EP3669168A1 - Water vapour permeation - Google Patents
Water vapour permeationInfo
- Publication number
- EP3669168A1 EP3669168A1 EP18759701.8A EP18759701A EP3669168A1 EP 3669168 A1 EP3669168 A1 EP 3669168A1 EP 18759701 A EP18759701 A EP 18759701A EP 3669168 A1 EP3669168 A1 EP 3669168A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- moisture
- barrier layer
- optical
- sensitive material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
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- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/8422—Investigating thin films, e.g. matrix isolation method
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
- G01N2015/0846—Investigating permeability, pore-volume, or surface area of porous materials by use of radiation, e.g. transmitted or reflected light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
- G01N2015/086—Investigating permeability, pore-volume, or surface area of porous materials of films, membranes or pellicules
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
- G01N21/81—Indicating humidity
Definitions
- This invention relates to a method of analysing water vapour permeation through a barrier layer.
- the invention relates to a method of method of analysing water vapour permeation through a barrier layer for flexible optoelectronic devices.
- OLEDs Organic Light Emitting Diodes
- the devices need to be encapsulated or protected by barrier layers. Encapsulation in glass can be effective for certain applications. However, flexible barrier layers are preferred for flexible optoelectronic applications.
- barrier layers for example, transparent polymer films.
- thin oxide-based or nitride-based coatings have been used to further reduce the permeation of gas species.
- a calcium test may be employed.
- a layer of calcium is used to react with water vapour that permeates through the polymer film under test.
- the reaction results in the conversion of calcium metal to calcium hydroxide.
- the permeability of the polymer film may be determined.
- the extent of reaction is determined by determining the change in electrical resistance of the layer of calcium.
- the water vapour permeation rate may be determined by the rate of change of the electrical resistance with time.
- the extent of reaction may be determined by measuring the transmission of light through the layer of calcium. When opaque calcium metal reacts with water, it forms calcium hydroxide, which is transparent. The rate of change of the intensity of light that permeates the polymer film, therefore, can provide an indication of the water vapour permeation rate of the film.
- Figure 1 is a schematic drawing of a sample containing a barrier layer constructed according to a prior art method
- Figure 2 is a schematic drawing of a sample containing a barrier layer constructed according to a method of an embodiment of the present invention
- Figures 3a is a plan view of an apparatus according to one embodiment of the present invention.
- Figure 3b is a cross-sectional view of the apparatus of Figure 3a;
- Figure 4 shows images from a calcium test according to one embodiment of the present invention conducted on an uncoated PEN barrier
- FIG. 5 is a graph showing how the water vapour transmission rate (WVTR) of a
- PEN barrier varies with time
- Figure 6 shows images from a calcium test according to one embodiment of the present invention conducted on a PEN barrier coated with aluminium oxide
- Figure 7 is a graph showing how the area covered by spots varies with time
- Figure 8 is a graph showing how the number of spots varies with time
- Figure 9 compares images from a calcium test according to one embodiment of the present invention at two separate time intervals.
- Figure 10 is a graph showing the WVTR of a spot on a PEN barrier coated with aluminium oxide.
- a method of analysing water vapour permeation through a barrier layer comprising:
- a sample comprising a barrier layer and a layer of moisture-sensitive material having optical properties that change on exposure to moisture, wherein the layer of moisture-sensitive material is in fluid communication with one face of the barrier layer; exposing an opposite face of the barrier layer to a humid environment to allow water vapour to permeate through the barrier layer;
- optically imaging the layer of moisture-sensitive material over time wherein the optical images are taken in situ while the opposite face of the barrier layer is exposed to the humid environment.
- Optically imaging the layer of moisture-sensitive material over time as described herein may comprise capturing images of the layer of moisture-sensitive material at different times. For example, images of the layer of moisture-sensitive material may be captured periodically. In some embodiments, at least one image of the layer of moisture- sensitive material is captured at least once every two hours or less. In some
- images may be captured more frequently. For example, at least one image of the layer of moisture-sensitive material may be captured at least once every hour, at least once every 30 minutes, at least once every 15 minutes or even once every 5 minutes or less. In some embodiments, multiple images of the layer of moisture-sensitive material may be captured every minute. For example, at least one image of the layer of moisture- sensitive material may be captured at least once every few seconds or even several times a second.
