Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
  • C23C18/122—Inorganic polymers, e.g. silanes, polysilazanes, polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
  • C23C18/1208—Oxides, e.g. ceramics
  • C23C18/1212—Zeolites, glasses
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
  • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
  • C23C18/1225—Deposition of multilayers of inorganic material
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
  • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02107—Forming insulating materials on a substrate
  • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
  • H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
  • H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
  • H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
  • H01L21/02222—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen the compound being a silazane
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
  • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/10—Semiconductor bodies
  • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
  • H10F77/169—Thin semiconductor films on metallic or insulating substrates
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/10—Semiconductor bodies
  • H10F77/16—Material structures, e.g. crystalline structures, film structures or crystal plane orientations
  • H10F77/169—Thin semiconductor films on metallic or insulating substrates
  • H10F77/1694—Thin semiconductor films on metallic or insulating substrates the films including Group I-III-VI materials, e.g. CIS or CIGS
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
  • H10K10/80—Constructional details
  • H10K10/88—Passivation; Containers; Encapsulations
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/84—Passivation; Containers; Encapsulations
  • H10K50/844—Encapsulations
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/84—Passivation; Containers; Encapsulations
  • H10K50/844—Encapsulations
  • H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7244—Oxygen barrier
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/541—CuInSe2 material PV cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]
  • Y10T428/24967—Absolute thicknesses specified
  • Y10T428/24975—No layer or component greater than 5 mils thick

Definitions

• the present invention relates to a multilayer structure providing improved gas tightness.
• this inorganic deposition generates mechanical stresses linked in particular to the differences in mechanical and thermal behavior between the inorganic layer and the polymer, ie the difference in elastic moduli, deformation capacities, the difference in thermal expansion, etc. These constraints cause a damage to the deposited inorganic layer, which has the effect of limiting its functional properties. Cracks may then appear which reduce the gas barrier properties of the polymer substrate and the inorganic deposition.
• US 2003/0203210 discloses a method of making alternate stacks inorganic layers and polymer layers having a thickness of 1 ⁇ m to a few ⁇ m on the thick polymeric substrate.
• the alternation of inorganic and organic layers then makes it possible to decorrelate the defects of each inorganic layer and thus considerably improve the gas barrier properties.
• the thus coated polymeric substrate has sufficient gas barrier properties to protect highly atmospheric sensitive devices such as organic optoelectronic devices or OLEDs (Organic Light Emitting Diodes).
• OLEDs Organic Light Emitting Diodes
• a multilayer structure formed of a substrate, at least one layer of SiO x N y H z type material and at least one layer of SiO 2 , the layer of SiO x N type material.
• y H z being intended to be interposed between the substrate and the layer of Si0 2.
• the SiO x N y H z layer forms a mechanical accommodation layer between the substrate and the layer of S1O 2 and adapts the constraints between the substrate and the layer of S1O 2 which avoids or limits the deterioration of the layer of Si0 2, thus improving gas tightness of the layer S1O2.
• the substrate is for example a polymer substrate, preferably transparent.
• This bilayer stack can be repeated, such a stack offers properties of outstanding gas barrier properties, much higher than expected by the sum of the gas barrier properties of two bilayer stacks.
• a layer of another material may be deposited on the bilayer structure, for example polymer.
• the structure according to the invention is obtained for example by the conversion by irradiation VUV and UV of a precursor liquid perhydropolysilazane type (PHPS).
• PHPS liquid perhydropolysilazane type
• the formation of the SiO 2 layer and the formation of the layer of SiO x N y H z material are simultaneous and occur under specific conditions depleted of oxygen and water.
• the subject of the present invention is therefore a multilayer structure comprising a substrate, and a first stack of an Si0 2 layer and a layer.
• type material SiO x N y H z disposed between the substrate and the S1O2 layer, wherein the layer of S1O2 and SiO x N-type material layer y H z have thicknesses such that the thickness of the layer of S1O 2 is less than or equal to 60 nm, the thickness of the layer of SiO x N y H z material is greater than twice the thickness of the SiO 2 layer and the sum of the thicknesses of the SiO 2 layer.
• the layer of SiOxNyHz material is between 100 nm and 500 nm and in which z is strictly less than the ratio (x + y) / 5, advantageously z is strictly less than the ratio (x + y) / 10.
• the value of x decreases from the interface between the layer of SiO x N y H z material and the SiO 2 layer to the substrate, and the value of y increases from the interface between the layer. of SiOxNyHz material and the S1O 2 layer to the substrate.
• x varies from 2 to 0 and / or y ranges from 0 to 1.
