to an organic light-emitting diode (OLED), organic photovoltaic cell (OPV) or thin-film organic transistor (OTFT) device, but not limited to, but also encompasses other applications requiring particularly the above-mentioned properties of transparency and barrier effect for the self-supporting film, such as, for example, flexible pouch type hermetic packaging.

In a known manner, organic optoelectronic devices of the aforementioned type must, for a certain number of applications, be protected or isolated vis-à-vis the oxidizing species of the atmosphere (mainly oxygen and water vapor). If this protection is not properly performed, the ensuing degradation is manifested mainly by the appearance of non-emissive black spots in the case of OLED devices, which are in fact the result of the penetration of water vapor. in the diode which then degrades the interface between cathode or anode and organic structure of light emission. This protection is currently performed in two different ways: either by a protective cover, for example glass or metal and having a peripheral edge bonded via a bead of adhesive to the periphery of the emission zone of the device, this bonding being usually carried out in a glove box under a nitrogen or argon atmosphere, or by one or more thin layers of encapsulation deposited under vacuum on the emission zone and typically comprising alternations of organic and inorganic materials in order to meet the required specifications in terms of permeabilities.

Moreover, if these organic optoelectronic devices are manufactured on flexible substrates, typically plastics such as PET or PEN, it is known that the application of thin layers of high barrier quality on the plastic substrates themselves is essential for the encapsulation. Indeed and unlike a rigid substrate made of glass or silicon which is totally airtight with respect to the atmosphere, these flexible substrates are relatively permeable to gases such as oxygen and water vapor. . Consequently, and in the case of the use of a flexible substrate in its raw form, an organic device for example OLED type manufactured directly on this substrate will have a relatively limited life. The barrier capacity of the encapsulating materials is frequently expressed in terms of stabilized flow of water through a given barrier material, or WVTR (Water Vapor Transmission Rate in English). For organic optoelectronic devices, the target value of the WVTR is of the order of 10-6 g / m2 / day, it being specified that there are currently no polymeric films that can respond to this grade of ultra high barrier (UHB). Thin barrier encapsulation layers are generally inorganic, generally consisting of oxides or nitrides when the transparency is sought or metals in the opposite case, transparent oxides or nitrides deposited under vacuum being preferred since the Photons must be absorbed or emitted through encapsulation. However, it is difficult to exceed a limit barrier quality for a given single layer due to the presence of defects (English pinholes or micro-cracks) within the inorganic layer, defects all the more present that the deposits are made at a lower temperature on a substrate whose surface, on a microscopic scale, is not technologically ideal (high roughness, defects, etc.) to guarantee growth without defects of the inorganic layer. This is the reason why in the past we have chosen to make polymeric soft layers alternating in the order of the pm and finer inorganic dense layers to decorrelate defects from one dense inorganic layer to another, in order to increase the sinuosity of the path for the water vapor and thus delay its diffusion through the encapsulation structure. This technique, used by the company Vitex under the name Barix, provides organic / inorganic / organic / inorganic / ... stacks where the lower polymeric layer of each organic / inorganic unit stack (this stack is called dyad in English) is deposited under vacuum by evaporation. The encapsulation structure thus obtained may have a water vapor permeability close to 10 -6 g / m 2 / day, which provides a sufficient shelf life for the commercialization of OLED display devices. The disadvantage of this technique is that it requires the superposition of a large number of layers on the flexible substrate, which makes it costly to implement.

It is also known from US-A-2002/0003403 to provide for an OLED device two encapsulation layers superimposed on the emission zone, which may consist of a polymer layer for example of parylene and a layer dielectric oxide for example AI2O3 the overlying and deposited by an atomic layer deposition (ALD for Atomic Layer Deposition). The ALD technique is derived from Chemical Vapor Deposition (CVD), but uses a specific mode in which the injection cycles of the different reactive precursors are sequential. This sequential nature of the deposition results in growths of self-limited layers via the saturation of the surface by the chemisorbed precursors. At the same time, the chemisorption of the precursors on the previously prepared layer guarantees the excellent recovery and good compliance of the deposited oxide layer. This ALD technique thus has the advantage of being highly compliant (i.e. with excellent step coverage in English) for each deposited inorganic layer, which thus has a small number of defects.

