text:
|Publication number
|Publication type
|Application number
|PCT number
|Publication date
|Jan 2, 2007
|Filing date
|Sep 16, 2004
|Priority date
|Sep 16, 2003
|Fee status
|Also published as
|Publication number
|Brian A Gregg
|Original Assignee
|Midwest Research Institute
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (8), Non-Patent Citations (4), Referenced by (20), Classifications (33), Legal Events (7)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is the National Stage of International Application No. PCT/US04/30201, filed Sep. 16, 2004, which claims the benefit under 35 U.S.C. �119(e) of U.S. Provisional Application 60/503,336, filed Sep. 16, 2003.
The present invention relates generally to photovoltaic cells and semiconductors and their manufacture, and more particularly, to organic photovoltaic cells and methods of manufacturing bi-layer organic photovoltaic cells with improved solar conversion efficiencies achieved by controlling the amount of recombination occurring at the p-n heterojunction or interface between the p-type and n-type semiconductor layers.
The conversion of solar energy into electrical energy is becoming more important as costs and shortages of more standard energy sources continue to increase. Standard solar cells made from inorganic semiconductors, such as silicon cells, have been studied since the 1950s and have been used as renewable electric power sources for generating power in a wide variety of applications ranging from orbiting satellites to solar farms to portable devices. While relatively efficient, inorganic solar cells often have high dollar and environmental costs associated with manufacturing as the cells are made of toxic materials that typically have to be grown as a single large crystal.
More recently, solar cells utilizing organic materials have appeared, which has raised the intriguing possibility of solar cells that are relatively inexpensive and can be fabricated on flexible substrates. It is envisioned that organic solar cells could be fabricated or even painted on large flexible substrates, which would allow the created cells to be folded or rolled up in a briefcase or backpack, to be worn, or to be deployed to provide electricity for wearable electronics, for recharging batteries, and for low-power devices. Unfortunately, the solar conversion efficiencies of existing organic solar or photovoltaic (PV) cells is typically less than 10 to 20 percent of the solar conversion efficiencies obtainable in inorganic PV cells or in some cases, only 1 to 2 percent conversion efficiency. There is a need to find a method of producing organic PV cells that are more efficient in converting solar energy to electricity and that still provide the advantages of working with organic materials, i.e., being inexpensive and relatively easy to manufacture in high volumes on flexible substrates. Once such a manufacturing method is found, flexible organic solar cells likely will be widely used to provide efficient distributed power to homes and buildings and to provide power in applications requiring portability, such as many military and consumer uses.
In developing an improved technique of manufacturing organic solar cells, it is important to understand the differences between organic solar cells and the more common inorganic solar cells and to understand manufacturing problems associated with organic solar cells. A key difference between organic photovoltaic (OPV) cells and conventional inorganic photovoltaic (IPV) cells, e.g., the silicon p-n junction cell, is the relative importance of interfacial processes between layers of semiconductor materials (such as between p-type and n-type semiconductor layers). This difference is closely related to the charge generation mechanism needed for producing a useful PV cell. In IPV cells, electron-hole pairs are generated immediately upon light absorption throughout the bulk of the material according to the exponential decrease of the incident light intensity. Since the electrons and holes are distributed spatially within the same material, the photoinduced chemical potential energy gradient drives both the electrons and holes in the same direction and recombination of the holes and electrons needs to be controlled throughout the bulk.
In contrast, light absorption in OPV cells typically results in the production of a mobile excited state, i.e., a tightly bound electron-hole pair often called an exciton, rather than a free electron-hole pair. Dissociation of the excitons occurs at the heterointerface between two dissimilar organic semiconductor materials or layers. Hence, light absorption results in free electrons in one of the two semiconductor materials and free holes on the other side of the interface in the other semiconductor material, with the free electrons and holes being driven in opposite directions away from the interface. In other words, carrier generation is simultaneous to, and identical with, carrier separation across the interface in OPV cells. Recombination of the free electrons with the holes is a bane of IPV and OPV cells. However, due to the differences in the dissociation mechanisms of OPV and IPV cells, recombination is a particular problem at the interface in OPV cells. Recombination is a larger problem at the interface in OPV cells due to the much larger concentration of carriers at the interface when compared to IPV cells in which the carriers are distributed in the bulk.
In practice, a uniform electric field is typically applied across the PV cell to cause the electrons to separate from the paired holes. This is an effective approach for IPV cells in which the electrons can only be separated from the holes by applying such an electrical potential-energy gradient, but application of a uniform electric field across the bulk has not proven effective in OPV cells where a critical efficiency limitation is recombination at the interface of the two semiconductor layers. More particularly, under "forward" bias, the OPV cell typically will only produce small current levels as a consequence of this interfacial recombination and of electrons being photogenerated on one side of an interface and holes on the other. When the applied bias drives the photogenerated carriers back toward the interface (i.e., forward bias for a p-n junction), the carriers typically recombine and only a small number is thermally emitted over the heterointerface energy barrier (i.e., an energy band diagram shows an energy offset at the interface).
To enhance efficiency including addressing a low forward bias current, IPV cells rely on the ability to dope semiconductors precisely both in magnitude and spatial extent. Unfortunately, doping of organic materials is a difficult and often impractical process that has not addressed the low efficiency issues in OPV cells. One difficulty with doping in OPV cells is that the integrity of the organic semiconductor materials are often chemically or morphologically disturbed, which can create exciton traps or quenching cites that block diffusion and/or cause recombination.
Crystalline organic semiconductors have been shown to have superior optical and electrical characteristics when compared to amorphous films of the same materials. However, single crystals of organic semiconductors generally cannot be used for devices, such as for OPV cells, because the crystals are quite small, i.e., 0.1 to 10 μm, and do not adhere well to most substrates or to other organic semiconductors. This lack of good adhesion is a problem that must be addressed in manufacturing an OPV cell because good crystal-to-crystal contact is required throughout the cell to maintain electron and hole paths. When the conventional method of sublimation is used to apply organics to a surface, the resulting film is commonly amorphous or nanocrystalline but is usually not strongly adherent and often causes serious interfacial adhesion problems. Attempts have been made to address this problem with annealing by heating or exposing the films to a solvent vapor, but to date, the resulting crystalline films have had numerous pinholes that have led to semiconductor devices with unacceptable electrical shorts.
Hence, there remains a need for improved organic photovoltaic cells, and methods of manufacturing such cells, that provide enhanced solar conversion efficiency while facilitating the manufacture of high efficiency, inexpensive, and flexible organic solar cells. Preferably, such cells will address the problem of recombination at the heterojunction interface while utilizing readily available and inexpensive materials that can be processed utilizing relatively well-known manufacturing techniques.
The present invention addresses the above problems by providing an improved method for fabricating photovoltaic or solar cells. In general, the method uses nanocrystalline semiconductors that are dispersed in a polymeric binder, such as epoxy cement, to create a bi-layer organic photovoltaic (OPV) cell. In one embodiment, n-type PPyEI is dispersed in epoxy and coated on a flexible contact or substrate and p-type TiOPc is dispersed in epoxy and coated in a thin film on a flexible contact or substrate. The n-type film is then bonded to the p-type film, such as with hot rolling or annealing, to form the bi-layer cell. In many embodiments, the process includes building in an electric field at the interface between the p-type and n-type films, i.e., the p-n heterojunction or interface. For example, charge additives (i.e., materials that provide cations and anions, respectively) are dispersed in the n-type material and in the p-type material before application to the contacts. Upon bonding of the semiconductor films, uncompensated positive and negative charges or cations and anions are produced proximal to the interface or p-n heterojunction, which results in an electric field being integrally formed with the OPV cell at the interface or being dropped at the interface rather than uniformly across the cell as in prior cells. While the cell fabrication method is particularly useful in solving numerous problems related to the use of organic semiconductors in solar cells, the method may be modified to employ inorganic semiconductor nanocrystals (such as quantum dots, quantum rods, and the like) in place of or in combination with the nanocrystalline organic semiconductors.
The method of the invention and cells fabricated according to the method address a number of problems previously associated with using organic materials to form solar cells. The method effectively controls the generation of pinholes in crystalline films associated with doping of organic semiconductors and, thus, allows the use of single crystal semiconductors that provide superior mobilities and exciton diffusion lengths. The method utilizes polymers that are readily available, are easily processed with known polymer fabrication techniques, and create a flexible finished product, e.g., OPV cells that are flexible and durable. The nanocrystalline organic semiconductors can be selected to achieve both a desired effective bandgap, such as about 1.4 eV, and a thickness that is relative small such that cells of the invention absorb light without adding unnecessary resistance, wasting energy, or adding material costs (e.g., cells manufactured according to the method of the invention can absorb all or nearly all sunlight with wavelength in the range of 350 to 900 nm).
