US20140314958A1 - Inorganic/organic hybrid nanolaminate barrier film - Google Patents
Inorganic/organic hybrid nanolaminate barrier film Download PDFInfo
- Publication number
- US20140314958A1 US20140314958A1 US14/274,527 US201414274527A US2014314958A1 US 20140314958 A1 US20140314958 A1 US 20140314958A1 US 201414274527 A US201414274527 A US 201414274527A US 2014314958 A1 US2014314958 A1 US 2014314958A1
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- mixture
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- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
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- 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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
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- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2998—Coated including synthetic resin or polymer
Definitions
- the present invention is directed to barrier films and more particularly to multilayer barrier coatings.
- the active elements of polymer-based LEDs may require incorporation of barrier layers with oxygen permeability levels as low as 10 ⁇ 5 cc/m 2 /day and water vapor permeability levels as low as 10 ⁇ 6 g/m 2 /day.
- a 7 mil thick coating of polyethylene teraphthalate (PET) has an oxygen transmission rate of 8.7 cc/m 2 /day and a water vapor permeability of 10 g/m 2 /day.
- PET polyethylene teraphthalate
- State of the art plastics such as Alcar can protect components with oxygen and water vapor permeability levels of about 7 cc/m 2 /day and 0.016 g/m 2 /day respectively.
- Single barrier coatings of thin films of inorganic materials such as Al, SiO 2 Al 2 O 3 and Si 3 N 4 can be vacuum deposited on polymer substrates to improve barrier impermeability.
- Such single layer coatings can reduce oxygen and water vapor permeability to levels of about 10 ⁇ 3 cc/m 2 /day and 10 ⁇ 3 g/m 2 /day respectively.
- Multilayer barrier coatings have been developed using a “sandwich” strategy with an inorganic layer is situated between two polymer layers to further improve the aggregate barrier properties.
- Sheats and coworkers U.S. Pat. No. 6,146,225
- a 35 nm thick silicon nitride as an inorganic layer
- a one micron thick layer of an acrylate as the polymer material to achieve a barrier with a water-vapor permeation rate of 1.8 ⁇ 10 ⁇ 7 g/m 2 /day, which is about 40 times better than the requirement for most optoelectronic devices.
- this material is not optically transparent, limiting its use to certain applications only.
- the vacuum-based deposition methods limit both the area upon which a coating can be placed (the area must be smaller than the deposition chamber), which in turn limits their use for larger area devices.
- flash evaporation and sputter deposition do not tend to provide for uniform conformal coatings of large area surfaces, especially for non-planar substrates with inherent curvature (or even three-dimensional barrier-protection targets). It would be desirable to have a multi-layer, transparent, and durable film that provides for uniform, inexpensive and conformal coating of larger areas with effective environmental resistance in a range of environments.
- FIG. 1 is a cross-sectional schematic diagram of an inorganic/organic hybrid nanolaminate barrier film according to an embodiment of the present invention.
- the organic layers 104 are polymers such as polyethylene naphthalate (PEN), polyether etherketone (PEEK), or polyether sulfone (PES).
- PEN polyethylene naphthalate
- PEEK polyether etherketone
- PES polyether sulfone
- polymers created from styrene polymer precursors, methyl styrene polymer precursors, (meth)acrylate polymer precursors, both fluorinated and non-fluorinated forms of these precursors, and combinations of two or more of these precursors can be used as the organic layers 104 .
- These organic materials are desirable because of their superior thermal properties and excellent gas barrier characteristics.
- one or more of the organic layers 104 e.g., an uppermost layer 110 , may optionally be a superhydrophobic layer such as fluoroalkylsilane.
- Fluoroalkylsilane thin films are described, e.g., by Akira Nakajima et al., in “Transparent Superhydrophobic Thin Films with Self-Cleaning Properties”, Langmuir 2000, 16, 7044-7047, which is incorporated herein by reference.
- the layer structure of the barrier film 100 provides a long path for water or oxygen to penetrate the barrier film to an underlying substrate 106 , e.g., via pinholes and/or gaps at interfaces between layers as indicated by the path 108 .
- the permeability of the nanolaminate barrier film 100 to oxygen and water vapor can be adjusted by changing the number of layers. By using hundreds to thousands of interdigitated inorganic layers 102 and organic layers 104 within the barrier film 100 , the large number of layers combined with randomly located pinholes within the nanolaminate results in tortuous paths for molecules such as water vapor and oxygen that might enter from the environment outside of the barrier film 100 . The more layers, the more tortuous the path for permeating molecules. Thus, the more layers, the less permeable the barrier film 100 is to water vapor and oxygen. In embodiments of the present invention, there can be 100 or more, 1000 or more, 10,000 or more or 100,000 or more individual layers in the composite barrier film 100 .
- hydrophobic groups can be incorporated into or eliminated from the polymer precursors used to form the organic layers 104 to tune (increase and/or decrease) the hydrophobicity of the resulting organic layers 104 and, in turn, adjust the permeability of the barrier film 100 .
- non-polar hydrophobic groups including but not limited to methyl groups and benzyl (aromatic) groups, can be attached to the polymer precursors.
- increasing ionic strength increases hydrophobic interactions.
- the anions and cations listed below are in a series from those that highly favor hydrophobic interactions to those that decrease hydrophobic interactions.
- any of these anions and/or cations and/or similar compounds can be incorporated into the polymer precursors, resulting in polymers with tuned hydrophobicity.
- hydrophobic amino acids such as tryptophan, isoleucine, phenylalanine, tyrosine, leucine, valine, methionine, and alanine could be used as side chains for the polymer precursors.
- Gemini surfactants are highly reactive and could be used as structure-directing agents. Gemini surfactants have two hydrophilic head groups and two hydrophobic groups in the molecule, in contrast to conventional surfactants that have only single hydrophilic and single hydrophobic groups.
- the oxygen permeability of the barrier film 100 can be made less than about 1 cc/m 2 /day, 0.1 cc/m 2 /day, 0.01 cc/m 2 /day, 10 ⁇ 3 cc/m 2 /day, 10 ⁇ 4 cc/m 2 /day, 10 ⁇ 5 cc/m 2 /day, 10 ⁇ 6 cc/m 2 /day, or 10 ⁇ 7 cc/m 2 /day.