US-B1-6 358 863 teaches to manufacture by CVD a dielectric multilayer film by depositing on a rigid silicon substrate a stack of units each consisting of an organic layer of a parylene surmounted by an inorganic layer for example of SiO2. As described in Example 7 of this document which has such a stack of seven units, the film thus obtained has a total thickness of only 382 nm, which is very insufficient for it to be self-supporting by separation from it. substrate.

An object of the present invention is to provide a flexible film, transparent and gas barrier effect based on one or more units each comprising a polymeric organic layer surmounted by an inorganic layer forming a gas barrier, which allows to overcome the aforementioned drawbacks by being particularly self-supporting (ie without covering the original substrate on which it was deposited) and advantageously having a satisfactory thermal resistance. For this purpose, a multilayer film according to the invention is obtained by delamination with respect to its original rigid substrate, for example glass or silicon, by means of an adhesive rupture with this substrate of the invention. one of the two faces of the film formed by the one or one of the organic layer (s), this delaminated face of the film being based on at least a first transparent polymer which has a reduced adhesion with this substrate and which is selected from the group consisting of parylenes and fluorocarbon polymers, the organic and inorganic layers of the or each unit having thicknesses respectively between 2 pm and 20 pm and between 20 nm and 200 nm and selected so that the film has a total thickness equal to or greater than 10 pm to allow this delamination. It should be noted that this minimum thickness of 10 μm is required for the film to be self-supporting, following its release from the original (temporary) substrate by this delamination or take-off. It will also be noted that this film according to the invention makes it possible to dispense with a flexible plastic substrate supporting this film, such a flexible substrate usually having limited optical and surface qualities and a thermal resistance that may be insufficient. As will be developed below, it will be further appreciated that the self-supporting film according to the invention has the advantage of being easy to report on a sensitive optoelectronic device. Advantageously, this film according to the invention may comprise several units, the organic layer of which (s) which overcomes (s) the unit having said delaminated face being based on at least one transparent polymer which is identical or not to said first polymer and may be selected from the group consisting of parylenes, fluorocarbon polymers and polyacrylates. Preferably, this film has from two to four units, the organic and inorganic layers of each of them having thicknesses respectively between 5 pm and 15 pm and between 25 nm and 100 nm which are chosen so that this film has a total thickness of less than 50 μm. According to another characteristic of the invention, these units are optionally connected two by two to each other by an intermediate adhesion layer designed to improve the adhesion between the inorganic layer 20 of a unit and the adjacent organic layer of the unit. overcoming it. This intermediate bonding layer may be provided between each pair of adjacent units forming the film (ie with n-1 intermediate layers for n superposed units), or only between one or more of these pairs (ie with from 1 to n -2 intermediate layers for n units, where n 4). According to a preferred embodiment of the invention, the polymer of the delaminated face is a parylene deposited on the original substrate by CVD to form the corresponding organic layer, this parylene being preferably a high temperature-resistant parylene such a parylene denomination PPX-HT marketed by SCS company whose temperature resistance is at least 350 ° C without significant degradation in the long term.

It will be noted that the film according to this example of the invention, which incorporates a parylene at least in its lower unit having said delaminated surface, thus advantageously has a high temperature withstand, in addition to the aforementioned properties of flexibility, transparency, d barrier and self-lifting effect. By parylene is meant in a manner known in the present description a poly (para-xylylene) or PPX abbreviated, substituted or not and may be in particular a fluorinated parylene type HT (PPX-HT) a parylene type C (PPX- C of formula C8H8Cl), an N type parylene (PPX-N of formula C8H8) or a type D parylene (PPX-D of formula C8H8Cl2). According to one variant of the invention, the polymer of the delaminated face is a fluorocarbon polymer deposited on the original substrate by a liquid route to form the corresponding organic layer, preferably a polymer derived from tetrafluoromethane, tetrafluoroethylene or hexafluoroacetone . Preferably, the or each inorganic layer is based on at least one inorganic compound that can be chosen from the group consisting of aluminum oxides, silicon oxides, zinc oxides, silicon nitrides and oxynitrides. silicon. Even more preferably, and especially in the case where the polymer of the delaminated face is a parylene, the or each inorganic layer consists of an aluminum oxide of formula Al Oy deposited by a method selected from the group consisting of ALD, CVD and Physical Vapor Deposition (PVD) deposits, which is preferably an ALD method. According to a first application of the invention, the self-supporting film is shaped to form by itself a transparent and airtight flexible pouch type packaging, for example intended to contain medical instruments.

