HK1189852A - An inorganic multilayer stack and methods and compositions relating thereto - Google Patents

Abstract

The present invention describes a multi-layer stack.The multilayer stack comprises: (i) one or more inorganic barrier layers for reducing the passage rate of gas molecules or vapor molecules;(ii) an inorganic reaction layer adjacent to one or more inorganic barrier layers,The inorganic reaction layer can react with gas molecules or water vapor molecules;(iii) Among them,During the operation of the multi-layer stack,The gas molecules or vapor molecules permeating through the one or more inorganic barrier layers react with the inorganic reaction layer,So that gas molecules or vapor molecules are essentially unable to pass through the multilayer stack.

Description

Inorganic multilayer stack and related manufacturing method and composition

RELATED APPLICATIONS

This application claims priority to U.S. provisional applications 61/436,726, 61/436,732, and 61/436,744, filed on day 27 of 2011, the contents of which are incorporated herein by reference.

Technical Field

The present invention generally relates to multilayer stacks and related methods of manufacture and compositions. In particular, the invention relates to flexible multilayer stacks for use as packaging in the technical field of solar cells, electrolysis cells, semiconductor lighting and Light Emitting Diode (LED) displays and the like.

Background

Many products, such as electronic devices, medical devices and pharmaceuticals, are sensitive to water vapor or ambient gases. These products may deteriorate and/or degrade when exposed to water vapor or ambient gases. In view of this, the provision of a barrier coating is often used as a protective measure against such adverse exposure.

Plastic coatings or layers are often used as barrier coatings. However, such barrier coatings suffer from their poor gas and liquid permeability resistance, which is generally lower than the resistance necessary for the productPermeability requires several orders of magnitude. By way of example, some LED displays and solar cells require a moisture vapor transmission rate of less than about 10 during the packaging application process^-4Gram per square meter per day, in contrast, for a commonly used plastic substrate, polyethylene terephthalate (PET), the moisture passage rate is approximately 1 to 10 grams per square meter per day. As will be appreciated by those skilled in the art, the water vapor transmission rate can be considered to be inversely proportional to the water permeation resistance.

Some other methods prevent exposure to undesirable elements by reducing water vapor permeability by applying a barrier coating to a plastic film such as PET. The barrier coating is typically a single coating of an inorganic coating material, such as aluminum, silicon oxide, AIO, or a single layer of an inorganic coating material_xAnd S1₃N₄These inorganic materials are deposited on the plastic substrate by well-known vacuum deposition processes. This single coating of inorganic cover material generally reduces the permeability value of PET to moisture from 1.0 g/m/day to 0.1 g/m/day. Nevertheless, the coatings on a single plastic substrate still do not meet the necessary permeation resistance requirements.

Fig. 1 is a schematic illustration of a pair of layers 10, such as the one shown in fig. 1, with an inorganic barrier layer or inorganic barrier coating 12 formed over an organic film 14 (e.g., acrylic). The pair of layers 10 may be deposited on the polymer substrate as a protective film. The inorganic barrier layer 12 is composed of dense oxide particles, and the inorganic barrier layer 12 serves as a conventional permeation-preventing barrier against permeation of gas or moisture. In any event, such conventional barrier layers suffer from the common disadvantage of allowing moisture or gas to pass through the oxide particles, ultimately degrading the performance of electronic devices, such as solar cells and organic light emitting diodes, that are located beneath the barrier layer. To overcome these deficiencies, the provision of the organic layer 14 on the barrier layer 12 serves to eliminate such deficiencies as described above, while the organic layer 14 also serves as the underlying surface for the polymer matrix. Other particular methods of depositing multiple pairs of layers onto a polymer matrix provide a predictable effect, the defects of misalignment present between the multiple pairs of layers further reducing gas and water vapor permeability. However, depositing multiple pairs of layers results in a more expensive barrier, while reducing the flexibility of the final barrier.

Whether a single layer barrier coating, a single pair of layers, or multiple pairs of layers is used as a method of protection, the conventional diffusion mitigation approaches described above do not meet the requirements for protecting the underlying polymer layer in certain applications (e.g., solar cell applications, LED display applications). In particular, inorganic layers have the disadvantage that they are not themselves filled very efficiently and that they themselves provide channels for the diffusion movement of moisture and ambient gases from the barrier layer to the surface of the polymeric substrate. Conventional polymer matrices do not adequately protect the product beneath their packaging from exposure to moisture and adverse gaseous environments. As a result, the properties of the product underlying these polymeric matrices degrade over time, ultimately resulting in a greatly reduced service life.

Therefore, there is an urgent need for a new protective layer and design which not only effectively protects the products which are located under the protective layer and are sensitive to moisture and gases from moisture and gases which are detrimental to the surrounding environment, but also overcomes the disadvantages of the conventional barrier layer and paired layer structure.