- Water vapour may permeate through macrodefects and/or nanodefects in a barrier layer. It has been found that water vapour permeation through macrodefects can cause optical changes to appear as localised optical features (e.g. spots or lines) in the optical images of the layer of moisture sensitive material, while water vapour permeation through nanodefects can cause optical changes in the background optical brightness of the optical images of the layer of moisture sensitive material. In the present method, the growth of these localised optical features and/or the changes in the background optical brightness can be monitored to provide diagnostic information on the barrier layer.
- localised optical features e.g. spots or lines
- the present invention provides a method of analysing water vapour permeation through a barrier layer, said method comprising:
- a sample comprising a barrier layer and a layer of moisture-sensitive material having optical properties that change on exposure to moisture, wherein the layer of moisture-sensitive material is in fluid communication with one face of the barrier layer; exposing an opposite face of the barrier layer to a humid environment to allow water vapour to permeate through the barrier layer
- optically imaging the layer of moisture-sensitive material over time analysing the optical images for changes in localised optical features in the optical images with time, and/or
- an apparatus for analysing water vapour permeation through a barrier layer comprising:
- a humidity chamber for housing a sample comprising the barrier layer in a humid environment
- a light source for transmitting light through the sample contained in the humidity chamber
- an optical sensor for obtaining optical images of a sample contained within the humidity chamber over time
- a processor for analysing the growth in any localised optical features in the images obtained and for analysing changes in background optical brightness of the images obtained.
- the analysis steps may be carried out using imaging software, for example, Image JTM.
- the analysis may allow a user to distinguish between water vapour permeation rates through nanodefects and permeation rates through macrodefects. It may also be possible to determine water vapour permeation rates through nanodefects and permeation rates through macrodefects.
- optical images may be taken in situ while the opposite face of the barrier layer is exposed to the humid environment.
- the localised optical features may be localised spots and/or localised lines in the optical images. Spots may arise as a result of permeation through e.g. pin-hole or point macrodefects in the barrier layer. Lines may arise, for example, as a result of cracks or scratches in the barrier layer.
- changes in the localised spots and/or lines are determined by analysing the growth in the number and/or the growth in the size of one or more of the localised spots and/or lines. As mentioned above, this analysis may be carried out using imaging software, for example, Image JTM.
- Changes in the background optical brightness of the layer of moisture sensitive material may comprise changes in a spatially averaged or integrated optical brightness of the moisture sensitive material. Again, changes in this background brightness may be analysed using imaging software e.g. Image JTM.
- Analysis of optical images as contemplated herein may include determining a change in one or more properties of the optical images between images taken at different times.
- the one or more properties of the optical images may include at least one property indicative of water vapour permeation through nanodefects in the barrier layer and at least one property indicative of water vapour permeation through macrodefects in the barrier layer.
- a property of an optical image which is indicative of water vapour permeation through nanodefects may comprise a spatially averaged or integrated brightness level of the optical image.
- the spatial average or integration may be made over the entire optical image or at least over a majority of an optical image of the moisture sensitive material. Analysing changes in a spatially averaged or integrated brightness level of the optical images with time may provide an indication of water vapour permeation through
- a property of an optical image which is indicative of water vapour permeation through macrodefects may comprise a property associated with one or more localised features in the image, such as spots and/or lines which appear in the image.
- a property of an optical image which is indicative of water vapour permeation through macrodefects may comprise the number of localised features which appear in the image, the size of one or more localised features which appear in the image, the proportion of the image which is occupied by localised features and/or the total and/or average brightness of all localised features which appear in the image.
- the analysis of optical images as contemplated herein may, for example, comprise identifying localised features (e.g. spots and/or lines) in the optical images.
- identifying localised features e.g. spots and/or lines
- standard image processing techniques such as edge detection may be used to identify localised features indicative of macrodefects in the barrier layer in an optical image.
- the analysis may further comprise characterising one or more identified localised features in the optical image, for example, by determining at least one property of the identified localised optical features in each image.
- the at least one determined property of the identified localised optical features in each image may include at least one of: the total number of identified localised optical features in each image, the proportion of the area of each image which is occupied by the identified localised optical features and/or a measure of the size of the identified localised optical features.
