Thermochromic filters and stopband filters for use with same

Information

  • Patent Grant
  • 8867132
  • Patent Number
    8,867,132
  • Date Filed
    Friday, October 29, 2010
    13 years ago
  • Date Issued
    Tuesday, October 21, 2014
    9 years ago
Abstract
Thermochromic filters use combinations of absorptive, reflective, thermoabsorptive, and thermoreflective elements covering different portions of the solar spectrum, to achieve different levels of energy savings, throw, shading, visible light transmission, and comfort. Embodiments include stopband filters in the near-infrared spectrum.
Description
BACKGROUND

1. Technical Field


The subject matter described herein relates to the design of devices for controlling the flow of light and radiant heat through selective reflection, transmission, and/or absorption and re-emission. The technology has particular, but not exclusive, application in passive or active light-regulating and temperature-regulating films, materials, and devices, especially as construction or building materials.


2. Description of the Related Art


Numerous electrochromic building materials have been developed, such as the electrochromic windows manufactured by Sage Electrochromics and Research Frontiers. In addition, numerous thermochromic building materials have been developed, including the thermoabsorptive and thermoreflective window filters manufactured by RavenBrick LLC. Such systems are often described as “dynamic glazings” or “dynamic windows.” Thermochromic and electrochromic materials may also be incorporated into opaque wall panels.


All thermochromic and electrochromic building materials share a number of common traits. First, they all transmit a variable amount of energy in the form of ultraviolet, visible, and near infrared light. Second, they all possess minimum and maximum transmission values in their clear and tinted states. The difference between these two values is sometimes referred to as the “throw.” Third, they all possess a minimum and a maximum wavelength over which their variable properties operate. The difference between these two values is called the “bandwidth” of the device, and the values themselves are known as the “band edges.” Finally, they all possess one or more wavelength ranges over which they do not operate. Typically the ultraviolet wavelengths are simply blocked to prevent them from damaging the dynamic building material and/or to prevent them from passing through into the building interior. In addition, while it may seem desirable to extend the band edge of a dynamic building material to cover the entire solar spectrum, in practice it becomes increasingly difficult to extend the band edge deep into the infrared, and the benefits of doing so are increasingly sparse as the energy of sunlight peaks at around 460 nanometers and tails off thereafter according to Boltzmann's law.


Thus, a band edge of 1000 nanometers encompasses roughly 73% of the sun's energy and a band edge of 1200 nanometers encompasses roughly 81% of the sun's energy, while a band edge encompassing 99% of the sun's energy does not occur until a wavelength of 4000 nanometers. In practice, this diminishing return means that dynamic building materials rarely exhibit band edges significantly beyond 1200 nm. For purposes of this document, the infrared output of the sun that falls outside the band edge of a dynamic building material shall be referred to as the “unswitched infrared band,” and represents a substantial energy resource that is typically wasted.


The information included in this Background section of the specification, including any references cited herein and any description or discussion thereof, is included for technical reference purposes only and is not to be regarded as subject matter by which the scope of the invention is to be bound or limited.


SUMMARY

Combinations of absorptive and reflective filters yielding a thermochromic or thermoreflective filter optimized for desirable combinations of several different variables, including but not limited to cost, return-on-investment, energy savings, human comfort, visible light transmission, and “throw”. In one exemplary implementation, a thermochromic filter device has either a thermoabsorptive element or a thermoreflective element operating across one or more regions of spectrum and a passive stopband element operating across one or more overlapping or non-overlapping regions of spectrum. The total energy throughput of the thermochromic filter device is optimized to a desired value for each of a hot state and a cold state.


In another exemplary implementation, a thermochromic filter device has a thermoabsorptive element operating across one or more regions of spectrum and a thermoreflective element operating across one or more overlapping or non-overlapping regions of spectrum. A total energy throughput of the thermochromic filter device is optimized to a desired value for each of a hot state and a cold state.


In a further exemplary implementation, a switchable filter device has a thermoabsorptive element operating across one or more regions of spectrum and a thermoreflective element operating across one or more overlapping or non-overlapping regions of spectrum. A total energy throughput of the switchable filter device is optimized to a desired value for each of a block state and a pass state. The switchable filter device may be photochromatic, electrochromatic, or magnetochromatic.


In yet another exemplary implementation, an optical or infrared stopband filter attenuates solar energy that occurs outside a band edge of a dynamic optical material or device. The stopband filter has a reflective or absorptive property that is mildly attenuating or non-attenuating across a functional bandwidth of the dynamic optical material or device and a reflective or absorptive property that is strongly attenuating across an unswitched solar radiation band of the dynamic optical material or device. An energy throughput and an operating temperature of the dynamic optical material or device are altered. Also a total building energy savings associated with the dynamic optical material or device is improved more than would be by extending a bandwidth of the dynamic optical material across a same region of the solar spectrum.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a schematic representation of a thermochromic (e.g., thermoreflective) filter laminated to a sheet of glass in its cold, or transparent, state.



FIG. 2 is a schematic representation of a thermochromic (e.g., thermoreflective) filter laminated to a sheet of glass in its hot, or blocking, state.



FIG. 3 is a graph showing the sea-level energy output of the sun as a function of wavelength.



FIG. 4 is a graph representing the absorption spectrum of an exemplary narrowband thermoabsorptive device in its hot and cold states.



FIG. 5 is a graph representing the reflection spectrum of an exemplary narrowband thermoreflective device in its hot and cold states.



FIG. 6 is a graph representing the reflection spectrum of an exemplary broadband thermoreflective device in its hot and cold states.



FIG. 7 is a graph representing the absorption spectrum of the exemplary thermoabsorptive device from FIG. 4 plus the reflection spectrum of an infrared stopband filter to be integrated into the device.



FIG. 8 is a graph representing the reflection spectrum of the exemplary narrowband thermoreflective device from FIG. 5 plus the reflection spectrum of an infrared stopband filter integrated into the device.



FIG. 9 is a graph representing the absorption spectrum of an exemplary thermoabsorptive device with high visible light transmission plus the reflection spectrum of an infrared stopband filter integrated into the device.



FIG. 10 is a graph representing the absorption spectrum of an exemplary thermoabsorptive device with high visible light transmission plus the reflection spectrum of an exemplary infrared thermoreflective filter integrated into the device.



FIG. 11 is a graph representing the same device as FIG. 10, except that one of the infrared reflective polarizers forming the infrared thermoreflective filter has been deleted.



FIG. 12 is a graph showing the energy savings for various embodiments of the present invention in an exemplary building and climate zone.



FIG. 13 is a graph showing the absorption spectra of two different materials that are suitable for use as absorptive infrared stopband filters.



FIG. 14 is a graph showing the absorption spectrum of an ideal absorptive infrared stopband filter.



FIG. 15 is a graph showing the reflection spectrum of a representative reflective infrared stopband filter.





DETAILED DESCRIPTION


FIG. 1 is a schematic representation of an exemplary thermoreflective filter 105 laminated to a sheet of glass 104 in its cold or transparent state. The thermoreflective filter 105 is composed of an outer polarizer layer 101, and inner polarizer layer 103 with a polarity generally perpendicular to the outer polarizer 101, and a liquid crystal layer 102 with a low clearing point temperature between 0° C. and 40° C. When unpolarized light enters the device, it passes through the outer polarizer 101, where up to 50% of the light is reflected because it is of perpendicular polarity to the polarizer 101. The remaining light, with the same polarity as the polarizer, is transmitted through the twisted nematic liquid crystal layer 102, where its polarity is rotated by approximately 90 degrees to match the polarity of the inner polarizer 103. The light is therefore able to propagate through the inner polarizer 103 and thus approximately 50% of the incident light is able to pass through the glass substrate 104. The same principles apply to thermoabsorptive/thermodarkening filters made from absorptive rather than reflective polarizers.