• the material of the S1O 2 layer has a Young's modulus greater than or equal to 30 GPa and the SiOxNyHz material layer has a Young's modulus less than or equal to 20 GPa.
• the stack may have a refractive index greater than 1.5.
• the stack or stacks is obtained by conversion of an inorganic precursor of the perhydropolysilazane type, the stack having a transmittance corresponding to the Si-H bond greater than 80%, advantageously greater than 90%. %, of the transmittance of the Si-H bond of the perhydropolysilazane-type inorganic precursor before conversion, measured by infrared reflection spectrometry in the case of a substrate of polymer material.
• the stack or stacks is obtained by conversion of an inorganic precursor of the perhydropolysilazane type, the stack having an absorbance corresponding to the Si-H bond of less than 20%, advantageously less than 10%, of absorbance of the Si-H bond of the perhydropolysilazane-type inorganic precursor before conversion, measured by infrared transmission spectrometry in the case of a silicon substrate.
• the layer of S i0 2 and the layer of SiO x N y H z type material are for example of amorphous materials.
• the substrate is of polymeric material.
• the multilayer structure may comprise a layer of polymer material on the SiO 2 layer of the first stack on the face opposite to that in contact with the layer of SiO x N y H z type material.
• the multilayer structure may comprise n stacks, n being a positive integer greater than or equal to 1, each stack each comprising a layer of (S i0 2 ) i and a layer of SiO X iN yi type material.
• H Z i, i being a positive integer between 1 and n
• layers (Si02) and i-type material SiO x in yi H Z i of each stack having thicknesses such that the thickness of the layers (S i0 2 ) i is less than or equal to 60 nm, the thickness of the layers of material of the type SiO X iN yi H zi is greater than twice the thickness of the layer of (S i02) i and the sum of the thicknesses of the layer of (S i0 2 ) i and of the layer of material of SiO X iN yi H Z i type is between 100 nm and 500 nm and in which z ⁇ is strictly less than the ratio (xi + yi) / 5, advantageously z ⁇ is strictly less than the ratio (xi + yi) / 10, where xi, y ⁇ , z ⁇ being identical or different for the different values of i.
• the multilayer structure may also comprise at least one layer of polymeric material disposed between the layer (S i0 2 ) i of a stack and the layer of SiO X iN y iH Z i material of the next directly stack.
• the multilayer structure comprises n-1 layers of polymer material, each of the layers of polymer material being disposed between two stacks.
• the present invention also relates to a method for producing a multilayer structure according to the invention, comprising:
• the production method may comprise step c) of depositing a layer of polymer material after step b).
• the production method comprises the repetition of steps a) and b) or a), b) and c).
• the present invention also relates to a method for producing a multilayer structure, comprising:
• step b ' the conversion by irradiation with ultraviolet radiation at a wavelength greater than 220 nm under an atmosphere having an oxygen content and a water content of less than 10 ppm, and c') the deposition on the layer formed in step b ', of a perhydropolysilazane liquid inorganic precursor on the substrate,
• FIG. 1 is a schematic side view of an example of a structure according to the invention
• FIG. 2 is a schematic side view of another exemplary structure
• FIG. 3 is a graphical representation of the measurement of the flow of water of the structure of FIG. 2 as a function of time in days,
• FIG. 4 is a schematic side view of another example of a structure according to the invention.
• FIG. 5 is a schematic side view of a variant of the structure of FIG. 4.
• FIG. 1 shows a structure S1 according to the invention comprising a substrate 2 and a stack E1 of a first layer A in S10 2 and a second layer B of material of the type SiO x N y H z .
• the layers A and B are distinct from one another and are made of different materials.
• the substrate 2 is for example a polymer material, for example of polyester type such as PET
• polyethylene terephthalate polyethylene terephthalate
• PEN polyethylene naphthalate
• polyolefin type such as PE
• polyethylene polyethylene
• PP polypropylene
• polyamide polyamide
• substrate for example monocrystalline or amorphous silicon, or glass.
• the substrate is transparent.
• the second layer B is deposited directly on the substrate 2 and interposes between the substrate 2 and the first layer A.
• the first layer A has a thickness e A , and a Young's modulus M A
• the second layer B has a thickness e B , and a Young's modulus M B.
• the thicknesses of the first A and second B layers B are such that:
• coefficients x for oxygen, y for nitrogen and z for hydrogen of the chemical formula of SiO x N y H z layer material B are such that 0 ⁇ and z ⁇ (x + y) / 5, advantageously 0 ⁇ z ⁇ (x + y) / 10.
• the coefficients x and y vary from the interface between layer A and layer B towards the interface between the substrate and layer B.
