WO2005051525A1 - Revetement ou couche de protection contre la penetration presentant des proprietes modulees et procedes de fabrication - Google Patents

Revetement ou couche de protection contre la penetration presentant des proprietes modulees et procedes de fabrication Download PDF

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Publication number
WO2005051525A1
WO2005051525A1 PCT/CA2004/002006 CA2004002006W WO2005051525A1 WO 2005051525 A1 WO2005051525 A1 WO 2005051525A1 CA 2004002006 W CA2004002006 W CA 2004002006W WO 2005051525 A1 WO2005051525 A1 WO 2005051525A1
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Prior art keywords
coating
barrier
substrate
layer
organic
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PCT/CA2004/002006
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English (en)
Inventor
Grzegorz Czeremuszkin
Mohamed Latreche
Michael Robert Wertheimer
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Polyvalor, Limited Partnership
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Publication of WO2005051525A1 publication Critical patent/WO2005051525A1/fr

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    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • 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
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/80—Composition varying spatially, e.g. having a spatial gradient

Definitions

  • This invention relates to an improved barrier layer, as a barrier to permeation of gases and vapors, especially for use in organic electronic devices.
  • the invention also relates to an organic electronic device incorporating the improved barrier layer.
  • the invention also relates to a method for producing the barrier layer, and to a method of producing an organic electronic device incorporating the barrier layer.
  • OLEDs are susceptible to deterioration by even trace amounts of oxygen and water.
  • This invention relates to extending the lifetime of such organic electronic devices (e.g., organic light emitting diode- and/or photovoltaic devices) by protecting them against oxygen and water vapor, using a barrier material comprising an impermeable coating with modulated properties.
  • This invention also relates to methods of producing such coatings for such devices.
  • glass plates have been the supporting substrate of choice, since glass has excellent barrier and transparency properties, and a metal sheet or a second glass plate has been used as the encapsulating means.
  • glass has the drawbacks of brittleness, high-weight, and rigidity. Replacing glass with impermeable plastic substrates according to the invention will resolve those problems, thereby enabling non-breakable, flexible, light and inexpensive display devices.
  • OLED-based displays high-quality images can be created by a matrix of many light emitting diodes encapsulated in transparent materials.
  • the diodes are patterned to form a pixel matrix, where a single pixel junction emits light of a given color.
  • All organic displays developed so far, contain oxygen- and moisture-sensitive components, namely, organic semiconductors and electron- injecting metals. Therefore, it is necessary to use materials with ultra-high barrier properties against permeation of water and oxygen for organic long-life display devices.
  • Device manufacturers estimate that transmission rates, which are several orders of magnitude lower than those characteristic for coatings used in flexible food packaging, are required to provide organic electronic devices with lifetimes of at least 10,000 hrs.
  • thermal stability An additional important requirement from a device manufacturer's standpoint is thermal stability. Certain processes in display production lines require the substrate to be heated above 200°C; this limits the number of suitable plastic materials available, to polymeric films with high Tg (glass transition) values, and it also limits designs of permeation barriers (discussed below) to those which are stable at elevated temperatures. Enhanced thermal stability is a particular characteristic of coatings according to the present invention. Another solution to the thermal stability problem may be depositing the barrier coating onto the plastic substrate after the latter has undergone processes requiring excessive heating. This, however, may not always be feasible; by using the invention, it is not necessary to change the manufacturing process sequence.
  • the prior art describes single- and multi-layer inorganic coatings, deposited on plastic substrates in order to decrease permeation of gases and vapors. It is also known in the display manufacturing art, to coat polymer films or sheets with thin inorganic coatings or composite inorganic/organic multilayer coatings, to render the polymer films or sheets essentially impermeable to oxygen and water vapor.
  • the latter types of structures consist of several distinct layers of different materials having finite thicknesses, for example, comprising alternating polymeric and inorganic layers, or stack(s) of various ceramic coatings.
  • patent application US 2003/0025448 describes a display encapsulated with a single-layer carbon coating that limits oxygen and water permeation through the backside of the display. [0009] It has also been proposed to improve impermeability of flexible polymeric substrates and of OLED encapsulation means by depositing multilayer coatings.
  • U. S. Patent 6,413,645 shows the OLED device with a multilayer barrier coating composed of several alternating stacks of a metal oxide and acrylate polymer. Such a system, however, does not possess sufficient thermal stability for the plastic substrate for OLEDs.
  • U. S. Patent 6,492,026 describes the same types of coatings using polymer substrates with glass transition temperatures higher than 120°C, thereby improving thermal stability.
  • Patent 6,146,225 describes a barrier for preventing water or oxygen molecules from reaching the OLED device, produced by depositing an organic coating and subsequently an inorganic coating between the device and the surrounding environment.