According to a second application of the invention explained below, the self-supporting film can be used in an organic optoelectronic device by itself forming the flexible substrate of the device.

In connection with this second application, the film according to the invention then furthermore comprises an electrically conductive and transparent outer layer, which is deposited on the inorganic layer of the underlying unit in a thickness preferably of between 50 nm and 150 nm. nm and which is based on a transparent conductive oxide (OTC), for example a sputtered tin-indium oxide (ITO) or ZnO deposited by an atomic layer deposition (ALD). As a variant, the outer layer may be based on a compound chosen from the group consisting of OTC / metal / OTC structure compounds, for example ITO / metal / ITO structure IMIs, carbon nanotubes for example single-walled carbon nanotubes ( SWNT for Single Wall Nanotubes) and graphene monolayer compounds, especially for light panels with large emission areas. An optoelectronic device of organic or hybrid organic / inorganic type according to the invention, such as an organic light-emitting diode (OLED), organic photovoltaic cell (OPV) or organic thin-film transistor (OTFT) device, is such that it incorporates a multilayer film forming: a transparent and electrically conductive flexible substrate for this device, this flexible substrate being obtained by prior etching of the film on said original rigid substrate, this film then being as defined above in relation to with the aforementioned second application of the invention, or - according to a third application of the invention, a transparent and sealed encapsulation structure for this device covering an electrically conductive flexible substrate, this film then being as defined above at except for said electrically conductive outer layer which is not required for encapsulation. This device according to the invention can be advantageously flexible and / or large emission area.

It should be noted that the use of the temporary rigid substrate made of silicon or glass, for example, which is a priori flawless and exhibits an excellent surface quality, for producing the film according to the invention makes it possible, in particular, to confer on the latter once reported on the flexible substrate of an organic optoelectronic device, improved gas barrier properties in comparison with those of the prior art where the barrier structure was deposited on a flexible plastic substrate of PET or PEN type. A manufacturing method according to the invention of a film as defined above, this film being in particular flexible, transparent, self-supporting and with a gas barrier effect, essentially comprises: a) a deposit on said rigid substrate d for example from glass or silicon, from the unit or units to one another to obtain a film of thickness equal to or greater than 10 μm, the lowest organic layer of which is based on at least said first transparent adhesive polymer reduced to this original substrate, then b) a delamination of the film thus deposited by adhesive breaking of its interface with this original substrate to obtain the self-supporting film, which has preferably a thickness of less than 50 μm. Advantageously, to promote the delamination in step b): it is possible to deposit, prior to step a) on said original substrate, an underlayer of oxide which is preferably an aluminum oxide of formula Al Oy deposited by ALD, or it may be provided that this original substrate is made of silicon on which is formed a native oxide SiO2. Preferably, the organic layer of the or each unit is deposited by a CVD deposit of a parylene or by a liquid deposit of a fluorocarbon polymer, and the inorganic layer of the or each unit by ALD, CVD, PVD, plasma or wet (in the latter case, inorganic liquid precursors are used to obtain dense layers of SiOX, see for example the article Yongchai Kwon, Jongwon Seok, Japanese Journal of Applied Physics, Vol 44, 6A, 2005, pp. 3893-3902). The important thing for the or each inorganic layer is that it is transparent and above all sufficiently dense to satisfactorily exert its function as a gas barrier.

Advantageously, the inorganic layer of the or each unit is based on at least one inorganic compound that can be chosen from the group consisting of oxides of aluminum, silicon, zinc, silicon nitrides and silicon oxynitrides. and is preferably deposited by ALD. Even more advantageously, the inorganic layer of the or each unit may be based on an aluminum oxide of formula Al Oy which is deposited by ALD, preferably by means of a pair of trimethylaluminum / H 2 O precursors.