Disclosure of Invention

In view of the foregoing, in one aspect, the present invention provides a multilayer stack. The multilayer stack includes: (i) one or more inorganic barrier layers for reducing the rate of passage of gas molecules or water vapor molecules; (ii) an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with gas molecules or vapor molecules; (iii) wherein during operation of the multilayer stack, gas molecules or vapor molecules permeating through the inorganic barrier layer react with the inorganic reactive layer such that gas molecules or vapor are substantially prevented from passing through the multilayer stack.

The vapor or gas molecules include at least one component selected from the group consisting of: moisture, oxygen, nitrogen, hydrogen, carbon dioxide, argon, and hydrogen sulfide. According to a preferred embodiment of the present invention, the inorganic barrier layer comprises at least one member selected from the group consisting of: metals, metal oxides, metal nitrides, metal oxynitrides, metal carbonitrides, metal oxycarbides. The metal composite in the inorganic barrier layer preferably comprises at least one component selected from the group consisting of: aluminum, silver, silicon, zinc, tin, titanium, tantalum, niobium, ruthenium, gallium, platinum, vanadium, indium, and carbon.

The inorganic reaction layer preferably comprises at least one component selected from the group consisting of: alkali metal oxides, zinc oxide, titanium dioxide, metal-doped zinc oxide and silicon oxide. In certain particular embodiments, the inorganic layers of the present invention are doped with one or more non-oxide chemistries.

The inorganic barrier layer and the inorganic reaction layer have a thickness ranging from about 10nm to 1 micron. In certain embodiments of the present invention, the one or more barrier layers comprise two barrier layers, and the reactive layer is sandwiched between the two barrier layers. The reaction layer preferably includes a columnar structure. Each of the one or more barrier layers may be comprised of one or more amorphous materials. The inorganic barrier layer, which is preferably substantially transparent, is used in the field of light transmission.

In another aspect, the present invention provides a solar cell module. The solar cell module includes: (i) a solar cell and a solar cell package at least partially encapsulating the solar cell, the solar cell package comprising: a) one or more inorganic barrier layers for reducing the passage rate of gas molecules or vapor molecules; b) an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with gas molecules or water vapor molecules; c) when the solar cell package is in a working state, gas molecules or vapor molecules permeated by the one or more inorganic barrier layers react with the inorganic reaction layer, so that the solar cell package protects the solar cell from being damaged by the gas or vapor molecules. In one embodiment, the solar cell of the present invention is selected from one of a silicon-based solar cell, a thin film solar cell, an organic photovoltaic solar cell, and a dye-sensitized solar cell. The thin film solar cell preferably includes at least one of copper, indium, gallium, arsenic, cadmium, tellurium, selenium and sulfur.

In another aspect, the present invention provides a light generating module. The light generation module includes: (i) a light source; and (ii) a light source package for at least partially packaging the light source; the light source package includes: a) one or more inorganic barrier layers for reducing the rate of passage of gas molecules or water vapor molecules; b) an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with gas molecules or water vapor molecules; c) when the light source package is in a working state, gas molecules or vapor molecules permeated by the one or more inorganic barrier layers react with the inorganic reaction layer, so that the light source package protects the light source from being damaged by the gas or vapor molecules. In certain embodiments, the light sources of the present invention comprise organic or inorganic light emitting diodes.

In another aspect, the invention includes a Light Emitting Diode (LED) display screen. The LED display screen comprises: (i) a light emitting diode; and (ii) a light emitting diode package for at least partially packaging the light emitting diode; the light emitting diode package includes: a) one or more inorganic barrier layers for reducing the rate of passage of gas molecules or water vapor molecules; b) an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with gas molecules or water vapor molecules; c) when the light emitting diode package is in a working state, gas molecules or water vapor molecules permeated by the one or more inorganic barrier layers react with the inorganic reaction layer, so that the light emitting diode package protects the light emitting diode from being damaged by the gas or water vapor molecules. In certain embodiments, the LEDs of the present invention comprise organic light emitting diodes, also known as OLEDs.

In another aspect, the present invention provides an electrolytic cell. The electrolytic cell comprises: (i) a cathode; (ii) an anode; (iii) an electrolyte; and (iv) an electrolytic cell package encapsulating at least a portion of the cathode, a portion of the anode, and a portion of the electrolyte; the electrolytic cell package includes: a) one or more inorganic barrier layers for reducing the rate of passage of gas molecules or water vapor molecules; b) an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with gas molecules or water vapor molecules; c) when the electrolytic cell package is in a working state, gas molecules or water vapor molecules permeated by the one or more inorganic barrier layers react with the inorganic reaction layer, so that the electrolytic cell package protects the electrolytic cell from the gas or water vapor molecules. In certain embodiments, the electrolytic cell of the present invention is flexible.