FIG. 2 is a schematic representation of the thermoreflective filter 105 laminated to a sheet of glass 104 in its hot or reflective state. When unpolarized light enters the device, it passes through the outer polarizer 101 where approximately 50% of it is reflected because it is of perpendicular polarity to the outer polarizer 101. The remaining light, with the same polarity as the outer polarizer 101, is transmitted through the liquid crystal layer 102. However, because the liquid crystal 102 is above its clearing point temperature, it is in an isotropic or disorganized state rather than an organized state and does not affect the polarity of the light passing through it. The transmitted light is therefore of perpendicular polarity to the inner polarizer 103 and is reflected by the inner polarizer 103, which has a polarity perpendicular to that of the outer polarizer 101. Thus, very little of the incident light is able to pass through the glass substrate 104. Again, the same principles apply to thermoabsorptive/thermodarkening filters made from absorptive rather than reflective polarizers.



FIGS. 1 and 2 are provided for exemplary purposes only, as the methods and devices described herein, and the principles governing them, may be applied to “smart” optical filters of any sort including thermochromic, electrochromic, photochromic, or magnetochromic filters, of either absorptive, reflective, or diffusive varieties, or combinations thereof, that switchably block and pass optical wavelengths. For example, a thermoreflective filter composed of a low-clearing-point liquid crystal sandwiched between two reflective polarizers is disclosed in U.S. Pat. No. 7,755,829, which has particular, but not exclusive, application as a component of building materials, e.g., as a window film. Similarly, in U.S. Patent Application Publication No. 2009/0167971, a thermodarkening filter composed of a low-clearing-point liquid crystal sandwiched between two absorptive polarizers is disclosed, which has particular, but not exclusive, application as a component of building materials, e.g., as a window film.



FIG. 3 is a graph showing the sea-level intensity of sunlight in Watts per square meter per micrometer as a function of wavelength. Sunlight intensity peaks at around 460 nanometers, corresponding to blue light roughly 21% of the way between ultraviolet and infrared, and tails off thereafter according to Boltzmann's law. Approximately 45% of the energy of sunlight occurs in the visible spectrum (380-750 nm), with another 7% occurring in ultraviolet range (200-370 nm), and 48% occurring in the infrared range (760-4000 nm). The near infrared band from 760-2200 nm contains approximately 43% of the sun's energy and is a primary contributor to solar heat gain in buildings, while contributing no lighting perceptible to the human eye.



FIG. 4 is a graph representing the absorption spectrum of an exemplary thermoabsorptive device in its hot (blocking) and cold (pass through) states. The solid line represents the device in its cold (transparent) state, and the dashed line represents the device in its hot (tinted) state. Such a filter may be constructed using standard absorptive polarizers made from iodine-doped polyvinyl alcohol (PVA) available from a variety of different manufacturers around the world. Because the bandwidth of this device encompasses the entire visible spectrum, but only 7% of the near infrared, its total solar “throw” is approximately 40-45% of what it would be if its band edge were extended to 2200 nm. In addition, because this device is thermoabsorptive rather than thermoreflective, it may absorb a significant amount of energy in direct sunlight. As a result, its operating temperature in direct sunlight may significantly exceed the ambient temperature. This may tend to decrease its operational lifetime, since the chemical reactivity of many organic materials may increase dramatically with temperature. In addition, because the filter is more absorptive in its hot state, and thus absorbs even more solar energy, it may have a tendency to “latch” in the on state while direct sunlight is striking it, even if the ambient temperature drops significantly below the transition temperature of the device.


In addition, in order to maximize energy savings by limiting solar heat gain in hot weather, this device is highly attenuating (˜97%) to visible light in its hot state, and in order to maximize “throw” the device is approximately 35% transmissive to visible light in its cold state. This may be acceptable for applications where energy savings are more important than visible light transmission, but may be problematic in applications where large amounts of interior daylight are desired.



FIG. 5 is a graph representing the reflection spectrum of an exemplary narrowband thermoreflective device, in its hot and cold states. The solid line represents the device in its cold (transparent) state and the dashed line represents the device in its hot (reflective) state. Once again, because the bandwidth of this device encompasses the entire visible spectrum, but only ˜7% of the near infrared, its “throw” is approximately 40-45% of what it would be if its band edge were extended to 2200 nm. A device matching these specifications can be made using 3M reflective polarizers in the DBEF family.



FIG. 6 is a graph representing the reflection spectrum of an exemplary broadband thermoreflective device, in its hot and cold states. The solid line represents the device in its cold (transparent) state, and the dashed line represents the device in its hot (reflective) state. In this case, because the bandwidth of the device extends past 2200 nm, the “throw” of the device is much larger than for the exemplary devices of FIGS. 4 and 5. In addition, because the filter is thermoreflective rather than thermoabsorptive, it is generally more efficient at rejecting heat (e.g., when applied to windows in a building or vehicle). A device matching these specifications can be constructed using wire grid polarizers of the type manufactured by Moxtek, Inc.


Because the devices of FIGS. 5 and 6 are highly reflective across the visible spectrum, it should be noted that they may present a zoning problem in some jurisdictions where the reflectivity of windows and other building materials is restricted. For example, many cities in the U.S. set a limit of 20% visible light reflection.



FIG. 7 is a graph representing the absorption spectrum of the exemplary thermoabsorptive device from FIG. 4, plus the reflection spectrum of an infrared stopband filter integrated into the device. The addition of the stopband filter does not affect the throw or bandwidth of the device. However, it does reduce the total energy flux through the device by reflecting the majority (in this example, approximately 90%) of solar energy in the near infrared band. In full, direct sunlight, this may also reduce the operating temperature of the device, which may tend to increase its useful lifespan and also make the device more responsive to ambient temperature and less responsive to the heating effects of direct sunlight. This allows greater control over the switching state and thus greater comfort and energy savings in a building material application such as windows and exterior wall panels by, for example, reducing the “latching” effect. Thus, in certain applications—particularly in structures and climate zones primarily needing cooling—this configuration may allow much higher energy savings and comfort ratings than the thermoabsorptive filter by itself.



FIG. 8 is a graph representing the reflection spectrum of the exemplary narrowband thermoreflective device from FIG. 5, plus the reflection spectrum of an infrared stopband filter integrated into the device. As in the previous example, the addition of the stopband filter does not affect the throw or bandwidth of the device. However, it does reduce the total energy flux through the device by reflecting the majority (in this example, approximately 90%) of solar energy in the near infrared band. Thus, in certain applications—particularly in structures and climate zones primarily needing cooling—this configuration may allow much higher energy savings and comfort ratings than the narrowband thermoreflective filter by itself.



FIG. 9 is a graph representing the absorption spectrum of an exemplary thermoabsorptive device with high visible light transmission, plus the reflection spectrum of an infrared stopband filter integrated into the device. In this case, unlike the exemplary devices of FIGS. 4 and 7, a high transmission of daylight is desired, and some “throw,” or control over solar heat gain, is consequently sacrificed. Thus, the device is approximately 45% transmissive to visible light in its cold state and 27% transmissive to visible light in its hot state.


In the case of a polarizing device, this increased transmissivity may be achieved, for example, by reducing the thickness of an iodine-doped polyvinyl alcohol (PVA) layer that is the active polarizing element. This reduces polarization efficiency and contrast ratio, while increasing transmissivity. Myriad other methods may be used to reduce polarization efficiency as well, depending on the exact nature of the polarizer being used. In general, decreasing the efficiency of a polarizer is less difficult than increasing it. Alternatively, the transmissivity in the hot state may be increased by misaligning the polarizers, although this will tend to slightly decrease the transmissivity in the cold state and may thus be a less desirable solution.