  • U. S. Patent 5,757,126 describes a method of passivating organic devices by overcoating the plastic substrate with a multilayer overcoating; the latter consists of alternating layers of a transparent polymer film and of a transparent dielectric material.
  • Typical single- and multilayer coatings including organic/inorganic or inorganic/inorganic layers, are all characterized by the presence of abrupt interfaces between the substrate and the coating, as well as between subsequent coating layers.
  • a coating with modulated properties exhibits smooth transitions of a given physical property between any two points across the coating thickness; therefore, the coating is free from abrupt interfaces.
  • modulated, or “graded index” layers are known from the optical coating art, where modulated properties include multiple gradual, or oscillating changes of the refractive index within the coating, thus providing particular light-reflection and light-transmission properties.
  • Such optical filters known as “rugate filters”, have precisely-controlled refractive index profiles (Angstrom unit precision) of successive layers across the coating thickness, and they can provide excellent narrow-band filters.
  • Patent 6,392,801 shows a polarizing beam-splitter including a rugate filter, which contains multiple layers of modulated composition, thereby comprising a surface coating with oscillating higher and lower index across its thickness.
  • the filter is produced from at least two materials having different indices of refraction.
  • the coatings may consist of two layers displaying graded index of refraction, as described in U. S. Patent 6,436,541, which presents conductive antireflective coatings consisting of two or more layers of anti-static film coating deposited on a substrate.
  • the surface of the film is roughened to provide a graded index of refraction.
  • U. S. Patent 6,432,478 reveals a ceramic heat barrier coating of low thermal conductivity, and a process for depositing of said coating.
  • a ceramic heat barrier coating is deposited on a substrate in such a way that the coating has a columnar growth pattern, which is interrupted and repeated a number of times throughout its thickness by successive renucleations of the ceramic deposit growth. This is achieved by a vapor phase deposition process, wherein a nucleating gas is introduced intermittently during deposition.
  • coatings with columnar structure are known to exhibit high permeation to gases and vapors, and they can therefore not be used for enhanced barrier purposes.
  • An optical filter having a profiled multilayer structure is described in U. S. Patent 6,256,148. It presents a rugate filter coating for reflecting electromagnetic waves, comprising a transparent coating on a substrate; the coating has incrementally varying depths of constant index of refraction. This optical filter therefore differs from the ones with modulated structure, by comprising distinguishable sub-layers of finite thickness and constant refractive index.
  • U. S. Patent 6,425,987 describes a technique for depositing multilayer interference thin films, using silicon as the only coating material.
  • the technique involves using only one coating material (pure silicon) to deposit thin films under high vacuum, by using an ion source with a working gas (or gases) to control the varying refractive index of the thin film during growth.
  • This technique can be used to deposit different kinds of optical thin films with different refractive indices or index gradients, and to make different kinds of multilayer interference filters without opening the vacuum chamber during the process.
  • This invention seeks to provide a barrier layer functioning as a barrier to permeation of gases and vapors.
  • this invention seeks to provide a composite sheet comprising an organic support film supporting the barrier layer.
  • the invention also seeks to provide an organic electronic device incorporating the aforementioned composite as a support substrate and/or barrier covering of the encapsulation envelope of the device. [0019] The invention also seeks to provide a method for producing the barrier layer.
  • the invention seeks to provide a method of producing the composite.
  • the invention also seeks to provide a method of producing an organic electronic device incorporating the composite of the invention.
  • a barrier layer as a barrier to permeation of gases and vapors, the barrier layer exhibiting a modulated property across its thickness such that the layer is free from abrupt interfacial variation in said property across its thickness.
  • a composite sheet for an organic electronic device comprising an organic polymer support film and a barrier layer of the invention, supported on the support film.
  • a method of producing a barrier layer of the invention comprising vapour depositing on a support surface to form a coating layer on said support surface, and changing at least one characteristic of the vapour deposition in a controlled manner effective to produce said modulated property in said coating layer.
  • the support surface is defined by an organic polymer support film, and recovering a composite of said film and said coating layer.
  • an organic electronic device in which photovoltaic devices or light emitting diodes are encased in a barrier envelope comprising a substrate supporting said devices or diodes and a barrier covering, said substrate and covering being impermeable to oxygen and water vapor, the improvement wherein at least one of said substrate and covering comprises a composite sheet of the invention.
  • an organic electronic device in which light emitting organic diodes are encased in a barrier envelope comprising a substrate supporting said diodes and a barrier covering, said substrate and covering being impermeable to oxygen and water vapor, the improvement wherein at least one of the substrate and covering comprises a composite sheet of the invention.