- the water vapor permeability of the barrier film 100 can be made less than about 1 g/m 2 /day, 0.1 g/m 2 /day, 0.01 g/m 2 /day, 10 ⁇ 3 g/m 2 /day, 10 ⁇ 4 g/m 2 /day, 10 ⁇ 5 g/m 2 /day, 10 ⁇ 6 g/m 2 /day, or 10 ⁇ 7 g/m 2 /day.
- the nanolaminate barrier film 100 can be made in a single-step (or few sequential step) process by self-assembly using sol-gel techniques.
- Self-assembly of nanocomposite materials using sol-gel techniques is described, e.g., in U.S. Pat. No. 6,264,741 to Brinker et al., the entire contents of which are incorporated by reference.
- a sol can be prepared, e.g., by combining one or more alkoxides, an alcohol, water and dilute hydrochloric acid (HCl) and heating the resulting mixture.
- a coupling agent is then introduced to the mixture followed by a surfactant (or Gemini surfactant), in a quantity sufficient that the initial surfactant concentration is below the critical micelle concentration.
- a surfactant or Gemini surfactant
- one or more polymer precursors e.g., monomers suitable for the formation of PEN, PEEK or PES are then added followed by a cross-linker agent and an initiator.
- the polymer precursors can include styrene polymer precursors, methyl styrene polymer precursors, (meth)acrylate polymer precursors, either fluorinated or non-fluorinated forms of these, precursors and combinations of two or more of these precursors.
- a substrate is coated with the sol and the alcohol is allowed to evaporate. The alcohol evaporation drives a self-assembly reaction that forms the multilayer barrier structure described with respect to FIG. 1 .
- Suitable alkoxides are structured around a central element X.
- Suitable central elements X include Al, B, Ba, Pb, Se, Si, and Sn.
- Other suitable central elements X include transition metals, e.g., Ag, Au, Cd, Co, Cr, Cu, Fe, Ir, Mn, Mo, Nb, Ni, Sr, Ta, Ti, V, W, Y, Zn, Zr, etc.
- suitable alkoxides include polysiloxanes such as tetraethylorthosilicate (TEOS).
- TEOS tetraethylorthosilicate
- titanium (Ti)-based inorganic layers 102 examples of suitable alkoxides include titanium ethoxide or titanium isopropoxide.
- a sol can be prepared, e.g., by combining tetraethylorthosilicate (Si(OCH 2 CH 3 ) 4 , also known as TEOS), ethanol, water and dilute HCl (dilute so as to minimize the siloxane condensation rate) in molar ratios of 1:3.8:1:5 ⁇ 10 ⁇ 5 respectively and heated at about 60° C. for about 90 minutes.
- the sol is then diluted with ethanol in a 1:2 ration after which water and dilute HCl are added.
- a coupling agent such as 7-octenlytrimethoxysilane (OTS), or methacryloxypropyl trimethoxysilane (MPS) is then introduced to the mixture followed by a surfactant such as cetyltrimethylammonium bromide (CTAB) so that the initial surfactant concentration is below the critical micelle concentration.
- a surfactant such as cetyltrimethylammonium bromide (CTAB)
- a monomer e.g., 2,6-Dimethylnaphthalene (DMN; to create polyethylene naphthalate (PEN)
- PEN polyethylene naphthalate
- B/FS di-para-fluorophenylsulfone
- HDM hexanedioldimethacrylate
- BME benzoin dimethylether
- ACBN 1,1′-azobis(1-cyclohexane carbonitrile
- the concentration of the surfactant, water, ethanol, TEOS, and organic monomers can be varied.
- various structures for the inorganic layers 102 and organic layers 104 such as lamellar layers, tubules, or nanostructures exhibiting 1- and 3-dimensional connectivity (e.g., hexagonal or cubic) of the constituent phases, respectively, can be produced and the characteristic dimension (d-spacing) of the composite architecture controlled.
- the organic and inorganic precursors a wide range of materials combinations can be prepared. Annealing the films at about 125° C.-150° C. or greater (and/or below the decomposition temperature of the organic materials) further densifies the siloxane material and improves impermeability.
- the substrate 106 can be coated with the sol mixture by any suitable technique, such as dip coating, spin coating, spray coating, web coating, or microgravure web coating.
- suitable coating machines are commercially available, e.g., from Faustel, Inc., of Germantown, Wisconsin.
- a Continuous Coater Type BA from Werner Mathis AG of Zurich, Switzerland may be used to coat the substrate with the sol mixture.
- the substrate can be rapidly coated with the sol, e.g., by dip coating (e.g., about 25 cm/min dip and withdrawal rate; for large area substrates) or spin coating (e.g., about 1500 rpm for about 1 minute for small area substrates).
- dip coating e.g., about 25 cm/min dip and withdrawal rate; for large area substrates
- spin coating e.g., about 1500 rpm for about 1 minute for small area substrates.
- the ethanol component of the sol begins to evaporate, and the increasing concentrations of water and surfactant cause the surfactant concentration to exceed the critical micelle concentration, resulting in both micelle formation and the incorporation of the alcohol-soluble organic monomers into the micellar interiors.
- This TEOS and CTAB-based sol gel chemistry provides for self-assembly of nanostructures whose chemical backbones condense into dense, stable materials.
- Evaporation-induced partitioning provides a means to promote the co-dispersion of both organic and inorganic components throughout the nascent and emerging siloxane framework of the sol gel.
- the silica-surfactant-monomer micelles self-assemble into interfacially organized liquid crystal, lyotropic mesophases on a time scale of about 10 seconds.
- Polymerization of the organic material in the alternating interfacial layers can be induced by either ultraviolet light or heat, which also stabilizes the polymerizing inorganic siloxane framework.
- the resulting nanocomposite structure in the multi-layer film is stabilized by (a) organic polymerization, (b) inorganic polymerization, and (c) covalent bonding at the organic interfacial surfaces.
- a single coating step can produce films at least 1000 nm thick comprised of individual layers, each roughly 1 nm thick. By taking advantage of the self-assembling nature of the materials, each set of 1000 layers can be formed in only seconds. A greater number of layers in the resulting barrier film can be obtained by repeating the coating and evaporation sequence multiple times and/or by depositing thicker coatings.