In another aspect, a reflective display module is provided. The reflective display module includes: (i) a reflective display; and (ii) a reflective display package enclosing at least a portion of the reflective display; the reflective display package includes: a) one or more inorganic barrier layers for reducing the rate of passage of gas molecules or water vapor molecules; b) an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with gas molecules or water vapor molecules; c) gas molecules or water vapor molecules permeating through the one or more inorganic barrier layers react with the inorganic reactive layer when the reflective display package is in an operating state, such that the reflective display package protects the reflective display from the gas or water vapor molecules. The reflective display comprises an electrophoretic display or a multi-layer liquid crystal display.

In another aspect, the present invention provides a method of making a multilayer stack. The method comprises the following steps: (i) loading a flexible substrate on a coating machine; (ii) moving the flexible substrate or part of the mechanism of the coating machine to place the flexible substrate at a first position inside the coating machine; (iii) fabricating one or more inorganic barrier layers on a flexible substrate while the flexible substrate is at a first location, the inorganic barrier layers capable of reducing the passage rate of vapor or gas molecules; (iv) moving the flexible substrate or part of the coating machine mechanism to enable the flexible substrate to be arranged at a second position in the coating machine, wherein the second position is different from the first position; and (v) forming a reactive layer adjacent to the one or more inorganic barrier layers, the reactive layer capable of reacting with vapor or gas molecules permeating through the inorganic barrier layers to form a multilayer stack upon bonding of the one or more barrier layers and the corresponding reactive layer on the flexible substrate.

In the above method, it is preferable that the multilayer stack is applied to at least one component selected from the group consisting of: solar cell, light source, LED display screen and electrolytic cell. The step of producing comprises at least one technique selected from the group consisting of: sputtering, reactive sputtering, evaporation, reactive evaporation, chemical vapor deposition, solution coating processes and plasma enhanced chemical vapor deposition. For the same reason, said forming of said reactive layer preferably comprises at least one technique selected from the group consisting of: sputtering, reactive sputtering, evaporation, reactive evaporation, chemical vapor deposition, solution coating processes and plasma enhanced chemical vapor deposition. The fabricating step may be performed at a temperature in a range between about-20 ℃ and about 200 ℃. The step of forming the reaction layer may be performed at a temperature ranging between about-20 ℃ to about 200 ℃. The fabricating step and the forming step may both be performed in a roll-to-roll fashion.

The loading step described above preferably comprises: (a) positioning the flexible substrate on the coater to wind the flexible substrate on a reel, (b) extending and holding the flexible substrate along the reel to expose at least a portion of the flexible substrate to facilitate the step of forming the inorganic barrier layer.

During the fabrication steps and the forming steps of the above-described process, the flexible substrate may contact a roller having a temperature set in the range of about-20 ℃ to about 200 ℃.

In another aspect, the present invention provides a composition for a multilayer stack. The components comprise: (i) an inorganic barrier layer that reduces the gas or vapor molecular permeation throughput, and the inorganic barrier layer comprises at least one substance from the group consisting of metals, metal oxides, metal nitrides, metal oxynitrides, metal carbonitrides, and metal oxycarbide nitrides; and (ii) the inorganic reaction layer includes an amount of a reactive material capable of reacting with the gas or vapor molecules permeated through the inorganic barrier layer, the reactive material including at least one substance selected from the group consisting of alkali metal oxides, zinc oxide, titanium oxide-based, metallic zinc-doped oxides, and silicon oxide. The weight percentage of at least one component in the inorganic barrier layer is between about 1% and 100%, and similarly, the weight percentage of the at least one reactive material is between about 1% and 100%.

The invention, however, both as to organization and method of operation, together with additional objects and advantages thereof, may best be understood from the following description of specific embodiments when read in connection with the accompanying drawings.

Drawings

Fig. 1 is a cross-sectional view of a conventional barrier layer for encapsulating a solar cell;

FIG. 2 is a schematic view of one embodiment of a multilayer stack for protection against moisture and other adverse environmental gases as described herein;

FIG. 3 is a side cross-sectional view of another embodiment of a multilayer stack for protection against moisture and other adverse environmental gases as described herein;

FIG. 4 is a perspective view of a columnar-type reaction layer structure that may be used in the multilayer stack embodiment shown in FIG. 2 and/or FIG. 3;

fig. 5 is a top view of an embodiment of a coating machine that facilitates the multi-layer stack processing described herein in a roll-to-roll fashion.

Detailed Description

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without some or all of these specific details. In other instances, well known process steps have not been described in detail in order not to unnecessarily obscure the present invention.