  • Fig. 1 illustrates graphically dependence of oxygen transmission rate on coating thickness
  • FIG. 2 illustrates schematically a support substrate of the invention
  • FIG. 3 illustrates schematically a support substrate of the invention in another embodiment
  • FIG. 4 illustrates schematically a support substrate of the invention in yet another embodiment
  • FIG. 5 illustrates schematically an OLED device of the invention
  • Fig. 6 illustrates schematically an OLED device of the invention in another embodiment
  • Fig. 7 illustrates schematically an OLED device of the invention in yet another embodiment
  • FIG. 8 illustrates schematically an OLED device of the invention in still another embodiment
  • Fig. 9 illustrates schematically an OLED device of the invention in yet another embodiment.
  • OLED DESCRIPTION AND PREFERRED EMBODIMENTS [0037]
  • Organic electronic devices, especially OLEDs and organic photovoltaic devices, are susceptible to deterioration by even small traces of oxygen and water.
  • a particular object of this invention is to provide an organic electronic device, having a flexible film substrate and an encapsulation, both of which possess enhanced impermeability to oxygen and water vapor.
  • the flexible film substrate and/or the encapsulation comprise an organic polymer film having thereon a barrier coating or layer with modulated properties, in which degradation of barrier characteristics arising from mechanical stresses in the coating during heating, bending or flexing are greatly reduced.
  • the coating contains no abrupt interfaces therein, the absence of abrupt interfaces leading to a dissipation of possible internal stresses. This, in turn, allows one to produce modulated-property coatings of increased thickness, and thereby enhanced impermeability to oxygen and water vapor.
  • the coating contains no abrupt interfaces therein, which leads to a dissipation of possible internal stresses. This, in turn, allows one to produce modulated- property coatings of increased thickness, and thereby enhanced impermeability to oxygen and water vapor.
  • Another particular object of this invention is to provide a flexible film barrier support substrate for an OLED device.
  • Yet another particular object of this invention is to provide a method of producing a single layer barrier coating with graded or modulated properties for application in oxygen- and water-sensitive organic electronic devices, such as OLED, organic photovoltaic devices, and other types of organic electronic devices (e.g., liquid crystal-, electrophoretic displays, etc.).
  • OLED organic light-emitting diode
  • OLED organic photovoltaic devices
  • other types of organic electronic devices e.g., liquid crystal-, electrophoretic displays, etc.
  • organic electronic components are supported on a transparent substrate impermeable to oxygen and water vapor
  • the transparent substrate comprises: i) an organic polymer support film, and ii) a single coating layer on the support film and disposed intermediate the support film and the light emitting diodes, the single layer having multiple gradual or oscillating changes of at least one property of the coating material, changes of which are spatially continuous, so that the coating exhibits modulated properties across its thickness.
  • the changing property may include at least one of the following physical, chemical and structural parameters of the coating material: composition, chemical structure, morphology, density, nanoporosity, solubility and diffusivity towards small inorganic and organic molecules, electrical conductivity, real and imaginary parts of the dielectric permitivity, polarizability, free energy, free volume, crystallinity, degree of crosslinking, viscosity, Young modulus, hydrophobicity, hydrophilicity, electron affinity, rigidity, and chemical reactivity toward oxygen and water molecules, including the capability of forming hydrogen bonds and chemical covalent or ionic bonds.
  • Those properties are known to be directly or indirectly related to permeability of the coating material.
  • organic light emitting diodes are supported on a transparent substrate which is impermeable to oxygen and water vapor, and they are encapsulated with a flexible barrier having improved impermeability, where the improvement comprises a single coating layer having multiple gradual or oscillating changes of at least one property of the coating material, which are spatially continuous thus exhibiting modulated properties along its thickness.
  • the modulated property can include at least one of the following physical, chemical and structural properties of the coating material: composition, chemical structure, morphology, density, nanoporosity, solubility and diffusivity of inorganic and organic small molecules, electrical conductivity, real and imaginary parts of the dielectric permitivity, polarizability, free energy, free volume, crystallinity, degree of crosslinking, viscosity, Young modulus, hydrophobicity, hydrofilicity, electron affinity, rigidity, and chemical reactivity toward oxygen and water molecules, including the capability of forming hydrogen bonds and chemical covalent or ionic bonds.
  • organic light emitting diodes are supported on a flexible transparent substrate with improved impermeability to oxygen and water vapor according to the invention, and they are encapsulated with a flexible barrier having improved impermeability according to the invention, thus providing a flexible and transparent OLED or photovoltaic device.
  • a method of producing a transparent support substrate and of producing an encapsulating envelope for use in organic electronic devices such as OLED, photovoltaic, liquid crystal and electrophoretic displays, involving: i) exposing a transparent polymer film to a vacuum process, for example, to a low temperature electric discharge plasma, and/or to a vacuum annealing at elevated temperature, and ii) coating the polymer film surface with a coating layer having modulated properties, using the physical vapor deposition (PVD) or the plasma enhanced chemical vapor deposition (PECVD) process, or their combination, where modulated properties of the coating result from continuously and repetitively changing, in a controlled manner, at least one of the characteristics of the deposition process.