- the analysis may further comprise analysing changes in the determined at least one property of the identified localised optical features between different images taken at different times. Such an analysis may provide an indication of water vapour permeation through macrodefects in the barrier layer with time.
- optical features such as lines or spots in an image may be indicative of macrodefects in the barrier layer, whereas the background or spatially averaged optical brightness of the image may be indicative of the nanodefects in the barrier layer.
- optical images are analysed to obtain both an indication of water vapour permeation through macrodefects and to obtain an indication of water vapour permeation through nanodefects.
- the obtained indication of water vapour permeation through macrodefects may be compared to the obtained indication of water vapour permeation through nanodefects. Such a distinction and/or comparison may inform any changes to be made in manufacturing parameters (which might reduce the water vapour permeation of a barrier layer).
- the method of the present disclosure may be used to determine water vapour permeation through any barrier layer.
- the barrier layer may be any barrier layer.
- the barrier layer may be a barrier layer suitable for use as packaging materials.
- the barrier layer may be a barrier layer for any material or device requiring encapsulation, and, in particular, protection from exposure to moisture.
- the barrier layer may be a barrier layer for a flexible optoelectronic device, for example, an organic light emitting diode (OLED) or an organic photovoltaic device (OPV).
- OLED organic light emitting diode
- OCV organic photovoltaic device
- the barrier layer may comprise a supporting substrate, for example, a flexible supporting substrate.
- the substrate may be a polymer substrate, for example, a polymer film.
- Suitable polymer substrates may be formed of polyethylene, polypropylene, polyethylene terephthalate and polyethylene napthalate.
- the polymer substrate may have a thickness of 5 ⁇ to 200 ⁇ , preferably 12 ⁇ to 125 ⁇ , more preferably 12 ⁇ to 30 ⁇ .
- the barrier layer may have water vapour transmission rate (WVTR) of less than 1 x 10 "6 g/m 2 / day.
- WVTR water vapour transmission rate
- the polymer substrate may have an oxygen transmission rate of less than 1 x 10 "3 cm 3 /m 2 /day.
- the barrier layer may comprise a coating deposited on the (e.g. polymer) substrate.
- the coating may be a coating of transparent inorganic material, for instance, oxides and/or nitrides. Suitable examples include ceramics, for instance, aluminium oxide, silicon oxide, titanium oxide, titanium nitride and aluminium oxynitride.
- the coating may have a thickness of 5nm to 2000nm, preferably 10nm to 500nm.
- the barrier layer may be a multi-layer structure.
- the multi- layer structure may include a polymer substrate comprising a coating as described above. Additional layers may be present, for example, over the coating, under the polymer substrate or intermediate the coating and polymer substrate. The additional layers may be organic and/or carbon-rich layers.
- the sample may be positioned such that it is the substrate (e.g. polymer substrate) that is exposed to the humid environment, with the coating in contact with the layer of moisture-sensitive material.
- the substrate e.g. polymer substrate
- the coating may be applied by any suitable deposition technique. Examples of such techniques include chemical vapour deposition (CVD), atomic layer deposition (ALD), evaporation and sputtering. In one embodiment, the coating may be formed by sputtering.
- the barrier layer may include macrodefects and/or nanodefects.
- Macrodefects are defects that may induced by handling, process defects or substrate contamination.
- nanodefects may be inherent to the barrier layer material itself, arising, for example, from the intergranular boundaries in the structure or from the disorder of the amorphous material. Typical sizes might be greater than 100nm for macrodefects, up to mm-scale, and below 100nm for nanodefects where transport of permeation is
- macrodefects characterized by Knudsen flow, and below about 5nm where transport would be limited to surface diffusion.
- the difference between macrodefects and nanodefects can be characterized by a) the activation energy of permeation (as measured from the gradient in a plot of InWVTR vs 1/T) - for macrodefects this reflects that of the underlying substrate and for nanodefects this is some value greater than this and/or b) the localized nature of the defects observed where permeation can be imaged (e.g. in Ca test) in cases in which the macrodefect density is sufficiently low to resolve individual defects.
- macrodefects can typically be imaged directly by microscopy, arising from scratches or cracks in the ceramic layer, or particles or pin-holes.
- Macrodefects and nanodefects may need to be limited to improve or maintain barrier performance, but the route to doing this may be different in the two cases.
