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    • 专利摘要:
    electrochromic devices, assemblies that incorporate electrochromic devices, and / or methods of manufacturing them. the present invention relates to electrochromic devices (ec), assemblies that incorporate electrochromic devices, and / or methods of manufacturing them. more particularly, certain exemplary embodiments of this invention refer to improved ec materials, ec device batteries, process integration schemes compatible with high volume manufacturing (hvm), and / or factories, equipment, and deposition sources. low cost and high productivity.
    公开号:BR112012008048B1
    申请号:R112012008048-2
    申请日:2010-08-24
    公开日:2020-12-15
    发明作者:Vijayen S. Veerasamy
    申请人:Guardian Glass, LLC；
    IPC主号:
    专利说明:

    CROSS REFERENCE TO RELATED ORDER
    [0001] This application claims the benefit of North American Series Order No. 61 / 237,580, deposited on August 27, 2009, the full contents of which are hereby incorporated by reference. FIELD OF THE INVENTION
    [0002] Certain exemplary embodiments of this invention refer to electrochromic devices (EC), assemblies that incorporate electrochromic devices, and / or methods of manufacturing them. More particularly, certain exemplary embodiments of this invention relate to improved EC materials, to EC device batteries, to process integration schemes compatible with high-volume manufacturing (HVM), and / or to factories, equipment, and deposition sources. low cost and high productivity. BACKGROUND AND SUMMARY OF EXEMPLIFICATIVE EMBODIMENTS OF THE INVENTION
    [0003] Windows provide natural light, fresh air, access, and connection with the outside world. However, they also represent a significant source of lost energy. With the growing tendency to increase the use of architectural windows, the balance of conflicting interests in energy efficiency and human comfort is becoming increasingly important. In addition, concerns about global warming and carbon coverage areas are added to the impetus for new energy-efficient glazing systems.
    [0004] In this regard, windows are unique elements in most buildings where they have the ability to "supply" energy to the building in the form of solar gain and natural light in the winter all year round. In common applications, they account for about 5% of all energy consumption in the United States, or about 12% of all energy used in buildings. Common window technology often results in excessive heating costs in winter, excessive cooling in summer, and often fails to capture the benefits of natural light, which would allow the lights to dim or be turned off for much of the day. commercial stock in the country. These factors result in an energy "cost" of more than 5 Quads: 2.7 Quads of energy use annually in homes, about 1.5 Quads in the commercial sector, and another 1 Quad of potential lighting energy savings with natural light strategies. In the past two decades, advances have been made mainly in reducing the U-value of windows through the use of low-emissivity static coatings, and in reducing the solar heat gain coefficient (SHGC) through the use of spectrally selective low-emissivity coatings . However, further improvements are still possible.
    [0005] With the ability to dynamically control solar heat gain, loss, and brightness without blocking the view, electrochromic windows (ECWs) can provide a significant reduction in energy use. Certainly, ECWs have the potential to impact all end uses of window energy, for example, by reducing cooling loads in climates where windows contribute substantially to substantial cooling loads while allowing the same window to admit solar gain in the winter to reduce heating, and by modulating natural light to allow electric lighting to be reduced in commercial buildings while also controlling brightness. For example, as the exterior light and heat levels change, the window's performance can be automatically adjusted to suit the conditions through an automated feedback control.
    [0006] Electrochromic windows (EC) are known. See, for example, US Patent Nos. 7,547,658, 7,545,551, 7,525,714, 7,511,872, 7,450,294, 7,411,716, 7,375,871 and 7,190,506, the description of each of which is incorporated herein for reference.
    [0007] Some common EC dynamic windows provide transmissions ranging from about 3% in the colored state to about 70% in the translucent state. As indicated above, the solar heat gain control (SHGC) range is somewhat large. Certainly, some common EC dynamic windows provide a SHGC range from about 0.09 in the colored state to about 0.48 in the translucent state. Inorganic lithium-based EC technology also offers the advantages of durability, low voltage operation (less than about 5V), clarity (70%), transparency when the power is off, and low power consumption. energy. Despite these wide ranges, common inorganic lithium-based ECWs unfortunately offer limited color variation, and maximum opacity could be improved (for example, with respect to other types of switchable glazing). Another disadvantage with common lithium-based inorganic ECWs is their slow switching times. Undoubtedly, common switching times for inorganic lithium-based ECWs typically range from about 5-10 minutes. Proton-based organic and inorganic polymer device mechanisms have somewhat faster switching (for example, 15 seconds to 5 minutes), but unfortunately suffer from degradation of the ionic conductor in the former case and polymer degradation in the latter case. The operating voltage for EC devices like organic and inorganic proton-based as well as inorganic lithium-based polymer typically operates with a 1-5 V direct current and typically consumes 2-3 W / m2 when switching and 0.5 -1 w / m2 while maintaining the colored state.
    [0008] Figure 1 (a) is a schematic diagram of a typical electrochromic window, and figure 1 (b) is a schematic diagram of a typical electrochromic window in a colored or colored state. The active cell 100 shown in figure 1 (a) includes four components, that is, a first and a second transparent current collector 102 and 104, a cathode 106 (and often the coloring layer), an electrolyte 108 (which it is ionically conductive, although electrically insulating), and an anode 110, which is the source of active ions (for example, Li, Na, H, etc.) that switches the glazing properties with transfer to and from the cathode. Anode 110 can be a staining layer, if staining occurs anodically, for example, as the ions leave the layer. These components are sandwiched between a first and a second glass substrate 112 and 113. Fundamentally, the electrochromic device dynamically changes the optical absorptivity, with the movement (interleaving and deinterleaving) of Li to and from cathode 106. This, in turn, , modulates the interaction with solar radiation, thus modulating the SHGC for energy control, as well as visibility and brightness (important for human comfort). Due to the fact that Li is at cathode 106, the electrochromic window in a colored state and only a portion of the incident light and heat are transmitted through the ECW.
    [0009] Unfortunately, ordinary ECW films do not meet the required performance in appearance (including color), switching speed, consistency of quality, and long-term reliability. Adequate supply and useful window sizes are additional issues.
    [0010] One reason why the common high-cost ECW structure is above the market limit is that the manufacture of EC devices is incompatible with the manufacturing flow of the glazing industry. A critical safety requirement in the building code is that the outermost glass in an insulating glass (IG) unit is tempered. Also, according to practice in the coated glass industry, large sheets of glass (typically up to 3.2 m wide) are first coated, then sized, and finally tempered. Ideally, finished EC glass could be tempered and cut to size. However, tempered glass cannot be cut. Consequently, the practice in the coated glass industry is that large sheets of glass (typically up to 3.2 m wide) are first coated and then sold to window manufacturing locations where they are sized and tempered. Unfortunately, tempered glass cannot be cut after that, and EC glass cannot be tempered after making EC because tempering temperatures would destroy the EC device. Consequently, common ECW manufacturing techniques rely on already cut and tempered glass for EC manufacturing. This is problematic for several reasons. For example, tempered entry glass has a wide variation in thickness leading to a substantial variation in coating properties. In addition, the presence of multiple substrate sizes and types leads to challenges in control, production and process yield, which makes reproducible high-volume, high-yield manufacturing difficult.