Achieving the thermochromic (e.g., thermoabsorptive or thermoreflective) effect through polarization has an added advantage when used in building material applications because the transmission numbers stated above are representative of a polarizing device that is being used to shutter non-polarized light. However, the Earth's sky, as seen from ground level, may include a broad band of highly polarized light approximately 90 degrees away from the sun. At sunrise and sunset, this band may extend from south to north across the zenith of the sky. At noon, it may extend in a circle around the horizon. The blue sky is approximately ⅙th as bright as direct sunlight and should be considered a significantly pre-polarizing light source. Thus, if the thermochromic (e.g., thermoabsorptive or thermoreflective) device is oriented such that its polarization in the cold state matches that of the sky, then the filter will appear significantly more transmissive than for an unpolarized light source such as direct sunlight. Thus, in the exemplary device of FIG. 9, the cold-state visible light transmittance may be approximately 54% when looking at the blue sky 90 degrees away from the sun.


The same effect works in reverse, i.e., in the hot state the visible light transmission may be as low as 22% when looking at the blue sky approximately 90 degrees away from the sun, because in the hot state the device is polarizing perpendicular to the sky as well as parallel to it. In addition, both effects may be inverted by rotating the device 90 degrees around the vision line, such that the cold-state transmission may drop to approximately 37% and the hot-state transmission may increase to approximately 33%. This very small separation between hot-state and cold-state transmissivity means the device has been effectively neutralized by the polarization of the sky. Thus, the orientation of a polarization-based thermochromic (e.g., thermoabsorptive or thermoreflective) filter can be selected to increase or decrease the “throw” of the device with respect to the blue sky approximately 90 degrees from the sun, and that this orientation sensitivity is an important element of the device's design. These values and geometries are stated here for explanatory purposes only



FIG. 10 is a graph representing the absorption spectrum of an exemplary thermoabsorptive device with high visible light transmission, plus the reflection spectrum of an exemplary infrared thermoreflective filter integrated into the device. The device of FIG. 10 does not have any stopband filters, just a thermotropic liquid crystal and two different sets of polarizers (one absorptive and one reflective) covering different ranges of wavelengths. The dashed and solid black lines represent the absorption spectrum of the thermoabsorptive portion of the device in the hot and cold states, respectively, while the dotted and solid gray lines represent the infrared reflection spectrum of the thermoreflective portion of the device in the hot and cold states, respectively.


This configuration allows the switchable bandwidth of the device to be extended all the way to 2200 nm, which may significantly improve its comfort rating and energy savings when used in building material applications such as windows and exterior wall panels. In addition, because the device is thermoreflective in the near-infrared portion of the solar spectrum, it may be extremely efficient at rejecting solar heat gain in its hot state. And because it is thermoabsorptive in the visible spectrum, it is capable of switching on and off a significant portion of the available solar energy without producing high reflectivity that may, in some cases, produce legal or zoning complications.


In addition, the exemplary thermoreflective filter has been configured such that it has a low, but nonzero, polarization efficiency across the visible spectrum, yielding a maximum 20% reflectivity in the hot state. This may allow the energy savings and comfort ratings of the device to be maximized within the constraints of allowable visible-light reflection for some jurisdictions, and within the additional constraint of high visible light transmission in the hot and cold states.


Exemplary devices that achieve thermochromic effects through polarization are described in U.S. Pat. No. 7,755,829 and in U.S. Patent Application Publication No. 2009/0167971. The absorption and reflection effects of such devices may be aligned such that throw and visible light transmission are enhanced, well beyond what is possible with non-polarizing tints. For example, if the absorptive and reflective polarizers are alternated as described, for example, in U.S. Patent Application Publication No. 2009/0268273, then a 20% reflective (80% transmissive) polarizer placed in series with a 45% absorptive (55% transmissive) polarizer at the same polarization alignment yields a net light transmission of approximately 55%, rather than the 36% transmission that would occur if a static, non-polarizing 20% reflector and 45% absorber were placed in series.


Moreover, the stack appears 20% reflective only when seen from the reflective side. When seen from the absorptive side, the light reflecting from the reflective polarizer is largely absorbed by the absorptive polarizer (since their polarization vectors match), so the effective reflection is approximately 6%. Thus, when incorporated into a window with the reflective surface facing outside and the absorptive surface facing inside, the total device in its cold state may be approximately 55% transmissive to visible light, 20% reflective to visible light, and 25% absorptive to visible light from an outside source (e.g., the sun), and 55% transmissive to visible light, 6% reflective to visible light, and 39% absorptive to visible light from an inside source (e.g., a light fixture). Total solar transmission (visible and infrared) for this exemplary device may then be approximately 45% in the cold state and 19% in the hot state, for a throw of 26%. These values are stated for exemplary purposes only.


In addition, for the polarizing form of this exemplary device the same sky polarization effects apply as described above for FIG. 9. Thus, both the throw and the cold-state visible light transmission can be increased if the filter is oriented such that its cold-state polarization axis matches that of the sky. Once again, this is not possible with non-polarizing tints. This performance advantage of polarizing over non-polarizing tints allows reflective and absorptive elements to be combined with very high efficiency, and is explicitly claimed as an embodiment of the present invention.



FIG. 11 is a graph representing the same device as FIG. 10, except that one of the two infrared reflective polarizers has been removed. Thus, the device is approximately 50% reflective to near-infrared wavelengths in both its hot and cold states. This allows a lower overall solar heat gain coefficient than the thermoabsorptive filter alone, while preserving the zoning compliance and visible light transmission characteristics of the embodiment in FIG. 10. In addition, it may be less expensive to manufacture than the embodiment of FIG. 10, because it contains fewer polarizing layers. However, in the visible light wavelengths there is much greater light transmission than if a non-polarizing 20% reflective layer were used instead of a 20% reflective polarizer, and in the region of overlap between the bandwidths of the visible-light absorptive polarizers and the infrared reflective polarizer, there is much greater light transmission in the cold state than would be possible if a non-polarizing, 50% reflective layer were used instead.



FIG. 12 is a graph showing the energy savings for various exemplary embodiments of the present invention, in an exemplary building and climate zone. Embodiment “R” corresponds to the exemplary device of FIG. 6, a broadband thermoreflective filter configured for modest visible light transmission and large “throw.” Embodiment “A” corresponds to the exemplary device of FIG. 4, a thermoabsorptive filter operating primarily in the visible spectrum, configured for low visible light transmission and large “throw.” Embodiment “V” corresponds to the exemplary device of FIG. 10, a visible-light thermoabsorptive and infrared thermoreflective filter which is configured for high visible light transmission, modest visible light reflection, and large “throw.” Embodiment “VR” corresponds to the exemplary device of FIG. 9, a thermoabsorptive filter operating primarily in the visible spectrum, configured for high visible light transmission and with an infrared stopband filter to reduce solar heat gain coefficient. Embodiment “VH” corresponds to the exemplary device of FIG. 11, a visible-light thermoabsorptive filter configured for high visible light transmission with an infrared polarizer to reduce solar heat gain coefficient.


This graph indicates that all of these exemplary devices show roughly comparable energy savings in an exemplary building and climate zone, but that they achieve such energy savings through very different combinations of absorption, reflection, and transmission, both static and switchable, and in both the visible and near-infrared spectrum. Thus, energy savings can be traded off against other properties that may be desirable for particular applications including, but not limited to, visible light transmission, visible light throw, total solar throw, shading of direct sunlight, peak heating and cooling loads, and various human comfort metrics.



FIG. 13 is a graph showing the absorption spectra of two different materials that are suitable for use as absorptive infrared stopband filters for the exemplary dynamic building material of FIG. 4. These exemplary embodiments are passive filters that operate on the unswitched infrared band outside a dynamic building material's band edge (i.e., the near infrared band not affected by the thermochromic material that switches with a temperature threshold), for the purpose of maximizing the energy performance of that material without extending its bandwidth.