- Conformal or non-conformal nanolaminate barrier coatings of the type described above can be applied to a variety of planar and non-planar surfaces, in two- and three-dimensions. More specifically, this nanolaminate approach could be used to encapsulate and or protect optoelectronic devices (e.g., LEDs, solar cells, FETs, lasers), pharmaceutical products (tablets in packages, etc), medical devices, food products (packaged foods, beverages, candies), display screens (touch panel displays, flat panel displays), and electroluminescent windows and other windows and transparent films and coatings, electronic components as well as the chassis for appliances used in rugged environments.
- optoelectronic devices e.g., LEDs, solar cells, FETs, lasers
- pharmaceutical products tablets in packages, etc
- medical devices e.g., food products (packaged foods, beverages, candies), display screens (touch panel displays, flat panel displays), and electroluminescent windows and other windows and transparent films and coatings, electronic components as well as the chassis for
- the nanolaminate could be colored to provide for use as an optical filter in a variety of optoelectronic devices.
Abstract
An inorganic/organic hybrid nanolaminate barrier film has a plurality of layers of an inorganic material that alternate with a plurality of layers of an organic material. Such a barrier film can be fabricated using nanocomposite self-assembly techniques based on sol-gel chemistry.
Description
- This application is a divisional of U.S. application Ser. No. 10/698,988, to Brian Sager and Martin R. Roscheisen, filed Oct. 31, 2003 and entitled INORGANIC/ORGANIC HYBRID NANOLAMINATE BARRIER FILM, the entire contents of which are incorporated herein by reference.
- The present invention is directed to barrier films and more particularly to multilayer barrier coatings.
- Many products that are sensitive to their environment require a barrier that is highly impermeable to water, oxygen and other gases while remaining lightweight and durable. For example, optoelectronic devices require transparent barrier materials to extend their useful operating lives. Currently, glass is used as a transparent barrier material. Unfortunately, glass is often undesirable because it is either too fragile or too heavy or both. Plastics are more lightweight and less fragile materials. Unfortunately, commercially available plastics lack the desired level of environmental resistance for many optoelectronic applications.
- For example, to build durable devices, the active elements of polymer-based LEDs may require incorporation of barrier layers with oxygen permeability levels as low as 10−5 cc/m2/day and water vapor permeability levels as low as 10−6g/m2/day. A 7 mil thick coating of polyethylene teraphthalate (PET) has an oxygen transmission rate of 8.7 cc/m2/day and a water vapor permeability of 10 g/m2/day. State of the art plastics such as Alcar can protect components with oxygen and water vapor permeability levels of about 7 cc/m2/day and 0.016 g/m2/day respectively.
- Single barrier coatings of thin films of inorganic materials such as Al, SiO2 Al2O3 and Si3N4 can be vacuum deposited on polymer substrates to improve barrier impermeability. Such single layer coatings can reduce oxygen and water vapor permeability to levels of about 10−3 cc/m2/day and 10−3 g/m2/day respectively.
- Multilayer barrier coatings have been developed using a “sandwich” strategy with an inorganic layer is situated between two polymer layers to further improve the aggregate barrier properties. Sheats and coworkers (U.S. Pat. No. 6,146,225) used a 35 nm thick silicon nitride as an inorganic layer and a one micron thick layer of an acrylate as the polymer material to achieve a barrier with a water-vapor permeation rate of 1.8×10−7 g/m2/day, which is about 40 times better than the requirement for most optoelectronic devices. However, this material is not optically transparent, limiting its use to certain applications only.
- More recently, Graff and colleagues (U.S. Pat. No. 6,413,645; U.S. Pat. No. 6,573,652 and U.S. Pat. No. 6,623,861) have developed barrier materials using a multi-stack approach where each stack includes a sputter-deposited, 40 nm barrier layer of a metal oxide, metal nitride, or metal carbide, followed by a flash-evaporated, one micron layer of an acrylate polymer or multilayer thin films comprised of flash-evaporated plastic. While these multi-stack barrier films have useful environmental resistance relative to many previously developed materials, their vacuum-based mode of production is time-consuming and relatively expensive, especially for multiple-stack coatings. Further, the vacuum-based deposition methods limit both the area upon which a coating can be placed (the area must be smaller than the deposition chamber), which in turn limits their use for larger area devices. In addition, flash evaporation and sputter deposition do not tend to provide for uniform conformal coatings of large area surfaces, especially for non-planar substrates with inherent curvature (or even three-dimensional barrier-protection targets). It would be desirable to have a multi-layer, transparent, and durable film that provides for uniform, inexpensive and conformal coating of larger areas with effective environmental resistance in a range of environments.
- Thus, there is a need in the art, for a barrier film that overcomes the above disadvantages and a corresponding method for making such a film.
- The teachings of the present invention can be readily understood by considering the following detailed description in conjunction with the accompanying drawings, in which:
-
FIG. 1 is a cross-sectional schematic diagram of an inorganic/organic hybrid nanolaminate barrier film according to an embodiment of the present invention. - Although the following detailed description contains many specific details for the purposes of illustration, anyone of ordinary skill in the art will appreciate that many variations and alterations to the following details are within the scope of the invention. Accordingly, the exemplary embodiments of the invention described below are set forth without any loss of generality to, and without imposing limitations upon, the claimed invention.