According to another optional feature of the invention, an intermediate adhesion layer is additionally deposited between the inorganic layer of one unit and the organic layer of another unit intended to overcome it, the or each intermediate layer being able to be obtained by a surface treatment selected from the group consisting of plasma treatments, thin layer deposition of an adhesion promoter and surface chemical treatments, the thin layer deposition of a adhesion promoter being preferably implemented in the case where the organic layer concerned is based on a parylene. According to another also optional feature of the invention relating in particular to the aforementioned second application, is deposited moreover, on the inorganic layer of the last deposited unit, an electrically conductive and transparent outer layer according to a thickness preferably between 50 nm and 150 nm and which can be as defined above in connection with this second application. In this case, it is previously carried out in step b) of delamination of the etching operations on the film deposited on said original substrate, in order to use this film once delaminated as a flexible substrate of the optoelectronic device. According to the aforementioned first and third applications of the invention, the film obtained after delamination step b) is shaped so as to obtain, respectively, a transparent and hermetic packaging of the flexible pouch type, or a transparent encapsulation structure and waterproof membrane intended to be carried on a flexible substrate of an organic or hybrid organic / inorganic optoelectronic device. Other advantages, features and details of the invention will emerge from the additional description which will follow with reference to the accompanying drawings, given solely by way of example and in which: FIG. 1 is a diagrammatic cross-sectional view of FIG. an example of multilayer film according to the invention being manufactured, this film covering a rigid original substrate used for its deposition, FIG. 2 is a schematic cross-sectional view of the film of FIG. 1 finally self-supported by delamination screws with respect to its original substrate, and FIG. 3 is a schematic cross-sectional view of another example of multilayer film according to the invention being manufactured, this film covering the original rigid substrate used for its deposit 15 as in Figure 1.

The multilayer transparent film 1 illustrated in FIG. 1 is deposited on a temporary rigid substrate 2 which may consist for example of virgin silicon on which is deposited an inorganic sub-layer 3 of a metal oxide capable of promoting subsequent takeoff by delamination. of film 1 with this substrate 2 (it being specified that, in a variant, this oxide could be a native SiO 2 oxide on silicon, thus avoiding the deposition of sublayer 3). This film 1 consists of two elementary units 10 and 20 deposited successively and each comprising a transparent polymeric layer 11, 21 for example from 5 μm to 10 μm in thickness directly surmounted by an inorganic layer 12, 22 dense, transparent and with a barrier effect of, for example, 25 nm to 50 nm in thickness, and an electrically conductive and transparent external layer 4 of thickness for example close to 100 nm which is deposited on the layer 22 of the second unit 20. The underlayer 3 and the inorganic layers 12 and 22 are each preferably based on an aluminum oxide of formula Al 2 O 3 deposited by ALD, via a pair of trimethylaluminium / H 2 O precursors.

The lower polymeric layer 11 is preferably based on a parylene such as PPX-HT, for example, which is deposited by CVD. Alternatively, the layer 11 may be based on a liquid-deposited fluoropolymer, such as poly (tetrafluoromethane), poly (tetrafluoroethylene) or poly (hexafluoroacetone). As regards the upper polymeric layer 21, it is in this example also based on a parylene identical to that of the layer 11, it being nevertheless specified that the polymer of this layer 21 could be very different from that of the layer 11 by being for example a polyacrylate deposited by flash polymerization or by any other route. Thus, examples of polymers that can be used for the layers 11/21 are the parylene / parylene, fluoropolymer / parylene, parylene / polyacrylate and fluoropolymer / polyacrylate pairs, respectively. As for the outer layer 4, it is for example based on a transparent conductive oxide, such as a spray-deposited ITO or ZnO deposited by ALD. It should be noted that in this example of FIG. 1, it is possible to dispense with an intermediate adhesion layer between the inorganic layer 12 of the lower unit 10 and the organic layer 21 of the upper unit 20. However, it is advantageous to use such an intermediate layer in the form of a thin layer deposition of an adhesion promoter such as for example HDMS, aC, FDTS or a promoter for PPX such as those sold under the names KBM-503 or A-174. As illustrated in FIG. 2, after the successive deposition of the units 10 and 20 and of the outer layer 4 and the implementation of the etching steps of the film 1 on the substrate 2 which are required as a function of the application sought for that here, the film 1 is released by adhesive breaking of its interface 5 with this substrate 2 covered with the underlayer 3 (see arrows A for the direction of the separation forces), this interface 5 based on parylene or fluorinated polymer thus forming the delaminated surface of the finally separated film 1. It will be noted that this delamination is made possible by the sufficient thickness of the film 1 deposited on the substrate 2, which is greater than 10 μm and which makes it possible to grip this film 1.