The bonding techniques of the method and materials selections, such as using epoxy or other polymers, lends itself to providing effective bonding at the p-n interface and crystal-to-crystal contact. These techniques eliminate, or at least better control, the serious interfacial adhesion problem of prior organic semiconductor devices. The OPV cells made according to the invention may be utilized in numerous manners and products such as in conventionally designed solar cell devices, in power windows that incorporate the OPV cells of the invention with contacts and p and n-films selected to be transparent or partially transparent to visible light, and in other products.
According to one aspect of the invention, PV cells are formed that provide the desired concentrated interfacial electric field with one or both of the binder layers made from polymers that already contain ionic groups. These cells do not require added cation or anion additives. In one example, poly(vinylpyridine) is quaternized with, for example, methyl iodide to produce a polymer with bound cationic groups. Such a polymer is then used as the binder layer for the n-type side without any additional ionic additives. Likewise, commercially available poly(styrene) terminated with sodium carboxylate groups or other similar materials are used for the binder layer for the p-type side without any additional ionic additives.
According to another aspect of the invention, the method is modified such that the bound ions are incorporated into the OSCs (crystalline organic semiconductors) themselves, rather than into the binders. For example: (1) PPyEI can be partially quaternized to create bound positive charges; and (2) TiOPc can be partially sulfonated to create bound negative charges. These OSCs with bound ions can then be dispersed in electrically neutral polymer binders to provide the same overall effect of applying an electric field at the interface between the two semiconductor layers and of controlling recombination in the cell.
The present invention is directed generally to a method of fabricating a bi-layer organic photovoltaic (OPV) cell that includes dispersing semiconductor nanocrystals in a binder, such as a polymer binder (e.g., an epoxy) that is applied to conductive substrates to form an n-type substrate and a p-type substrate. The two substrates are then bound together such that there is good adhesion between the n-layer and p-layer and crystals within these layers to form a bi-layer OPV cell with improved efficiency (i.e., up to 5 percent or more whereas existing OPV cells typically have 2 percent or lower efficiencies). As will become clear from the following description, one important aspect of the method of the invention is building an electric field at the p-n heterojunction or interface between the semiconductor films so as to control detrimental recombination which occurs almost solely at this interface. The electric field is provided integral to the OPV cell by covalently binding ions to the binder in each of the p-layer and the n-layer, with oppositely charged ions dispersed in each layer near the interface.
The inventor recognized that OPV cells in general have differing characteristics than inorganic PV cells and that disassociation occurs at the p-n heterojunction. Further, the heterojunction is the location of all or most of the recombination of free electrons and holes. Prior devices applied the electric fields at the ends of the cells, which created a relatively constant or uniform electric field across the cell. This led to very inefficient organic PV cells with a significant amount of recombination occurring at the junction or interface. The inventor further recognized that organic PV cells differ from inorganic PV cells in that excitons are formed rather than relatively uniform electron-hole pairs as with inorganic PV cells, and further, the band diagram for an organic PV cell shows a significant offset at the junction or interface.
With an understanding of these differences between organic and inorganic PV cells, the inventor designed the method of the present invention for dropping or applying a concentrated electric field or dipole at or near the p-n heterojunction or semiconductor interface so as to control recombination, i.e., to apply the energy in a built-in manner at the location in the cell where the energy is most needed to allow electron flow through the cell. The following description stresses the use of the fabrication method for producing OPV cells, but the fabrication method is equally applicable to nanocrystalline inorganic semiconductors, such as quantum dots, quantum rods, and the like, which may be used in place of or in combination with nanocrystalline organic semiconductors to, in some cases, provide an even more effective solar cell.
Preferably, the nanocrystals selected for the p and n layers of the cell are selected to provide an effective bandgap that is at or near the optimal effective bandgap of 1.4 eV. In one embodiment, the nanocrystals are organic semiconductors comprising n-type PPyEI and p-type TiOPc. However, numerous other semiconductor crystals could be used to practice the invention with this selection being only exemplary of one pair that provides a 1.4 eV bandgap with materials that are readily available and processible. The quantity of crystals or ratio relative to other materials in the p and n layers is preferably as high as practical to still allow proper binding so as to provide better crystal-to-crystal contact. In this regard, the n-type and p-type crystals may make up 40 to 70 percent or more and typically, around 60 percent of the material volume in these layers (with the specific volume percentage of the materials varying somewhat with the particular materials selected).
As discussed below, a built-in electric field at the interface is provided by dispersing a small quantity, such as less than about 5 percent by volume, of charge additives or cation additives and anion additives to provide uncompensated charges at the interface upon bonding of the p and n layers. The electric field is produced by covalently binding ions to the binder, such as an epoxy. On the n-type side, one useful charge additive is quaternized triethanolamine, and on the p-type side, several charge additives can be used such as glycerol-2-phosphate, glucose-6-phosphate, and the like (while solubility issues with some solvent materials used in forming the p and n layers should be considered). The important point for creating OPVs is that the materials selected for the charge additives be such that positive charges or positively charged ions are produced in the n-layer near the interface and negative charges or negatively charged ions are produced in the p-layer near the interface so as to produce the desired electric field or dipole to control recombination.
The materials selected for the contact layers or substrates may be nearly any useful contact materials well known in the semiconductor and solar cell industry. In many embodiments, the substrate is formed so as to be flexible which can be achieved using relatively thin substrates of materials such as aluminum (AL), stainless steel, indium tin oxide (ITO) or ITO on a polymer, and the like. In some cases, one contact is a reflector, such as AL, with the other contact allowing sunlight to pass freely, i.e., is transparent, such as ITO. In other cases, such as in the power window example discussed below, it is preferable that the materials selected for both contacts be transparent or at least partially transparent (as well as the semiconductor crystals selected).
Crystalline organic semiconductors (OSCs) have superior optical and electrical characteristics compared to amorphous films of the same materials. A problem that has to be overcome, though, is that single crystals of OSCs have not been successfully used for devices because the crystals are quite small (e.g., 0.1 to 10 μm) and do not adhere well to most substrates or to other organic semiconductors. This lack of good adhesion across interfaces is a major problem for the use of organic semiconductors, even as amorphous films. The following method steps are believed to address this adhesion problem and to allow OSCs to be effectively utilized in a bi-layer OPV cell.
Referring again to
At 130, a thin p-layer or film is formed on the p-substrate. Generally, step 130 includes mixing a binder, such as epoxy, with nanocrystalline organic semiconductors. In one embodiment, nanocrystalline OSCs are dispersed in a polymer matrix at a high concentration (such as about 60 percent by volume) with the polymer simply being used as a binder with its concentration kept to a practical minimum. Dispersion is achieved by ball milling (or some other appropriate technique for mixing the polymer matrix and OSCs) the nanocrystalline powder with a polymer and a solvent. Then, the dispersion is formed on the substrate such as with spin coating, blade coating, and the like to make a film on the substrate. To provide a built-in electric field, a charge additive is also dispersed at a much lower volume, such as less than 5 percent by volume, during the mixing or dispersing portion of step 130. The charge additive generally provides an anion to provide an uncompensated negative charge after bonding at 160 and may take many forms including glycerol-2-phosphate, glucose-6-phosphate and other anion providers.
At 140, the n-substrate or second contact is fabricated (or received as a pre-fabricated piece) in a manner similar to that described for the p-substrate or first contact at 120. At 150, a thin n-layer or film is formed on the n-substrate. As with step 130, the n-layer is formed by first dispersing, such as with ball milling or other techniques, a volume of organic (or in some cases, inorganic) nanocrystals in a polymer matrix usually in powder form. Solvent or other mixing additives are used to facilitate the mixing of these components of the n-layer. In one embodiment, the noncrystals are n-type PPyEI crystals and a cation additive is also dispersed during 150 so as to provide cations at the interface upon binding of the n-layer to the p-layer. The percent by volume of each component may vary to practice the invention with the organic semiconductor nanocrystals preferably making up the largest percentage, such as up to 60 percent, the cation additive (such as quarternized triethanolamine, and the like) being a relatively small percentage such as 1 to 5 percent, and the polymer matrix and solvent being the remaining volume of the material for the n-layer.