The solid gray line represents an infrared-tinted PVB film called “8.6 Green/.090 SGP/Clear” produced by Cardinal Glass Industries, which exhibits roughly 80-90% transmission across the functional bandwidth of the dynamic building material and approximately 70% absorption across the unswitched infrared band. The solid black line represents an even better (though more costly) infrared stopband filter material: KG-2 glass from Schott, which exhibits roughly 95% transmission across the functional bandwidth of the dynamic building material and roughly 95% absorption across the unswitched infrared band of the dynamic building material. Because the KG-2 spectrum begins absorbing where the dynamic building material's absorption band stops, an infrared stopband filter made of KG-2 is particularly well suited to “plugging the hole” and preventing transmission of solar energy from 900 to 2200 nanometers. If the infrared stopband filter is integral to, adjacent to, or otherwise in thermal contact with the dynamic building material (e.g., through conduction, convection, or radiative heat transfer), this configuration will also have the effect of raising the internal temperature of the dynamic building material and thus driving it more toward its “hot state” behavior (e.g., greater tinting) for the purpose of increasing the overall energy savings of the system.


The two materials described for use as infrared stopband filters are described here for exemplary purposes. A large plurality of other materials, or combinations of materials, could be used to create almost any desired absorption spectrum across the functional bandwidth and the unswitched infrared band of a dynamic building material.


It is generally assumed that extending the band edge of a dynamic building material will improve its energy-saving capabilities, since the material is then capable of switching a greater percentage of the sun's energy on or off. However, this view presumes that the response of the material is not altered by the throughput of additional energy. In practice, transmitting the unswitched infrared band into the building interior raises the building temperature, which may alter the behavior of building occupants, thermostats, mechanical systems, automated control systems for dynamic materials, and autonomous behavior of so-called “smart” materials. Absorbing the unswitched infrared band raises the temperature of the dynamic window system which, in the case of a thermochromic system, will increase the level of tinting; in the case of a thermoreflective system, will increase the amount of reflection; and in the case of an electrochromic system, may trigger automated responses from the electrochromic control system. Further, reflecting the unswitched infrared band lowers the amount of absorbed energy and thus lowers the temperature of the dynamic building material, with similarly nonlinear effects on system performance, and also lowers the amount of solar heat gain within the building and thus alters the behavior of people and systems within the building.


Therefore, the result (which may be counterintuitive) is that extending the band edge of a dynamic building material may decrease, rather than increase, the total energy savings of the building over time. This result depends primarily on the exact nature and setpoints of the dynamic building material. However, it also depends on the building type, size, orientation, climate zone, window-to-wall ratio, surrounding landscape, HVAC system, thermostat control algorithms, and occupant behavior. The only reliable methods for assessing the total-building energy performance of dynamic materials are (a) live testing, and (b) detailed building simulation.


The former is problematic because long test times (in general, a year or more) are required to evaluate the performance of different materials and setpoints across all seasons. Thus, trade studies could reasonably take decades to unfold, or require the testing of large numbers of similar buildings. Therefore, while live testing plays an important role in the validation of particular designs, it is generally an adjunct to large numbers of computer simulations that are used to find optimal combinations of materials and setpoints.


This simulation process has been facilitated by the U.S. Department of Energy's Lawrence Berkely National Laboratory, which has produced a suite of standardized software tools and building models that can be used to evaluate different materials, or different dynamic setpoints for the same material, under rigorously controlled and easily reproducible conditions, across an entire model year, in multiple building types and climate zones, over a period of hours or days as opposed to the years required for live testing. For example, Window 6, Optics 5, EnergyPlus 3.0, and the TMY weather file database have been used for this purpose with extremely effective results, although other software tools and data files may be used to produce similar results.


Through such modeling, it has been determined that under some conditions (generally identified through computer simulation, although closed-form theoretical calculations may serve the same purpose) it may be desirable to control the unswitched infrared band in one of three specific ways: total absorption, total reflection, or total transmission. This can be accomplished with an infrared filter, which may be a separate material layer within the dynamic building material, may be external to the dynamic building material, or may take the form of a dopant, dye, or additive to one or more layers within the dynamic building material. The result is a device for increasing the energy savings of a dynamic building material without extending its bandwidth. For the purposes of this document, such a filter is referred to herein as an “infrared stopband filter.”


It is undesirable for such control of the unswitched infrared band to interfere with the dynamic properties of the dynamic building material across its functional bandwidth. Thus, the infrared stopband filter should have relatively constant response across the dynamic building material's functional bandwidth. In many cases, it will be desirable for the absorption or reflection of the infrared stopband filter to be zero, or near zero, across the functional bandwidth of the dynamic material. In other cases, it may be desirable for the infrared stopband filter to have some other absorption or reflection property (e.g., 50%) across the functional bandwidth of the dynamic building material in order to raise or lower the operating temperature of the dynamic building material in full sunlight.


In either case, the infrared stopband filter may have a reflection or absorption property that rises sharply, to a high value (e.g., 100% or some close approximation thereof), at the band edge of the dynamic building material. For example, Raven Brick's RavenWindow™ window filter product has a large “throw” across its bandwidth between 300 and 900 nanometers, but does not switchably affect the transmission of radiation past the band edge at around 900 nanometers. An exemplary infrared stopband filter for use in conjunction with the RavenWindow™ window filter product may have an extremely low (e.g., <10%) reflection or absorption between 300 and 900 nanometers, a sharply rising reflection or absorption at around 900 nanometers, and a very large reflection or absorption (e.g., >90%) across the “unswitched infrared” band from 900 to 2200 nanometers.


In practice, very sharp band edges and very large transmission differences are difficult to achieve with absorptive materials. However, reasonable approximations do exist. For example, G. James Corporation of Australia manufactures a PVB film called HL5P19 that is approximately 30% absorptive across the visible spectrum, has increasing absorption between 700 and 900 nanometers, is approximately 70% absorptive between 900 and 1700 nanometers, and then rises to approximately 90% absorption between 1700 and 2200 nanometers. This film has a slight blue tint, but is nevertheless acceptable for use as an infrared stopband filter to enhance the energy-saving properties of a dynamic building material. Similarly, the U.S. company Cardinal Glass Industries produces a PVB film called “8.6 Green/.090 SGP/Clear” that is approximately 10% absorptive to visible light, with absorption increasing linearly between 600 and 900 nanometers to a value of 65% absorption, which then remains relatively constant out to 2200 nanometers. This material has a very slight green tint, similar to the color of ordinary float glass, and is also suitable for use as an infrared stopband filter to enhance the energy savings of dynamic building materials.


Numerous infrared pigments also exist. Ferro Corporation's Color Division produces an inorganic infrared pigment called “iron chromite infrared black.” BASF makes Sicomix brand infrared pigments, which include both organic and inorganic components. Keystone Aniline Corporation of Chicago, Ill. manufactures infrared pigments such as Keysorb 970 and Keysorb 1026 whose absorption peak centers in nanometers are specified in the product names. Other infrared pigments are available from Polatechno, Sanritz, Arisawa, Nippon Kayaku, and Sumitomo and have mainly been used in the manufacture of infrared polarizers. When such dyes are used in sufficient quantity to block a substantial majority (e.g., greater than 90%) of infrared light within a particular wavelength band, they are often significantly attenuating to visible light as well.


However, other materials exist that absorb infrared light while being highly transparent to visible light. For example, Schott corporation makes “heat absorbing glass” (for example, KG-1, KG-2, KG-5, BG-18, BG-38, BG-9, and VG-9) that is >90% transmissive to visible light and >99% absorbing to infrared radiation beyond approximately 800 nm. For many of these materials the transmissivity rises to approximately 80% again by 1750 nanometers, but only approximately 8% of the sun's energy occurs beyond this wavelength. Thus, the Schott glass can be used to make fairly precise infrared stopband filters that do not significantly interfere with visible light transmission, and are thus extremely suitable for enhancing the energy-saving properties of dynamic building materials. However, while the KG glass is colorless in the visible spectrum, Schott's BG and VG materials have band edges that lend a blue, green, or violet tint, which may be acceptable for some applications and problematic for others.