Fig. 2 shows a multilayer stack 200 comprising a barrier layer 202 and a reactive layer 204, the reactive layer 204 being disposed adjacent to the barrier layer 202. The multilayer stack 200 is bonded to a substrate, preferably a flexible plastic substrate. As a preferred embodiment, the multilayer stack described in the present invention can be used as a package in a variety of technical fields. For example, a plastic substrate having a multilayer stack 200 disposed thereon is used to encapsulate solar cells, electrolytic cells, light generating modules, Light Emitting Diode (LED) displays, reflective displays, and the like, and prevent the encapsulated portion thereof from being exposed to moisture, undesirable gases, or ambient gases.

In multilayer stack 200, barrier layer 202 acts as a barrier to moisture and undesirable gases, such as oxygen, nitrogen, hydrogen, carbon dioxide, argon, and hydrogen sulfide. The barrier layer 202 includes at least one material selected from the group consisting of metal, metal oxide, metal nitride, metal oxynitride, metal carbonitride, and metal oxycarbide. Furthermore, the barrier layer 102 preferably includes elemental carbon and elemental oxygen, which may be present in their atomic form or as part of a compound. For example, one barrier layer 202 includes silicon dioxide, aluminum oxide, aluminum nitride, aluminum oxynitride, tantalum oxide, niobium oxide, silicon nitride, silicon oxynitride, silicon oxycarbide, and silicon carbonitride.

The barrier layer 202 may be made of a single layer or multiple layers of inorganic materials. In a preferred embodiment of the present invention, the barrier layer 202 comprises an amorphous material. When more than one layer is used, as a preferred embodiment, the different layers are stacked adjacent to each other. The type of inorganic material of each layer need not be the same, and in some particular embodiments of the invention the type of material of each layer is different. Although barrier layer 202 may be made of any inorganic material that serves as a barrier to the aforementioned undesirable gases, in a preferred embodiment of the present invention, barrier layer 202 comprises a metallic composition that may be present in barrier layer 202 in its elemental form or as a compound (such as the aforementioned compounds) comprising a metal selected from at least one of the group consisting of aluminum, silver, silicon, zinc, tin, titanium, tantalum, niobium, ruthenium, gallium, platinum, vanadium, and indium. For example, one metal oxide includes Al_xO_yOr SiO_x. The presence of an amount of metal or metal oxide on the barrier layer 202 reduces the passage of undesirable gas or vapor molecules through the barrier layer. In a preferred embodiment of the present invention, the metal or metal oxide is present in the barrier layer 202 in an amount of about 1 to 100% by weight, preferably about 1 to 50% by weight.

The barrier layer 202 has a thickness of between about 10nm and 1 micron, and preferably has a thickness in the range of 20nm to 300 nm.

The purpose of barrier layer 202 is to reduce the passage of gas or vapor molecules, but not to completely prevent water molecules and certain undesired gases. In response to this, the present invention adds a reactive layer 204 that functions to react with moisture and undesirable gases such as oxygen, nitrogen, hydrogen, carbon dioxide, argon, and hydrogen sulfide that pass through the barrier layer 202. It is known from conventional technical knowledge that the reaction layer 204 is not suitable for application in solar cells and other application fields due to its own reaction characteristics, because it absorbs moisture and unfavorable gases in the surrounding environment, degrades product performance, and ultimately leads to product failure. The present invention, however, innovatively exploits this characteristic of the reactive layer 204, which is capable of absorbing moisture and ambient gases, in a manner that facilitates the use of the barrier film. Specifically, moisture, ambient gas, or undesired gases that permeate through barrier layer 202 further react with reactive layer 204 such that moisture, ambient gas, or undesired gases do not substantially permeate and pass through multilayer stack 200.

The reactive layer 204 may be made of any inorganic material, preferably chemically homogeneous. However, in a preferred embodiment of the present invention, the reactive layer 204 comprises at least one reactive material from the group consisting of alkali metal oxides, zinc oxide, titanium dioxide, metal-doped zinc oxide and silicon oxide. In some embodiments of the present invention, the reactive layer 204 is doped with one or more non-oxide chemistries. As representative examples, such non-oxide dopant materials include alkali metals, such as calcium, sodium, and lithium, among others.

One or more of the reactive layers may be made of the same material or different materials. Like the barrier layer 202, the reactive layer 204 may also include one or more reactive layers disposed adjacent to each other. The reactive layer 204 includes an effective amount of reactive material that is capable of reacting with moisture, undesired gases, or ambient gases that permeate through the barrier layer adjacent to the reactive layer 204. In a preferred embodiment of the present invention, the reactive material is present in the reactive layer 204 in a range of about 1% to about 100% by weight. However, as a more preferred embodiment, the reactive material of the reactive layer 204 of the present invention is in the range of about 90% to about 100% by weight.