- Embodiments of the present invention are directed to an inorganic/organic hybrid barrier nanolaminate film and methods for making the film. The
film 100, shown schematically inFIG. 1 , generally includes multiple alternating layers oforganic material 102 andinorganic material 104. The thickness of theinorganic layers 102 andorganic layers 104 can be from about 0.1 nm to about 1 nm or from about 1 nm to about 10 nm or from about 1 nm to about 100 nm. Theinorganic layers 102 can be silicates, although other inorganic materials can be formed from suitable alkoxides as described below. Thebarrier film 100 can be made substantially transparent by appropriate choice of the number, thickness, and composition of theinorganic layers 102 andorganic layers 104. Although a relatively small number of layers is shown inFIG. 1 for the sake of clarity, a barrier film for a typical device can have many more layers, e.g., several thousand. - The
organic layers 104 are polymers such as polyethylene naphthalate (PEN), polyether etherketone (PEEK), or polyether sulfone (PES). In addition, polymers created from styrene polymer precursors, methyl styrene polymer precursors, (meth)acrylate polymer precursors, both fluorinated and non-fluorinated forms of these precursors, and combinations of two or more of these precursors can be used as theorganic layers 104. These organic materials are desirable because of their superior thermal properties and excellent gas barrier characteristics. Furthermore, one or more of theorganic layers 104, e.g., anuppermost layer 110, may optionally be a superhydrophobic layer such as fluoroalkylsilane. Fluoroalkylsilane thin films are described, e.g., by Akira Nakajima et al., in “Transparent Superhydrophobic Thin Films with Self-Cleaning Properties”, Langmuir 2000, 16, 7044-7047, which is incorporated herein by reference. - The layer structure of the
barrier film 100 provides a long path for water or oxygen to penetrate the barrier film to anunderlying substrate 106, e.g., via pinholes and/or gaps at interfaces between layers as indicated by thepath 108. The permeability of thenanolaminate barrier film 100 to oxygen and water vapor can be adjusted by changing the number of layers. By using hundreds to thousands of interdigitatedinorganic layers 102 andorganic layers 104 within thebarrier film 100, the large number of layers combined with randomly located pinholes within the nanolaminate results in tortuous paths for molecules such as water vapor and oxygen that might enter from the environment outside of thebarrier film 100. The more layers, the more tortuous the path for permeating molecules. Thus, the more layers, the less permeable thebarrier film 100 is to water vapor and oxygen. In embodiments of the present invention, there can be 100 or more, 1000 or more, 10,000 or more or 100,000 or more individual layers in thecomposite barrier film 100. - Furthermore, hydrophobic groups can be incorporated into or eliminated from the polymer precursors used to form the
organic layers 104 to tune (increase and/or decrease) the hydrophobicity of the resultingorganic layers 104 and, in turn, adjust the permeability of thebarrier film 100. For example, non-polar hydrophobic groups, including but not limited to methyl groups and benzyl (aromatic) groups, can be attached to the polymer precursors. In general, increasing ionic strength increases hydrophobic interactions. For example, the anions and cations listed below are in a series from those that highly favor hydrophobic interactions to those that decrease hydrophobic interactions. -
Anions: PO4 3−, SO4 2−, CH3COO−, Cl−, Br−, NO−, ClO4 −, I−, SCn −. -
Cations: NH4 +, Rb+, K+, Na+, Cs+, Li+, Mg2+, Ca2+, Ba2+. - Any of these anions and/or cations and/or similar compounds can be incorporated into the polymer precursors, resulting in polymers with tuned hydrophobicity.
- In addition, hydrophobic amino acids such as tryptophan, isoleucine, phenylalanine, tyrosine, leucine, valine, methionine, and alanine could be used as side chains for the polymer precursors.
- Furthermore, Gemini surfactants (also called dimeric surfactants) are highly reactive and could be used as structure-directing agents. Gemini surfactants have two hydrophilic head groups and two hydrophobic groups in the molecule, in contrast to conventional surfactants that have only single hydrophilic and single hydrophobic groups.
- By suitable choice of the number and composition of layers, the oxygen permeability of the
barrier film 100 can be made less than about 1 cc/m2/day, 0.1 cc/m2/day, 0.01 cc/m2/day, 10−3 cc/m2/day, 10−4 cc/m2/day, 10−5 cc/m2/day, 10−6 cc/m2/day, or 10−7 cc/m2/day. Similarly, the water vapor permeability of thebarrier film 100 can be made less than about 1 g/m2/day, 0.1 g/m2/day, 0.01 g/m2/day, 10−3 g/m2/day, 10−4 g/m2/day, 10−5 g/m2/day, 10−6 g/m2/day, or 10−7 g/m2/day. - The
nanolaminate barrier film 100 can be made in a single-step (or few sequential step) process by self-assembly using sol-gel techniques. Self-assembly of nanocomposite materials using sol-gel techniques is described, e.g., in U.S. Pat. No. 6,264,741 to Brinker et al., the entire contents of which are incorporated by reference. Generally speaking, a sol can be prepared, e.g., by combining one or more alkoxides, an alcohol, water and dilute hydrochloric acid (HCl) and heating the resulting mixture. A coupling agent is then introduced to the mixture followed by a surfactant (or Gemini surfactant), in a quantity sufficient that the initial surfactant concentration is below the critical micelle concentration. Subsequently, one or more polymer precursors, e.g., monomers suitable for the formation of PEN, PEEK or PES are then added followed by a cross-linker agent and an initiator. Alternatively, the polymer precursors can include styrene polymer precursors, methyl styrene polymer precursors, (meth)acrylate polymer precursors, either fluorinated or non-fluorinated forms of these, precursors and combinations of two or more of these precursors. A substrate is coated with the sol and the alcohol is allowed to evaporate. The alcohol evaporation drives a self-assembly reaction that forms the multilayer barrier structure described with respect toFIG. 1 . - Suitable alkoxides are structured around a central element X. Suitable central elements X include Al, B, Ba, Pb, Se, Si, and Sn. Other suitable central elements X include transition metals, e.g., Ag, Au, Cd, Co, Cr, Cu, Fe, Ir, Mn, Mo, Nb, Ni, Sr, Ta, Ti, V, W, Y, Zn, Zr, etc. For silicon (Si)-based
inorganic layers 102 examples of suitable alkoxides include polysiloxanes such as tetraethylorthosilicate (TEOS). For titanium (Ti)-basedinorganic layers 102 examples of suitable alkoxides include titanium ethoxide or titanium isopropoxide. - By way of example, and without loss of generality, a sol can be prepared, e.g., by combining tetraethylorthosilicate (Si(OCH2CH3)4, also known as TEOS), ethanol, water and dilute HCl (dilute so as to minimize the siloxane condensation rate) in molar ratios of 1:3.8:1:5×10−5 respectively and heated at about 60° C. for about 90 minutes. The sol is then diluted with ethanol in a 1:2 ration after which water and dilute HCl are added. A coupling agent such as 7-octenlytrimethoxysilane (OTS), or methacryloxypropyl trimethoxysilane (MPS) is then introduced to the mixture followed by a surfactant such as cetyltrimethylammonium bromide (CTAB) so that the initial surfactant concentration is below the critical micelle concentration. After stirring for about one hour, a monomer (e.g., 2,6-Dimethylnaphthalene (DMN; to create polyethylene naphthalate (PEN)), or a set of monomers such as bisphenol A and di-para-fluorophenylsulfone (B/FS, to create polyether sulfone (PES)) is then added followed by a cross-linker agent (such as hexanedioldimethacrylate (HDM) and an initiator. For ultraviolet initiation benzoin dimethylether (BME), can be added. For thermal initiation, 1,1′-azobis(1-cyclohexane carbonitrile) (ACHN) can be used).