  • PVD physical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • Such characteristics may include: deposition rate, flux and energy of ion bombardment, bias voltage, UV-, visible- and near infrared light emission from the deposition zone, the plasma's electron energy distribution function, ion temperature, concentration of specific ions, total thickness of the deposited coating, intensity and polarization of light reflected from the coating. Those characteristics can be measured in real time during the deposition, and they thereby allow one to monitor and control the process during its operation.
  • characteristics of the deposition process with modulated coating properties are modified by continuously, repetitively, and controUably changing at least one of the following process parameters: power delivered to the deposition zone, contribution of power delivered from independent power sources to the deposition zone, external electrical bias voltage, local gas flow and pressure in the deposition zone, reactive gas flow rate and composition, inert gas flow rate and composition, supplying additional UV vacuum UV (VUV) or infrared radiation, substrate positioning in the deposition zone, substrate movement, web speed, geometry of applied electromagnetic, magnetic and electric fields, intensity and frequency of electromagnetic, magnetic and electric fields and temperature.
  • VUV UV vacuum UV
  • modulated properties are produced by using PECVD, where modulated properties can be obtained by repetitive oscillating changes of power delivered to the deposition zone in the form of direct current (DC), alternating current (AC), radio frequency (RF), microwave (MW) or combinations thereof.
  • DC direct current
  • AC alternating current
  • RF radio frequency
  • MW microwave
  • Such changes can consist of sequential gradual transitions from high power delivered to the discharge to low power delivered to the discharge and vice versa, where the repetition rate and profile in time of those changes are predetermined.
  • modulated properties can be provided by changing the substrate position with respect to at least one of the powered- and grounded electrodes, to the gas feed inputs, or to the pumping outlet, where the gas flow field and the electromagnetic-, magnetic- or electric fields in the plasma display spatial gradients.
  • the barrier coating or layer in this invention is of any coating material employed for gas and vapor barrier properties, and especially impermeability to oxygen and water vapor.
  • coating materials that are depositable on a support film by vapor deposition, for example, physical vapor deposition (PVD) or plasma enhanced chemical vapor deposition (PECVD) or a combination thereof.
  • the barrier coating or layer may in effect be a single layer, a property of which, including chemical composition, is modulated across the thickness of the coating or layer. This is to be contrasted with prior barriers employing a plurality of discrete coatings or layers, in which abrupt interfacial variations occur at the junctions of the coatings.
  • OLED Organic light emitting diode devices rely on electroluminesce, their general structure is well established and is not the subject of this invention. Such devices employ component layers which are sensitive to oxygen and water molecules and must thus be effectively sealed from ingress of oxygen and water vapor while maintaining transparency to light and different desired physical characteristics.
  • an OLED comprises a plurality of light emitting diodes mounted on a support substrate.
  • the support substrate must have high transparency to light, and present a barrier to oxygen and water vapor.
  • the diodes placed on the support substrate are covered by a barrier covering, also impermeable to oxygen and water vapor.
  • the support substrate and covering together form a barrier envelope encasing the diodes.
  • Polymer support films may be employed both for the support substrate and the barrier covering of the OLED device.
  • the support films of the support substrate and barrier covering may be the same or different.
  • the support film should be transparent and of any suitable organic polymer, including homopolymers, copolymers and terpolymers which can be fabricated as a suitably thin film having the necessary and desirable physical characteristics to form a barrier support substrate or covering for the diodes, physical characteristics of particular importance are strength and flexibility at desired film thicknesses for the OLED device.
  • Suitable polymers for the polymer film include, by way of example, polyolefins, for example, polyethylene and polypropylene; cyclopolyolefins, for example, polynorbornenes; polycarbonates; polyesters; polyarylates, polyacrylates, polyethyleneterephthalate; polyethylenenaphthalate; polystyrene; polyamides; polyimides; polyethersulfone, and polyorganosilicones, as well as other transparent polymers and copolymers including other high T g polymers.
  • the polymer film may include one or more layered polymer components.
  • Preferred polymer films are chosen from high T g polymers, for example, cyclopolyolefins, polyethersulfones, polyarylates, and from polyethyleneterephthalate and polyethylenenaphthalate.
  • the polymer films will suitably have a thickness of 5 ⁇ m to 1000 ⁇ m, preferably 25 ⁇ m to 500 ⁇ m.
  • Modulated Barrier Layer [0060]
  • the barrier layer provides a barrier to oxygen and water vapor and may be of a single or variable chemical composition when formed as a modulated coating impermeable to oxygen and water vapor.