While numerous polymers and other materials may be used for the binder portion of the n and p layers, epoxy or epoxy cements (such as b-phase epoxy polymer) are one preferred binder material. There are several reasons for this choice: (1) epoxies wet numerous types of surfaces extremely well, which should eliminate or control adhesion problems at the interface and also minimize or control the number of pinholes in the resulting films or layers; (2) once cross-linked (i.e., cured), epoxies are rugged, flexible, and practically insoluble; (3) because of the epoxy polymer chemistry, it is easy to add extra functionalities that will be immobilized (i.e., covalently bound) during the curing process, such as the charge additives; (4) epoxies can have excellent transparencies from the near ultraviolet to approximately 2500 nm wavelengths while also having high dielectric breakdown potentials; (5) epoxies have refractive indexes nearly identical to glass, which will minimize reflective losses; (6) decades of experience have made epoxy polymers one of the engineering polymers of choice for a wide range of applications, which should result in manufacturing of solar cells based on epoxy films being simple and inexpensive. In addition to epoxy, other polymer binders may be useful such as cross-linkable polymers, e.g., polyurethanes, polyacrylates, and the like.
Referring again to
In some embodiments, byproducts of the bonding process include mobile ions (such as water, HCl, precipitating ions (e.g., NaCl and other salts) and the like) produced when the cation and anion additives react to produce uncompensated positive and negative charges or charged particles in the p and n layers. Hence, at 170, the method 100 may include a step of removing these mobile counter ions such as by applying a vacuum to the interface. In other embodiments, step 170 is not performed and the counter ions are allowed to remain in the bi-layer substrate. At 180, the bi-layer substrate is further processed to form a finished product, such as by cutting the substrate to a desired shape and size and adding leads to the first and second contacts to form an OPV solar cell, using the substrate as part of a window fabrication process to produce a power window (such as by using the substrate with leads as one or more panes in a window or in addition to glass panes), and by otherwise including the bi-layer product (basic OPV cell of the invention) as part of products that utilize a component for converting light to electrical energy. As can be seen from the above discussion, the method 100 provides a low energy, low temperature, low cost manufacturing process that provides many advantages over existing inorganic PV cell manufacturing methods.
The formation of an OPV (or IPV) cell according to the method 100 can be seen in
The bi-layer substrate 300 effectively addresses problems associated with prior organic solar cells. The bi-layer substrate or PV device 300 is preferably made from ultrathin films 308, 316 (i.e., 100 nm or less, and more preferably about 50 nm or less in thickness). The exciton-dissociating interface 320 between the p side 308 and n side 316 ensures the facile generation of electrons and holes from the initially formed excitons (e.g., at first exposure to light at one of the contacts 204, 212). Such cells or devices 300 do not require illumination through a semi-transparent metal electrode, as one of the contacts 204, 212 may be transparent, such as a F—SnO2 contact.
The use of ultrathin films 308, 316 minimizes or limits resistive losses with 50 nm typically being all that is needed in thickness of each film 308, 316 to absorb all or most of the received light. Even without the inclusion of charge additives in the layers 308, 316 these cells 300 are expected to have a relatively high efficiency, such as up to 5 percent or more, relative to existing OPV cells, with efficiency being limited by interfacial carrier recombination at the p-n junction 320 and to a lesser degree by the relatively slow transport from one crystal to another through the polymer binder. To further improve efficiency by 20 or more times, the charge additives are included in the layers 208, 216 such that upon bonding the layers 308, 316 include oppositely charged areas 322, 324 that create a dipole or electric field at the interface 320.
One aspect of the invention is creating OPV cells with an electric field integrally formed at the p-n junction or interface. This is an important aspect of the invention as conventional inorganic solar cells relied on doping of semiconductors precisely both in magnitude and in spatial extent, but this is very difficult if not impossible with organic semiconductors. The dropping of the built in field at the interface aspect of the invention is achieved by separating electrically inert ions in the two abutting p and n films, and this results in an effect almost identical to doping for an organic semiconductor in the electric field. The process of forming this field may include a variety of steps and processes but generally involves separating ions that are external to the semiconductor crystals, which allows any semiconductor to be used, as no chemical changes to the semiconductor are required. In other words, intrinsic semiconductors of any kind that reside in an electric field will behave as if they are doped. Specifically, if a bi-layer film (layers 308, 316 of
This is illustrated in simplified form in
To further explain the creation of an electric field at the p-n heterojunction or semiconductor layer interface, it may be useful to provide another example of the manufacture of an OPV cell according to the invention (such as with method 100 or a method that varies in some ways from method 100). Generally, charge additives are provided in the form of salts in which the cation (for the n-type side) and the anion (for the p-type side) will react with the epoxy (or other polymer binder) as it cures and therefore, is covalently bound in place. In some embodiments, the reactive half of the salt or charge additive may contain multiple alcohol groups. Alcohols react with epoxy adhesives only under force conditions during curing (i.e., at high temperatures) and will, therefore, not cause the premature crosslinking of the polymer binder or epoxy. The counter ions produced upon binding of the semiconductor layers preferably are small and exchangeable, such as with the negative OH ion and the positive H ion. One useful pair of salts is triethanolamine quaternized with 1-bromobutane (n-type) and glycerol-2-phosphate, sodium salt (p-type).
The exemplary process includes adding glycerol-2-phosphate, sodium salt to epoxy and TiOPc (titanyl phthalocyanine) in appropriate solvent (e.g., ethyl acetate). The mixture is then ball milled or otherwise mixed until well dispersed. A thin film (such as about 50 to 250 nm or about 150 nm or less) is made on F—SnO2 (note, it is preferable for this step to use a TiOPc particle size less than 50 nm to achieve the desired layer thickness). The epoxy is then cured, such as by heating at about 120� C. for about 2 hours. The substrate is soaked in dilute aqueous toluene sulfonic acid to exchange the sodium for protons without allowing anions, i.e., tosylates (excluded by size), to enter the film. The substrate is then soaked in deionized water to remove any adsorbed ions and then dried.
The process further includes adding triethanolamine quaternized with 1-bromobtane to epoxy and PPyEI (perylene-bis-2-pyridylethylimide) in appropriate solvent and ball milled until well dispersed. A thin film, such as about 150 nm thick or less, of the mixed materials is formed on top of the already deposited TiOPc film (note, it is preferable for this step to use PPyEI particles that are less than about 150 nm to achieve the desired layer thickness). The epoxy is then cured and the new multi-layer substrate is soaked in dilute aqueous TBAOH to exchange the bromide for the negative OH ions. The substrate is then soaked in deionized water to remove adsorbed ions and dried.
The bi-layer films are then dehydrated in a vacuum oven at a raised temperature, such as up to 150� C. or higher. This step is useful for removing a portion of the mobile counter ions (such as positive H ions and negative OH ions that have formed volatile water) leaving a macroscopic electric field across the p-n junction or interface between the semiconductor layers. The maximum interfacial potential difference resulting from this manufacturing approach should be about 1 V. The spatial extent of the electric field is controlled by the concentration of ions, just as the doping density controls the spatial extent of the space charge region in inorganic solar cells. Concentrating the field just over the exciton-dissociating heterojunction, rather than having it drop uniformly across the whole device, is important in achieving high efficiency in cells made according to the method. The aluminum back contact is provided, such as by evaporating, and the bi-layer OPV cell can be encapsulated with a sealant, such as silicone sealant, to avoid rehydration, which would diminish the built-in electric field.
Because the method of manufacturing improved solar cells, such as OPV cells with an electric field concentrated at the p-n heterojunction, is versatile, it is easy to envision numerous products that can be made with such solar cells and extensions of the invention to new applications. One implementation (in addition to standard uses of and products that include PV cells which are within the breadth of the description) that could readily utilize PV cells manufactured by the methods of the invention is power windows. Generally, power windows are solar cells that are transparent in the visible region and, thus, can serve as optical windows while simultaneously generating power from the non-visible light that the solar cell absorbs. Most inorganic semiconductors are not amenable to power window applications because they have wide conduction bands and, thus, absorb light for 2 to 3 eV beyond their absorption threshold. To be transparent, most inorganic semiconductors must therefore have bandgaps greater than about 3 eV and can correspondingly absorb only a tiny fraction of the incident solar flux. Organic semiconductors, on the other hand, have narrow bandwidths and absorb light only over a specific range of energy.