- macrodefects may be limited by limiting handling damage, arcing and/or abrasion during deposition, or substrate surface contamination or asperities, whereas to limit nanodefect populations may require appropriate surface treatment (e.g. roughness, chemistry) of the substrate, and process parameters e.g. deposition power, speed, layer thickness, vacuum environment, as well as control of barrier layer chemistry.
- process parameters e.g. deposition power, speed, layer thickness, vacuum environment, as well as control of barrier layer chemistry.
- the layer of moisture-sensitive material may be formed of any suitable material.
- the layer may be a layer of calcium metal.
- calcium metal Upon contact with water vapour, calcium metal reacts to form calcium hydroxide. While the metal is opaque, calcium hydroxide is transparent. The reaction of calcium metal with water, therefore, provides a visual indication of water vapour permeating through the barrier layer.
- the layer of moisture-sensitive material may be applied by any suitable technique. Examples include chemical vapour deposition (CVD), atomic layer deposition (ALD), evaporation and sputtering. In a preferred embodiment, the layer of moisture- sensitive material may be applied by evaporation.
- the layer of moisture-sensitive material may have a thickness of 10nm to 1000nm, preferably 50nm to 300nm, more preferably 150nm to 250nm.
- one face of the barrier layer is placed in fluid communication with a layer of moisture-sensitive material.
- a layer of moisture-sensitive material is placed in contact with the barrier layer.
- the opposite face of the layer of moisture-sensitive material may be isolated or sealed from other sources of water vapour. Accordingly, most, if not substantially all, of the water that contacts the layer of moisture-sensitive material passes through the barrier layer.
- the layer of moisture-sensitive material may be deposited onto the barrier layer, for example, by chemical vapour deposition (CVD), atomic layer deposition (ALD), evaporation or sputtering.
- CVD chemical vapour deposition
- ALD atomic layer deposition
- evaporation or sputtering atomic layer deposition
- the layer of moisture-sensitive material may be in contact with the barrier layer.
- a sheet of glass or other optically transparent material may be placed over the opposite face of the barrier layer. This may help to prevent moisture from contacting the opposite face of the barrier layer.
- a sealant e.g. a transparent sealant
- a sample comprising the barrier layer and layer of moisture-sensitive material is sealed using glass and an epoxy resin in a dry or moisture- reduced or moisture-free atmosphere, for example, a glove box.
- an epoxy resin e.g. a transparent epoxy resin
- an epoxy resin is used as a sealant.
- a protective layer over the layer of moisture-sensitive material.
- the protective layer may be applied prior to application of any glass or epoxy layer.
- the protective layer may allow epoxy and/or glass to be applied over the layer of moisture- sensitive material in e.g. a moisture-containing atmosphere without the risk of extensive degradation of the moisture-sensitive material taking place.
- a layer of moisture-sensitive material having optical properties that change on exposure to moisture, wherein the layer of moisture-sensitive material is contact with one face of the barrier layer;
- the glass layer is sealed to the barrier layer by a moisture- impermeable seal.
- the sample may be prepared by a method comprising:
- the protective layer may be formed of metal.
- an optically transparent layer of metal may be applied.
- suitable metals include copper silver, gold, platinum, ruthenium, rhodium, palladium, osmium, iridium, rhenium, titanium, niobium, and tantalum.
- metal alloys e.g. metal alloys containing at least some of the metals mentioned above
- alloys may also be employed, for example, alloys that are resistant to water.
- the protective layer may be applied using the same technique used to apply the layer of moisture-sensitive material. For example, chemical vapour deposition (CVD), atomic layer deposition (ALD), evaporation or sputtering may be used.
- CVD chemical vapour deposition
- ALD atomic layer deposition
- evaporation evaporation or sputtering
- the protective layer is applied using the same apparatus as that used to apply the layer of moisture-sensitive material.
- the layer of moisture sensitive material is a layer of e.g. calcium metal deposited onto the barrier layer using a particular deposition technique (e.g. evaporation)
- a protective layer of e.g. copper may be formed over the calcium layer using the same deposition technique (e.g. evaporation).
- the resulting structure may then be removed from e.g. the evaporator to the atmosphere. Glass and epoxy layers may be applied over the protective layer e.g. under normal atmospheric conditions without the risk of significant moisture degradation of the moisture- sensitive material.