The total thickness of the reactive layer 204 may be between about 10nm and 1 micron, with a preferred range of about 20nm to 500 nm. In some applications, where the multilayer stack 200 is disposed on a plastic substrate product as a sealant, there is a risk that moisture, undesirable gases, or environmental gases may permeate through the plastic substrate and react with the reactive layer 204 during transportation, handling, and storage of the product. As a result, the reactive property of the reactive layer 204 is depleted to disappear in advance, thereby causing the isolation function of the multilayer stack 200 to fail. In this regard, certain preferred embodiments of the present invention add a barrier layer between the plastic substrate and the reactive layer.

If the composition of the reactive layer 204 is similar to that of the barrier layer 202, then the reactive layer 204 preferably differs substantially from the barrier layer 202 in structure, composition doping ratio, degree of crystallinity (including one that is amorphous while the other is crystalline), reactivity to moisture, adverse gas or ambient gas combinations, and the like.

Fig. 3 shows another embodiment multilayer stack 300 of the present invention. The multilayer stack 300 includes a barrier layer 302, a barrier layer 306, and a reactive layer 304 between the barrier layers. The reactive layer 304 shown in figure 3 is substantially the same as the reactive layer 204 shown in figure 2, and the barrier layer 302 and the barrier layer 306 shown in figure 3 are substantially the same as the barrier layer 202 shown in figure 2. As with multilayer stack 200 described above, multilayer stack 300 may also be generally disposed on any substrate. As a preferred embodiment, the multilayer stack 300 is provided on a flexible plastic substrate.

In view of the structural properties of the multilayer stack shown in fig. 3, those gases that pass through moisture, adverse gases or ambient atmosphere on the plastic substrate are already separated by the barrier layer 302 before they reach the reactive layer 304. Therefore, the barrier layer 302 can protect the reactive layer 304 from moisture, undesired gases, or ambient gases that may permeate through the polymer substrate.

Whether the reactive layer 204 is employed in the multilayer stack 200 shown in fig. 2 or the reactive layer 304 is employed in the multilayer stack 300 shown in fig. 3, the reactive layer of one component preferably has a columnar structure 404, as shown in fig. 4, configured as a reactive layer (e.g., the reactive layer 204 shown in fig. 2 or the reactive layer 304 shown in fig. 3). A reaction layer having a columnar structure organization represents a preferred embodiment of the present invention because such columnar structure can increase the surface area of the reaction layer that can react with the diffusing chemical.

Although the barrier layer and the reactive layer of the present invention are shown in contact with each other in fig. 2 and 3, it is not necessary to do so in the practice of the present invention. In certain embodiments of the present invention, an intermediate layer having one or more different functions may be disposed between the barrier layer and the reactive layer. For example, when it is desired to flatten the surface of the barrier layer, or flatten the surface of the reaction layer, or flatten the surfaces of both the barrier layer and the reaction layer, an intermediate layer may be interposed between the reaction layer and the barrier layer for this purpose. The present specification describes the use of the word "adjacent" when a barrier layer is attached adjacent to a reactive layer, however, in this use the meaning of "adjacent" is not limited to only the meaning of a contact attachment between the barrier layer and the reactive layer, but also encompasses the meaning of an "adjacent" relationship between the barrier layer and the reactive layer when one or more intervening layers are interposed between the barrier layer and the reactive layer.

Furthermore, according to the preferred embodiments described above, the barrier layer and the reactive layer to which the invention relates are both made of one or more different types of inorganic materials. However, in other embodiments of the present invention, the materials of the barrier layer and the reactive layer are not limited thereto. In certain embodiments of the present invention, the barrier layer and the reactive layer are made of one or more different types of organic materials.

In a preferred embodiment of the present invention, the multilayer stack 200 of FIG. 2, and the multilayer stack 300 of FIG. 3 are used as a package. As an example, in the field of solar cell applications, the multilayer stack of the present invention is used to encapsulate a solar cell. As another example, the multilayer stack of the present invention is used to encapsulate light sources in the field of lighting applications with light generating modules. As a further example, in the field of electrolytic cell applications, the multilayer stack of the present invention is used to encapsulate a cathode, an anode and an electrolyte. As a further embodiment, in the field of display applications, the multilayer stack of the present invention is used for encapsulating displays, such as LED displays or reflective displays. Those skilled in the art will recognize that packaging of solar cells, light generating modules, electrolytic cells, LED displays, and reflective displays can be accomplished using existing techniques.

In accordance with conventional wisdom, when one layer is stacked with another adjacent layer to form a multilayer stack, defects associated with one layer are transferred to the adjacent layer. This phenomenon of defect propagation is further exacerbated when the number of layers of the multilayer stack is greater. In sharp contrast to the above, the present inventors have surprisingly found that a layer composed of an inorganic material not only covers the defects of the layer adjacent thereto, but also flattens the surface of the adjacent layer. The field of application of the multilayer stacks of the invention for the insulation of water and gas is therefore highly advantageous, since the invention prevents or greatly reduces the occurrence of defects or the propagation of a defective structure from one layer to another.