  • Suitable coating components may be formed from transparent materials, such as oxides, nitrides, mixed compositions, and salts; for example, SiO x , SiO x C y , Si x N y , Si x N y C z , SiO x N y , TiO x , Al x O y , SnO y , indium-tin oxide, magnesium fluoride, magnesium oxyfluoride, calcium fluoride, tantalum oxide, yttrium oxide, zirconium oxide, barium oxide, magnesium oxide, titanium oxide, niobium oxide, hafnium oxide, and mixtures thereof, wherein x is from 1 to 3, y is 0.01 to 5, and z is 0.01 to 5.
  • Preferred coating materials are stoichiometric or non-stoichiometric silicon oxide deposited by plasma, stoichiometric or non-stoichiometric silicon nitride, silicon oxynitride and their mixtures deposited by plasma; and modulated structures including one or both of silicon dioxide, silicon nitride and silicon oxynitride, and polymer coatings, for example, polyacrylates or organic plasma polymers obtained from organosilicones, hydrocarbons or acrylates.
  • the barrier coating layer suitably has a thickness of 10 nm to 10 ⁇ m, preferably 60 nm to 5 ⁇ m and more preferably 100 nm to 2 ⁇ m.
  • the coating layer may alternate in composition, in a modulated manner, with, for example, inorganic and organic zones.
  • the composite sheet comprising the support film and the barrier layer should be transparent to light and suitably will have a transparency greater than 65% and preferably greater than 85%, measured according to ASTM D
  • the barrier coating layer which forms the barrier to oxygen and water vapor should suitably display an oxygen transmission rate lower then 1 cm 3 /(m 2 day-atm), and preferably lower than 0.01 cm 3 /(m 2 day-atm) and more preferably lower than 0.005 cm /(m day-atm) measured according to ASTM F
  • the method of producing the composite sheet essentially involves coating the organic polymer film, as described hereinbefore, with a coating layer, as described hereinbefore.
  • the barrier coating layer may be applied by various coating techniques, but preferably by physical vapor deposition (PVD), for example, evaporation or sputtering or by chemical vapor deposition (CVD), for example, plasma enhanced chemical vapor deposition (PECVD) or organic vapor phase deposition (OVPD). These methods are capable of producing very thin coatings, which are stable and flexible but of satisfactory hardness, and which exhibit low oxygen and water vapor permeations. PVD and PECVD are carried out under partial vacuum.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • OVPD organic vapor phase deposition
  • the coating technique is modified, in accordance with the invention and as described herein, so that the formed barrier coating layer exhibits a modulated property across its thickness.
  • the composite sheet forms the front, transparent support of an OLED device, the diodes of the device being encapsulated on the other side by a suitable non-transparent barrier covering, also impermeable to oxygen and water vapor, thus providing the OLED device having one-side light emission.
  • a suitable non-transparent barrier covering material may be of a metal can, plate, foil or an evaporated film, as is well known in the OLED art.
  • the composite sheet forms the front, transparent background of an OLED device, and the barrier covering on the other side is also formed of a transparent support substrate of the invention, thus providing an OLED device that is transparent and emits light on both sides.
  • a composite sheet according to the invention thus encapsulates the diodes both as the front support and as the rear barrier covering, together forming a barrier envelope.
  • the composite sheet of the invention forms the barrier covering and the front support of the OLED device is of another material, for example, glass, as known in the OLED art.
  • an OLED device is supported on a plastic barrier support and a barrier layer of the invention is deposited on the
  • the OLED device whereby the OLED device is thin film encapsulated.
  • an OLED device is supported on a glass support, and a barrier layer of the invention is deposited on the OLED device.
  • the composite sheet according to the invention may be used also in other types of devices, such as liquid crystal displays or in organic photovoltaic devices, which are known in the prior art to require transparent materials impermeable to oxygen and water vapor.
  • OLED is suitably formed under vacuum conditions to minimize introduction of contaminants which may chemically or physically damage the OLED or alter its characteristics. Small molecule diode components, sensitive to oxygen and water molecules, are deposited onto the support substrate by vacuum evaporation.
  • organic light emitting diode namely, polymeric light emitting diodes (PLED) may, for example, be deposited onto the composite sheet, for example, from a solution in a suitable organic solvent in an inert atmosphere.
  • PLED polymeric light emitting diodes
  • the composite sheet is produced as outlined hereinbefore. Thereafter, in a vacuum process a transparent conductive layer, for example, indium-tin oxide, is deposited on the composite sheet.
  • a transparent conductive layer for example, indium-tin oxide
  • the transparent conductive layer is patterned to form the lower electrode of the diode, which is the hole-injecting layer.