With this in mind, one embodiment of the invention involves producing a solar cell manufactured according to method 100 of
The above disclosure sets forth a number of embodiments of the present invention. Other arrangements or embodiments, not precisely set forth, could be practiced under the teachings of the present invention and as set forth in the following claims. Again, it should be understood that the methods of fabricating a PV cell with a built-in electric field at the p-n heterojunction are very general in application. For example, these techniques can be used with almost any nanocrystalline semiconductor, organic or inorganic, with a large number of polymer binders, and a large number of charge additives (e.g., large number of salts). The PV cells that can implement the ideas of the invention may include multiple variations while still being understood and covered by the general ideas described above and claimed below.
Another preferred embodiment of the invention is to form PV cells with one or both of the binder layers made from polymers that already contain ionic groups. Therefore, they do not require added cation or anion additives. For example: poly(vinylpyridine) can be quaternized with, for example methyl iodide, to produce a polymer with bound cationic groups. Such a polymer can be used as the binder layer for the n-type side without any additional ionic additives. Likewise, commercially available poly(styrene) terminated with sodium carboxylate groups can be used for the binder layer for the p-type side without any additional ionic additives. As will be appreciated by those skilled in the art, the methods and cells in this description are substantially broader than simply cells that use epoxies or other polymers with added ionic groups. Instead, once the concept of applying or dropping an electric field at the p-n heterojunction is understood extensions of the inventive method and resulting PV cells will be apparent to many in the field of solar cells.
In yet another embodiment, the bound ions are incorporated into the OSCs themselves, rather than into the binders. For example: (1) PPyEI can be partially quaternized to create bound positive charges; and (2) TiOPc can be partially sulfonated to create bound negative charges. These OSCs with bound ions can then be dispersed in electrically neutral polymer binders to provide the same overall effect of applying an electric field at the interface between the two semiconductor layers and of controlling recombination in the cell.
As can be seen from the foregoing discussion with reference to
By itself, the use of charge additives is useful for generating a substantial electric field. Further, the magnitude of this equilibrium field can be enhanced in several ways. If volatile, the mobile ion pairs (such as H2O or HCL) can be removed by heat and vacuum applied during the annealing process, thereby shifting the equilibrium toward a higher field. If performed under reverse electrical bias, the shift is even greater. If the solubility product of the mobile ion pairs is low in the polymeric binder, ionic species (such as NaCl) precipitate, again shifting the equilibrium. Additionally, the mobile ions from each film can be expelled (for example, electrochemically) before the films are brought into contact. This allows, in principle, the setting of any desired interfacial potential that is less than the heterojunction bandgap (1.4 eV in some of the above-described examples). Of course, there are numerous other possible methods for enhancing the electric field obtained according to the invention.
The end result of any of these procedures is the creation of a large electrical field dropping across the junction between the n-type and p-type sides, rather than across the bulk of the device as in other OPV cells. The width of this space charge region is inversely proportional to the total concentration of dopants (not the ionized concentration). Therefore, it can be adjusted at will and made to extend more over one side (e.g., the p-type side) than the other if this is desirable. As discussed above, the films may be formed separately on their individual substrates and subsequently laminated together or they may be coated one on top of the other, with the top electrical contact added subsequently. Typically, the manufacturing technique(s) that is more optimal for both efficiency and manufacturability will be implemented to create the bi-layer cells of the present invention.
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|Aug 2, 2011
|Daniel Luch
|Substrate and collector grid structures for integrated series connected photovoltaic arrays and process of manufacture of such arrays
|Mar 31, 2010
|Dec 13, 2011
|Daniel Luch
|Collector grid and interconnect structures for photovoltaic arrays and modules
|Aug 25, 2011
|Feb 7, 2012
|Daniel Luch
|Collector grid, electrode structures and interrconnect structures for photovoltaic arrays and methods of manufacture
|Jun 29, 2010
|Mar 20, 2012
|Daniel Luch
|Collector grid and interconnect structures for photovoltaic arrays and modules
|Oct 6, 2011
|Jun 12, 2012
|Daniel Luch
|Substrate structures for integrated series connected photovoltaic arrays and process of manufacture of such arrays
|Oct 11, 2011
|Jul 17, 2012
|Daniel Luch
|Collector grid, electrode structures and interconnect structures for photovoltaic arrays and methods of manufacture
|Oct 6, 2011
|Nov 6, 2012
|Daniel Luch
|Substrate and collector grid structures for integrated series connected photovoltaic arrays and process of manufacture of such arrays
|Mar 4, 2009
|Nov 27, 2012
|Daniel Luch
|Substrate and collector grid structures for integrated series connected photovoltaic arrays and process of manufacture of such arrays
|Oct 9, 2012
|Mar 4, 2014
|Daniel Luch
|Collector grid and interconnect structures for photovoltaic arrays and modules
|Jan 15, 2013
|May 20, 2014
|Daniel Luch
|Collector grid and interconnect structures for photovoltaic arrays and modules
|Jan 14, 2013
|Sep 2, 2014
|Daniel Luch
|Collector grid and interconnect structures for photovoltaic arrays and modules
|Mar 15, 2013
|Nov 11, 2014
|Daniel Luch
|Collector grid and interconnect structures for photovoltaic arrays and modules
|Feb 4, 2013
|Apr 14, 2015
|Solannex, Inc.
|Collector grid and interconnect structures for photovoltaic arrays and modules
|Dec 1, 2010
|Apr 14, 2015
|Versatilis Llc
|Static-electrical-field-enhanced semiconductor-based devices and methods of enhancing semiconductor-based device performance
|Jun 26, 2008
|Jan 8, 2009
|Daniel R Luch
|Collector grid and interconnect structures for photovoltaic arrays and modules
|Jan 21, 2009
|Jul 30, 2009
|Victor Karpov
|Nanodipole photovoltaic devices, methods of making and methods of use thereof
|U.S. Classification
|136/263, 136/256, 257/465, 257/461, 257/40, 257/464, 257/431, 136/252, 438/63, 438/98, 438/85, 438/82, 136/250, 257/43, 136/291
|International Classification
|Cooperative Classification
|European Classification
|May 19, 2005
Owner name: MIDWEST RESEARCH INSTITUTE, MISSOURI
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GREGG, BRIAN A.;REEL/FRAME:017352/0611
Effective date: 20040920
|Aug 22, 2005
Owner name: ENERGY, UNITED STATES DEPARTMENT OF, DISTRICT OF C
Free format text: CONFIRMATORY LICENSE;ASSIGNOR:MIDWEST RESEARCH INSTITUTE;REEL/FRAME:016959/0684
Effective date: 20050712
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Owner name: ALLIANCE FOR SUSTAINABLE ENERGY, LLC,COLORADO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MIDWEST RESEARCH INSTITUTE;REEL/FRAME:021603/0337
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text:
|Número de publicación
|Tipo de publicación
|Número de solicitud
|Fecha de publicación
|26 Sep 2000
|Fecha de presentación
|11 Ene 1999
|Fecha de prioridad
|11 Ene 1999
|Número de publicación
|Michael Lee Carroll
|Cesionario original
|Carroll; Michael Lee
|Exportar cita
|BiBTeX, EndNote, RefMan
|Citas de patentes (12), Citada por (31), Clasificaciones (9), Eventos legales (11)
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet
1. Field of the Invention
The present invention relates generally to the composition of photoluminescence polymers, the process for making and the methods of use.
More particularly, the present invention relates to the composition of novel photoluminescence polymers that provide extremely long afterglow characteristics. The novel composition contains known moisture sensitive photoluminescence pigments and a polyvinyl alcohol polymer which is water soluble, and which imparts moisture stability to the photoluminescence pigment. The resulting photoluminescence polymers are capable of repeating the light-absorption/light-emission cycle numerous times.
Further, the present invention relates to the method of preparing the novel photoluminescence polymers by combining photoluminescence pigments and polyvinyl alcohol under specific conditions.
Additionally, the present invention relates to the methods of using of these photoluminescence materials.
2. Description of the Prior Art
Products providing glow in the dark or fluorescence properties are well known in many consumer applications. These products are used in applications such as clothing, toys, novelty items, fire protection products, emergency products, safety products, sporting goods such as diving sticks, plastic tubing, stationary, signs, military applications, synthetic leathers, construction uses such as bridges and monuments, outdoor decoration and the like. Generally, when a phosphorescent pigment is incorporated in a synthetic resin, the phosphorescent pigment is not easily dispersed uniformly in the synthetic resin and the resultant phosphorescent synthetic resin inevitably emits light of uneven color.