• x decreases from the interface between layer A and layer B. direction of the interface between the substrate and layer B, preferably from 2 to 0; It grows from the interface between layer A and layer B towards the interface between the substrate and layer B, preferably from 0 to 1.
• the Young's moduli of the first A and second B layers are such that:
• the measurement of the Young moduli of the layers A and B can be carried out according to the techniques described in the documents "A simple guide to determines the properties of films on substrates from nanoindentation experiments ", S. Bec, A. Tonck and J. Loubet, in Philosophical Magazine, Vol.86, Nos. 33-35, 21 Nov.-ll Dec.2006, pp5347-5358 and in the document “In vivo measurements of the elastic mechanical properties of human skin by indentation tests", in Medical Engineering & Physics, 30 (2008) pp599-606.
• the refractive index of the structure SI is preferably greater than 1.5.
• the materials of layers A and B may be amorphous.
• the second layer B being thicker than the first layer A and being less rigid than the layer A, because of its lower Young's modulus, the latter makes it possible to adapt the stresses between the first layer A and the substrate 2 and thus to avoid breaking the first layer A.
• the second layer B limits the deformation of the structure formed by the substrate 2 and the bilayer structure related to the differential deformation phenomenon between the first layer A and the substrate 2, which could result in a curvature of 1 set.
• the first layer A in S1O 2 because of its density naturally offers gas-tight properties. Due to the presence of the second layer B which forms a mechanical adaptation layer, the gas-tightness properties of the first layer A are not or only slightly degraded.
• the amount of Si-H bonds remaining after conversion of PHPS in layers A and B is very small. This characteristic can be measured in transmission infrared spectrometry; the band corresponding to the Si-H bonds is between 2100 and 2300 cm -1 (wavenumber).
• the absorbance corresponding to the Si-H bond of the structure of the invention is less than 20%, preferably less than 10%, of the absorbance of the Si-H bond of the PHPS before treatment.
• This transmission absorbance can be measured when the deposition is carried out on an infrared-transparent substrate, such as a silicon substrate.
• This small amount of Si-H can also be detected when the structure is deposited on a polymer substrate. The measurement is then carried out in reflection and the transmittance in the wave number range 2100-2300 cm -1 is greater than 80%, preferably greater than 90%.
• One side of the substrate 2 is covered with a liquid inorganic precursor, for example of the perhydropolysilazane type.
• the precursor is then irradiated by means of ultraviolet far radiation or ("VUV: Vacuum Ultraviolet” in English terminology) of wavelength less than or equal to 220 nm and UV radiation having a wavelength greater than or equal to at 220 nm.
• VUV Vacuum Ultraviolet
• the irradiation is by means of a low-pressure mercury lamp which combines a VUV wavelength of 185 nm and a UV wavelength of 254 nm. Deposition and conversion are done, for example, at room temperature.
• the dose received for The radiation at 185 nm is for example less than 20 days / cm 2 .
• the layers A and B are produced simultaneously in a one-step process.
• the conversion step is carried out in a medium depleted of oxygen and water in order to limit the thickness of the layer A as well as the conversion of the layer B, which makes it possible to obtain the characteristics of the layers mentioned above.
• the depleted medium presents:
• the process can be carried out in two steps: in a first step, a layer of a liquid inorganic precursor, for example of the perhydropolysilazane type, is deposited on the substrate, this layer is then subjected to UV irradiation wavelength greater than 220 nm with a negligible presence of oxygen and water, ie less than 10 ppm.
• a second step another layer of the same inorganic precursor as that of the first layer is deposited on the first layer, this second layer is irradiated by VUV at a wavelength greater than 220 nm in the presence of oxygen. the oxygen concentration is then between 10 ppm and 500 ppm.
• the structure S2 comprises a substrate 2, a first stack El, which is identical to that of the structure SI, and a stack E2 comprising a layer S1O2 A2 and a layer B2 made of SiO X 'N y .H z material.
• the layer B2 is deposited directly on the first layer Al of the structure S1 as described above. in relation to FIG. 1.
• the thicknesses of the layers A2 and B2 are such that:
• the coefficients x 'for the oxygen, y' for the nitrogen and z 'for the hydrogen of the chemical formula of the material of the layer B2 are identical or different from the coefficients x', y, z of the material of the layer B1 in SiO x N y H z respectively.
• x ', y', z ' are such that z' ⁇ (x'+y') / 5, advantageously z ' ⁇ (x' + y ') / 10.