- To tune the chemistry of the sol, the concentration of the surfactant, water, ethanol, TEOS, and organic monomers can be varied. Through variation of the nature of the surfactant and its concentration, various structures for the
inorganic layers 102 andorganic layers 104, such as lamellar layers, tubules, or nanostructures exhibiting 1- and 3-dimensional connectivity (e.g., hexagonal or cubic) of the constituent phases, respectively, can be produced and the characteristic dimension (d-spacing) of the composite architecture controlled. Through variation of the organic and inorganic precursors, a wide range of materials combinations can be prepared. Annealing the films at about 125° C.-150° C. or greater (and/or below the decomposition temperature of the organic materials) further densifies the siloxane material and improves impermeability. - The
substrate 106 can be coated with the sol mixture by any suitable technique, such as dip coating, spin coating, spray coating, web coating, or microgravure web coating. Suitable coating machines are commercially available, e.g., from Faustel, Inc., of Germantown, Wisconsin. In particular, a Continuous Coater Type BA from Werner Mathis AG of Zurich, Switzerland may be used to coat the substrate with the sol mixture. It is desirable to coat the substrate with the sol in a wet layer approximately 1 microns to 10 microns to 100 microns thick. Thicker wet layers, e.g., about 100 microns to about 1 millimeter thick, can also be used. Since thebarrier film 100 can be fabricated without the use of vacuum equipment, the processing is simple and comparatively low in cost. - By way of example, the substrate can be rapidly coated with the sol, e.g., by dip coating (e.g., about 25 cm/min dip and withdrawal rate; for large area substrates) or spin coating (e.g., about 1500 rpm for about 1 minute for small area substrates). After coating, the ethanol component of the sol begins to evaporate, and the increasing concentrations of water and surfactant cause the surfactant concentration to exceed the critical micelle concentration, resulting in both micelle formation and the incorporation of the alcohol-soluble organic monomers into the micellar interiors. This TEOS and CTAB-based sol gel chemistry provides for self-assembly of nanostructures whose chemical backbones condense into dense, stable materials.
- Evaporation-induced partitioning provides a means to promote the co-dispersion of both organic and inorganic components throughout the nascent and emerging siloxane framework of the sol gel. As the ethanol continues to evaporate, the silica-surfactant-monomer micelles self-assemble into interfacially organized liquid crystal, lyotropic mesophases on a time scale of about 10 seconds. Polymerization of the organic material in the alternating interfacial layers can be induced by either ultraviolet light or heat, which also stabilizes the polymerizing inorganic siloxane framework. The resulting nanocomposite structure in the multi-layer film is stabilized by (a) organic polymerization, (b) inorganic polymerization, and (c) covalent bonding at the organic interfacial surfaces. A single coating step can produce films at least 1000 nm thick comprised of individual layers, each roughly 1 nm thick. By taking advantage of the self-assembling nature of the materials, each set of 1000 layers can be formed in only seconds. A greater number of layers in the resulting barrier film can be obtained by repeating the coating and evaporation sequence multiple times and/or by depositing thicker coatings.
- Conformal or non-conformal nanolaminate barrier coatings of the type described above can be applied to a variety of planar and non-planar surfaces, in two- and three-dimensions. More specifically, this nanolaminate approach could be used to encapsulate and or protect optoelectronic devices (e.g., LEDs, solar cells, FETs, lasers), pharmaceutical products (tablets in packages, etc), medical devices, food products (packaged foods, beverages, candies), display screens (touch panel displays, flat panel displays), and electroluminescent windows and other windows and transparent films and coatings, electronic components as well as the chassis for appliances used in rugged environments.
- Furthermore, by incorporating dyes or pigments into the film, the nanolaminate could be colored to provide for use as an optical filter in a variety of optoelectronic devices.
- While the above is a complete description of the preferred embodiment of the present invention, it is possible to use various alternatives, modifications and equivalents. Therefore, the scope of the present invention should be determined not with reference to the above description but should, instead, be determined with reference to the appended claims, along with their full scope of equivalents. The appended claims are not to be interpreted as including means-plus-function limitations, unless such a limitation is explicitly recited in a given claim using the phrase “means for.”
Claims (11)
1. A method for making an inorganic/organic hybrid nanolaminate barrier film, comprising:
combining an alkoxide, an alcohol, water dilute HCl and heating the resulting mixture. Introducing a coupling agent to the mixture,
introducing a surfactant to the mixture in a quantity sufficient that the initial surfactant concentration is below the critical micelle concentration;
adding to the mixture one or more polymer precursors suitable for the formation of a polymer selected from the group of, polyethylene naphthalate (PEN), polyether etherketone (PEEK), polyether sulfone (PES), fluorinated or non-fluorinated styrene polymer precursors, fluorinated or non-fluorinated methyl styrene polymer precursors, fluorinated or non-fluorinated (meth)acrylate polymer precursors, and combinations and/or derivatives of two or more of these precursors;
adding a cross-linker agent and an initiator to the mixture;
coating a substrate with the mixture; and
allowing the alcohol to evaporate so that the sol forms a film having alternating organic and inorganic layers.
2. The method of claim 1 further comprising incorporating one or more hydrophobic groups into the polymer precursors or eliminating one or more hydrophobic groups from the polymer precursors to increase and/or decrease the hydrophobicity of the organic layers.