One well-known method for providing glow in the dark or fluorescence properties is zinc sulfide phosphorescent phosphor (ZnS:Cu). Zinc sulfide phosphorescent phosphor is decomposed by ultraviolet radiation in the presence of moisture and thus blackens or reduces the luminance thereof Therefore, it is difficult to use this phosphorescent phosphor in fields where it is placed outdoors and exposed to a direct sunlight.
Another well-known method for providing glow in the dark or fluorescence properties is found by combining zinc sulfide with radioactive substances. The radioactive substance, however, has the problem that it must be handled under a rigid standard of safety control and, moreover, the disposal of the waste arising therefrom incurs great expense. Further, when the phosphorescent pigment is incorporated into a synthetic resin in an amount sufficient to increase the fluorescence properties, the problem ensues that the resultant phosphorescent resin will not easily acquire sufficient strength necessary for a resinous product.
Another well-known method for providing glow in the dark or fluorescence properties is sulfide phosphorescent phosphors. Examples of sulfide phosphorescent phosphors include CaS:Bi (which emits light of violet blue), CaSrS:Bi (which emits light of blue), ZnS:Cu (which emits light of green) and ZnCdS:Cu (which emits light of yellow or orange). However, any of these sulfide phosphorescent phosphors is chemically unstable and shows degraded light resistance, i.e., it suffers from problems that must be solved for practical use.
Other methods for providing glow in the dark or fluorescence properties are disclosed in U.S. Pat. Nos. 5,424,006 and 5,686,022. Both the 5,424,006 and the 5,686,022 patents disclose phosphorescent phosphors which can be utilized both indoors and outdoors as a nighttime display and show extremely long afterglow characteristics. However, these phosphorescent phosphors must be incorporated into chemical hydrocarbon solvent-based systems as moisture or aqueous systems adversely affect them. These references are incorporated by reference in their entirety.
Yet another method for providing glow in the dark or fluorescence properties is an alkaline earth metal aluminate oxide europium doped which has the chemical composition of SrOSrAl4 O7-Eu and is marketed under the trade name of NightLight20. NightLight20 or SrOSrAl4 O7-Eu is a commercially available phosphorescent pigment. However, similar to the phosphorescent phosphors disclosed in the 5,424,006 and 5,686,022 patents, Nightlight20 is adversely affected by moisture or aqueous systems and therefor are only suitable for blending with oil based materials.
U.S. Pat. No. 5,665,793 discloses a composition where phosphorescent phosphors, such as those in the 5,424,006 and 5,686,022 patents, are combined with polyurethane resins which are water soluble, and which imparts moisture stability to the phosphorescent phosphors. As a result, this novel composition when used in water-based highway paints imparts an extended road surface life, and is environmentally friendly because it does not contaminate the surrounding environment with organic hydrocarbon products via vaporization or runoffs. However, these phosphorescent phosphor polyurethane resins are not moldable or formable as in the present invention.
U.S. Pat. 5,607,621 discloses a composition where phosphorescent phosphors, such as those in the 5,424,006 and 5,686,022 patents, are combined with synthetic resins to provide a phosphorescent synthetic resin material that possesses ample strength enough for enabling a formed article made of this material to withstand repeated use. However, these phosphorescent synthetic resin materials are not water-soluble.
U.S. Pat. Nos. 5,244,429 and 4,634,395 disclose gas barrier coating and coated elastomeric toy balloons. Although not relating to the photoluminescence art, the coatings described herein are polyvinyl alcohol based solutions. These solutions provide neither photoluminescence nor the ability to be molded. These references are incorporated by reference in their entirety.
The prior art as disclosed by the 5,424,006 and 5,686,022 patents as well as an analysis of the disclosures of Nightlight 20 teach away from using these moisture sensitive pigments in aqueous systems such as polyvinyl alcohol. Although the 5,665,793 patent discloses using these moisture sensitive pigments with a water-soluble polyurethane resin, the resulting products are not moldable. Accordingly, a continuing need exists for a moldable, non-toxic, non-radioactive, environmentally friendly photoluminescence polymers which do not require solvent based systems and that provides a uniform, bright afterglow for extended periods of time and are usable both indoors and outdoors.
An object of the present invention is to develop moldable, non-toxic, non-radioactive, environmentally safe photoluminescence polymers. A further object of the present invention is to provide commercial methods for making said photoluminescence polymers. Still a further object of the present invention is to provide methods of use for said photoluminescence polymers.
To accomplish the objects mentioned above, the present invention provides photoluminescence polymers obtained by having one or more phosphorescent pigments dispersed in polyvinyl alcohol aqueous solutions in ratios from about 2:1 to 1:5 by weight.
The novel photoluminescence polymers are prepared by the steps consisting of preparing polyvinyl alcohol aqueous solution then mixing one or more of the selected photoluminescence pigments into the polyvinyl alcohol aqueous solution.
A polyvinyl alcohol aqueous solution is prepared by sprinkling polyvinyl alcohol solids into the vortex formed by rapidly stirring cold water. Rapid stirring is continued for about 10 minutes in order to thoroughly wet and disperse the solids. Heat is then supplied to warm the slurry to about 90 degrees Centigrade in order to dissolve the polyvinyl alcohol. This heating step is continued for about 4 hours or until the polyvinyl alcohol solids are completely dissolved.
The amount of polyvinyl alcohol in the solution can range from as little as about 3 percent by weight to as high as about 50 percent by weight of the total solution. Higher concentrations of polyvinyl alcohol become too viscous to allow for easy mixture of the photoluminescence pigments at room temperature. In any event, it is recognized that the concentration of polyvinyl alcohol is a function of the average molecular weight of the polyvinyl alcohol utilized and of the temperature at which the mixing of the photoluminescence pigments is desired. Higher concentrations of polyvinyl alcohol are possible when using lower molecular weight polymers or when the photoluminescence pigments mixing step occurs at an elevated temperature.
The average molecular weight of the polyvinyl alcohol can range from about 11,000 to about 186,000. The preferred embodiment is a polyvinyl alcohol having an average molecular weight of 124,000 to 186,000 and used at a concentration of about 10 to 15, percent by weight. Although the preferred embodiment employs a polyvinyl alcohol which is about 87.0 to 89.0 percent hydrolyzed, other polyvinyl alcohols having a degree of hydrolysis up to over 99 percent can be used.
The term "polyvinyl alcohol" as used throughout the specification refers to water soluble polyhydroxy compounds which can be generally characterized, for instance, by the presence of (--CH2--CHOH--) units in the polymer chain. The term "polyvinyl alcohol" is also intended herein to include suitable derivatives of the water-soluble polyhydroxy compounds mentioned above, particularly those in which some of the hydroxyl groups are acetylated. These polymers are ordinarily prepared by the replacement of the acetate groups of polyvinyl acetate with hydroxyl groups as by, for example, hydrolysis or alcoholysis. The percent of acetate groups replaced by hydroxyl groups is the degree of hydrolysis of the polyvinyl alcohol thus formed and indicates the percent of hydroxyl groups present in the polyvinyl alcohol out of the total possible hydroxyl groups. This invention relates to polyvinyl alcohols with a degree of hydrolysis above about 85 percent.
It will be appreciated by those skilled in the art that polyvinyl alcohol as discussed herein includes those polyvinyl alcohols, chemically modified, altered or otherwise, that can be used in accordance with the teachings of the present invention. For example, water resistance of the dried polyvinyl alcohol film can be enhanced by the addition of organic materials that are aldehydes or aldehyde donors to the aqueous liquids.
In another example, the polyvinyl alcohols may be partially etherified by reaction with alkaline oxides.
In yet another example, the hydroxyl groups on the polyvinyl alcohol backbone in general may be partially reacted to form, for example, ethers, esters, acetals, and/or ketals using techniques well known in the art. It is intended that those suitable derivatives of these and the above polyvinyl alcohol derivatives so obtained and the like are within the scope of the present invention.
It should be clear that other ingredients could be added to the novel photoluminescence polymers without substantially altering the manner in which it functions to obtain the desired result. For example, the formation of undesirable gel in the novel photoluminescence polymers prior to addition of pigments and molding into desired shapes can be inhibited through the addition of up to 0.3 percent by weight "Triton" X-100.™. (Rohm & Haas Co.). The viscosity of the novel photoluminescence polymers can be lowered somewhat by the addition of up to 3 percent by weight of hydrogen peroxide to aid in the molding process. One or more photoluminescence pigments are then mixed into the polyvinyl alcohol aqueous solution as prepared above.