After this take-off, a supple, transparent, self-supporting film 1 with satisfactory barrier effect is obtained, in particular with respect to the atmospheric water vapor, thanks in particular to the dense inorganic layers 12 and 22 deposited by ALD. and further having a satisfactory high temperature withstand in the preferred case of the use of PPX-HT for the polymeric layers 11 and 21. The film 1 'illustrated in Figure 3 once deposited on the rigid temporary substrate 2 ( before delamination) is essentially different from that of Figure 1, in that it comprises a third unit 30 comprising a polymeric layer 31 surmounted by an inorganic layer 32, these two layers 31 and 32 being for example deposited as indicated by reference in Figure 1 (in the example of Figure 3, the polymeric layers 21 and 31 are chosen identical to be different from the lower polymeric layer 11). In this figure 3 are further visible two intermediate adhesion layers 40 and 50 interconnecting the inorganic layer 12 of the first unit 10 deposited to the polymeric layer 21 of the second unit 20, and the inorganic layer 22 of the latter to the polymeric layer 31 of the last unit 30 deposited, respectively. Each intermediate layer 40, 50 may for example be obtained by thin-layer deposition of an adhesion promoter such as those mentioned above. It will be noted that this manufacture of the film 1, 1 'according to the invention on the temporary rigid substrate 2, which is chosen for its excellent surface condition in anticipation of successive deposits and possible etching operations, has the essential advantage of conferring to the film 1, 1 ', when transferred onto a flexible substrate of an organic optoelectronic device to ensure encapsulation, excellent gas barrier properties that are greater than those that would have been obtained by depositing the multilayer film of encapsulation directly on a usual flexible plastic substrate of the PET or PEN type, for example.

The use of a substrate 2 specific to the production of the film 1, 1 'makes it possible to choose for this substrate 2 a material (for example silicon or glass) allowing the deposition of the layers covering it (in particular inorganic layers 22, 32 and the outer layer 4) at higher temperature, which allows to obtain layers with better qualities. It will also be noted that the electrically conductive outer layer 4 of the film 1 and 1 'according to the invention, which may be made of a transparent conductive oxide (OTC) such as those presented above or, alternatively, a structural compound OTC / metal / OTC, such as an ITO / metal / ITO structure IMI, a carbon nanotube or a graphene monolayer compound, is simply optional depending on the intended application of the film 1, 1 '.

Thus, in the case of a film intended to form after forming a thin airtight flexible bag type packaging for example in the medical field, such an outer layer 4 is not necessary. In this context, the Applicant has manufactured by this method successive deposits and delamination according to the invention a self-supporting flexible film for such a package, consisting of a single unit formed of a layer of PPX of 10 μm thick deposited by CVD on a silicon substrate treated with an Al 2 O 3 sublayer to promote subsequent delamination, and a layer of AIZO 3 25 nm thick covering it and deposited by ALD like the underlayer delamination. This self-supporting film thus obtained satisfactory barrier properties, especially with water vapor.