Although the multilayer stacks of the present invention can be manufactured using any technique known to those skilled in the art, as a preferred embodiment, a manufacturing production technique in roll-to-roll format is used, which allows a relatively high throughput. Fig. 5 is a top view of a coater 500 as one embodiment of the present invention. The coater, also known as a "roll coater", houses a roll of flexible film. The coater 500 includes an unwind roll 502, guide rolls 504, take-up rolls 506, temperature controlled deposition drum 508, one or more deposition zones 510, and deposition chamber 512. The one or more deposition zones 510 each include a target material, a power source, and louvers, which will ultimately be used for deposition on a flexible substrate, as described in more detail below.

As one embodiment of the present invention, the coating process begins by first loading the flexible substrate 514 onto the unwind roll 502. The flexible substrate 514 is preferably wound around a spool that is loaded onto the unwind roll 502. Generally, a portion of the flexible substrate 514 wound around the rotating shaft is pulled out, and the pulled-out flexible substrate 514 is sequentially wound around the outer surfaces of the supporting roller 504 and the drum 508 along the direction of the outer wall of the guide roller 504 and the drum 508, wherein the drum 508 can rotate, and finally one end of the flexible substrate 514 is connected to the winding roller 506. During operation of coater 500, unwind roll 502, wind-up roll 506, and deposition drum 508 are all rotated to enable flexible substrate 514 to cool deposition drum 508 from multiple locations.

When the flexible substrate 514 is loaded into the coating machine 500, the coating process then includes striking a plasma into the deposition zone 510. In the coating region, the louvers direct charged particles of the plasma field to collide with each other and eject the target material, eventually depositing the target material on a flexible substrate. During the coating process, the temperature of the flexible substrate 514 is preferably controlled by the deposition drum 508 so that the substrate is not damaged. In embodiments of the present invention in which the flexible substrate 514 comprises a polymeric material, the deposition drum 508 is cooled to ensure that the temperature of the deposition drum 508 is near or below the glass transition temperature of the polymeric material. This cooling prevents the polymer substrate from melting during deposition, thereby avoiding degradation of the polymer substrate itself that may not have reached the deposition drum 508.

As can be seen in fig. 5, a plurality of deposition zones are provided, each deposition zone affecting the deposition of only one specific material on the polymeric substrate. For example, in one deposition region, the target material includes at least one of a metal, a metal oxide, a metal nitride, a metal oxynitride, a metal carbonitride, and a metal oxycarbide, each of which can facilitate deposition of a barrier layer (e.g., including the barrier layer 202 of FIG. 2 or at least one of the barrier layers 302 and 306 of FIG. 3). As yet another example, the target material in the other deposition zone includes at least one of an alkali metal oxide, zinc oxide, titanium dioxide, metal-doped zinc oxide, and silicon oxide, which is used to fabricate a reactive layer (e.g., reactive layer 204 in fig. 2 or reactive layer 304 in fig. 3). By moving the flexible substrate 514 from one location to another, different types, thicknesses, and deposition zones of target material can be deposited on the substrate. The coater 500 may be used to implement techniques including at least one selected from the group consisting of sputtering, reactive ion sputtering, evaporation, reactive evaporation, chemical vapor deposition, and plasma enhanced chemical vapor deposition.

It should be noted that the inventive features of the present invention are characterized by facilitating the deposition of multiple layers by moving at least a portion of the coating machine while holding the substrate stationary or by moving both the substrate and the coating machine, rather than by moving the substrate from one location to another.

Regardless of the specific process by which deposition is achieved, it will be appreciated that the roll-to-roll technique of the present invention can allow for the rapid deposition of different types and thicknesses of coatings on a substrate that are ultimately deposited to form the multilayer stack of the present invention. The inventive roll-to-roll manufacturing process of the present invention enables high throughput, thereby increasing revenue. In the present situation, the solar cell industry is facing a new challenge, and the solar cell industry may become a new technical solution feasible in commercial aspect and replace the traditional energy industry, and the multilayer stack and the processing method of the invention are greatly improved compared with the traditional technology and processing method.

As described above, the barrier and reactive layers of multilayer stack 300 of fig. 3 can be made of suitable inorganic oxide materials, thereby providing the resulting multilayer stack with both flexibility and water resistance. It is known from the present invention that the reactive layer located inside the multilayer stack has a longer service life if the amount of water vapour passing through the barrier layer due to adsorption is limited. Further, according to the present invention, it is possible to achieve the effect of the barrier layer having a limited amount of water vapor adsorbed by the barrier layer by minimizing the amount of water vapor reaching the interface between the barrier layer and the reaction layer.