    [0011] Figure 2 is a block diagram that illustrates a common ECW manufacturing process. The outermost glass is cut to size and tempered at 202, which corresponds to an EC glass manufacturing process. The EC device is manufactured, for example, so that it has the layer structure shown in figure 1 (a), at 204. After the EC layers have been deposited, the EC device is standardized at 206, for example, to reduce defects and improve performance and appearance. Collector bars are added in a spaced relation to the EC device, for example, as shown in figures 1 (a) and 1 (b). Together, 202, 204, 206 and 208 represent a manufacturing process for an insulating glass (IG) unit. This IG unit can finally be incorporated into an ECW, for example, as shown on the left side of figure 1 (b).
    [0012] Another impediment to progress has been the limited capabilities and resources of manufacturers to develop deposition sources, platforms, and automation that are compatible with large-scale, high-productivity manufacturing techniques.
    [0013] The most practical place to have the EC coating is on the inner surface of the outermost light. Placing the collector bars on this surface for electrification (for example, electrical installation) presents challenges not only for ordinary IG manufacturers, but also for glazing companies. Architects, commercial building owners, and end users demand information about the durability of the EC window over long durations. The reliability of the IG unit seal is therefore a concern. The EC IG unit differs from conventional windows in that the interconnections to power the device have to pass through the moisture barrier seal. There is no standard for interconnections and passageways that preserve the integrity of the seal. What is on the market is patented. There are also concerns about the durability of the EC film stack when exposed to the range of solar and environmental stresses that a window experiences throughout its existence.
    [0014] Finally, the performance of the device in terms of appearance, color, switching speed, consistency, SHGC range, and existence needs to be taken into account. For example, architects have a strong preference for a neutral colored window that ranges from dark gray to perfectly translucent. Most EC windows on the market today exhibit a dark blue hue when colored, and a yellowish hue in the translucent state. A more neutral color and improved transmission in the translucent state would expand the accessible architectural market.
    [0015] Therefore, it will be appreciated that there is a need in the technique of improved electrochromic dynamic windows, and / or methods of manufacturing them. For example, it will be appreciated that there is a need in the technique for (1) high-productivity, large-scale, low-cost coating techniques that are compatible with high-volume manufacturing (HVM), (2) a better performing EC formulation, (3) a low defect, high productivity and robust EC formation for large light sources, and / or (4) the connection of such new manufacturing techniques with existing post-glass manufacturing and auxiliary technologies to produce complete windows. These and / or other techniques can help to solve some of the above problems and / or other problems, while also providing a more complete construction control integration.
    [0016] Certain exemplary embodiments refer to top-to-bottom and / or bottom-to-top changes in (a) materials, (b) electrochromic device stack, (c) high volume compatible process integration schemes, and (d) low-cost, high-productivity deposition equipment and techniques. In doing so, certain exemplary embodiments can be used to provide low cost EC assemblies for "Buildings with Zero Net Energy Consumption".
    [0017] One aspect of certain exemplary embodiments involves the incorporation of new electrochromic materials. For example, certain exemplary embodiments involve an optically doped cathode and / or anode for greater visible transmission in the translucent state, a greater solar heat gain control (SHGC) delta between these states, an improved appearance, and better reliability. The control of WOx stoichiometry (for example, so that it is sub-stoichiometric) can advantageously result in improvements with respect to the SHGC delta and in a better appearance (for example, in terms of coloring). Anode staining of the counter electrode can also increase the SHGC delta.
    [0018] Another aspect of certain exemplary embodiments involves the incorporation of a new electrochromic device battery. For example, the inclusion of a low-iron, low-cost half-light substrate can help reduce the need for substrate device barrier layers. An optimized transparent common collector (TCC) with a much higher conductivity and transmittance than ITO can be provided for higher switching speed and reduced cost. The inclusion of a lithium phosphorus oxynitride (LiPON) electrolyte material can be selected for reliability purposes in certain exemplary embodiments. In addition, the use of transparent conductive / dielectric layers can occur to change the color based on selective interference in certain exemplary embodiments.
    [0019] In addition, another aspect of certain exemplary embodiments involves new techniques for integrating an electrochromic device. For example, certain exemplary embodiments may involve the use of laminated / glued glass for the external light of the EC IG unit. This can advantageously result in the complete elimination of the use of tempered glass in the EC manufacturing step, reducing the need for sizing and tempering the glass prior to EC processing, allowing the use of a single sized and standard glass in EC manufacturing for better reproducibility and economies of scale of the process, and / or allow the sizing of post-EC glass manufacturing. It can also advantageously allow standardization after all EC layers have been deposited, thereby reducing the likelihood of defects and improving performance and appearance.
    [0020] Yet another aspect of certain exemplary embodiments concerns the development of a deposition source compatible with HVM. For example, a new LiPON deposition source capable of achieving high deposition rates and modular growth kinetics can, in turn, allow for high productivity and better film characteristics in certain exemplary embodiments. Certain exemplary embodiments may also use a new Li evaporator based on a linear sprinkler with normal and remote environmentally compatible Li sources.
    [0021] In certain exemplary embodiments, a method of forming electrochromic windows is provided. A first glass substrate is provided. The electrochromic device layers are arranged on the first substrate, with such layers comprising at least one counter electrode (CE), an ion conductor (IC), and electrochromic layers (EC). The electrochromic device layers are standardized, and the first glass substrate with the electrochromic device layers disposed thereon is cut to form a plurality of EC device substrates. A plurality of second glass substrates is provided. The plurality of EC device substrates are glued or laminated to the plurality of second glass substrates, respectively. A plurality of third glass substrates is provided. A plurality of insulating glass (IG) units are formed, comprising first and second substrates respectively in substantially parallel relation and spaced apart from the third glass substrates.
    [0022] In certain exemplary embodiments, a method of forming an electrochromic assembly (EC) is provided. A first, a second and a third glass substrate are provided, where the second substrate is thermally tempered and the first substrate is not thermally tempered. A plurality of layers of EC device is deposited by sputtering, directly or indirectly, on the first substrate, with the plurality of layers of EC device comprising a first conductive transparent coating (TCC), a counter electrode layer (CE), a layer of ion conductor (IC), an EC layer, and a second CBT. The first and second substrates are laminated or glued together. The second and third substrates are provided in substantially parallel relation and are spaced apart. The CE and EC layers are both color changeable when the EC assembly is in operation.
    [0023] In certain exemplary embodiments, a method of forming an electrochromic assembly (EC) is provided. A plurality of EC device layers are deposited by sputtering, directly or indirectly, onto a first glass substrate, with the plurality of device layers comprising, in order to move away from the first substrate, a first transparent conductive coating (TCC) , a cathode layer, an electrolyte layer, an anodically colored anode layer, and a second TCC. The first substrate with the plurality of device layers deposited by sputtering on it is connected to a second substrate in such a way that the first and second glass substrates are in substantially parallel relationship and are spaced apart.