  • the hole-injecting layer there is deposited, successively, the hole-transporting layer and the electron-transporting layer, both of which are organic layers, and thereafter the electron- injecting layer which forms the upper electrode, and which may be, for example, of calcium, lithium, magnesium or aluminium, or suitable metal alloys.
  • the afore-mentioned layers may be deposited by vacuum evaporation, well known in the OLED art.
  • the organic layers and the upper electrode may also be deposited by printing, for example, ink jet printing, stamping or other transfer techniques in an inert atmosphere, as well known in the PLED art.
  • Advantages of the invention are related to (i) the mechanical properties of the coatings and to (ii) the permeation mechanism of gases and vapors through these ultra-high permeation barrier-coatings.
  • Single- and multilayer coatings described in the prior art possess abrupt interfaces between the substrate and the coating, and between successive component layers. On a microscopic scale, this results in stress accumulation at the interfaces which, beside dust particles, is the main source of coating defects during handling and processing of the substrate.
  • Plastic substrates for OLEDs are typically thicker than 100 ⁇ m and the encapsulated flexible OLED devices are typically thicker than 200 ⁇ m; therefore, their exposure to excessive tensile deformation during a production process, although possible, is rather unlikely.
  • bending and flexing of these substrate films and of the encapsulated flexible devices occurs frequently during processing, handling, and in final use.
  • Fig. 1 shows dependence of oxygen transmission rate, OTR in [cm
  • Fig. 2 shows a support substrate for organic electronics (100) comprising a flexible film (20) and a barrier coating (10) thereon with modulated properties.
  • Fig. 3 shows a support substrate for organic electronics (100) consisting of a composite flexible film (20) comprising film layers (21 and 22), and a barrier coating (10) thereon with modulated properties.
  • Fig. 4 shows a support substrate for organic electronics (100) comprising a flexible film (20), a barrier coating thereon with modulated properties (10) and a surface layer (60).
  • Fig. 5 shows an OLED device (200) on a flexible film substrate
  • the coating is deposited onto a flexible film (420) and attached to the OLED layer (50) using a resin layer (460).
  • the OLED components include bottom conductive layer (ITO or/and TFT-silicon) (52), hole transporting layer (54), electron transporting layer (56), and top electrode (58).
  • Fig. 6 shows an OLED device (200) on a flexible film substrate
  • FIG. 7 shows an encapsulation (40) and glass (30) based OLED device (200) comprising a coating with modulated properties (410); a) thin film encapsulation, where the coating with modulated properties (410) is deposited onto a passivation layer (440), which, in turn, is in contact with OLED components (50).
  • the latter include bottom conductive layer (ITO or/and TFT- silicon) (52), hole transporting layer (54), electron transporting layer (56), and top electrode (58); b) thin film encapsulation, where the coating with modulated properties (410), which is deposited onto a passivation layer (440) is additionally protected by a polymer layer (420); c) thin film encapsulation consisting of the coating with modulated properties (410).
  • Fig. 8 shows an OLED device (200) on a flexible substrate (100) comprising a barrier-coating with modulated properties (10) therein, and enclosed using an encapsulating mean (40) which comprises the coating with modulated properties (410).
  • the latter include bottom conductive layer (ITO or/and TFT-silicon) (52), hole transporting layer (54), electron transporting layer (56), and top electrode (58); b) thin film encapsulation, where the coating with modulated properties (410), which is deposited onto a passivation layer (440) is additionally protected by a polymer layer (420); c) thin film encapsulation using the coating with modulated properties (410).
  • Fig. 9' shows an OLED device (200) on a flexible substrate (100), which comprises the flexible film (20) and the coating with modulated properties (10).
  • the OLED device is enclosed using an encapsulating means (40), which also comprises the coating with modulated properties (410).
  • the coating is deposited onto a flexible film (420) and attached to the OLED layer using an intermediate layer (460).
  • the sample across its entire thickness, was then composed of the PET substrate in contact with silica, which gradually changed to plasma-polymerized HMDSO, then gradually changing back to silica, which was finally modified at the surface by the final exposure to oxygen/argon plasma.
  • the sample had a hydrophilic surface, displaying a low water contact angle ( ⁇ 10°).
  • a coupon of optical grade PET film substrate was placed in a
  • PECVD vacuum chamber directly onto the powered electrode.
  • the chamber was evacuated and deposition of a silica coating was performed in an RF plasma discharge (13.56 MHz, 80 W) using a mixture of HMDSO/ O 2 /Ar at an approximate molar ratio of 1 :8:3, respectively.
  • the oxygen flow was manually modulated from a high content (1 :8:3) to a low content (1 :0:3), and back again to a high content.
  • oxygen flow was stopped, this time causing a gradual decrease in the concentration of oxidizing gas in the plasma.