- a sample comprising the barrier layer and layer of moisture- sensitive material may be tested in, for example, a humidity chamber.
- a humidity chamber may define an enclosure in which a humid atmosphere may be maintained.
- the chamber can be controlled to provide an atmosphere having a predefined humidity.
- the chamber may include control means for keeping the humidity constant. Additionally, the chamber may include control means for controlling the temperature within the enclosure.
- the chamber may be provided with a reservoir of water or other aqueous solution (e.g. salt solution).
- the chamber may also be provided with a heater, for example, a heating platform that heats the contents of the reservoir to evaporate water and create a humid atmosphere within the chamber.
- the humidity within the chamber may be controlled at a humidity within the range of 0%RH to 100%RH, preferably 50%RH to 100%RH, more preferably 85%RH to 88%RH.
- the temperature within the chamber may be controlled at a temperature within a wide range.
- the temperature range may be constrained in practical terms by other factors: e.g. the freezing point of water at the lower bound and the softening point of components of the barrier layer (e.g. polymer substrate) at the upper bound.
- the chamber may comprise temperature control means to control the
- the temperature control means can control the temperature within the chamber from 25degC to 40, 50, 60 or 70 deg C.
- water vapour may permeate through macrodefects and/or nanodefects in a barrier layer. It has been found that water vapour permeation through macrodefects can cause optical changes to appear as localised features (e.g. bright spots, lines or regions) in the optical images of the layer of moisture sensitive material, while water vapour permeation through nanodefects can cause optical changes in the background optical brightness of the optical images of the layer of moisture sensitive material. In the present method, the growth of these localised spots and/or the changes in the background brightness can be monitored in situ to provide diagnostic information on the barrier layer.
- localised features e.g. bright spots, lines or regions
- water vapour permeation through nanodefects can cause optical changes in the background optical brightness of the optical images of the layer of moisture sensitive material.
- the growth of these localised spots and/or the changes in the background brightness can be monitored in situ to provide diagnostic information on the barrier layer.
- the chamber may be provided with an optically transparent window through which optical images can be taken.
- This window allows in situ monitoring to take place using optical sensors located outside the humid environment.
- optical sensors may be positioned within the chamber to image the changes in the layer of moisture-sensitive material in situ.
- FIG. 1 This Figure depicts a sample containing a barrier layer whose water vapour permeation characteristics require analysis.
- the sample 10 is of a prior art construction.
- the sample 10 comprises a barrier layer 12, a layer of moisture sensitive material 14 (e.g. calcium metal), a transparent sealant 16 (e.g. epoxy resin) and a layer of glass 18.
- a barrier layer 12 e.g. calcium metal
- a transparent sealant 16 e.g. epoxy resin
- the layer of moisture-sensitive material 14 may be deposited on the barrier layer 12 by evaporation in a dry evaporation chamber (not shown).
- a dry evaporation chamber (not shown)
- the partially assembled sample is removed from the chamber and transferred to e.g. a glove box (not shown), which provides a dry atmosphere for further assembly of the sample.
- a transparent sealant 16, for example, epoxy resin may be applied over the layer 14 of moisture sensitive material under the dry conditions of the glove box.
- a layer of glass 18 is then applied over the sealant 16, which seals the glass 18 to the barrier layer 12 in a moisture-impermeable seal. Accordingly, once assembled, substantially all of the moisture reaching the layer 14 of moisture-sensitive material permeates through the barrier layer 12.
- Figure 2 illustrates a sample constructed according to a method of an
- the sample 1 10 is similar to the sample 10 of Figure 1 and like parts have been labelled with like numerals. However, unlike the sample 10 of Figure 1 , the sample 1 10 may be assembled without e.g. a glove box. Specifically, an optically transparent protective layer 1 15 may be applied over the layer of moisture sensitive material 14.
- the layer 1 15 may be a transparent layer of metal (e.g. copper) that may be evaporated using the same dry evaporation chamber (not shown) used to evaporate the layer 14 onto the barrier layer 12. Where a metal is evaporated, a mask 1 17, for example, of KaptonTM tape may be applied over exposed areas of the barrier layer 12 to allow an adherent layer of the optically transparent protective layer 1 15 to deposit over the sample.
- metal e.g. copper
- KaptonTM tape may be applied over exposed areas of the barrier layer 12 to allow an adherent layer of the optically transparent protective layer 1 15 to deposit over the sample.