Claims (23)

1) multilayer film (1, 1 ') flexible, transparent and self-supporting based on one or more units (10, 20, 30) each comprising a polymeric organic layer (11, 21, 31) surmounted by an inorganic layer ( 12, 22, 32), characterized in that the film is obtained by delamination with respect to a rigid original substrate (2), for example glass or silicon, by means of an adhesive rupture with this substrate of one of the two faces (5) of the film formed by the one or one of the organic layer (s) (11), this delaminated face (5) of the film being base of at least a first transparent polymer which has a reduced adhesion with this substrate and which is selected from the group consisting of parylene and fluorocarbon polymers, the organic and inorganic layers of the or each unit having thicknesses respectively between 2 pm and 20 pm and between 20 nm and 200 nm and chosen so that the film near a total thickness equal to or greater than 10 μm to allow this delamination. 2) multilayer film (1, 1 ') according to claim 1, characterized in that it comprises several units (10 to 30), the organic layer (21, 31) of that (s) (20, 30) which overcomes (nt) the unit (10) having said delaminated surface (5) being based on at least one transparent polymer which is identical or not to said first polymer and which is selected from the group consisting of parylenes, fluorocarbon polymers and polyacrylates. 3) Multilayer film (1, 1 ') according to claim 2, characterized in that it has from two to four units (10 to 30), the organic (11 to 31) and inorganic (12 to 32) layers of each of them having thicknesses respectively between 5 pm and 15 pm and between 25 nm and 100 nm which are chosen so that the film has a total thickness of less than 50 pm. 4) multilayer film (1 ') according to claim 2 or 3, characterized in that the units (10 to 30) are connected in pairs to each other by an intermediate adhesive layer (40, 50) designed to improve the adhesion between the inorganic layer (12, 22) of a unit (10, 20) and the adjacent organic layer (21, 31) of the unit (20, 30) overlying it. 5) multilayer film (1, 1 ') according to one of claims 1 to 4, characterized in that the polymer of said delaminated face (5) is a parylene deposited on said original substrate (2) by chemical vapor deposition (CVD) to form the corresponding organic layer (11), this parylene being preferably a high temperature parylene such as a parylene PPX-HT denomination. 6) multilayer film (1, 1 ') according to one of claims 1 to 4, characterized in that the polymer of said delaminated surface (5) is a fluorocarbon polymer deposited on said original substrate (2) by liquid route to form the corresponding organic layer (11), preferably a polymer derived from tetrafluoromethane, tetrafluoroethylene or hexafluoroacetone. 7) multilayer film (1, 1 ') according to one of the preceding claims, characterized in that the or each inorganic layer (12 to 32) is based on at least one inorganic compound selected from the group consisting of oxides of aluminum, silicon oxides, zinc oxides, silicon nitrides and silicon oxynitrides. 8) multilayer film (1, 1 ') according to claims 4 and 7, characterized in that said or each inorganic layer (12 to 32) consists of an aluminum oxide of formula AIxOy which is deposited by a chosen method in the group consisting of atomic layer deposition (ALD), chemical vapor deposition (CVD) and physical vapor deposition (PVD), and preferably by atomic layer deposition (ALD). 9) Multilayer film (1, 1 ') according to one of the preceding claims, characterized in that it is shaped to form a thin transparent and hermetic pouch-type flexible packaging which is for example intended to contain medical articles or instruments. 10) multilayer film (1, 1 ') according to one of claims 1 to 8, characterized in that it further comprises an outer layer (4) electrically conductive and transparent, which is deposited on the inorganic layer (22, 32) of the underlying unit (20, 30) in a thickness preferably between 50 nm and 150 nm. 11) multilayer film (1, 1 ') according to claim 10, characterized in that said outer layer (4) is based on at least one transparent conductive oxide, preferably a tin-indium oxide deposited by spraying or deposited ZnO by an atomic layer deposition (ALD). 12) Multilayer film (1, 1 ') according to claim 10, characterized in that said outer layer (4) is based on at least one compound selected from the group consisting of transparent conductive oxide / metal oxide compounds 1 conductive transparent oxide, carbon nanotubes and graphene monolayer compounds. 