The photoluminescence pigments that may be added to the polyvinyl alcohol aqueous solution to form the novel photoluminescence polymers are selected from the group consisting SrOSrAl4 O7-Eu, a matrix MAl2 O4 in which M is at least one metal element selected from the group consisting of calcium, strontium and barium; and a matrix MAl2 O4 in which M is a plurality of metal elements comprised of magnesium and at least one element selected from the group consisting of calcium, strontium and barium. The matrix MAl2 O4 further contains europium as an activator in which the concentration of the activator is from about 0.001 mol % to about 20 mol %, the mol % being relative to the metal element expressed by M. The matrix MAl2 O4 further contains a co-activator selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, tin and bismuth in which the concentration of the co-activator is from about 0.001 mol % to about 20 mol %, the mol % being relative to the metal element expressed by M.
The one or more of the photoluminescence pigments can be added in ratios ranging from about 2:1, 1:1, 1:2, 1:3, 1:4, or 1:5, preferably 1:1, of the total weight of the polyvinyl alcohol solution to the weight of the photoluminescence pigments. If the content of the selected pigment is less than a ratio of 2:1, the luminescence of the produced photoluminescence polymers will not be sufficient because the amount of the photoluminescence pigment is unduly small and will not be easily perceived visually in the dark. Conversely, if the content exceeds a ratio of 1:5 by weight, although providing sufficient luminance, the unduly large amount of the pigment will impair the dispersibility of the pigment in the polymers and make the product too expensive to commercialize.
In the incorporation of photoluminescence pigments possessing such outstanding photoluminescence properties as mentioned above into the novel photoluminescence polymer, it is necessary that due consideration be given to enabling the pigment to manifest the properties fully and, at the same time, avoid impairing the physical properties of the polymers themselves. For instance, maintaining the crystalline structure is necessary to maximize the luminescence from the contemplated photoluminescence pigments. The mixture of the pigments with the polyvinyl alcohol aqueous solution does not disturb this crystalline structure, thus maximizing luminescence.
It will be appreciated by those skilled in the art that the photoluminescence polymers according to the present invention produced as described herein can be incorporated into any of the uses for polyvinyl alcohol polymers to provide luminescent properties. For instance, the photoluminescence polymers according to the present invention can be manufactured into formed articles or molded articles of a desired shape by many molding methods such as, for example, injection molding, extrusion molding, transfer molding, compression molding and the like. It can be sprayed into films for making balloons, bags, coatings, bottles, containers and the like.
Since the photoluminescence polymers of the present invention have the selected pigments uniformly dispersed in the polymer as described above, it provides uniform high luminance for a long time in the absence of light. Further, the photoluminescence polymers of the present invention are minimally deteriorated by ultraviolet light and as such can be used either indoors or outdoors with improved durability.
Additionally, water-based-coloring agents can be added in varying amounts to change the color of the photoluminescence polymers of the present invention. The water-based-coloring agents may be added to the polyvinyl alcohol before the addition of the photoluminescence pigments.
The texture of the photoluminescence polymers of the present invention may also be varied. The addition of sand and the like can be blended into the photoluminescence polymers to give the final product a textured surface. The contemplated texturing agents include those selected from the group consisting of natural texturing material and synthetic texturing material.
Alternately, the novel photoluminescence polymers may also be prepared by the steps consisting of mixing polyvinyl alcohol solids with one or more of the photoluminescence pigments in solid form in the ratios described above. Then the polyvinyl alcohol-photoluminescence pigment mixture is hydrated as described above.
Although only a few exemplary embodiments of the present invention have been described in detail above, those skilled in the art will readily appreciate that many modifications and substitutions are possible in the exemplary embodiments without materially departing from the novel teachings and advantages of the invention. Accordingly, all such modifications and substitutions are intended to be included within the scope of the invention as defined in the following claims.
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|Clasificación de EE.UU.
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|23 Nov 2004
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Effective date: 20040926
|26 Ago 2005
|Surcharge for late payment
|26 Ago 2005
|Fee payment
Year of fee payment: 4
|26 Sep 2005
|Patent reinstated due to the acceptance of a late maintenance fee
Effective date: 20050927
|7 Abr 2008
|Maintenance fee reminder mailed
|26 Sep 2008
|Lapse for failure to pay maintenance fees
|18 Nov 2008
|Expired due to failure to pay maintenance fee
Effective date: 20080926

subset: commoncrawl


text:
Malpractice Award Cap Won't Trim Budget Costs, Opponents Say
Consumer advocates and trial attorneys said a state proposal to cap malpractice awards takes away a key protection for patients – and wouldn't save the state budget any money.
Medicaid – whose multi-billion dollar budget Governor Andrew Cuomo is trying to trim -- doesn't actually pay malpractice claims. But hospitals and doctors for years have said they need "relief" from malpractice suits. They rarely pay the actual damages, but their costly malpractice insurance coverage does, and premiums have steadily increased.
The effects of malpractice caps on insurance premiums has long been in dispute.
Stephen Younger, president of the New York State Bar Association, said capping damage awards doesn't necessarily mean hospitals and doctors will have cheaper malpractice insurance.
"We've looked at the states where this has been put into place, for example in Texas," Younger said. "Texas adopted caps. Have insurance rates gone down? No. They haven't gone down one cent."
Consumer advocates and attorneys argue that damages lawsuits are among the strongest ways to protect patients and pay for long-term care when something goes very wrong.
Hospitals and doctors say such claims lead to more and more costly "defensive medicine," such as unnecessary tests.
Younger said hospital groups got the limit in malpractice awards as a trade-off for accepting lower payments from Medicaid.
The state's two main hospital trade groups have long said high malpractice awards and insurance coverage are among the top drivers of high treatment cost.


text:
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Many States have a different Winter blend of gasoline. Mileage suffers as a result. I have a Camry Hybrid. My gas mileage drops to 34 in town in the Winter from 37 in the Summer.
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text: Ballerina Bird Print by Annika Wilkinson Illustration £24$52€35.51$39.48 In stock £6.95$15.06€10.28$11.43 delivery to United States Receive this item 5-10 working days from dispatch International delivery available quantity by Annika Wilkinson Illustration Location: Avon, GB read seller's profile see seller's complete range more items from this seller Fly Away Screen Print £32$69.34€47.35$52.64 Twirl Transformation £19$41.17€28.11$31.25 Sunset Pirouette £45$97.51€66.59$74.03 Charcoal Original Signed Drawing' Taste Th... £100$216.70€147.99$164.52 Touch The Rainbow £30$65.01€44.39$49.35 Swan Lake Canvas £111$240.53€164.26$182.61 view all you may also like PRODUCT DETAILS DELIVERY RETURNS Made in Britain exclusive eco-friendly ask seller a question save for later A beautiful screen printed background and hand rendered stencil has been stunningly reproduced as a print on 230 gsm card. A perfect piece for any room. Elegant yet unusual, This unique print is a limited edition of five. The artist has screen printed the sunset background and over her stencil work has combined her photography to create this unique piece. The four colour separation print was miss - registered to create the illusive dream like double vision effect of the stencil. For art you can really look into this is a must have piece. Perfect for a lady's bedroom, encapsulating the beauty of dance and birds. printed on supreme quality artist paper and signed by the Artist herself. made from: 160gsm gloss artists paper dimensions: 31 x 22cm product code: 261199 This product is dispatched to you by Annika Wilkinson Illustration. MAINLAND UK order now and receive this item on or before price Free Delivery Monday 12 October FREEFREEFREEFREE Express Next Day Thursday 8 October £4.95$10.72€7.32$8.14 Express Next Day 1pm Thursday 8 October £6.95$15.06€10.28$11.43 Saturday Delivery Saturday 10 October £12.95$28.06€19.16$21.30 NON-MAINLAND UK estimated delivery price Highlands & Islands of Scotland 2-5 working daysfrom dispatch £1.75$3.79€2.58$2.87 Northern Ireland 2-5 working daysfrom dispatch £1.75$3.79€2.58$2.87 Other UK Islands 2-5 working daysfrom dispatch £3.95$8.55€5.84$6.49 INTERNATIONAL DELIVERY estimated delivery price Western Europe 2-5 working daysfrom dispatch £5.00$10.83€7.39$8.22 Rest of Europe 5-10 working daysfrom dispatch £5.00$10.83€7.39$8.22 USA & Canada 5-10 working daysfrom dispatch £6.95$15.06€10.28$11.43 Asia & Australasia 5-10 working daysfrom dispatch £7.25$15.71€10.72$11.92 Rest of the world 5-14 working daysfrom dispatch £7.25$15.71€10.72$11.92 You have 28 days, from receipt of cancellable goods, to notify the seller if you wish to cancel your order or exchange an item. Please note: goods that are personalised, bespoke or made-to-order to your specific requirements, perishable products and personal items sold with a hygiene seal (cosmetics, underwear) in instances where the seal is broken are non-refundable, unless faulty. Read more about our returns policy.Should you choose to return or exchange your order you will need to deliver the item(s) to the UK, where this seller is based. Annika Wilkinson Illustration's return policy


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text:
|ShelterBox USA
|Volunteer teams deliver emergency
tented shelter and supplies to people
made homeless by disasters.
|Has provided shelter,
warmth and dignity
for more than a million
people in over 80
countries since 2000.