3. The method of claim 2 wherein the one or more hydrophobic groups are selected from the group of non-polar hydrophobic groups, methyl groups, benzyl (aromatic) groups, PO4 3−, SO4 2−, CH3COOO−, Br−, NO−, ClO4 −, I−, SC− anions, NH4 +, Rb+, K+, Na+, Cs+, Li+, Mg2+, Ca2+, Ba2+ cations, tryptophan, isoleucine, phenylalanine, tyrosine, leucine, valine, methionine, alanine
4. The method of claim 3 wherein the surfactant includes one or more Gemini surfactants.
5. The method of claim 1 wherein the alkoxide includes tetraethylorthosilicate (Si(OCH2CH3)4 and the alcohol is ethanol.
6. The method of claim 5 wherein in molar ratios of the tetraethylorthosilicate, ethanol, water, and HCl are present in the mixture in molar ratios of 1:3.8:1:5×10−5 respectively.
7. The method of claim 6 , wherein the coupling agent is 7-octenlytrimethoxysilane, or methacryloxypropyl trimethoxysilane.
8. The method of claim 7 wherein the surfactant is cetyltrimethylammonium bromide.
9. The method of claim 1 wherein the one or more polymer precursors include 2,6-Dimethylnaphthalene, or a set of monomers such as bisphenol A and di-para-fluorophenylsulfone.
10. The method of claim 1 , further comprising annealing the film at a temperature of about 125° to about 150° C. or greater and/or below the lowest decomposition temperature of any of the organic materials in the film.
11. The method of claim 1 wherein coating a substrate with the mixture includes depositing the mixture on the substrate by dip coating, spin coating, spray coating, web coating, or microgravure web coating.
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US14/274,527 US20140314958A1 (en) | 2003-10-31 | 2014-05-09 | Inorganic/organic hybrid nanolaminate barrier film |
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US10/698,988 US8722160B2 (en) | 2003-10-31 | 2003-10-31 | Inorganic/organic hybrid nanolaminate barrier film |
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US (2) | US8722160B2 (en) |
EP (1) | EP1682339A4 (en) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Families Citing this family (62)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6866901B2 (en) | 1999-10-25 | 2005-03-15 | Vitex Systems, Inc. | Method for edge sealing barrier films |
US20100330748A1 (en) | 1999-10-25 | 2010-12-30 | Xi Chu | Method of encapsulating an environmentally sensitive device |
US8808457B2 (en) | 2002-04-15 | 2014-08-19 | Samsung Display Co., Ltd. | Apparatus for depositing a multilayer coating on discrete sheets |
US8900366B2 (en) | 2002-04-15 | 2014-12-02 | Samsung Display Co., Ltd. | Apparatus for depositing a multilayer coating on discrete sheets |
US20050271893A1 (en) * | 2004-06-04 | 2005-12-08 | Applied Microstructures, Inc. | Controlled vapor deposition of multilayered coatings adhered by an oxide layer |
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US7227066B1 (en) * | 2004-04-21 | 2007-06-05 | Nanosolar, Inc. | Polycrystalline optoelectronic devices based on templating technique |
WO2005121397A2 (en) * | 2004-06-04 | 2005-12-22 | Applied Microstructures, Inc. | Controlled vapor deposition of multilayered coatings adhered by an oxide layer |
US7879396B2 (en) * | 2004-06-04 | 2011-02-01 | Applied Microstructures, Inc. | High aspect ratio performance coatings for biological microfluidics |
US20090032108A1 (en) * | 2007-03-30 | 2009-02-05 | Craig Leidholm | Formation of photovoltaic absorber layers on foil substrates |
US7838868B2 (en) * | 2005-01-20 | 2010-11-23 | Nanosolar, Inc. | Optoelectronic architecture having compound conducting substrate |
US7772487B1 (en) | 2004-10-16 | 2010-08-10 | Nanosolar, Inc. | Photovoltaic cell with enhanced energy transfer |
US8927315B1 (en) | 2005-01-20 | 2015-01-06 | Aeris Capital Sustainable Ip Ltd. | High-throughput assembly of series interconnected solar cells |
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US20070005024A1 (en) * | 2005-06-10 | 2007-01-04 | Jan Weber | Medical devices having superhydrophobic surfaces, superhydrophilic surfaces, or both |
US7767498B2 (en) | 2005-08-25 | 2010-08-03 | Vitex Systems, Inc. | Encapsulated devices and method of making |
US7767904B2 (en) * | 2006-01-12 | 2010-08-03 | Heliovolt Corporation | Compositions including controlled segregated phase domain structures |
US20070160763A1 (en) | 2006-01-12 | 2007-07-12 | Stanbery Billy J | Methods of making controlled segregated phase domain structures |
US8084685B2 (en) * | 2006-01-12 | 2011-12-27 | Heliovolt Corporation | Apparatus for making controlled segregated phase domain structures |
US7943846B2 (en) * | 2006-04-21 | 2011-05-17 | Innovalight, Inc. | Group IV nanoparticles in an oxide matrix and devices made therefrom |
US8158450B1 (en) * | 2006-05-05 | 2012-04-17 | Nanosolar, Inc. | Barrier films and high throughput manufacturing processes for photovoltaic devices |
KR100763933B1 (en) | 2006-07-11 | 2007-10-05 | 인하대학교 산학협력단 | The method for synthesizing organic-inorganic hybrid materials |
US8088502B2 (en) * | 2006-09-20 | 2012-01-03 | Battelle Memorial Institute | Nanostructured thin film optical coatings |
US8034317B2 (en) | 2007-06-18 | 2011-10-11 | Heliovolt Corporation | Assemblies of anisotropic nanoparticles |
AU2008304553B2 (en) * | 2007-09-24 | 2013-02-14 | Qspex Technologies, Inc. | Method for manufacturing polarized ophthalmic lenses |
JP2009221541A (en) * | 2008-03-17 | 2009-10-01 | Fujifilm Corp | Vacuum film formation method for inorganic layer, barrier laminate, device, and optical component |