  • Example 3 Across its entire thickness, the sample was then composed of the PET substrate in contact with silica, which then gradually changed to plasma- polymerized HMDSO, then gradually changed back to silica, which again gradually changed to plasma-polymerized HMDSO.
  • the sample had a highly hydrophobic surface, displaying a high water contact angle (>70°).
  • the chamber was evacuated and deposition of a silica coating was performed in an RF plasma discharge (13.56 MHz, 150 - 10 W) using a mixture of HMDSO/O 2 /He at an approximate molar ratio of 1 :5:3, respectively.
  • the discharge power was gradually decreased from 150 W to 10 W, then gradually increased from 10 W to 150 W.
  • This procedure was repeated three times, so that the coating was deposited during oscillating changes of power fed to the plasma.
  • the intensities of optical emission lines characteristic for SiH 1" and O * were used to control the process.
  • the sample across its entire thickness, was then composed of the PET substrate, in contact with highly densified silica, which gradually changed to silica of lower densification degree, which then gradually changed back to high-density silica, etc.
  • a coupon of optical grade, hard-coated polyarylate (substrate film) was placed in the PECVD vacuum chamber, directly onto the powered electrode.
  • the chamber was evacuated and deposition of a silica coating was performed in an RF plasma discharge (13.56 MHz, 350 - 5 W) using a mixture of HMDSO/O /He at an approximate molar ratio of 1:5:3, respectively.
  • the negative DC self-bias voltage was gradually changed from -600 V to -50 V, and then gradually from -50 V to -600 V. This was achieved simply by varying the discharge power.
  • the procedure was repeated three times, so that the coating was deposited during oscillating changes of the self-bias voltage at the substrate, thus it was exposed to controlled, varying ion bombardment of slowly oscillating intensity.
  • the sample across its entire thickness, was then composed of the PET substrate, the interphase between the substrate and the silica coating, and high- density silica, which gradually changed to silica of lower density, then changing back to high-density silica, etc.
  • a coupon of optical grade, hard-coated polyester substrate film was placed in the PECVD vacuum chamber, onto the powered electrode.
  • the chamber was evacuated and deposition of a silica coating was performed in an RF plasma discharge (13.56 MHz, 350 - 5 W) using a mixture of HMDSO/O 2 He at an approximate molar ratio of 1 :5:3, respectively.
  • the negative DC self-bias voltage was varied sinusoidally between -600 V and - 50 V. This was achieved by controlling the discharge power, using an external function generator operating at 1 Hz.
  • the process was continued for 3 minutes, so that the coating was deposited during rapid profiled changes of the self-bias voltage at the substrate thus being exposed to ion bombardment of (1Hz) oscillating intensity.
  • the sample across its entire thickness, was then composed of the PET substrate / the interphase region between the substrate and the silica coating comprising high-density silica, which then gradually changed to silica of lower density, then back again to high-density silica, etc.
  • the plasma process used in this experiment is not equivalent to so-called "pulsed plasma", which consists of sequential ON and OFF phases of discharge plasma.

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Abstract

L'invention concerne un revêtement de protection amélioré contre la pénétration des gaz et des vapeurs, utilisé en particulier dans des substrats de dispositifs électroniques organiques et dans l'encapsulation de ces dispositifs, et comprenant une couche de matériau présentant des propriétés modulées. Les propriétés modulées permettent de multiples changements progressifs, périodiques ou oscillants d'au moins un paramètre physique, chimique ou structurel du matériau, lesdits changements se produisant uniformément et de manière continue dans le revêtement. Les propriétés physiques du matériau de revêtement de protection présentent ainsi une transition uniforme entre deux points de l'épaisseur du matériau, le revêtement ne présentant donc pas d'interfaces abruptes. Le revêtement de protection amélioré présente également une meilleure stabilité mécanique.