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affected by disaster
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in Haiti, the Dominican
Republic and Eleuthera
have increased to six;
number of missionary
families served now
numbers more than 300.
|To expand mission
flight service to other
nations of the
|Global Outreach
|Introducing computer literacy
into secondary schools in
central Tanzania.
|Global is providing
computer learning for
more than 1,000 students
per year.
|To change the face
of post-primary
education and more
toward bridging the
digital divide.
|Sea to Share
|Caribbean manatee conservation.
|Implemented speed zones
and no-wake signage
in waters off Belize City;
decreased poaching
incidents in Belize to
nearly zero.
|To inspire policy and behavioral changes
toward manatees and their habitats in
Cuba and Belize.
|Perlman Music
Program Suncoast
|PMP Sarasota Winter Residency
provides one-of-a-kind professional
development for approximately 35
gifted musicians from around the
world, ages 12-20+.
|13,000 members of general
public attend approximately
20 free events featuring
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of concert artists and
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Education" Program educates
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two seminars per month
in four-county area,
benefiting more than
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new naturalization processes of citizens
in Southwest Florida.
Local Nonprofits' Work Reaches Around the World
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Don't have them in your kitchen? Well now you can; and they won't even take up any counter, or drawer, space.
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Demi mak disqualified over score
Alex Jenkins
Most Popular
Pre-tournament favourite Demi Mak Jun-wi was sensationally disqualified from the Helene et Henri Ladies' Close Amateur Championship of Hong Kong as her twin sister Ginger Jun-ki put one hand on the trophy with a steady 78 to open up a nine-shot lead going into today's final round.
Ginger, 15, who fired an impressive 72 on day one, had two back-nine birdies to finish on a total of eight-over-par 150 over the New Course at Hong Kong Golf Club. She was nine shots clear of second-placed Raniasih Pomareda, who carded a 79. Eleana Collins was a further five strokes adrift in third.
Demi, who has enjoyed an excellent run of results on the Asian amateur circuit of late, including wins in Macau and Malaysia at the back end of last year, was disqualified after signing for an incorrect score following Wednesday's first round. Tournament director Candi Anna Chan said: 'Demi signed for a bogey six on the 10th hole when she scored a seven. This is a breach of rule 6-6 and the penalty is disqualification.'


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The goal of our nonprofit organization is to provide shelter for homeless and nearly homeless single parents raising minor children. We help break cycles of poverty by providing financial literacy classes, opportunities for fellowship and community service, and emergency rental assistance. Our vision for the future is to provide transitional housing for single parent families.
The Hernandez family called Why Not Ministries because their time at the extended stay hotel ended the next day. The family would be homeless in a few hours. The 13 year old son was tense and embarrassed to ask for help as he translated for his mother. I wish you could have seen the joy on his face when he realized we paid for another week's stay! Please consider supporting us so we can lighten another family's load.
Why Not Ministries is happy to announce our 2nd Annual 5K Home Run and 1 Mile Fun Run on September 26, 2015. Check out our events page for more details.
Register today at www.runsignup.com/Race/Ga/Lawrenceville/whynot5k and pass our race info on to your friends!
Donate now by designating Why Not Ministries as your charity when you make purchases through Amazon and at Kroger! www.krogercommunityrewards.com It costs you nothing! Amazon will donate 0.%5 of your purchase to us! Read more on the How You Can Help tab!
Want to know more about Why Not Ministries and our projects? Then click here to read more about the work we do.
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Stacey McBride, author of God's Supernatural Tapestry of Grace, is donating part of the proceeds of his book to us. You can download a copy of this inspirational true story on Amazon.com.
Life Church International has a heart for single parent families! Thank you for your monthly support! www.lifechurchatl.com
Why Not Ministries is grateful to our race sponsors!www.runnersfit.com/whynot
Many thanks to Wells Fargo for donating $1,000 to help us house more families!
Office Depot awarded us office supplies and a gift card as one of 14 winners of The Elf Who Helps Small Businesses national contest.


text:
Mass Effect 2: Cleared!
I finally did it. I finally finished Mass Effect 2. I can't believe I never did a post on ME1. If I had to pick a favorite game, right now I'd go with ME2.
I put off the end for a very long time. My boyfriend harassed me constantly, asking me why I wouldn't just beat it already. But see, I couldn't just beat it – not that simply. Because…well, because then I'd have no more Mass Effect to play.
So instead, I spent time flitting from star cluster to star cluster, exploring every single world until my star map was littered with 100%'s everywhere. It's quite possible that I did every side-mission (or definitely every side mission I detected.)
The reason I was so reluctant to finish might've had a few reasons… I didn't want to lose any characters. When it comes time to make decisions knowing that there's a possibility that they might not all survive, it makes those choices a little bit harder to make. I was anxious about matching the right people to the right tasks.
I think I said this about Bioware when I did my Dragon Age review, but I love that they have a small place in their hearts for us lady gamers. Fem-Shep was awesome, and I gotta give props to Jennifer Hale because her voice acting brought the character to life in ways that wouldn't have happened with many other people. She did a fantastic job – in both games.
So, I finally ran out of worlds to scan and I had to continue on with the suicide mission. And I'll be damned if I didn't regret pissing around after I got there. I kind of wish I'd just rushed into it after getting told off by my crew doctor. But, come on, Chakwas! I had loyalties to earn! I had weaponry to collect and ship improvements to make!
And I had a space hamster to buy.
Couldn't very well rush off to my death without a cuddly, fuzzy wuzzy, now could I?
But aside from all of these tiny (awesome) details, this game is chocked full of entertainment. I love the battle interface. I'm not the best with FPS games, and while this isn't really an FPS, I still have that "newbness" that comes with using a gun in a game. My aim is not that great really. And when I'm getting shot at from ten different directions, I am prone to panic and just simply die.
In Mass Effect, you have that "freeze" feature – where you can bring up the menu and it'll momentarily pause the game while you select powers for your characters to use on specific enemies. I get a moment to say to myself, "Okay, don't be an idiot. Take cover behind that crate, use a medi-gel, and then select some cryo ammo." So in other words, I get a moment or two to strategize.
But the game play isn't what makes this my favorite game, it adds to my overall judgment, but it's not the main factor. I'm a writer, first and foremost. And I'm mostly a character-writer. I absolutely love to see people grow and develop in books and movies, and yeah, especially in games. I love to see a character's introspection, but that's often lost outside of novels. It's harder to portray in movies and games. Not impossible, just harder.
Often people pay more attention to setting, costumes, special effects, etc. in movies and games. They tend to forget that the story is nothing without the people involved. Without the people you have a bunch of flashy lights and big booms and pretty landscapes. It's the characters that bring all of this to life – it's their reaction to it, their love or hate for it. Because, by extension, that character is you. Character is the best and maybe the only way of drawing you in and making you care.
When we see a habitat being destroyed, why do we care? Because we care about the beings it affects, the "characters." If there are no animals or native people being displaced, do we still care that they're destroying the land? Yes, sometimes, we do…and why is that? Because we personify the earth. We're destroying "Mother Nature" or "killing" the planet. So this is my point…
And now to get back to Mass Effect – the concept of earning your crew's loyalty was a brilliant addition to this game. That bridged the gap between characters building relationships through dialogue and gave us the ability to prove we cared about that relationship by going out of our way to complete a mission that mattered only to that one individual crew member.
When it was revealed that Legion had fused a piece of Shepard's armor to his body, that was excellent character work. This tiny bit of dialogue made me like Legion a little bit more. When Jack asks you why you keep coming down to talk to her when no one else ever gave a shit, that was a glimpse further into the character. I might've never otherwise taken Jack on my team, I didn't much care for the character before that.