- the layer 115 provides a temporary moisture barrier that protects the layer of moisture sensitive material 14 for sufficient time to allow the sealant 16 and glass 18 to be applied without the need for the dry atmosphere of a glove box.
- FIGS 3a and 3b are schematic plan and side views of an apparatus in accordance with one embodiment of the present invention.
- the apparatus comprises a humidity chamber 200; a light source 210; an optical camera 220 and a processor (not shown).
- the chamber 200 includes an optically transparent window 222 through which images may be taken by the optical sensor 220.
- the chamber 200 comprises a heated stage 224 onto which a reservoir of salt solution 226 is placed. Heating the stage 224 causes the salt solution 226 to evaporate, creating a humid atmosphere.
- the chamber 200 may be sealed and the stage 224 heated to cause the salt solution 226 to evaporate.
- the level of humidity and temperature within the sealed chamber may be controlled to a desired level using a controller (not shown).
- a sample for instance, a sample illustrated in Figure 1 or 2
- Light may be transmitted through the sample using light source 210 and optical images of the sample may be taken using camera 220.
- the moisture in the atmosphere permeates the barrier layer 12 of the sample and contacts the layer of moisture sensitive material 14. This causes the moisture sensitive material to degrade.
- the moisture sensitive material 14 is calcium metal
- the calcium metal reacts to form calcium hydroxide.
- calcium metal is opaque, while calcium hydroxide is transparent. The reaction of calcium with water, therefore, can be detected as a visual change. For example, when light is transmitted through the barrier layer 12, this visual change can be detected as a change in the amount of light that can be transmitted through the barrier layer 12.
- Fluence of water is the mass of water transported across the layer per unit
- Fluence 2 * mass of Ca reacted * Mr wa ter/(Area of Ca * Mr Ca )
- Fluence 2 * volume of Ca reacted * p Ca Mr wa ter/(Area of Ca * Mr Ca )
- Fluence 2 * thickness of Ca reacted * pc a Mr wa ter/Mrc a [0072]
- the thickness of Ca reacted is given by in terms of the light transmitted, Tr:
- the WVTR is thus the gradient of the fluence vs time trace in the linear region between the completely opaque and completely transparent regions.
- Figure 4 shows Images from a calcium test conducted on an uncoated PEN barrier sample at 24°C using an apparatus as shown in Figure 3 above. The water vapour transmission rate of the sample was calculated at various time intervals and the results plotted in Figure 5.
- the experimental fluence (y-axis) is a measure of the amount of water that is passing through the barrier sample. There are three regions clearly visible in the graph, the initial transient lag time, the increase to steady state and finally the plateau. This plateau is a result of all the calcium having been reacted and hence there is no further increase in measured fluence.
- the spots seen in Figure 4 are most likely a result of incomplete coverage during Ca deposition or the presence of inclusions on the surface of the barrier sample
- ⁇ is the activation energy associated with the barrier, which in this case is PEN polymer
- R is the gas constant
- T is the temperature.
- WVTR was measured over a range of temperatures :
- the test was used to observe the more complex situation where a thin ceramic oxide layer had been deposited on a polymer to improve its barrier properties.
- a first step to analysing the images was to observe the evolution of spots within the calcium. To begin with, the percentage area of spots was plotted as a function of time ( Figure 7):
- the graph representing the evolution of spots over time, displays an initial transient followed by an increase in spot area. From the graph, it appears to have two different linear regions, an initial steeper portion from ⁇ 1 .2 days to 2.6 days, followed by a longer less steep portion at >2.8 days.
- the graph shows the rapid increase in the number of spots once the lag time has passed.
- the rate of increase is smooth, although there is slight curvature to the graph. This reduction in gradient can be associated with the fact that there are only a limited number of macrodefects present and therefore as time passes, the probability of a macrodefect revealing itself decreases.
- Another explanation for the higher initial gradient may be to do with the PEN having to reach equilibrium with the chamber.
- the PEN has a uniform water concentration across the polymer (40% RH).
- the polymer side exposed to the humidity of the oven increases in water concentration at a higher rate than the decrease in water concentration of the polymer side in contact with AIOx. This would lead to a period where the concentration gradient across the AIOx layer is greater and thus the flux of water out of the barrier through the macrodefects is higher.