The foregoing is only a few embodiments of the present invention and other modifications, variations and equivalents are within the scope of the disclosure. By way of example, the present invention discloses a barrier layer for blocking gas and water; in addition, the invention also discloses a using method for reducing the passing rate of organic matters through the barrier layer, a processing method of the barrier layer and a composition of the barrier layer. Accordingly, the appended claims are to be construed broadly and in a manner consistent with the scope of the invention as set forth in the following claims.

Claims (36)

1. A multilayer stack, comprising:

one or more inorganic barrier layers for reducing the passage rate of gas molecules or vapor molecules;

an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with the gas molecules or water vapor molecules;

wherein, when the multilayer stack is in an operational state, gas molecules or vapor molecules permeating through the one or more inorganic barrier layers react with the inorganic reactive layer such that the gas molecules or vapor molecules cannot permeate through the multilayer stack.

2. The multilayer stack of claim 1, wherein the vapor or gas molecule comprises at least one component selected from the group consisting of: moisture, oxygen, nitrogen, hydrogen, carbon dioxide, argon, and hydrogen sulfide.

3. The multilayer stack of claim 1, wherein the inorganic barrier layer comprises at least one component selected from the group consisting of: metals, metal oxides, metal nitrides, metal oxynitrides, metal carbonitrides and metal oxycarbides.

4. The multilayer stack of claim 3, wherein said inorganic barrier layer comprises at least one component selected from the group consisting of: aluminum, silver, silicon, zinc, tin, titanium, tantalum, niobium, ruthenium, gallium, platinum, vanadium, and indium.

5. The multilayer stack of claim 1, wherein said inorganic reactive layer comprises at least one component selected from the group consisting of: alkali metal oxides, zinc oxide, titanium dioxide, metal-doped zinc oxide and silicon oxide.

6. The multilayer stack of claim 5, wherein the inorganic reactive layer is doped with one or more non-oxide chemical constituents.

7. The multilayer stack of claim 5, wherein said inorganic reactive layer comprises an inorganic matrix.

8. The multilayer stack of claim 1, wherein the inorganic barrier layer has a thickness between about 10nm and about 1 μ ι η.

9. The multilayer stack of claim 1, wherein the inorganic reactive layer has a thickness between about 10nm and about 1 μ ι η.

10. The multilayer stack of claim 1, wherein the one or more barrier layers comprises two inorganic barrier layers, wherein the inorganic reactive layer is sandwiched between the two inorganic barrier layers.

11. The multilayer stack of claim 1, wherein the inorganic reactive layer comprises a columnar structure.

12. The multilayer stack of claim 1, wherein any one of the one or more inorganic barrier layers is made of one or more amorphous materials.

13. The multilayer stack of claim 1, wherein said inorganic barrier layer is substantially transparent.

14. A solar cell module comprising:

a solar cell; and

a solar cell package at least partially encapsulating a solar cell, the solar cell package comprising:

one or more inorganic barrier layers for reducing the rate of passage of gas molecules or water vapor molecules;

an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with gas molecules or vapor molecules;

when the solar cell package is in a working state, gas molecules or vapor molecules permeated by the one or more inorganic barrier layers react with the inorganic reaction layer, so that the solar cell package protects the solar cell from being damaged by the gas or vapor molecules.

15. The solar cell module of claim 13 wherein the solar cell is selected from one of the group consisting of: silicon-based solar cells, thin-film solar cells, organic photovoltaic solar cells and dye-sensitized solar cells.

16. The solar cell module as claimed in claim 13, wherein the thin film solar cell comprises at least one component selected from the group consisting of: copper, indium, gallium, arsenic, cadmium, tellurium, selenium and sulfur.

17. A light generating module comprising:

a light source; and

a light source package for at least partially packaging the light source; the light source package includes:

one or more inorganic barrier layers for reducing the passage rate of gas molecules or vapor molecules;

an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with gas molecules or vapor molecules;

when the light source package is in a working state, gas molecules or vapor molecules permeated by the one or more inorganic barrier layers react with the inorganic reaction layer, so that the light source package protects the light source from being damaged by the gas or vapor molecules.

18. The light-generating module of claim 16, wherein the light source comprises an organic or inorganic light-emitting diode.

19. A light emitting diode display screen comprising:

a light emitting diode; and

a light emitting diode package for at least partially encapsulating the light emitting diode, the light emitting diode package comprising:

one or more inorganic barrier layers for reducing the passage rate of gas molecules or vapor molecules;

an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with gas molecules or vapor molecules;

when the light-emitting diode package is in a working state, gas molecules or vapor molecules permeated by the one or more inorganic barrier layers react with the inorganic reaction layer, so that the light-emitting diode package protects the light-emitting diode from being damaged by the gas or vapor molecules.

20. The light emitting diode display screen of claim 18 wherein said light emitting diodes comprise organic light emitting diodes, also known as OLEDs.