    [0024] In certain exemplary embodiments, an electrochromic assembly (EC) is provided. A first, a second and a third glass substrates are provided, with the second and third substrates being substantially parallel and spaced apart. A plurality of layers of EC device deposited by sputtering is supported by the first substrate, with the plurality of layers of EC device comprising a first transparent conductive coating (TCC), a counter electrode layer (CE), an ion conductor layer ( IC), an EC layer, and a second TCC. The first and second substrates are laminated or glued together. The second substrate is thermally tempered and the first substrate is not thermally tempered.
    [0025] In certain exemplary embodiments, an electrochromic assembly (EC) is provided. At least one first and a second glass substrate are provided, with the first and second substrates being substantially parallel and spaced apart. A plurality of device layers deposited by sputtering is supported by the first substrate, with the plurality of layers of EC device comprising a first transparent conductive coating (TCC), a doped and anodically colored counter electrode layer (CE), a conductor layer of ions (IC), a doped EC layer comprising WOx, and a second TCC.
    [0026] In certain exemplary embodiments, an electrochromic device is provided including a plurality of thin film layers supported by a first substrate. The plurality of layers comprises an anodically colored doped anode layer, an electrolyte layer comprising Li, and a doped cathode layer comprising WOx.
    [0027] The characteristics, aspects, advantages and exemplary embodiments described here can be combined to carry out additional embodiments. BRIEF DESCRIPTION OF THE DRAWINGS
    [0028] These and other characteristics and advantages can be better and more fully understood with reference to the following detailed description of the exemplary illustrative embodiments in conjunction with the drawings, of which: figure 1 (a) is a schematic diagram of a typical electrochromic window ; figure 1 (b) is a schematic diagram of a typical electrochromic window in a colored state; figure 2 is a block diagram illustrating a common ECW manufacturing process; figure 3 is a block diagram illustrating an ECW manufacturing process according to an exemplary embodiment; figure 4 is an illustrative electrochromic substrate and battery according to an exemplary embodiment; figure 5 is an illustrative conductive transparent coating (TCC) usable in connection with certain exemplary embodiments; figure 6 (a) is a first illustrative electrochromic insulating glass (IG) unit according to an exemplary embodiment; figure 6 (b) is a second illustrative electrochromic insulating glass (IG) unit according to an exemplary embodiment; figure 7 is a third illustrative electrochromic insulating glass (IG) unit according to an illustrative embodiment; figure 8 (a) is an SEM image of a 600nm Al layer deposited by conventional evaporation; and figure 8 (b) is an SEM image of a 600 nm Al layer deposited using a plasma activated evaporation according to certain exemplary embodiments. DETAILED DESCRIPTION OF EXEMPLIFICATIVE EMBODIMENTS OF THE INVENTION
    [0029] One aspect of certain exemplary embodiments involves the incorporation of new electrochromic materials. For example, certain exemplary embodiments involve an optically doped cathode and / or anode for greater visible transmission in the translucent state, a greater solar heat gain control (SHGC) delta between these states, an improved appearance, and better reliability. The control of WOx stoichiometry (for example, so that it is sub-stoichiometric) can advantageously result in improvements with respect to the SHGC delta and in a better appearance (for example, in terms of coloring). The anodically colored counter electrode can also increase the SHGC delta.
    [0030] Another aspect of certain exemplary embodiments involves the incorporation of a new electrochromic device battery. For example, the inclusion of a low-iron, low-cost half-light substrate can help reduce the need for substrate-device barrier layers. An optimized transparent common collector (TCC) with a much higher conductivity and transmittance than ITO can be provided for higher switching speed and reduced cost. The inclusion of an electrochromic assembly of lithium phosphorus oxynitride (LiPON) can be selected for reliability purposes in certain exemplary embodiments. In addition, the use of transparent conductive / dielectric layers can occur to change the color based on selective interference in certain exemplary embodiments.
    [0031] Yet another aspect of certain exemplary embodiments involves new techniques for integrating an electrochromic device. For example, certain exemplary embodiments may involve the use of laminated / glued glass for the external light of the EC IG unit. This can advantageously result in the complete elimination of the use of tempered glass in the EC manufacturing step, reducing the need for sizing and tempering the glass before EC processing, allowing the use of a single standard sized glass in EC manufacturing for better reproducibility process and economies of scale, and / or allow the sizing of post-EC glass. It can also advantageously allow the device to be standardized after all layers have been deposited, thereby reducing the likelihood of defects and improving performance and appearance.
    [0032] Yet another aspect of certain exemplary embodiments concerns the development of a deposition source compatible with HVM. For example, a new LiPON deposition source capable of achieving high deposition rates and modular growth kinetics can, in turn, allow for high productivity and better film characteristics in certain exemplary embodiments. Certain exemplary embodiments may also use a Li-evaporator based on a sprinkler with normal and remote environmentally compatible Li sources.
    [0033] Certain exemplary embodiments involve changes in EC materials, in the EC device stack, in HVM-compatible process integration schemes, and / or in factories, equipment, and low-cost, high-productivity deposition sources. These aspects of certain exemplary embodiments are discussed, in turn, below.
    [0034] Certain exemplary embodiments refer to advantages in terms of one or more of these: cost, device performance, durability, aesthetics and / or scalability. For example, certain electrochromic products cost more than $ 50 / square foot, while the techniques of certain exemplary embodiments can provide electrochromic products at a cost that is preferably less than $ 25 / square foot, more preferably less than $ 20 / square foot. square foot, and even more preferably less than $ 15 / square foot. Although it is difficult to implement the control and electrical installation infrastructure for common products, certain exemplary embodiments can provide relatively simple modular products, with wireless control and / or power options. While many common products can achieve a switching speed of 3-5 minutes maximum, certain exemplary embodiments can provide a switching speed of less than 3 minutes, more preferably less than 2 minutes, and sometimes less than 1 minute, although the total size of the product can be increased. Advantageously, delta E can be less than about 1.5, more preferably less than about 1.25, and even more preferably less than about 1. In terms of color / hue, certain exemplary embodiments can reduce the yellowish tint in the translucent state and in the multiple colors that are sometimes present in the colored state, instead of providing a more neutral color in the translucent state with a choice of one of multiple colors in the colored state. In addition, certain exemplary embodiments can reduce switching uniformity problems, for example, by making at least latitude appear to change "all at once" (at least, as compared to variability in shadow lines and individual controls in systems common). Finally, although common EC devices are generally limited to 1m wide designs, certain exemplary embodiments can be extended to 3.2m wide (or even wider) designs to be in line with stock sheets of glass commonly available. Exemplary Manufacturing Processes
    [0035] Figure 3 is a block diagram illustrating an ECW manufacturing process according to an exemplary embodiment. The process of figure 3 differs from the process of figure 2 in several ways, in that the process of figure 3 is designed to provide an EC device on an EC substrate that can be glued, laminated, or otherwise connected to a temperable glass substrate. For example, a material, such as PVB, EVA or similar, can be used, as well as "Optibond technology", which is commercially available from Litemax. The laminate that is used can incorporate a UV blocker (for example, a UVA blocker). Preferably, a UVA blocker can be included, with Tuv <1%, more preferably <75%, and even more preferably <5%. The UV blocker can be a thin film coating comprising one or more of Bi, BiO, Zn, ZnO, TiO, BiSnO, AgO, Ce, CeO, and the like. Alternatively, or in addition, a PET coating can be provided, with a UV blocking material provided on it and / or on it. For example, the ITO-coated PET layer can be provided in certain exemplary embodiments. It will be appreciated that organic and / or inorganic materials can be used in connection with certain exemplary embodiments. In any case, the laminate can be selected so that its refractive index matches the adjacent layers and / or substrates. This will advantageously keep the reflectance low. The reflectance can also be decreased, for example, with the incorporation of one or more anti-reflective (AR) layers. Due to the fact that the EC device is provided on a separate substrate that can later be glued, laminated, or otherwise connected to a temperable substrate, efficiencies can be realized, for example, where larger sheets can be spray-coated cathodic or similar and subsequently cut to size. Exemplary structural details are provided below.