• x 'and y' vary from the interface between the layer A2 and the layer B2 towards the substrate, x 'decreases from the interface between the layer A2 and the layer B2 towards the substrate, preferably from 2 to 0; y 'grows from the interface between the layer A2 and the layer B2 towards the substrate, preferably from 0 to 1.
• the layer thicknesses A2 and B2 as well as their Young moduli may be equal to those of the layers Al and Bl, respectively, or different.
• the layer B2 makes it possible to preserve the integrity of the layer A2 and thus to optimize its functional properties. Furthermore, during the deposition of the layers A2 and B2, the layer B 1 makes it possible to limit the mechanical problems, in particular the curvature of the structure formed by the substrate 2 and the two bilayer stacks.
• the structure S2 shows remarkable gas barrier properties as shown in the graphical representation of FIG. 3. On this one can see the measurement of the water flow in g. m -2 . day 1 , designated WVTR, as a function of time in days.
• Table 1 lists the barrier properties and the refractive indices of the structures SI and S2 in comparison with the structure forming a PET substrate and a layer of silica alone of 250 nm or of 600 nm thick made by temperature hydrolysis (80 ° C) of perhydropolysilazane or a 50 nm silica layer obtained by VUV conversion.
• the barrier properties are expressed in terms of "Barrier Improvement Factor (BIF) which expresses the improvement factor with respect to the PET substrate alone.” Water and helium permeation measurements have been made.
• BIF Barrier Improvement Factor
• S2 according to the present invention has significantly improved gas barrier properties compared to structures comprising only a substrate and a silica layer.
• the most remarkable property is the considerable increase in the stabilization time of the measurement (or "time lag" in English) of the structure S2 with respect to the structure SI, since for the structure SI, the stabilization time is 1 , 8 hours and for the structure S2, it is 1000 hours, it is multiplied by factor greater than 500.
• the layer B2 has a high tenacity and a density, its density which is lower than that of the layer A2 however remains much greater than that of the polymer substrate.
• the layer B2 between the Al layer and the A2 layer slows the progression of the gases through the Al and A2 layers.
• n a positive integer.
• the effect on increasing the gas barrier is further increased.
• the layers of each stack have relative thicknesses and a Young's modulus as described above.
• the structure S2 can be realized by repeating the method of realization of the structure SI. It covers the layer of S1O 2 of the IF structure of an inorganic precursor perhydropolysilazane type, converts it by means of VUV and UV radiation of wavelengths corresponding to those described above; depositing the second bilayer stack can also be performed in one step in an atmosphere fulfilling the conditions specified above.
• FIG. 4 another example of structure S3 according to the invention can be seen.
• the structure is a diagrammatic representation of FIG. 4
• the 53 comprises the structure S1 of FIG. 1 and a layer 4 of polymer material, this material may be identical to or different from that of the substrate 2.
• layer 4 could be made with hybrid materials such as organosilanes.
• the structure S4 can form, in addition to a gas barrier, a barrier to other elements, for example UV rays. It can form a heat-sealable barrier or a barrier having an additional function, such as for example forming a printing zone.
• the layer B the mechanical problems during the deposition of the layer of polymer material 4 are limited, such as the curvature of the entire stack.
• the layer 4 is deposited for example in solution and then by evaporation and / or polymerization if this is required.
• the thicknesses of the layers A1 and A2, B1 and B2 respectively may be identical or different.
• the layer of polymer material 4 can enhance the mechanical adaptation effect provided by the layer B2 and / or provide other specific properties, for example as the flexibility of the assembly or anti-UV properties or moisture absorbers.
• Structure S4 offers functional properties, in particular gas barriers similar to those of structure S2.
• the method for producing the structure S4 comprises the production of the structure 3 and the method of producing the structure S1 on the layer 4.
• the structure according to the invention deposited on a substrate made of polymer material has improved gas barrier properties and can be transparent. Such a level of tightness can not be obtained by conventional deposition technologies, such as physical vapor deposition, chemical vapor deposition or sputtering.
• the wet deposition mode makes it possible to limit the cost of the process and to make membranes forming barriers that are very efficient at low cost, unlike technologies using vacuum chambers such as the deposition of atomic layers (ALD for "Atomic layer Deposition "in English terminology) or the Barix® process of VITEX.
• the structure formed by the polymer substrate and the stack according to the invention at low cost can be used as protection for devices sensitive to the atmosphere, in particular sensitive to water and oxygen, such as organic electronic devices. (OLED, OTFT), thin film solar devices (CIGS) or even more generally to make containers for moisture sensitive contents.
• OLED organic electronic devices
• OTFT organic electronic devices
• CGS thin film solar devices
• the reduced cost of such a structure allows for use in a wide variety of fields.

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• 2011
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