21. An electrolytic cell; the method comprises the following steps:

a cathode;

an anode;

an electrolyte; and

an electrolytic cell package at least partially enclosing the cathode, the anode, and the electrolyte, the electrolytic cell package comprising:

one or more inorganic barrier layers for reducing the passage rate of gas molecules or vapor molecules;

an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with gas molecules or vapor molecules;

wherein gas molecules or vapour molecules permeating through the one or more inorganic barrier layers react with the inorganic reaction layer when the cell package is in an operating state, thereby protecting the cell from the gas or vapour molecules.

22. The electrolytic cell of claim 21 wherein: the cell is flexible and lightweight.

23. A reflective display module; the method comprises the following steps:

a reflective display; and

a reflective display package at least partially encapsulating the reflective display, the reflective display package comprising:

one or more inorganic barrier layers for reducing the passage rate of gas molecules or vapor molecules;

an inorganic reaction layer disposed adjacent to the one or more inorganic barrier layers, the inorganic reaction layer capable of reacting with gas molecules or vapor molecules;

wherein gas molecules or vapor molecules that permeate through the one or more inorganic barrier layers react with the inorganic reactive layer when the reflective display package is in an operational state, such that the reflective display package protects the reflective display from the gas or vapor molecules.

24. The reflective display module of claim 23, wherein said reflective display comprises an electrophoretic display or a multi-layer liquid crystal display.

25. A method of manufacturing a multilayer stack, the method comprising:

loading a flexible substrate on a coating machine;

moving the flexible substrate or a part of a mechanism of a coating machine to enable the flexible substrate to be placed at a first position inside the coating machine;

fabricating one or more inorganic barrier layers on the flexible substrate while the flexible substrate is at a first location, the inorganic barrier layers capable of reducing the passage rate of vapor or gas molecules;

moving the flexible substrate or a part of the coating machine to enable the flexible substrate to be arranged at a second position inside the coating machine, wherein the second position is different from the first position; and

forming a reactive layer adjacent to the one or more inorganic barrier layers, the reactive layer capable of reacting with vapor or gas molecules permeating through the inorganic barrier layers to form a multilayer stack upon bonding of the one or more barrier layers and the corresponding reactive layer on the flexible substrate.

26. The method of making a multilayer stack according to claim 25, further comprising: applying the multilayer stack on at least one component selected from the group consisting of: solar cell, light source, LED display screen and electrolytic cell.

27. The method of claim 25, wherein said fabricating said one or more inorganic barrier layers comprises at least one technique selected from the group consisting of: sputtering, reactive sputtering, evaporation, reactive evaporation, chemical vapor deposition, solution coating processes and plasma enhanced chemical vapor deposition.

28. The method of making a multilayer stack according to claim 25, wherein said forming said reactive layer comprises at least one technique selected from the group consisting of: sputtering, reactive sputtering, evaporation, reactive evaporation, chemical vapor deposition, solution coating processes and plasma enhanced chemical vapor deposition.

29. The method of claim 25, wherein the fabricating the one or more inorganic barrier layers is performed at a temperature ranging from about-20 ℃ to about 200 ℃.

30. The method of claim 25, wherein said forming said reactive layer is performed at a temperature in a range between about-20 ℃ and about 200 ℃.

31. The method of claim 25, wherein the fabricating the one or more barrier layers or the forming the reactive layer are performed roll-to-roll.

32. The method of making a multilayer stack of claim 25, wherein said loading comprises:

positioning the flexible substrate on the coating machine such that the flexible substrate is wound on a reel;

extending and fixing the flexible substrate along the reel to ensure that at least one part of the flexible substrate is exposed, and facilitating the manufacturing.

33. The method of claim 25, wherein said flexible substrate is contacted with a roller having a temperature in the range of about-20 ℃ to about 200 ℃ during said forming of said one or more inorganic barrier layers and said forming of said reactive layer.

34. A composition of a multilayer stack comprising:

an inorganic barrier layer for reducing the passage of gas or vapor molecules, the inorganic barrier layer comprising at least one component of a metal, a metal oxide, a metal nitride, a metal oxynitride, a metal carbonitride, and a metal oxycarbonitride; and

an inorganic reactive layer comprising an amount of reactive material capable of reacting with gas or vapor molecules permeating through said inorganic barrier layer, the reactive material comprising at least one material selected from the group consisting of alkali metal oxides, zinc oxide, titanium dioxide, metal-doped zinc oxide, and silicon oxide.

35. The composition of the multilayer stack of claim 34, wherein: the inorganic barrier layer comprises at least one material with a weight percentage of between about 1% and 100%.

36. The composition of the multilayer stack of claim 34, wherein: the at least one reactive material is present in an amount of about 1 to 100% by weight.