    [0036] In terms of the exemplary process shown in figure 3, large size glass is provided in 302. An EC device is manufactured according to the exemplary techniques described below in 304. The standardization and dimensioning of the device is performed in 306, thus forming a plurality of EC devices on a plurality of corresponding EC glass substrates. As indicated above, this is an advantage over the conventional process shown in figure 2, where individual EC devices are manufactured directly on pre-cut and individually tempered glass substrates. In any case, collection bars can be formed by etching with selective laser etching away from the layers to carefully expose the CBT. For example, to selectively etch and electrically connect the device, both "integral" and "half" cuts can be made, for example, to expose the lower and upper TCCs. The strength of the laser can be controlled to selectively remove part or all of the layers.
    [0037] In 310, the external glass substrate to which the EC device and the glass substrate will be connected is sized and tempered. Then, in 312, the appropriately sized EC devices are laminated, bonded, or otherwise connected to the appropriately sized external substrates. Subassemblies comprising laminated, bonded, or otherwise connected EC devices to other glass substrates are then constructed in corresponding insulating glass (IG) units at 314, for example, as described in greater detail below. Exemplary Electrochromic Battery and Exemplary Materials Used in the Same
    [0038] Figure 4 is an illustrative electrochromic substrate and battery according to an exemplary embodiment. Figure 4 incorporates an electrochromic cell 400 which is somewhat similar to known electrochromic cells which incorporates conductive layers (TCCs), an electrochromic layer (EC), a counter electrode layer (CE), and an ion conductor layer (IC ). However, the electrochromic battery in Figure 4 400 differs from ordinary batteries in terms of materials, the entire design of the battery, and performance characteristics. For example, thermal performance, EC speed, long-term EC reliability, and aesthetics can be improved, for example, to optimize the performance of known materials and to develop new material systems that additionally improve the performance of the entire EC device. Changes to materials and stack designs are described in the following paragraphs.
    [0039] A first area of innovation involves cathode / EC and anode / EC electrode materials. The thermal performance of an ECW refers to the SHGC range between translucent and colored states. To increase the SHGC range, the absorptivity of the layers or cathode or anode, or both cathode and anode, can be reduced in the translucent state, and / or an anodically colored counter electrode can be created to decrease transmission (Tv) in the colorful state. Selecting appropriate material can also increase switching speed and reliability.
    [0040] These and / or other aspects can be achieved with the substitutional doping of active electrode materials in certain exemplary embodiments. A counter electrode typically includes NiO, with either Li + or H + ions. As described above, improving thermal performance, decreasing absorbance, and improving the reliability and stability of CE conductive electrodes are advantageous. With the use of additives, such as Mg, AI, Si, Zr, Nb and Ta, a significant reduction in EC and CE film absorption can be achieved, especially at short wavelengths. On the other hand, films containing V and Ag did not show the same improvements in optical properties compared to those of pure nickel oxide. Thus, the incorporation of Mg and / or another element, in a combinatorial mode, can be used to optimize its beneficial effect on both NiO and LiNiO systems to broaden the prohibited band and substantially improve the transmittance. Alternatively, or in addition, the inclusion of W in LiNiO is also possible in certain exemplary embodiments, and can be used to improve stability as a CE layer to UV radiation and moisture. This and / or other substitutional doping can be used to increase electrical conductivity (in some cases by 3 orders of magnitude, for example, LiCoO2 versus LiCo0.9Mg0.05O2). Surprisingly and unexpectedly, doping CE (and / or IC) with Mg also makes it a "faster" driver.
    [0041] Certain exemplary embodiments may also involve anode staining of the counter electrode, for example, for improved thermal performance. As is known, the CE is used to store the charge, which is, in turn, used to color the electrochromic layer. To do this effectively, the CE layer can allow charges to be easily interleaved, to be stable and durable for repeated cycles, and to be very transparent in the translucent state, and, if possible, to exhibit an electrochromism when fully discharged from interleaved ions (for example, example, anodically). Thus, in certain exemplary embodiments, the EC can become electrochromic. However, in such exemplary embodiments, the CE can be the "reverse" of the EC layer, for example, in such a way that it becomes transparent with ions, and provides a color change in the loss of ions. To realize these and / or other characteristics, certain exemplary embodiments can incorporate a CE based on NiO systems that have been shown to be stable with repeated load insertion / extraction cycles. These systems will sometimes exhibit a small amount of residual absorption when the device is completely interleaved, for example, in the LixNiO state (1 + y) in the reaction shown below. The challenge is to remove this absorption without sacrificing the wide dynamic range and good switching kinetics of the device. Substitutional doping, analogous to the discussion in the previous section using Li can better induce Tv and remedy the small absorbance that is contrary to the increase in the SHGC delta.
    [0042] The tendency for water to deteriorate in hydrated NiO systems (1 + y) has now been confirmed. Consequently, non-aqueous electrolytes and the cubic form of lithium nickel oxide can be a promising electrochromic system in certain exemplary embodiments. For example, LiNi1-xO nanocrystalline can have a wide optical dynamic range and a more neutral color than tungsten oxide, as well as better stability. In addition, LiNi1-xO can be anodically colored, thus providing the advantage of being complementary to cathodic tungsten oxide. A combination of these materials can be favorable with respect to electrochemical potentials, and also obtaining a deeper neutral color in the dark state. The photopic staining efficiency of this anodic staining material is typically high. The switching performance of a device that uses a solid state electrolyte as well as a lithium nickel oxide film as a counter electrode and an electrochromic tungsten oxide film has certain advantages over systems currently available. It is noted that the main reaction underlying this electrochromic activity is

    [0043] In certain exemplary embodiments, the absorbance and / or color modulation of EC tungsten oxide (WOx) can be changed for thermal performance and appearance. WO3 stoichiometric films are transparent to energies below the fundamental prohibited band at <3 eV. The intercalation of Li ions leads to an electrochromism manifested by a wide absorption band centered at ~ 1.2 eV, which produces a distinctly blue color. This phenomenon can be described in terms of interval charge transfer with electrons transferred from a W5 + location to an adjacent W6 + location. Polaron effects can be incorporated into a new model using a tight bond approach. According to this self-consistent model, the value of x in WOx slightly sub-stoichiometric can be optimized in certain exemplary embodiments so that the EC material is even more transparent and, with a greater lithium, increases the absorptivity. The substoichiometric value of x is preferably 2.4 <x <3, more preferably 2.6 <x <3. A value of about 2.88 was considered to be particularly advantageous. Such values help to reduce the "yellowing" and improve the color depth of the EC, which helps to improve the translucent and colored states.