US20100031997A1 (en) * | 2008-08-11 | 2010-02-11 | Basol Bulent M | Flexible thin film photovoltaic modules and manufacturing the same |
US8389050B2 (en) * | 2008-11-21 | 2013-03-05 | Corning Incorporated | Method of coating tubes using a self-assembly process |
US9073287B2 (en) * | 2008-12-15 | 2015-07-07 | Industrial Technology Research Insititute | Organic/inorganic multi-layered gas barrier film |
US9337446B2 (en) | 2008-12-22 | 2016-05-10 | Samsung Display Co., Ltd. | Encapsulated RGB OLEDs having enhanced optical output |
US9184410B2 (en) | 2008-12-22 | 2015-11-10 | Samsung Display Co., Ltd. | Encapsulated white OLEDs having enhanced optical output |
KR20110111369A (en) * | 2009-02-04 | 2011-10-11 | 헬리오볼트 코오퍼레이션 | Method of forming an indium-containing transparent conductive oxide film, metal targets used in the method and photovoltaic devices utilizing said films |
FR2956869B1 (en) | 2010-03-01 | 2014-05-16 | Alex Hr Roustaei | SYSTEM FOR PRODUCING HIGH CAPACITY FLEXIBLE FILM FOR PHOTOVOLTAIC AND OLED CELLS BY CYCLIC LAYER DEPOSITION |
US8418418B2 (en) | 2009-04-29 | 2013-04-16 | 3Form, Inc. | Architectural panels with organic photovoltaic interlayers and methods of forming the same |
TW201040299A (en) * | 2009-05-05 | 2010-11-16 | Fraunhofer Ges Forschung | Layer system having barrier properties and a structured conductive layer, method for producing the same, and use of such a layer system |
KR20130122693A (en) * | 2009-06-05 | 2013-11-07 | 헬리오볼트 코오퍼레이션 | Process for synthesizing a thin film or composition layer via non-contact pressure containment |
TWI391886B (en) * | 2009-06-12 | 2013-04-01 | Au Optronics Corp | Flexible touch display apparatus |
US8256621B2 (en) * | 2009-09-11 | 2012-09-04 | Pro-Pak Industries, Inc. | Load tray and method for unitizing a palletized load |
US8590338B2 (en) | 2009-12-31 | 2013-11-26 | Samsung Mobile Display Co., Ltd. | Evaporator with internal restriction |
US8021641B2 (en) * | 2010-02-04 | 2011-09-20 | Alliance For Sustainable Energy, Llc | Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom |
WO2011146115A1 (en) | 2010-05-21 | 2011-11-24 | Heliovolt Corporation | Liquid precursor for deposition of copper selenide and method of preparing the same |
US9142408B2 (en) | 2010-08-16 | 2015-09-22 | Alliance For Sustainable Energy, Llc | Liquid precursor for deposition of indium selenide and method of preparing the same |
US8772066B2 (en) * | 2011-02-08 | 2014-07-08 | Applied Materials, Inc. | Method for hybrid encapsulation of an organic light emitting diode |
US20140150843A1 (en) * | 2011-04-01 | 2014-06-05 | NuvoSun, Inc. | Shingle-like photovoltaic modules |
KR101891987B1 (en) * | 2011-05-31 | 2018-08-28 | 엘지디스플레이 주식회사 | Organic Light Emitting Device and Method for manufacturing the same |
KR101802024B1 (en) | 2011-12-21 | 2017-12-28 | 테나리스 커넥션즈 비.브이. | Corrosion resistant equipment for oil and/or gas applications |
DE102011056761A1 (en) | 2011-12-21 | 2013-08-08 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Pigmented, finely structured tribological composite material |
WO2013091685A1 (en) | 2011-12-21 | 2013-06-27 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Highly structured composite material and process for the manufacture of protective coatings for corroding substrates |
CN103374138A (en) * | 2012-04-25 | 2013-10-30 | 深圳富泰宏精密工业有限公司 | Shell and preparation method thereof |
US9105797B2 (en) | 2012-05-31 | 2015-08-11 | Alliance For Sustainable Energy, Llc | Liquid precursor inks for deposition of In—Se, Ga—Se and In—Ga—Se |
US9112275B2 (en) | 2012-09-05 | 2015-08-18 | Raytheon Company | Radome film |
CN104037352A (en) * | 2013-03-07 | 2014-09-10 | 海洋王照明科技股份有限公司 | Organic light emission diode and preparation method thereof |
JP2015069508A (en) * | 2013-09-30 | 2015-04-13 | 凸版印刷株式会社 | Touch panel |
EP3262445A1 (en) | 2015-02-25 | 2018-01-03 | Corning Incorporated | Optical structures and articles with multilayer stacks having high hardness and methods for making the same |
KR102421600B1 (en) | 2015-11-20 | 2022-07-18 | 삼성디스플레이 주식회사 | Touch sensing unit, display device and fabrication method of the touch screen |
CN107502003B (en) * | 2016-06-14 | 2020-06-02 | 中国科学院理化技术研究所 | Preparation method of hydrophobic inorganic powder material |
KR102127463B1 (en) * | 2017-08-18 | 2020-06-29 | 한국과학기술원 | Encapsulation structure for transparent flexible organic electronic device |
US10529951B2 (en) | 2017-08-18 | 2020-01-07 | Korea Advanced Institute Of Science And Technology | Encapsulation structure for transparent flexible organic electronic device |
CN108054289B (en) * | 2017-12-15 | 2020-03-06 | 京东方科技集团股份有限公司 | Packaging assembly, manufacturing method thereof and display device |
KR102578827B1 (en) | 2018-04-24 | 2023-09-15 | 삼성전자주식회사 | Flexible organic-inorganic passivation layer an method of fabricating the same |
CN109888128A (en) * | 2019-03-25 | 2019-06-14 | 京东方科技集团股份有限公司 | The production method of the packaging method and display panel of OLED display panel |
KR102417793B1 (en) * | 2020-12-15 | 2022-07-14 | 포항공과대학교 산학협력단 | Composition for an organic-inorganic hybrid gas barrier film containing a fluorine-based precursor and amphiphilic legged structured polymeric alkoxysilane precursor and a gas barrier film using the same |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4366239A (en) * | 1979-10-08 | 1982-12-28 | Fuji Photo Film Co., Ltd. | Polyester base drafting film with nitrocellulose and polymethylmethacrylate layer |