13) Optoelectronic device with flexible and / or large emission surface of organic or organic / inorganic hybrid type, such as an organic light-emitting diode (OLED), organic photovoltaic cell (OPV) or thin-film organic transistor device (OTFT), characterized in that it incorporates a multilayer film (1, 1 ') forming: a flexible transparent and electrically conductive substrate for this device, this flexible substrate being obtained by prior etching of the film on said rigid substrate of origin (2), this film being then as defined in one of claims 10 to 12, or - a transparent and sealed encapsulation structure for this device covering an electrically conductive flexible substrate, this film then being as defined in one of claims 1 to 8. 14) A method of manufacturing a multilayer film (1, 1 ') flexible, transparent, self-supporting and gas barrier effect according to one of claims 1 to 12, characterized in that it comprises essentially: a) a deposit on said original rigid substrate (2), for example made of glass or silicon, of the unit or units on top of one another (10 to 30) for obtaining a film of thickness equal to or greater than 10 μm, the lower organic layer (11) is based on at least said first transparent polymer of adhesion reduced to this original substrate, then b) a delamination of the film thus deposited by adhesive rupture of its interface (5) with this original substrate for obtaining self-supporting film, which preferably has a thickness less than 50 pm. 15) The manufacturing method according to claim 14, characterized in that, to promote delamination in step b): - either is deposited prior to step a) on said original substrate (2) a sub oxide layer (3) which is preferably an aluminum oxide of the formula AIXOY deposited by atomic layer deposition (ALD), or it is expected that this original substrate consists of silicon on which is formed a native SiO2 oxide. 16) The manufacturing method according to claim 14 or 15, characterized in that the organic layer (11 to 31) of the or each unit (10 to 30) is deposited by a chemical vapor deposition (CVD) of a parylene or a liquid deposit of a fluorocarbon polymer, and the inorganic layer (12 to 32) of the or each unit by an atomic layer deposition (ALD), a chemical vapor deposition (CVD) ), a physical vapor deposition (PVD), a plasma or wet. 17) A manufacturing method according to claim 16, characterized in that the inorganic layer (12 to 32) of the or each unit (10 to 30) is based on at least one inorganic compound selected from the group consisting of aluminum oxides, silicon oxides, zinc oxides, silicon nitrides and silicon oxynitrides, and is preferably deposited by atomic layer deposition (ALD). 18) The manufacturing method according to claim 17, characterized in that the inorganic layer (12 to 32) of the or each unit (10 to 30) is based on an aluminum oxide of formula AIxOy which is deposited by an atomic layer deposition (ALD), preferably by means of a pair of trimethylaluminum / H2O precursors. 19) The manufacturing method according to one of claims 14 to 18, characterized in that an intermediate adhesive layer (40, 50) is additionally deposited between the inorganic layer (12, 22) of a unit (10, 20) and the organic layer (21, 31) of another unit (20, 30) for overcoming it, the or each intermediate layer being obtained by a surface treatment selected from the group consisting of plasma treatments, thin layer deposition of an adhesion promoter and the surface chemical treatments, the thin-layer deposition of an adhesion promoter being preferably implemented in the case where the organic layer concerned is based on a parylene. 20) Manufacturing method according to one of claims 14 to 19, characterized in that is deposited further on the inorganic layer (22,32) of the last unit (20, 30) deposited, an outer layer (4) electrically conductive and transparent in a thickness preferably between 50 nm and 150 nm. 21) The manufacturing method according to claim 20, characterized in that said outer layer (4) is based: - either of at least one transparent conductive oxide such as a tin-indium oxide spray deposited or ZnO deposited by an atomic layer deposition (ALD), or at least one compound selected from the group consisting of conductive transparent oxide / conductive metal oxide / transparent oxide compounds, carbon nanotubes and graphene monolayer compounds . 22) Manufacturing process according to one of claims 14 to 19, characterized in that the film (1, 1 ') obtained after the delamination step b) is shaped in order to obtain either a transparent and hermetic pouch type packaging. flexible, or a transparent and sealed encapsulation structure for covering an electrically conductive flexible substrate of an organic or hybrid organic / inorganic optoelectronic device. 23) A method of manufacture according to claim 20 or 21, characterized in that is carried out prior to step b) delamination 25 etching operations on the film (1, 1 ') deposited on said original substrate (2), in order to use this film once delaminated as an electrically conductive flexible substrate of an organic or hybrid organic / inorganic optoelectronic device. 10 15 30