    [0044] The strong coupling of electron-phonons tends to favor the formation of complexes (W-W) 10 + which does not lead to optical absorption. However, uniquely charged oxygen vacancies produce absorption because of the transfer of interval charge. The analogy with the data for the ion interleaved film is expected, since W5 + sites are present in both cases. Thus, it appears that amorphous tungsten oxide films exhibit an electronic defect filter with paired electrons, according to the Anderson mechanism, and singularly charged oxygen vacancies, as the vacancy density is increased.
    [0045] In addition, irreversibility in charge insertion is commonly encountered during the first color / bleach cycles, and the films remain transparent up to an inserted charge limit (called color blind charge) as a result of which the color adjustments and subsequent cycles are reversible, so that electrochromism prevails. Lithium is irreversibly incorporated and is not recovered from the EC film during switching. The blind charge does not seem to interfere with the electrochemical kinetics of the insertion process. However, the variable amount of irreversible Li incorporation makes it difficult to accurately determine the amount of unstable Li needed for an optimal dynamic range of the EC device during switching. In addition, Li loss is not uniform over large areas of deposited film. Therefore, it will be appreciated that the amount of blind charge residing in the EC films as deposited can be controlled. One solution involves reducing (or minimizing) the amount of blind charge present in the film by understanding the root cause of Li "loss". One solution refers to the type of target used in the deposition of EC material, in addition to a ion beam, and in monitoring the process to judiciously control the stoichiometry of the films.
    [0046] This solution reduces the need to heat the substrate. In particular, in certain exemplary embodiments, EC films with acceptable electrochromic properties can be deposited from ceramic targets using ion-assisted twin magnetron configurations.
    [0047] Certainly, exemplary embodiments may employ substitutional doping and grain structure control to modulate the yellowish hue in the translucent state. A concern for ECW is the yellowish baseline color in the translucent state. The main causes are considered to be (1) the structural instability of metal oxide units (WOx) with Li insertion / disinseration cycles, leading to the Jan-Teller distortion and the corresponding displacement in the energy and color structure, (2) the base color of NiOx, the most commonly used base anode material, and (3) interference related to grain boundaries. Doping with appropriate metals (V, Mo, etc., in NiOx) and halides (for example, Cl) can be used in certain exemplary embodiments to address at least the first two root causes to change the prohibited band (and therefore , the interaction of varied light material) and / or intensify the structural stability WOx on the Li cycles. The grain structure can be modulated by optimizing the deposition process in certain exemplary embodiments, either with in situ treatments or with ex situ treatments post-deposition (for example, applying glass substrate polarizations and microwave or annealing enhancements). This can also be used to enhance the structural stability of WOx over Li cycles.
    [0048] The IC helps to maintain the internal electrical insulation between the EC and CE electrodes while providing ionic conductance for electrochromic behavior. The stability and reliability of electrochromism depends on the properties of the electrolyte. Lithium phosphorus oxynitride (LiPON) can be used as the electrolyte layer material in a certain example. The choice is based on its superior reliability and stability, as demonstrated in thin film battery applications. LiPON is an electrically insulating material (> 1E14Q-cm), so that RF sputtering is traditionally used and exhibits a low deposition rate (<1 μm / hr). This low deposition rate can be improved, as discussed below, and / or other materials and methods that are more sensitive to high productivity production can be used in connection with certain exemplary embodiments.
    [0049] It will be appreciated that it would be advantageous to reduce the electronic leakage current that happens through the IC. The leakage current can be divided into contributions that are associated with the thin film stack itself (limited diffusion), and that are associated with localized point defects, (both in mass and interfacial). You can model the EC / IC / sCE interfaces as heterojunctions. The front and reserve boom heights for the EC / CE junction can be optimized by changing the composition, structure, and interface chemistry of the IC. The evidence suggests that the leakage current can be reduced to negligible levels by selecting appropriate process and materials for the IC layer. Consequently, certain exemplary embodiments provide an IC layer where the integrity of the electron barrier structure is maintained with adequate ionic conductivity. In practice, greater ionic conductivity typically requires a more porous amorphous structure, and the possible incorporation of lithium, both of which can degrade the functionality of the electron barrier. The pile of materials described here, and the respective deposition processes described below, help to alleviate these issues. In addition, in certain exemplary embodiments, the optical indices of the materials can be matched to the surrounding layers.
    [0050] As shown in figure 4, the EC 400 device stack may include a first transparent conductive coating (TCC) 404, a counter electrode layer 406, an ion conductor layer 408, an electrochromic layer 410, and a second TCC 412. Each of the first and second TCCs 404 and 412 can be about 200 nm thick in certain exemplary embodiments. An exemplary layer system for one or both TCCs is provided below, for example, in connection with figure 5. The anodic CE layer 406 can be about 100-400 nm thick, and can include NiO and contain Li + and ions H +. An electrochromic / IC layer based on LiPON 408 can be about 1-3 microns. Similar to the CE 406 layer, the EC 410 layer can be 100-400 nm thick. Each or both the CE 406 layer and the EC 410 layer can be doped, for example, to provide a better and / or deeper color. Optionally, a barrier layer (not shown in the example in figure 4) can be provided over the outermost TCC 412, and such a barrier layer can allow for color change. In certain exemplary embodiments, the outermost TCC 412 itself may allow color change. The EC 400 device stack is provided on an EC 402 substrate which can, in certain exemplary embodiments, be provided as a large glass substrate of standard size / thickness. Certainly, in certain exemplary embodiments, the substrate EC 402 can be a low-iron, non-tempered substrate that is cut after the EC device is manufactured therein. Exemplary low-iron glass substrates are described, for example, in North American Serial Order No. 12 / 385,318, as well as in North American Publication No. 2006/0169316, 2006/0249199, 2007/0215205, 2009/0223252, 2010/0122728 and 2009/0217978, all the contents of each of which are incorporated herein for reference.
    [0051] The design of the EC device stack shown in figure 4 and described here differs from common designs in numerous aspects including, for example, the use of a new transparent conductor described below, of multiple dielectric layers for low cost substrates, of low iron content and interferometric color change in which EC layers are formed, LiPON as the electrolyte, and the optimization of pile thickness. These factors affect transmittance, color, transition speed and cost, as described elsewhere.
    [0052] The switching speed of an EC device is limited by the leaf resistance of the TCO layers, although the voltage drop in the EC layer also contributes to delays. This is due to the fact that the voltage that can be applied to the device is fixed, and the amount of charge that has to be transferred in order to completely color the device increases with the area. Given a series of fixed length devices, but with progressively wider widths, as the separation between the collecting bars becomes greater, the impedance of the EC cell itself (the part of the device where the current runs perpendicular to the glass surface) becomes smaller. In contrast, the impedance of the TCO layers where current is flowing parallel to the glass surface becomes greater. In addition, this change in the area leads to a greater potential drop in the TCO layers.
    [0053] This results in a lower potential applied directly to the battery, leading to slower switching. In this way, it will be appreciated that, to increase the switching speed of reasonably sized devices, for example, suitable for architectural applications, the conductivity of the TCO layers can be increased.