US4879041A (en) * | 1987-03-25 | 1989-11-07 | Hitachi, Ltd. | Process for producing ultra-pure water and process for using said ultra-pure water |
US20040168627A1 (en) * | 2003-02-27 | 2004-09-02 | Sharp Laboratories Of America, Inc. | Atomic layer deposition of oxide film |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3725338A1 (en) * | 1987-07-30 | 1989-02-09 | Nukem Gmbh | ENCLOSURE OF A PHOTOVOLTAIC ELEMENT |
CA2060294C (en) * | 1991-02-06 | 2000-01-18 | Kazufumi Ogawa | Chemically absorbed film and method of manufacturing the same |
JPH07270615A (en) | 1994-03-31 | 1995-10-20 | Central Glass Co Ltd | Holographic laminated body |
US5554670A (en) * | 1994-09-12 | 1996-09-10 | Cornell Research Foundation, Inc. | Method of preparing layered silicate-epoxy nanocomposites |
US5746631A (en) * | 1996-01-11 | 1998-05-05 | Mccarthy; Peter T. | High efficiency hydrofoil and swim fin designs |
US6057035A (en) * | 1997-06-06 | 2000-05-02 | Triton Systems, Inc. | High-temperature polymer/inorganic nanocomposites |
JPH11135820A (en) * | 1997-08-27 | 1999-05-21 | Canon Inc | Solar battery module and reinforcing member therefor |
US6146225A (en) | 1998-07-30 | 2000-11-14 | Agilent Technologies, Inc. | Transparent, flexible permeability barrier for organic electroluminescent devices |
US6264741B1 (en) * | 1998-11-25 | 2001-07-24 | Sandia Corporation | Self-assembly of nanocomposite materials |
US6818163B1 (en) * | 1999-02-12 | 2004-11-16 | Dow Global Technologies Inc. | Nanocomposite articles and process for making |
AU5488400A (en) * | 1999-06-17 | 2001-01-09 | Triton Systems, Inc. | High performance nanocomposites |
US6472467B1 (en) * | 1999-10-21 | 2002-10-29 | Dow Global Technologies Inc. | Inorganic/organic compositions |
US6573652B1 (en) * | 1999-10-25 | 2003-06-03 | Battelle Memorial Institute | Encapsulated display devices |
US6623861B2 (en) * | 2001-04-16 | 2003-09-23 | Battelle Memorial Institute | Multilayer plastic substrates |
US6413645B1 (en) * | 2000-04-20 | 2002-07-02 | Battelle Memorial Institute | Ultrabarrier substrates |
US6866901B2 (en) * | 1999-10-25 | 2005-03-15 | Vitex Systems, Inc. | Method for edge sealing barrier films |
TW490997B (en) * | 2000-03-31 | 2002-06-11 | Seiko Epson Corp | Method of manufacturing organic EL element, and organic EL element |
WO2001081487A1 (en) * | 2000-04-21 | 2001-11-01 | Science & Technology Corporation @ Unm | Prototyping of patterned functional nanostructures |
ES2282186T3 (en) * | 2001-01-19 | 2007-10-16 | 3M Innovative Properties Company | FLUOROCHEMICAL SILANOS WATER SOLUBLE OR WATER DISPERSABLE TO MAKE A SUBSTRATE REPELLENT TO OIL AND WATER. |
US8722160B2 (en) * | 2003-10-31 | 2014-05-13 | Aeris Capital Sustainable Ip Ltd. | Inorganic/organic hybrid nanolaminate barrier film |
-
2003
- 2003-10-31 US US10/698,988 patent/US8722160B2/en not_active Expired - Fee Related
-
2004
- 2004-10-18 EP EP04796054A patent/EP1682339A4/en not_active Withdrawn
- 2004-10-18 JP JP2006538120A patent/JP5703431B2/en not_active Expired - Fee Related
- 2004-10-18 WO PCT/US2004/034993 patent/WO2005044551A1/en active Application Filing
- 2004-10-18 TW TW093131587A patent/TWI376825B/en active
-
2013
- 2013-09-06 JP JP2013185134A patent/JP2013256132A/en active Pending
-
2014
- 2014-05-09 US US14/274,527 patent/US20140314958A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4366239A (en) * | 1979-10-08 | 1982-12-28 | Fuji Photo Film Co., Ltd. | Polyester base drafting film with nitrocellulose and polymethylmethacrylate layer |
US4879041A (en) * | 1987-03-25 | 1989-11-07 | Hitachi, Ltd. | Process for producing ultra-pure water and process for using said ultra-pure water |
US20040168627A1 (en) * | 2003-02-27 | 2004-09-02 | Sharp Laboratories Of America, Inc. | Atomic layer deposition of oxide film |
Non-Patent Citations (5)
Title |
---|
Coupek et al., "New hydrophilic materials for chromatography: glycol methacrylates," J. Polymer Sci., Symposium No. 42, 185-190 (1973). * |
Hait et al., "Gemini surfactants: A distinct class of self-assembling molecules," Current Science, Vol. 82, No. 9, 10 May 2002, 1101-1111. * |
Kolarik et al., "Mechanical properties of hydrophilic copolymers of 2-hydroxyethyl methacrylate with ethyl acrylate, n-butyl acrylate, and dodecyl methacrylate," Journal of Biomedical Materials Research, Vol. 17, 757-767 (1983). * |
Lu et al., "Evaporation-Induced Self-Assembly of Hybrid Bridged Silsesquioxane Film and Particulate Mesophases with Integral Organic Functionality," J. Am. Chem. Soc., 2000, 122, 5258-5261. * |
Sellinger et al., "Continuous self-assembly of organic-inorganic nanocomposite coatings that mimic nacre," Nature, Vol. 394, 16 July 1998, 256-260. * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107112200A (en) * | 2014-11-17 | 2017-08-29 | 赛智电致变色公司 | Many barrier layers encapsulate lamination |
CN109950418A (en) * | 2019-03-18 | 2019-06-28 | 云谷(固安)科技有限公司 | Display panel and display screen |
Also Published As
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TWI376825B (en) | 2012-11-11 |
US8722160B2 (en) | 2014-05-13 |
EP1682339A4 (en) | 2010-08-11 |
EP1682339A1 (en) | 2006-07-26 |
JP2013256132A (en) | 2013-12-26 |
WO2005044551A1 (en) | 2005-05-19 |
TW200520275A (en) | 2005-06-16 |
JP5703431B2 (en) | 2015-04-22 |
JP2007533430A (en) | 2007-11-22 |
US20050095422A1 (en) | 2005-05-05 |
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