Thus, different organic and inorganic materials can be combined to produce close to 100% absorption within a given range of infrared wavelengths (e.g., the unswitched infrared band of a dynamic building material), while allowing close to 100% transmission of visible light and near-infrared light with wavelength shorter than the desired band edge. Alternatively, the approximately 100% absorption of a specified band of infrared light may be accompanied with some specific amount of visible light transmission that is selected to optimize the energy-saving properties of the thermochromic building material as described above.


The situation is even more favorable with regard to reflective infrared stopband filters. Unlike the absorption spectra of infrared-absorbing materials, the reflection spectra of optical materials often have sharp, sudden, and clearly defined band edges that occur at precise wavelengths, and also extremely high transmission values outside their reflection bands. Thus, it is fairly straightforward to design bandblock reflectors, bandpass reflectors, and shortpass reflectors with band edges occurring at any desired wavelength. Types of reflective filters that can serve this purpose include distributed Bragg reflectors, Rugate filters, cholesteric liquid crystals, dichroic coatings, and other known interference-type coatings. There are also pigments having bright reflection spectrums in the wavelengths of concern (so-called “infrared white” materials). There are also materials that are highly transparent to visible light and highly reflective to infrared, such as tin oxide, which is less than 10% reflective to visible light, but more than 90% reflective to long-wavelength infrared. In addition, the transmissivity of a given material may be enhanced in the visible spectrum, or any other desired range of wavelengths, by introducing periodic openings into the material of appropriate size and spacing to allow those wavelengths to pass preferentially, as described for example in U.S. Patent Application Publication No. 2009/0128893.


Thus, different optical materials, combinations of materials, and microstructures can be combined to produce close to 100% reflection within a given range of infrared wavelengths (e.g., the unswitched infrared band of a dynamic building material) while allowing close to 100% transmission of visible light, and near-infrared light with wavelengths shorter than the desired band edge. Alternatively, the approximately 100% reflection of a specified band of infrared light may be accompanied with some specific amount of visible light transmission that is selected to optimize the energy-saving properties of the thermochromic building material as described above.


In other embodiments, reflective and absorptive properties can be combined, either in a single layer or in two or more separate layers, to produce an infrared stopband filter that has specific combinations of absorption and reflection (e.g., 50% absorption and 50% reflection) that are intended to optimize the performance of dynamic building materials in the unswitched infrared band outside their switchable bandwidth. Such combinations may be even more effective if they are polarizing rather than non-polarizing, as detailed above, although non-polarizing embodiments may also be efficacious.



FIG. 14 is a graph showing the absorption spectra of two exemplary infrared stopband filters designed to work with a dynamic, thermochromic or thermotropic building material whose band edge occurs at roughly 1200 nanometers (as opposed to the 900 nanometers of the exemplary dynamic building material of FIG. 2), and which has a fairly shallow tint-vs.-temperature curve (as opposed to the abrupt tint-vs.-temperature curve of the exemplary dynamic building material of FIG. 2). Such specifications may be achieved using a guest-host liquid crystal cell as described for example in U.S. Patent Application Publication No. 2010/025968. Alternatively, a film or coating containing one or more types of thermochromic pigment molecules may be used instead, as described for example in U.S. Pat. No. 6,084,702 to Byker et al. Both of these devices may be largely or completely non-polarizing, although polarizing versions of them could also be created.


The solid line on FIG. 14 represents the “ideal” absorption spectrum for this particular “smart” optical filter, wherein the infrared stopband filter absorbs approximately 50% of the light across the dynamic building material's functional bandwidth and approximately 95% of the light across the dynamic building material's unswitched infrared band. The dashed line represents a “compromise” material wherein the band edge of the infrared stopband filter is more gradual, and the absorption is smaller across the dynamic building material's functional bandwidth and also across its unswitched infrared band. These exemplary infrared stopband filters result in greater absorption of solar energy, and thus a higher operating temperature, and result in higher performance for the thermochromic building material (as measured by total building energy consumption over the course of a model year) than extending the band edge of the thermochromic building material to 2200 nanometers. In other words, the addition of this a stopband filter with these specifications is better, in terms of energy performance, than improving the infrared performance of the smart filter itself. This result (which may seem counterintuitive) has been confirmed through building simulations of the said thermochromic or thermotropic building material.



FIG. 15 is a graph showing the reflection spectrum of an exemplary, reflective infrared stopband filter designed to work, for example, with a thermoreflective building material having a band edge around 1200 nanometers. This reflection spectrum closely resembles that of the “Extended Hot Mirror” dichroic coating available from Quik-Mod optics, although its spectrum is shifted roughly 200 nm deeper into the infrared through an alteration of the dichroic properties of the coating. This exemplary reflective infrared stopband filter increases the total reflection of energy from the thermoreflective building material, thus lowering both its own operating temperature and the internal temperature of the building. Under some circumstances (e.g., in hot climates, in skylights, and in large buildings with a high window-to-wall ratio), this results in higher performance of the thermoreflective building material than extending the band edge of the thermoreflective building material to 2200 nanometers. This result, although counterintuitive, has been confirmed through building simulations and live tests of the thermochromic building material incorporating such a reflective infrared stopband filter.


Although these embodiments have been described with particular detail, these embodiments are described here for exemplary purposes, and that a plurality of other combinations of reflection, absorption, and transmission may be implemented without departing from the scope of the present disclosure. In addition, numerous additional variations and optional enhancements can be applied. For example, the addition of a low-emissivity coating may have significant effects on the energy and comfort performance of any of the stated embodiments. Alternatively, although reflective infrared stopband filters are employed in the exemplary devices described above, absorptive infrared stopband filters, or a combination of absorptive and reflective infrared stopband filters, could be used as well.


The exact arrangement of the various layers can be different than is disclosed herein and, depending on the materials and wavelengths selected, different layers can be combined as single layers, objects, devices, or materials, without altering the essential structure and function of the invention. For example, the infrared stopband filter could double as a structural element or could be integrated directly into the dynamic building material. Alternatively, the dynamic building material need not have a single operational bandwidth or a single unswitched radiation band, but could have multiple such bands spread across the solar spectrum, with each “hole” in the spectrum potentially being “plugged” by a different stopband filter. The band edges of an infrared stopband filter, whether reflective or absorptive, may be either gradual or sharp without altering the basic nature of the present invention.


Also, the bandwidth of the stopband filter or filters may occur in, or overlap with, the visible spectrum. In addition, the absorption and reflection spectra of multiple filters or filter components may be combined to produce particular color effects, including the “colorless” state of clear or neutral gray. Methods for designing “metameric” colors from individual spectral peaks are well described.


Furthermore, although various embodiments of this invention have been described above with a certain degree of particularity, or with reference to one or more individual embodiments, those skilled in the art could make numerous alterations to the disclosed embodiments without departing from the spirit or scope of this invention. It is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative only of particular embodiments and not limiting. All directional references (e.g., proximal, distal, upper, lower, inner, outer, upward, downward, left, right, lateral, front, back, top, bottom, above, below, vertical, horizontal, clockwise, and counterclockwise) are only used for identification purposes to aid the reader's understanding of the present invention, and do not create limitations, particularly as to the position, orientation, or use of the invention. Connection references (e.g., attached, coupled, connected, and joined) are to be construed broadly and may include intermediate members between a collection of elements and relative movement between elements unless otherwise indicated. As such, connection references do not necessarily imply that two elements are directly connected and in fixed relation to each other. Stated percentages of light transmission, absorption, and reflection shall be interpreted as illustrative only and shall not be taken to be limiting. Changes in detail or structure may be made without departing from the basic elements of the invention as defined in the following claims.