    [0054] It is possible to increase the conductivity of the upper TCO by simply making it thicker. However, this approach has certain disadvantages. For example, this approach introduces additional absorption and reflection, thereby reducing the targeted state transmission and decreasing the dynamic range. It will also cause the device to change the color asymmetrically, where the color will emerge from one of the collecting bars and cross to the other side of the device, resulting in a "curtain" or concertina effect. In addition, this approach adds materials and processing costs, since ITO (which is expensive) is typically used for TCO.
    [0055] To overcome these challenges, certain exemplary embodiments use battery cells including silver. Such stacks can have sheet resistances at least an order of magnitude less than those of commonly available TCOs. Additional advantages of this coating include its "low emissivity" functionality, which helps to improve SHGC and UV protection of active layers.
    [0056] Figure 5 is an illustrative transparent conductive coating (TCC) usable in connection with certain exemplary embodiments. The exemplary TCC in figure 5 includes a silver-based layer 506, sandwiched by a first and a second layer ITO 502 and 510. The first and second interlayer 504 and 508 can be provided between the silver-based layer 506 and the first and second layers ITO 502 and 510. Such interlayers may comprise NiCr (e.g. NiCrOx) and / or Cu. The silver-based layer 506 is preferably 100-200 angstroms thick, more preferably 120-180 angstroms thick, and sometimes 140 angstroms thick. Each ITO layer is preferably 1000-2000 angstroms thick, more preferably 1200-1600 angstroms thick, and sometimes about 1400 angstroms thick. The interlayers are preferably 1-20 angstroms thick, more preferably 5-15 angstroms thick, and sometimes 10 angstroms thick. When so designed, it is possible to provide a TCC that has a foil resistance preferably less than 20 ohms / square, more preferably less than 10 ohms / square, and sometimes as low as 5 ohms / square or even lower . The visible transmission of such layers can be optimized to provide visible transmission of preferably 65%, more preferably 75%, even more preferably 80%, and sometimes as high as 85% or greater. Optionally, low-emissivity coatings can be provided between a glass substrate and the lowest ITO layer in certain exemplary embodiments. Such low-emissivity coatings may include layers with alternating high and low refractive indices, for example, in a high-low-high-low-high arrangement. Although figure 5 shows a single TCC layer cell, other layer cells are also possible. In certain exemplary embodiments, a suitable TCC layer stack may include 2, 3, 4 or more of the layer stack shown in figure 5.
    [0057] In certain exemplary embodiments, TCCs can be based on graphene and / or CNT. See, for example, North American Serial Orders No. 12 / 461,349 and 12 / 659,352, the full contents of which are incorporated herein.
    [0058] As indicated above, an issue with common electrochromic devices is the yellowish tint in the translucent state and the desired neutral tint in the colored state. To overcome the challenges, certain exemplary embodiments use multiple layers of "color enhancement", which induce color change through Fabry-Perot interference. In certain exemplary embodiments, a color changing layer stack can be deposited adjacent to the EC coating stack, and can comprise sputter-sprayed metal and insulating layers. The optical properties as well as the thickness of the individual layers can be designed to provide functionality including, for example, increased solar performance, visible color coordinate changes in a more desirable neutral tone in both the non-colored and the colored state, and UV protection to the underlying EC battery, thus extending its life. In addition, these layers may increase the reliability of the EC window, for example, by acting as a barrier to oxidizing environments, when and if the seal on the IG unit breaks. It is also likely to use the TCC, discussed above to achieve this functionality.
    [0059] To reduce the likelihood of iron diffusion from the glass substrate to the EC device stack and therefore reduce the likelihood of degradation, it is possible, in certain exemplary embodiments, to use a thin barrier layer, such as a layer including silicon nitride (eg Si3N4 or other suitable stoichiometry). However, certain exemplary embodiments may alternatively use a glass product with a low iron content and a lower cost. The use of a glass substrate with low iron content and lower cost can reduce and sometimes even eliminate the need for a barrier layer, thus leading to a reduction in the complexity of the process, in the improvement of transparency , and lower EC manufacturing costs.
    [0060] The use of LiPON as the IC layer advantageously increases the reliability of the device. For example, reliability is increased at least in terms of the life cycle with the use of a more robust and electrochemically stable electrolyte (LiPON), which is stable up to 5.5V and against Li metal and whose life cycle in battery application thin film has been shown to be above 100,000 cycles with minimal losses in capacity. The loss of minimum capacity for the battery can translate to a reduced change in optical properties in electrochromics.
    [0061] The stack thickness can be optimized in certain exemplary embodiments to improve the switching speed of the EC device. For example, one way to improve the speed of the EC device is to reduce the thickness of the CE and IC layers. The switching rate was considered to increase with increases in lithium levels. However, it has also been found that, if the lithium level is further increased, the devices become electronically "broken", thus no longer being fully colored and also failing to reduce the switching rate. The stack materials and thickness ranges specified above were considered to be advantageous in terms of improving the switching speed, although it is also possible to adjust thicknesses and materials in other ways in different embodiments. Exemplary Process Integration Techniques
    [0062] A disadvantage associated with traditional EC process flows is the need for dimensioning and tempering the substrate before forming an EC device, which is related to the fact that post-manufacture tempering will damage the EC device and the dimensioning cannot be performed after hardening. This conventional process flow was illustrated in figure 2. In this process, any variation in the finished product requirement, such as, for example, the size of the substrate, thickness or type, etc., tends to lead to a manufacturing environment layer / complete device. For example, the EC coating process will be precisely tuned to each product separately for optimal results depending, for example, on the size and thickness of the substrate. For applications, such as ECW, with distinct contrast, especially in the colored state, such non-uniformity would be detrimental to the product.
    [0063] However, as indicated above (for example, in connection with figure 3), certain exemplary embodiments alternatively involve lamination, a single non-tempered type of glass for EC manufacture, sizing of glass for post-EC manufacture, and device standardization after deposition of EC layer cover. From the diagram and description of figure 3 provided above, it will be appreciated that there is an absence of tempering, together with the inclusion of lamination steps.
    [0064] In this laminated / glued EC glass concept, the external window glass (external light) includes a two-pane glass unit. A first sheet is provided for use as the EC sheet, and the other sheet is provided to meet tempering / safety and other product requirements. This arrangement is shown in figures 6 (a) and 6 (b), which show cross-sectional views for IG units according to certain exemplary embodiments. It will be appreciated from figures 6 (a) and 6 (b) that there are at least two options for bonding the EC glass. In the exemplary embodiment of figure 6 (a), the EC cell faces the open internal space, while the EC cell is directly glued to the external light in the exemplary embodiment of figure 6 (b). The exemplary embodiment of figure 6 (b) is particularly advantageous in that it is perhaps better protected from the IG unit sealing blast. An advantageous consequence of this bonded / lamination concept is that the quenching requirement for the glass used to manufacture the EC device can sometimes be completely eliminated. This, in turn, allows the use of single-type glass substrates and sizing of post-manufacture glass with non-tempered glass, consistent and compatible with the common manufacturing flows of coated glass and windows. Consequently, this helps to lead to a robust and stable production environment for optimal process control, productivity and yield, at a lower cost.