- a potential way to examine this further is to conduct the calcium test at differing level of humidity. A lower humidity calcium test would potentially show a less drastic change in gradient.
- the lag time portion is significantly longer than that of uncoated PEN.
- the size of a macrodefect is typically much smaller than the single pixel of the camera, so although the macrodefects can act as unhindered pathways for water to travel through, the actual area through which the water flows is smaller. This therefore means that a lower volume of water permeates through over the same period of time. This means that a longer time is required for a spot to appear and begin growing.
- the time-lapse function allows for a very large number of images of identical areas to be taken over a period of time. This not only results in a great number of data points, but it is in fact possible to observe the behaviour of single spots on the sample over time.
- Figure 9 shows two different types of spots that were observed.
- the spots that grow in size are indicative of the presence of a macrodefect, whilst the spots that remain constant were probably created at the deposition stage, the inclusion, for example, of dust particles.
- the percentage area increase of spots over time could then be equated to the volume of reacted calcium as discussed above. This can be used to analyse the water vapour transmission rate of the spots over time.
- the WVTR value was determined to be 8.6 ⁇ 0.3 x 10 "4 g/m 2 /day, which is about two orders of magnitude lower than that of the uncoated PEN at the same temperature (4.48 ⁇ 0.05 x 10 "1 g/m 2 /day). If we assume that the growth of spots are a direct result of macrodefects and that macrodefects provide no hindrance to water vapour, all barrier capabilities lie solely on the PEN within these defects. Thus we could assume that the permeation behaviour through
- Table WVTR values of PEN + AIOx obtained from the spot growth (as % area) over time at different temperatures. Errors calculated by compounding the accuracy of measurements, deviation from straight lines, variation in gradient, as well as taking into account a degree of experimental error. A plot of In(WVTR) against 1000/Temperature was used to calculate activation energy at 61 kJ/mol. This value is close to that of uncoated PEN (60 ⁇ 4 kJ/mol).
- the WVTR value obtained via change in opacity was 1.71 ⁇ 0.02x 10 "1 g/m 2 /day. It is therefore highly encouraging that this values lies very close to that obtained for the same spot via the spot expansion method (1.78 ⁇ 0.01 x 10 "1 g/m 2 /day).
- the size of single defects can potentially be calculated by measuring the mass of water through the defect and comparing to the absolute WVTR values previously obtained from the uncoated polymer. To estimate the size of the macrodefect, the mass of water per unit time is divided by the absolute WVTR of the substrate polymer at the same temperature.
- the range of macrodefect areas obtained for PEN + AIOx at 23°C was ⁇ 4-7 x 10 "8 m 2 . If we assume macrodefects as circular, we obtain a macrodefect size of ⁇ 200- 300 ⁇ . Physically, these sizes appear reasonable for that of macrodefects.
- the graph obtained contains an initial transient region followed by an increase in permeation, and finally a steady-state region.
- the observed change in gradient at ⁇ 2 days can be reasoned in a similar fashion as with the macrodefects.
- This steady state region of constant gradient was used to calculate the WVTR. Therefore a WVTR value of 5.4 ⁇ 0.1 x 10 "3 g/m 2 /day was from the change in background opacity. This was measured for PEN + AIOx samples across a range of temperatures :
- the activation energy calculated from the values is 74 ⁇ 7 kJ/mol. As expected this value is higher than that obtained for uncoated PEN (60 ⁇ 4 kJ/mol). These values were not measured with a calibration of the intensity measured during the experiment, and thus the values obtained are likely to be subject to some error. In particular, in samples with more bright spots from macrodefects (such as is observed at greater temperature) will have a greater underestimate of the transmitted intensity, i.e. the apparent WVTR will be lower than the true value, and more so at higher temperature, underestimating the measured activation energy.
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GBGB1713262.2A GB201713262D0 (en) | 2017-08-18 | 2017-08-18 | Water vapour permeation |
PCT/GB2018/052336 WO2019034888A1 (en) | 2017-08-18 | 2018-08-17 | Water vapour permeation |
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JP6299751B2 (en) * | 2013-04-02 | 2018-03-28 | コニカミノルタ株式会社 | Method and system for evaluating water vapor permeability of gas barrier film and method for producing gas barrier film |
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