Claims
  • 1. A thermochromic filter device comprising either a thermoabsorptive element or a thermoreflective element operating across a first wavelength region to block electromagnetic radiation in a hot state and pass through electromagnetic radiation in a cold state, the first wavelength region being bounded at an upper end by a first band edge; anda passive stopband element operating across a second electromagnetic wavelength region to block electromagnetic radiation, whereinat least a portion of second wavelength region is above the first band edge;the total energy passed through the thermochromic filter device is optimized to a desired value for each of the hot state and the cold state.
  • 2. The thermochromic filter device of claim 1, wherein the passive stopband element is reflective.
  • 3. The thermochromic filter device of claim 1, wherein the passive stopband element is absorptive.
  • 4. The thermochromic filter device of claim 1, wherein the either the thermoabsorptive element or the thermoreflective element is constructed with one or more polarizers.
  • 5. The thermochromic filter device of claim 4, wherein an orientation of the thermochromic filter device is selected to aligns with a polarization of the sky in order to maximize visible light transmission and throw.
  • 6. The thermochromic filter device of claim 1, wherein a reflection spectrum of the passive stopband element exceeds 20% reflectivity across the visible spectrum.
  • 7. The thermochromic filter device of claim 1, wherein a reflection spectrum of the passive stopband element does not exceed 20% reflectivity across the visible spectrum.
  • 8. The thermochromic filter device of claim 1, wherein the thermoabsorptive element or the thermoreflective element operates within an optical spectrum; andthe stopband element operates within a near-infrared spectrum.
  • 9. A thermochromic filter device comprising a thermoabsorptive element operating across a first wavelength region to block electromagnetic radiation in a hot state and pass through electromagnetic radiation in a cold state, the first wavelength region being bounded at an upper end by a first band edge; anda thermoreflective element operating across a second wavelength region to block electromagnetic radiation in the hot state and pass through electromagnetic radiation in the cold state, whereina total energy passed through the thermochromic filter device is optimized to a desired value for each of the hot state and the cold state.
  • 10. The thermochromic filter device of claim 9, wherein the either the thermoabsorptive element or the thermoreflective element is constructed using polarizers.
  • 11. The thermochromic filter device of claim 10, wherein an orientation of the thermochromic filter device is selected to align with a polarization of the sky in order to maximize visible light transmission and throw.
  • 12. The thermochromic filter device of claim 9, wherein a reflection spectrum of the thermoreflective element exceeds 20% reflectivity across the visible spectrum.
  • 13. The thermochromic filter device of claim 9, wherein a reflection spectrum of the thermoreflective element does not exceed 20% reflectivity across the visible spectrum.
  • 14. The thermochromic filter device of claim 9, wherein the thermoabsorptive element operates within an optical spectrum; andthe thermoreflective element operates within a near-infrared spectrum.
  • 15. The thermochromic filter device of claim 9, wherein at least a portion of second wavelength region is above the first band edge.
  • 16. A switchable filter device comprising a thermoabsorptive element operating across a first wavelength region to block electromagnetic radiation in a block state and pass through electromagnetic radiation in a pass state, the first wavelength region being bounded at an upper end by a first band edge; anda thermoreflective element operating across a second wavelength region to block electromagnetic radiation in the hot state and pass through electromagnetic radiation in the cold state, whereina total energy passed through the switchable filter device is optimized to a desired value for each of the block state and the pass state.
  • 17. The switchable filter device of claim 16, wherein the switchable filter device further comprises a photochromic filter combined therewith.
  • 18. The switchable filter device of claim 16, wherein the switchable filter device further comprises a magnetochromic filter combined therewith.
  • 19. The switchable filter device of claim 16, wherein the switchable filter device further comprises an electrochromic filter combined therewith.
  • 20. The switchable filter device of claim 16, wherein at least a portion of second wavelength region is above the first band edge.
  • 21. A switchable filter device comprising an absorptive element operating across a first wavelength region to block electromagnetic radiation in a block state and pass through electromagnetic radiation in a pass state, the first wavelength region being bounded at an upper end by a first band edge; anda reflective element operating across a second wavelength region to block electromagnetic radiation in the block state and pass through electromagnetic radiation in the pass state, whereina total energy passed through the switchable filter device is optimized to a desired value for each of the block state and the pass state.
  • 22. The switchable filter device of claim 21, wherein the switchable filter device further comprises a thermochromic filter combined therewith.
  • 23. The switchable filter device of claim 21, wherein the switchable filter device further comprises an electrochromic filter combined therewith.
  • 24. The switchable filter device of claim 21, wherein the switchable filter device further comprises a photochromic filter combined therewith.
  • 25. The switchable filter device of claim 21, wherein the switchable filter device further comprises a magnetochromic filter combined therewith.
  • 26. The switchable filter device of claim 21, wherein at least a portion of second wavelength region is above the first band edge.
CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority pursuant to 35 U.S.C. §119(e) of U.S. provisional patent application No. 61/256,853 entitled “Infrared stopband filter for use with thermochromic and electrochromic building materials” filed 30 Oct. 2009, which is hereby incorporated herein by reference in its entirety. This application is also related to the following: U.S. Pat. No. 7,768,693; U.S. Pat. No. 7,755,829; U.S. Patent Application Publication No. 2009/0167971; U.S. Patent Application Publication No. 2008/0210893; and U.S. Patent Application Publication No. 2009/0268273, the disclosures of each are hereby incorporated herein by reference in their entirety.