    [0065] As indicated above, the IG units 600a and 600b shown in figures 6 (a) and 6 (b) are similar to each other. Both include external glass substrates 602 that can be tempered, together with internal glass substrates 604. These substrates 602 and 604 are substantially parallel to each other and spaced apart, for example, using spacers 606, thus forming a gap insulation layer 608. A laminate 610 (for example, a PVB laminate sheet, an EVA laminate, an Optibond laminate, etc.) helps to connect the outer glass substrate 602 to EC 402 glass. In figure 6 (a), the laminate 610 connects the outer glass substrate 602 to the EC 402 glass substrate so that the stack of EC 400 layer faces the insulation gap 608. In contrast, in figure 6 (b), laminate 610 connects the substrate of external glass 602 to the EC 402 glass substrate so that the EC 400 layer stack is provided between these two glass substrates 602 and 402. Some or all of the glass substrates may be UltraWhite glass substrates, which are commercially available from the transferee. of the present invention.
    [0066] The integration modification to standardize the device after all EC layers are deposited is another advantage of certain exemplary embodiments, for example, as compared to the conventional process shown in figure 2, where multiple device patterns were needed, for example , as indicated by the bidirectional arrow. With standardization after all layers are complete, however, the probability of defects is reduced, leading to better performance and better ECW quality. This is related, in part, to the simplified process and the reduced likelihood of cross-contamination issues from both the standardization process and additional exposure to ambient (potentially impure) air.
    [0067] The EC integration flow that includes lamination, gluing or another connection of two sheets of glass to form a single external light from an IG unit, as illustrated in figures 6 (a) and 6 (b), for example, can lead to additional benefits. For example, such designs have the potential to expand product applications, for example, with the flexible combination of standard EC glass with any other glass product whose properties can be selected to meet the desired window requirements, including safety, color, sound barrier, and others. This process flow is consistent with the common value chain of the glass industry and would help to expand the applicable application areas to further amortize development and cost.
    [0068] The lamination, gluing and / or other connection of glass units in certain exemplary embodiments may be similar to these techniques used in both thin-film and glass solar photovoltaic industries (security products, etc.). Challenges related to thermal cycles and the effective temperature to which the "absorptive" EC device can be subjected can be mitigated, for example, with the selection of materials so that they match each other (for example, in terms of expansion coefficient thermal, etc.) to help ensure compatibility in a potentially dissonant environment.
    [0069] Figure 7 is a third illustrative electrochromic insulating glass (IG) unit according to an exemplary embodiment. The exemplary embodiment of figure 7 is similar to that of figure 6 (b) in that the EC layers deposited by sputtering 400 are disposed between the outer glass substrate 602 and the half-light 402. However, the exemplary embodiment of figure 7 differs from the exemplary embodiment of figure 6 (b) in that it includes numerous optional low-emissivity coatings. In particular, the exemplary embodiment of figure 7 includes a first low-emissivity coating 702 located on the inner surface of the outer glass substrate 602, a second and a third low-emissivity coatings 704 and 706 located on opposite surfaces of the half-light 402, and a fourth low-emissivity coating 708 on the surface of the inner substrate 604 facing the insulation gap 608. One or more of the optional low-emissivity coatings may be the SunGuard SuperNeutral 70 (SN70) low-emissivity coating commercially available from the assignee, although other low-emissivity coatings can also be used. For example, see U.S. Patent Nos. 7,537,677, 7,455,910, 7,419,725, 7,344,782, 7,314,668, 7,311,975, 7,300,701, 7,229,533, 7,217,461, 7,217. 460 and 7,198,851, the descriptions of which are hereby incorporated by reference. Exemplary High Productivity Equipment and Supplies
    [0070] Certain exemplary embodiments make EC technology more cost effective in providing high deposition rate deposition sources to allow for low capital and high productivity intensive EC plants. With regard to font development options, the table below identifies possible deposition methods for the usable EC layers in connection with certain exemplary embodiments. There are two basic approaches to lithium-provided layers, that is, a single-layer deposition from a sequential or target deposition composed of oxide and lithium. The use of highly reactive Li in a manufacturing environment can be problematic. However, the use of a target provided with lithium can lead to inconsistency in the stoichiometry on the target existence, when using a sputtering method. In any case, for sputtering techniques, certain exemplary embodiments can implement a two-step method. E-beam evaporation methods for metal oxides provided with lithium can also be used to address potential limitations involved in the use of sputtering techniques.

    [0071] As indicated above, the LiPON electrolyte can be used in certain exemplary embodiments because of its reliability and superior stability, as demonstrated in thin film battery applications. LiPON is an electrically insulating material (greater than 1E14 Q-cm), so conventional RF sputtering typically exhibits a low deposition rate (less than 1 μm / hr). The conventional deposition of Li by evaporation is also low. Consequently, certain exemplary embodiments can be accelerated to be compatible with a large, high-yield coating system.
    [0072] To overcome at least some of these conventional problems, certain exemplary embodiments can implement a source of plasma deposition based on multiple frequencies, in which the higher frequency plasma is superimposed with the common RF power. This can enhance the control of plasma density and coating stress. It can also increase the deposition rate, as well as give energy to the growing film, for example, to modulate the growth kinetics. This can also affect conformity, morphology, crystallinity, and small hole low density to produce films with better coating characteristics. This, in turn, will allow for the use of finer electrolytes, leading to a lower impedance EC device and higher manufacturing productivity with faster device switching speed. Figure 8 (a) is an SEM image of a 600 nm Al layer deposited by conventional evaporation. The image in figure 8 (a) reveals a columnar structure with a rough surface. Figure 8 (b) is a SEM image of a 600 nm AI layer deposited using a plasma activated evaporation according to certain exemplary embodiments. That is, Figure 8 (b) shows a multi-plasma sputtering concept for the RF-HF combination source. The SEM photograph in figure 8 (b) shows an example of the effects of imparting energy on a growing film, which includes a denser structure with a smooth surface.
    [0073] Common Li evaporation technologies are generally not compatible with HVM, as they typically require the use of multi-point sources and substantial downtime to recharge highly reactive Li or work out an inert ambient condition to withstand the self-feeding of an ex situ source. However, certain exemplary embodiments can incorporate a sprinkler-based source with a remote Li reservoir that can be refilled without disturbing the process or the vacuum system. The model results for the proposed evaporators are shown in the table below. From these results, a single linear source appears to be sufficient for an HVM system (greater than the rate of 1 μm / min)

    [0074] Li sputtering issues include "agglomeration" and a low deposition rate, which negatively affect uniformity. Agglomeration occurs when sputter species are much heavier (for example, Ar) and the coating tension is too high leading to a high moment. The use of lower atomic weight He and Ne will both reduce the deposition rate and incur a high cost. Consequently, a multiple frequency plasma source, analogous to that proposed for LiPON deposition, can be used in certain exemplary embodiments. However, RF can be overlaid with DC sputtering to increase plasma density and reduce coating stress. This will allow the use of lower cost air while also reducing clumping.