PCT/CA2004/002006 2003-11-25 2004-11-23 Revetement ou couche de protection contre la penetration presentant des proprietes modulees et procedes de fabrication WO2005051525A1 (fr)

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EP1727222A2 (fr) * 2005-05-27 2006-11-29 Novaled AG Élément transparent émetteur de lumière
WO2008057394A1 (fr) * 2006-11-01 2008-05-15 The Trustees Of Princeton University Couches hybrides pour revêtements appliqués sur des dispositifs électroniques ou d'autres articles
WO2008063266A1 (fr) * 2006-11-01 2008-05-29 The Trustees Of Princeton University Revêtements multicouches pour une utilisation sur des dispositifs électroniques ou autres articles
EP2051311A1 (fr) * 2007-10-15 2009-04-22 Applied Materials, Inc. Procédé pour la fourniture d'une pile de couches d'encapsulation, dispositif de revêtement et système de revêtement
US7915815B2 (en) 2005-03-11 2011-03-29 Novaled Ag Transparent light-emitting component
US7968146B2 (en) 2006-11-01 2011-06-28 The Trustees Of Princeton University Hybrid layers for use in coatings on electronic devices or other articles
JP2011520041A (ja) * 2008-05-07 2011-07-14 ザ、トラスティーズ オブ プリンストン ユニバーシティ 電子デバイス又は他の物品上のコーティングに使用するハイブリッド層
US7985188B2 (en) 2009-05-13 2011-07-26 Cv Holdings Llc Vessel, coating, inspection and processing apparatus
US8034419B2 (en) 2004-06-30 2011-10-11 General Electric Company Method for making a graded barrier coating
US8512796B2 (en) 2009-05-13 2013-08-20 Si02 Medical Products, Inc. Vessel inspection apparatus and methods
CN103483009A (zh) * 2013-08-30 2014-01-01 西北工业大学 具备抗裂纹扩展能力的多层环境障碍涂层结构的制备方法
US8766240B2 (en) 2010-09-21 2014-07-01 Universal Display Corporation Permeation barrier for encapsulation of devices and substrates
EP2800134A1 (fr) * 2013-04-30 2014-11-05 Samsung Display Co., Ltd. Substrat pour dispositif d'affichage et appareil d'affichage l'utilisant
DE102013105003A1 (de) * 2013-05-15 2014-11-20 Osram Opto Semiconductors Gmbh Organisches optoelektronisches Bauteil
WO2015002756A1 (fr) * 2013-06-21 2015-01-08 Universal Display Corporation Couche barrière hybride pour substrats et dispositifs électroniques
US8933468B2 (en) 2012-03-16 2015-01-13 Princeton University Office of Technology and Trademark Licensing Electronic device with reduced non-device edge area
US8987876B2 (en) 2013-03-14 2015-03-24 General Electric Company Power overlay structure and method of making same
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JP2016039078A (ja) * 2014-08-08 2016-03-22 株式会社ジャパンディスプレイ 表示装置、及びその製造方法
US9299630B2 (en) 2012-07-30 2016-03-29 General Electric Company Diffusion barrier for surface mount modules
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US9458536B2 (en) 2009-07-02 2016-10-04 Sio2 Medical Products, Inc. PECVD coating methods for capped syringes, cartridges and other articles
US9545360B2 (en) 2009-05-13 2017-01-17 Sio2 Medical Products, Inc. Saccharide protective coating for pharmaceutical package
US9554968B2 (en) 2013-03-11 2017-01-31 Sio2 Medical Products, Inc. Trilayer coated pharmaceutical packaging
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US9863042B2 (en) 2013-03-15 2018-01-09 Sio2 Medical Products, Inc. PECVD lubricity vessel coating, coating process and apparatus providing different power levels in two phases
US9878101B2 (en) 2010-11-12 2018-01-30 Sio2 Medical Products, Inc. Cyclic olefin polymer vessels and vessel coating methods
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US10183022B2 (en) 2014-09-29 2019-01-22 Ea Pharma Co., Ltd. Pharmaceutical composition for treating ulcerative colitis
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WO2020233173A1 (fr) * 2019-05-22 2020-11-26 京东方科技集团股份有限公司 Substrat souple, procédé de préparation de substrat souple et panneau d'affichage
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US7915815B2 (en) 2005-03-11 2011-03-29 Novaled Ag Transparent light-emitting component
EP1727222A2 (fr) * 2005-05-27 2006-11-29 Novaled AG Élément transparent émetteur de lumière
EP1727222A3 (fr) * 2005-05-27 2008-11-19 Novaled AG Élément transparent émetteur de lumière
JP2018018830A (ja) * 2006-11-01 2018-02-01 ザ、トラスティーズ オブ プリンストン ユニバーシティ 電子デバイス又は他の部品上のコーティングに使用するハイブリッド層
CN103187455A (zh) * 2006-11-01 2013-07-03 普林斯顿大学理事会 用于电子器件或其它制品上的涂层的杂化层
JP2014150063A (ja) * 2006-11-01 2014-08-21 Trustees Of Princeton Univ 電子デバイス又は他の部品上のコーティングに使用するハイブリッド層
US7968146B2 (en) 2006-11-01 2011-06-28 The Trustees Of Princeton University Hybrid layers for use in coatings on electronic devices or other articles
JP2010508640A (ja) * 2006-11-01 2010-03-18 ザ、トラスティーズ オブ プリンストン ユニバーシティ 電子デバイス又は他の部品上のコーティングに使用するハイブリッド層
CN103187455B (zh) * 2006-11-01 2017-07-04 普林斯顿大学理事会 用于电子器件或其它制品上的涂层的杂化层
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