US Referenced Citations (213)
Number Name Date Kind
3990784 Gelber Nov 1976 A
4006730 Clapham et al. Feb 1977 A
4155895 Rohowetz et al. May 1979 A
4268126 Mumford May 1981 A
4456335 Mumford Jun 1984 A
4475031 Mockovciak, Jr. Oct 1984 A
4491390 Tong-Shen Jan 1985 A
4512638 Sriram et al. Apr 1985 A
4579638 Scherber Apr 1986 A
4640583 Hoshikawa et al. Feb 1987 A
4641922 Jacob Feb 1987 A
4688900 Doane et al. Aug 1987 A
4688901 Albert Aug 1987 A
4755673 Pollack et al. Jul 1988 A
4756758 Lent et al. Jul 1988 A
4783150 Tabony Nov 1988 A
4789500 Morimoto et al. Dec 1988 A
4804254 Doll et al. Feb 1989 A
4848875 Baughman et al. Jul 1989 A
4859994 Zola et al. Aug 1989 A
4871220 Kohin Oct 1989 A
4877675 Falicoff et al. Oct 1989 A
4893902 Baughman et al. Jan 1990 A
4899503 Baughman et al. Feb 1990 A
4964251 Baughman et al. Oct 1990 A
5009044 Baughman et al. Apr 1991 A
5013918 Choi May 1991 A
5025602 Baughman et al. Jun 1991 A
5111629 Baughman et al. May 1992 A
5132147 Takiguchi et al. Jul 1992 A
5152111 Baughman et al. Oct 1992 A
5193900 Yano et al. Mar 1993 A
5196705 Ryan Mar 1993 A
5197242 Baughman et al. Mar 1993 A
5212584 Chung May 1993 A
5227115 Harnischfeger Jul 1993 A
5274246 Hopkins Dec 1993 A
5304323 Arai et al. Apr 1994 A
5308706 Kawaguchi et al. May 1994 A
5319478 Funfschilling et al. Jun 1994 A
5347140 Hirai Sep 1994 A
5377042 Chahroudt Dec 1994 A
5481400 Borden Jan 1996 A
5525430 Chahroudi Jun 1996 A
5530263 DiVincenzo Jun 1996 A
5574286 Huston et al. Nov 1996 A
5585640 Huston Dec 1996 A
5757828 Ouchi May 1998 A
5763307 Wang Jun 1998 A
5881200 Burt Mar 1999 A
5889288 Futatsugi Mar 1999 A
5897957 Goodman Apr 1999 A
5937295 Chen Aug 1999 A
5940150 Faris et al. Aug 1999 A
6040859 Takahashi Mar 2000 A
6055089 Schulz et al. Apr 2000 A
6099758 Verrall et al. Aug 2000 A
6122103 Perkins et al. Sep 2000 A
6208463 Hansen Mar 2001 B1
6218018 McKown et al. Apr 2001 B1
6226067 Nishiguchi et al. May 2001 B1
6240114 Anselm May 2001 B1
6260414 Brown et al. Jul 2001 B1
6281519 Sugiyama et al. Aug 2001 B1
6288840 Perkins et al. Sep 2001 B1
6294794 Yoshimura et al. Sep 2001 B1
6304784 Allee Oct 2001 B1
6320220 Watanabe Nov 2001 B1
6329668 Razeghi Dec 2001 B1
6333516 Katoh Dec 2001 B1
6381068 Harada Apr 2002 B1
6437361 Matsuda Aug 2002 B1
6446402 Byker Sep 2002 B1
6486997 Bruzzone et al. Nov 2002 B1
6487112 Wasshuber Nov 2002 B1
6493482 Al-hemyari et al. Dec 2002 B1
6498354 Jefferson Dec 2002 B1
6500555 Khaldi Dec 2002 B1
6504588 Kaneko Jan 2003 B1
6512242 Fan et al. Jan 2003 B1
6559903 Faris et al. May 2003 B2
6583827 Faris et al. Jun 2003 B2
6600169 Stintz Jul 2003 B2
6611640 LoCasclo Aug 2003 B2
6635898 Williams et al. Oct 2003 B2
6661022 Morie Dec 2003 B2
6671008 Li et al. Dec 2003 B1
6710823 Faris et al. Mar 2004 B2
6718086 Ford Apr 2004 B1
6730909 Butler May 2004 B2
6753273 Holonyak, Jr. et al. Jun 2004 B2
6770916 Ohshima Aug 2004 B2
6777718 Takagi Aug 2004 B2
6816525 Stintz Nov 2004 B2
6847662 Bouda Jan 2005 B2
6859114 Eleftheriades Feb 2005 B2
6912018 Faris et al. Jun 2005 B2
6926952 Weber et al. Aug 2005 B1
6933812 Sarabandi Aug 2005 B2
6946697 Pietambaram Sep 2005 B2
6963435 Mallya et al. Nov 2005 B2
6965420 Li et al. Nov 2005 B2
6978070 McCarthy et al. Dec 2005 B1
6985291 Watson Jan 2006 B2
6992822 Ma et al. Jan 2006 B2
7026641 Mohseni Apr 2006 B2
7038745 Weber et al. May 2006 B2
7042615 Richardson May 2006 B2
7046441 Huang May 2006 B2
7068234 Sievenpiper Jun 2006 B2
7099062 Azens et al. Aug 2006 B2
7113335 Sales Sep 2006 B2
7133335 Nishimura et al. Nov 2006 B2
7154451 Sievenpiper Dec 2006 B1
7161737 Umeya Jan 2007 B2
7166797 Dziendziel et al. Jan 2007 B1
7221827 Domash et al. May 2007 B2
7245431 Watson et al. Jul 2007 B2
7276432 McCarthy et al. Oct 2007 B2
7300167 Fernando et al. Nov 2007 B2
7306833 Martin et al. Dec 2007 B2
7318651 Chua Jan 2008 B2
7351346 Little Apr 2008 B2
7385659 Kotchick et al. Jun 2008 B2
7470925 Tamura Dec 2008 B2
7522124 Smith Apr 2009 B2
7532397 Tanaka May 2009 B2
7538946 Smith May 2009 B2
7561332 Little et al. Jul 2009 B2
7619816 Deng Nov 2009 B2
7655942 McCarthy et al. Feb 2010 B2
7755829 Powers et al. Jul 2010 B2
7768693 McCarthy et al. Aug 2010 B2
7911563 Hung Mar 2011 B2
8072672 Powers et al. Dec 2011 B2
8076661 McCarthy et al. Dec 2011 B2
8271241 Akyurtlu Sep 2012 B2
8593581 McCarthy et al. Nov 2013 B2
20020079485 Stintz et al. Jun 2002 A1
20020080842 An Jun 2002 A1
20020085151 Faris et al. Jul 2002 A1
20020114367 Stintz et al. Aug 2002 A1
20020118328 Faris Aug 2002 A1
20020141029 Carlson Oct 2002 A1
20020152191 Hollenberg Oct 2002 A1
20020180916 Schadt et al. Dec 2002 A1
20020190249 Williams Dec 2002 A1
20030059998 Holonyak, Jr. Mar 2003 A1
20030066998 Lee Apr 2003 A1
20030107813 Clabburn et al. Jun 2003 A1
20030107927 Yerushalmi Jun 2003 A1
20030129247 Ju et al. Jul 2003 A1
20030138209 Chan Jul 2003 A1
20030160292 Takagi Aug 2003 A1
20030214632 Ma Nov 2003 A1
20030218712 Kumar et al. Nov 2003 A1
20030227663 Agrawal Dec 2003 A1
20040005451 Kretman et al. Jan 2004 A1
20040012749 Freeman Jan 2004 A1
20040036993 Tin Feb 2004 A1
20040256612 Mohseni Dec 2004 A1
20050068629 Fernando et al. Mar 2005 A1
20050185125 Miyachi Aug 2005 A1
20050221128 Kochergin Oct 2005 A1
20050271092 Ledentsov Dec 2005 A1
20060011904 Snyder et al. Jan 2006 A1
20060118514 Little et al. Jun 2006 A1
20060147810 Koch Jul 2006 A1
20060151775 Hollenberg Jul 2006 A1
20060257090 Podolskiy Nov 2006 A1
20060262398 Sangu et al. Nov 2006 A1
20060274218 Xue Dec 2006 A1
20070070276 Tan Mar 2007 A1
20070121034 Ouderkirk May 2007 A1
20070215843 Soukoulis et al. Sep 2007 A1
20070279727 Gandhi Dec 2007 A1
20080008857 Kalkanoglu et al. Jan 2008 A1
20080013174 Allen et al. Jan 2008 A1
20080061222 Powers et al. Mar 2008 A1
20080117500 Narendran et al. May 2008 A1
20080138543 Hoshino et al. Jun 2008 A1
20080160321 Padiyath et al. Jul 2008 A1
20080204383 McCarthy et al. Aug 2008 A1
20080210893 McCarthy et al. Sep 2008 A1
20080246388 Cheon Oct 2008 A1
20080259254 Kikuchi et al. Oct 2008 A1
20090015902 Powers et al. Jan 2009 A1
20090040132 Sridhar Feb 2009 A1
20090059406 Powers et al. Mar 2009 A1
20090128893 McCarthy et al. May 2009 A1
20090128907 Takahashi et al. May 2009 A1
20090167971 Powers et al. Jul 2009 A1
20090219603 Xue Sep 2009 A1
20090266394 Tsubone Oct 2009 A1
20090268273 Powers et al. Oct 2009 A1
20090296190 Anderson et al. Dec 2009 A1
20100001008 McCarthy et al. Jan 2010 A1
20100015363 Chiang et al. Jan 2010 A1
20100027099 McCarthy et al. Feb 2010 A1
20100045924 Powers et al. Feb 2010 A1
20100051898 Kim, II Mar 2010 A1
20100060844 Sawatari et al. Mar 2010 A1