    [0075] In terms of HVM development, time savings can be realized in certain exemplary embodiments, since active layers can be processed in a single integrated deposition system where the substrates detect only the clean deposition chambers, thus reducing debris / defects affecting aesthetics and performance caused, for example, standardization, substrate sizing, exposure to air, etc. Limited exposure to air also reduces the requirement for a pure environment and again leads to total cost savings.
    [0076] In certain exemplary embodiments, the EC layer stack process can be accelerated at least 2 times compared to common practices, more preferably at least 3 times, and even more preferably at least 5 times. Multiple targets (for example, 2, 3, 4 or even 5 or more targets) can be used in the deposition process to increase line speed. Exemplary Electrochromic IG Unit
    [0077] An exemplary EC IG unit includes a tempered outer substrate, a half-light, and an inner glass substrate. The external glass substrate is a 6 mm thick UltraWhite glass substrate, and the half-light is a 1 mm thick UltraWhite glass substrate. The external glass substrate and the half-light are glued together using an Optibond laminate. Electrochromic layers are arranged on the surface of the half-light that faces the outer glass substrate. The TCCs used in connection with the electrochromic layers correspond to the exemplary layer stack in figure 5. A SunGuard SuperNeutral 70 low-e coating commercially available from the assignee is formed on both sides of the electrochromic layers. The internal glass substrate is a 6 mm thick sheet of Clear glass, commercially available from the transferee. A 12 mm insulation gap is present between the half-light and the internal glass substrate. This provision may have the following exemplary properties:

    [0078] As it is known, LSG represents gain of sunlight. In the table above, "% R Out" refers to the percentage of reflected direct solar energy. In certain exemplary embodiments, transmission in the colored state is preferably less than 5%, more preferably less than 4%, still preferably less than 3%, and sometimes up to about 2%. In certain exemplary embodiments, transmission in the non-colored state is preferably at least about 40%, more preferably at least about 45%, and sometimes 48% or even greater. SHGC preferably ranges from 0.03 to 0.5.
    [0079] As used here, the terms "in", "supported by" and the like should not be interpreted to mean that two elements are directly adjacent to each other, unless explicitly mentioned. In other words, a first layer can be considered to be "in" or "supported by" a second layer, even if there are one or more layers between them.
    权利要求:
    Claims (12)
    [0001]
    1. Electrochromic assembly (EC), comprising: a first (402), a second (602) and a third (604) glass substrates, the second (602) and the third (604) substrates being parallel and spaced from each other ; a plurality of sputtering EC device layers (404, 406, 408, 410, 412) supported by the first substrate (402), the plurality of EC device layers (404, 406, 408, 410, 412) comprising a first transparent conductive coating (TCC) (404), a counter electrode layer (CE) (406), an ion conductor layer (IC) (408), an EC layer (410), and a second TCC (412); wherein the first (402) and the second (602) substrates are laminated or glued together; and in which the second substrate (602) is thermally tempered and the first substrate (402) is not thermally tempered, characterized by the fact that each TCC includes a layer of silver (506) sandwiched by the first and second layers of ITO (502, 510 ), where first and second interlayer (504, 508) are provided between the silver layer (506) and the first and second ITO layer (502, 510), whose first and second interlayer (504, 508) comprise NiCR and / or Cu.
    [0002]
    2. Assembly, according to claim 1, characterized by the fact that the layers of EC devices face the second substrate.
    [0003]
    3. Assembly, according to claim 1, characterized by the fact that the layers of EC devices face the third substrate.
    [0004]
    4. Assembly according to claim 1, characterized by the fact that the sheet resistance of each TCC is less than 10 ohms / square.
    [0005]
    5. Assembly according to claim 1, characterized by the fact that the IC layer includes LiPON.
    [0006]
    6. Assembly according to claim 5, characterized by the fact that the EC layer comprises WOx.
    [0007]
    7. Assembly according to claim 6, characterized by the fact that WOx is substoichiometric.
    [0008]
    8. Assembly according to claim 7, characterized by the fact that 2.6 <x <3.
    [0009]
    9. Assembly according to claim 6, characterized by the fact that the CE layer, the IC layer, and / or the EC layer is / are doped with Mg.
    [0010]
    10. Assembly according to claim 1, characterized in that it additionally comprises one or more low-emissivity coatings, the low-emissivity coatings being supported by at least one of an internal surface of the second substrate, one or both surfaces of the first substrate and an internal surface of the third glass substrate.
    [0011]
    11. Assembly according to claim 10, characterized in that it additionally comprises a UV blocking coating on the inner surface of the second substrate.
    [0012]
    Assembly according to claim 1, characterized in that the EC device substrate is laminated or glued to the second glass substrate through a polymer-based layer.
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    同族专利:
    公开号 | 公开日
    EP2470954A2|2012-07-04|
    ES2712524T3|2019-05-13|
    WO2011028253A3|2011-04-28|
    US9140950B2|2015-09-22|
    JP2013503362A|2013-01-31|
    IN2012DN01952A|2015-08-21|
    ES2596652T3|2017-01-11|
    BR112012007879A2|2016-03-15|
    EP2470954B1|2018-12-05|
    JP5581387B2|2014-08-27|
    RU2012111663A|2013-10-27|
    EP2470953B1|2016-08-17|
    US20140111846A1|2014-04-24|
    BR112012008048A2|2016-03-01|
    MX2012002442A|2012-03-14|
    US20130016417A1|2013-01-17|
    RU2531063C2|2014-10-20|
    US8858748B2|2014-10-14|
    TW201116918A|2011-05-16|
    PL2470954T3|2019-04-30|
    US8289610B2|2012-10-16|
    JP2013503361A|2013-01-31|
    JP5667189B2|2015-02-12|
    BR112012007879B1|2021-02-02|
    EP2470953A2|2012-07-04|
    WO2011028254A3|2011-04-21|
    WO2011028253A2|2011-03-10|
    RU2012111658A|2013-10-10|
    TWI534519B|2016-05-21|
    RU2569913C2|2015-12-10|
    WO2011028254A2|2011-03-10|
    MX2012002443A|2012-03-14|
    IN2012DN01735A|2015-06-05|
    TR201902917T4|2019-03-21|
    US8638487B2|2014-01-28|
    TWI542934B|2016-07-21|
    US20110048614A1|2011-03-03|
    PL2470953T3|2017-03-31|
    TW201120552A|2011-06-16|
    US20110051221A1|2011-03-03|
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    法律状态:
    2019-01-08| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-09| B06T| Formal requirements before examination|
    2019-11-05| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2019-12-24| B25A| Requested transfer of rights approved|Owner name: GUARDIAN GLASS, LLC (US) |
    2020-09-01| B09A| Decision: intention to grant|
    2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 10 (DEZ) ANOS CONTADOS A PARTIR DE 15/12/2020, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US23758009P| true| 2009-08-27|2009-08-27|
    US61/237,580|2009-08-27|
    US12/805,144|US8289610B2|2009-08-27|2010-07-14|Electrochromic devices, assemblies incorporating electrochromic devices, and/or methods of making the same|
    US12/805,144|2010-07-14|
    PCT/US2010/002331|WO2011028253A2|2009-08-27|2010-08-24|Electrochromic devices, assemblies incorporating electrochromic devices, and/or methods of making the same|
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