20100118380 Xue May 2010 A1
20100232017 McCarthy et al. Sep 2010 A1
20100259698 Powers et al. Oct 2010 A1
20100271686 Powers et al. Oct 2010 A1
20100288947 McCarthy et al. Nov 2010 A1
20110025934 McCarthy et al. Feb 2011 A1
20110044061 Santoro et al. Feb 2011 A1
20110102878 McCarthy et al. May 2011 A1
20110216254 McCarthy et al. Sep 2011 A1
20110234944 Powers et al. Sep 2011 A1
20110292488 McCarthy Dec 2011 A1
Foreign Referenced Citations (50)
Number Date Country
1189224 Jul 1998 CN
1350648 May 2002 CN
1494091 May 2004 CN
1162496 Dec 2001 EP
2261989 Jun 1993 GB
49-94145 Jun 1974 JP
58 10717 Jan 1983 JP
59-231516 Dec 1984 JP
61223719 Oct 1986 JP
1178517 Jul 1989 JP
02-089426 Mar 1990 JP
05-147983 Jun 1993 JP
06-158956 Jun 1994 JP
07-043526 Feb 1995 JP
08-015663 Jan 1996 JP
09-124348 May 1997 JP
63-127594 Aug 1998 JP
10-287449 Oct 1998 JP
10-311189 Nov 1998 JP
2002-520677 Jul 2002 JP
2002-357815 Dec 2002 JP
2003-248204 Sep 2003 JP
2004-004795 Jan 2004 JP
2004-012818 Jan 2004 JP
2004-291345 Oct 2004 JP
2005-250119 Sep 2005 JP
2006-243485 Sep 2006 JP
2006-285242 Oct 2006 JP
2007-515661 Jun 2007 JP
2007-272016 Oct 2007 JP
2008-530766 Aug 2008 JP
2002-0044153 Jun 2002 KR
2003-0072578 Sep 2003 KR
1020040048916 Jun 2004 KR
10-2004-0108816 Dec 2004 KR
1020060000059 Jan 2006 KR
10-2007-0091314 Sep 2007 KR
10-2010-0039401 Apr 2010 KR
9402313 Feb 1994 WO
WO-9701789 Jan 1997 WO
0123173 Apr 2001 WO
02064937 Aug 2002 WO
WO-03029885 Apr 2003 WO
03096105 Nov 2003 WO
2005031437 Apr 2005 WO
WO-2006023195 Mar 2006 WO
2006088369 Aug 2006 WO
WO-2008092038 Jul 2008 WO
WO-2008106596 Sep 2008 WO
2008144217 Nov 2008 WO
Non-Patent Literature Citations (31)
Entry
Fan, et al., “Thin-film conducting microgrids as transparent heat mirrors”, Appl. Phys. Lett., vol. 28, No. 8, Apr. 5, 1976, 440-442.
Iyer, “Negative-Refraction Metamaterials: Fundamental Principles and Applications”, IEEE Press, John Wiley & Sons, Chapter 1, 2005, 4-5,16-30,321-330.
Author Unknown, “Liquid Crystal Research”, http://chirality.swarthmore.edu, printed Aug. 21, 2009.
Barbagallo, S., et al., “Synthesis of novel metamaterials,” Chapter 2 (VDM Verlag 2008).
Eleftheriades, G.V., et al. (Editors); Iyers, “Negative-Refraction Metamaterials,” Chapter 1 (Wiley 2005), pp. 4-5, 16-30, 321-330.
Fedotov, V. A., et al., “Asymmetric Propagation of Electromagnetic Waves through a Planar Chiral Structure,” The American Physical Society, PRL 97, Oct. 20, 2006, pp. 167401-1-167401-4.
Ginley, D. S., et al., “Transparent Conducting Oxides,” MRS Bulletin, Aug. 2000, pp. 15-18.
Goldhaber-Gordon, David, et al., “Overview of Nanoelectronic Devices,” Proceedings of the IEEE, vol. 85, No. 4, (Apr. 1997), pp. 521-533.
Hao, J. et al., “Manipulating Electromagnetic Wave Polarizations by Anisotropic Metamaterials,” Physical Review Letters, 2007, vol. 99, No. 063908.
Harrison, “Quantum Wells, Wires, and Dots: Theoretical & Computational Physics of Semiconductor Nanostructures” 2nd Edition, John Wiley & Sons, LTD (2005), 3 pages.
Lan, S., et al., “Survey on Roller-type Nanoimprint Lithography (RNIL) Process,” International Conference on Smart Manufacturing Application, Apr. 9-11, 2008, in KINTEX, Gyeonggi-do, Korea, pp. 371-376.
Leatherdale, C.A., et al., “Photoconductivity in CdSe Quantum Dot Solids,” Physical Review B, vol. 62, No. 4, (Jul. 15, 2000) pp. 2669-2680.
Manea, E., et al., “Optical Characterization of SnO2 thin Films Prepared by Sol Gel Method, for ‘Honeycomb’ Textured Silicon Solar Cells,” International Semiconductor Conference, 2006, vol. 1, Issue, Sep. 2006, pp. 179-182.
Manea, E., et al., “SnO2 Thin Films Prepared by Sol Gel Method for ‘Honeycomb’ Textured Silicon Solar Cells,” Romanian Journal of Information Science and Technology, vol. 10, No. 1, 2007, pp. 25-33.
Padilla, W.J., et al., “Electrically resonant terahertz metamaterials: Theoretical and experimental investigations,” Physical Review B 75, 041102(R) (2007).
Rogacheva, A.V., et al., “Giant gyrotropy due to electromagnetic-field coupling in a bilayered chiral structure,” Physical Review Letters 97, 177401 (Oct. 27, 2006).
Sarychev, et al., “Negative refraction metamaterials,” Chapter 8 (Wiley 2005).
Siegel, J. D., “The MSVD Low E ‘Premium Performance’ Myth,” International Glass Review, Issue 1, 2002, pp. 55-58.
Sung, J., et al., “Dynamics of photochemical phase transition of guest/host liquid crystals with an Azobenzene derivative as a photoresponsive chromophore,” Chemistry of Materials, vol. 14, No. 1, pp. 385-391, Jan. 21, 2002.
West, J. L., et al., “Characterization of polymer dispersed liquid-crystal shutters by ultraviolet/visible and infrared absorption spectroscopy,” Journal of Applied Physics, vol. 70, No. 7, pp. 3785-3790, Oct. 1, 1991.
Zhang, W., Giant optical activity in dielectric planar metamaterials with two-dimensional chirality, Journal of Optics A: Pure and Applied Optics, 8, pp. 878-890 (2006).
Korean Intellectual Property Office as International Searching Authority, International Search Report and Written Opinion for International Application No. PCT/US2008/051959, Jun. 6, 2008, 10 pages.
Korean Intellectual Property Office as International Searching Authority, International Search Report and Written Opinion for International Application No. PCT/US2008/069881, Sep. 30, 2008, 10 pages.
Korean Intellectual Property Office as International Searching Authority, International Search Report and Written Opinion for International Application No. PCT/US2008/087964, Mar. 31, 2009, 12 pages.
Korean Intellectual Property Office as International Searching Authority, International Search Report and Written Opinion for International Application No. PCT/US2009/041576, Nov. 25, 2009, 7 pages.
Notice of Allowance, U.S. Appl. No. 12/019,602, dated Jun. 9, 2010 (now Pat. 7,768,693).
Notice of Allowance, U.S. Appl. No. 12/172,156, dated Mar. 11, 2010 (now Pat 7,755,829).
Notice of Allowance, U.S. Appl. No. 12/843,218, dated Apr. 12, 2011.
Yamazaki, et al., “Polarisation-insensitive parametric wavelength conversion without tunable filters for converted light extraction”, Eletronic Letters, IEE Stevenage, GB, vol. 42, No. 6, Mar. 16, 2006, 365-367.
PCT Application No. PCT/US2010/054844.
United States Patent and Trademark Office as International Searching Authority, International Search Report and Written Opinion for International Application No. PCT/US2010/054844, Jul. 28, 2011, 9 pages.
Related Publications (1)
Number Date Country
20110102878 A1 May 2011 US
Provisional Applications (1)
Number Date Country
61256853 Oct 2009 US