I have to admit though…I never got past the fact that Morinth looked like Janet Jackson to me. It kind of made me want to giggle each time I talked to her, so I had a slightly harder time getting into the story of that character.
I loved going round to each of my crew between missions and talking to them. I loved the tiny bits of their story they shared with me. What I didn't like was how Miranda and Jacob were always too busy and rarely spoke to me. Pfft, I'm your Commander! Finish your work when I say finish it! I wanna chat, damn it!
The end of the game was one of the best I've ever seen. Not because of the game play, not because of some epic boss fight, not because of the amazing graphics… but because it wrapped up like a real story. There was this epic sense of closure…of going into the unknown -it was there for the characters too, not just the player who doesn't know how the game will end. The characters didn't know how it would end, they didn't know if they'd live or die. How many games can you say have your character fretting over the outcome of their last mission? How many games give any attention to that at all?
Your characters are typically just asked "This is the way forward. Have you prepared?" and you answer, "Yes, let's go!" or "No, I need more time to prepare" which really just means that you need to go to a merchant and buy more potions or better gear… It very rarely means that your characters are facing death and it's actually affecting them – as if they might actually be frightened. It was such a simple touch, giving the characters those small moments to express themselves, and yet, for me at least, it totally changed the game for the better.
When I finished the game, I didn't want it to be over. With other games, you beat the final boss and it's like an achievement. You're done. You've beaten it. And now, it's on to the next game, your next conquest. With both of the Mass Effect games, I felt sad leaving. It's an odd thing to say about a game, maybe, but it's how I feel when I close a good book. I don't want to depart from those characters. I spent time getting to know them, to care about them, to worry for them…and it's a little like leaving a good friend behind.
All of this is why Mass Effect probably currently stands as my favorite game. At least, on PC – I think FF7 might still hold the slot for favorite console game. I cannot wait for Mass Effect 3. It will be epic. I have no doubts. I have faith in Bioware's ability to churn out yet another fantastic game.
In the meantime, I'm playing Skyrim. And I should probably do a review on that shortly.
Skyrim is limitless but it's missing one key factor so far. There are no relationships in Skyrim. The characters are generic, they're the same old NPC devices as always. Might as well be a lump on a log with the ability to recite a few lines of dialogue. There's very little interaction. But maybe this is because I'm coming off of Mass Effect… Perhaps after I play Skyrim more and attend to more of the Main Story line, maybe then I'll be able to make a better comparison.
But for a closing, I'll just say this: If you haven't played Mass Effect 1 or 2…well, you should really try it out. Find the time to give it a chance – it really is just a fantastic experience.


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I'm Josh, 31, from Wyandotte, Michigan (a SE suburb of Detroit). I love the weather because its so interesting (and so changeable) around here. We get blizzards, heat waves, and everything in between! I love the outdoors (nothing beats the U.P.!), and love taking pics!. Nature takes the photo, I just press the button. I also enjoy others photos a lot.
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After the storm- BRUTAL cold
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Monday January 6, 2014
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January 6, 2014 Photo Series
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WilsonAmplifiers always offers the best value to our customers. We will match the price, at the time of purchase, on a Price Match Guarantee product if you find the same item at a lower price at Amazon, Bestbuy, or Walmart (excludes marketplace sellers).
Wilson 301202 Omni-Directional Antenna has been updated to the Wilson 311203 Omni-Directional Antenna


text:
"I just saw Sam passed it behind Louden Johnson and I was ready for it," Keith said. "We've worked hard all summer and all year for this game. We've been looking forward to it so much. This was a whole lot better than last year."
A season ago, Wayne beat Wynnewood 47-42 at home and wound up going on to win the school's first football state championship.
Wynnewood is hoping for a similar fate.
The Savages sealed the game with less than two minutes remaining when Trey Knowles gained six on fourth and three from the Wayne 18 to end any chance for a Bulldogs comeback.
"We were going to give it to our biggest back and run behind our best lineman, there was no doubt about that," O'Steen said.
The results of that play, Knowles said, showed the difference between this year's Savages and the team that fell to the Bulldogs last year.
"This team sticks together more," Knowles said. "We knew we were going to have to overcome some adversity tonight and we did that. Every time it got tough, we fought through it."
Knowles ran for 97 yards and a pair of touchdowns while Brown threw for two touchdowns, both more than 50 yards.


text:
Multiple reports are confirmed what everyone already knew: Eastern Washington running back Taiwan Jones is fast and athletic.
Stopwatches recorded times in the high 4.2's to low 4.3's on Jones' only forty-yard dash attempt. He also put up other athletic testing numbers that would have put him at the top of the running back (or even wide receiver) heap at the Combine. Jones' workout was pushed into mid-April because of a foot injury suffered in the Football Championship Subdivision play-offs. He appeared to be fully healthy in today's workout.
Jones' production and speed already had scouts pegging him in the third round of this year's draft, with the assumption he would run as well as he did today. He ran for 1,742 yards and 14 TD in just 12 games this fall, catching 24 passes for 342 yards and three scores. He showed great promise as a kick returner in 2008, averaging 36.3 yards a try with one touchdown but averaged just 20.4 a return in 2009, 20.9 this season.
Scouts won't like the fact he missed games with an "abdominal contusion" and foot injury this year--in addition to being nicked up with hip, hand, shoulder injuries in 2009 and sitting out with a broken leg in 2008.
He also fumbled 18 times the past three seasons (17 in 2009-2010), losing eight (seven).
That sort of injury track record and lack of ball security won't sit well with teams, who know the hits will come much harder and faster at the next level.
--Contributed by NFLDraftScout.com Senior Analyst Chad Reuter
Blog Entry
Jonesin' for Speed
Posted on: April 14, 2011 2:31 pm
Category: NFL Draft
Tags: Eastern Washington, Taiwan Jones


text:
Höegh Autoliners appointed Scandinavian Shipping & Logistics, which has already worked with the Norwegian ocean carrier in Sweden and Norway for several years, as its agent in Finland, effective Dec.
Norwegian shipping company GC Rieber Shipping ASA has entered into an agreement with Dolphin Geophysical to increase Dolphins competitiveness in a challenging market.
The Baltic Exchange's main sea freight index, which tracks rates for ships carrying dry bulk commodities, fell on Monday as demand dropped across all vessel categories.
Under new maritime laws all vessels and boats using Fiji waters have to abide by the rules and regulations under the Marine Transport Decree, reports FBC
Turkey launched the 140-meter amphibious ship "Bayraktar," the first of two vessels that are part of a domestic Landing Ship, Tank (LST) project, reports Local media.
The Coast Guard urges the public Thursday to use extreme caution and to prepare for the onset of heavy weather, extreme sea conditions, storm surge and high


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Horticultural charcoal is a substrate material that is essential in keeping your terrarium odor free and it also reduces moisture. You can also use it in your potting soil mix to reduce moisture for your houseplants. You will receive one 3 inch by 5 inch bag of charcoal that weighs about 2 oz. This is enough charcoal for 2 small to medium terrariums or one large one. This item ships first class mail. I am happy to help you create a one of a kind terrarium kit so convo me with any questions or requests.
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text:
Another new MotA song
At first I thought this said motW as in maudlin of the Well but this is awesome too
I'm excited for this album!
This is not a new song. This song was released almost a year ago on a Falling Down compilation.
this version is different
Digging: Caspian - Dust and Disquiet
whenever I see the "mot" with a capital letter at the end, I always immediately think maudlin of the Well. Stupid Mouth of the Architect.
nah these guys are better
Hey man, I love both bands, but Mouth of the Architect is no way close to being as good as maudlin of the Well.
whenever I see the "mot" with a capital letter at the end, I always immediately think maudlin of the Well. Stupid Mouth of the Architect.[2]
I was hoping the title was a typo.
Sorry for all the fucktards who confuse a W with an A. Just trying to share the sweet new Mouth Of The Architect song with ya'll.
Digging: Fluisteraars - Luwte
Maybe you should have capitalised the 'M'!!!
I'd rather capitalize an Architect than a mouth. Everyone has mouths. Besides A and W are very different letters, I'll give you that they are both letters as to not make you feel like... complete... shit lings.
lol ok sorry wack
whenever I see the "mot" with a capital letter at the end, I always immediately think maudlin of the Well. Stupid Mouth of the Architect. [3]
I feel dumb
for a second i almost thought it'd be maudlin of the Well
lol ok i'll check anyway
Digging: Crossed Out - 1990-1993
DAE Maudlin of the Well?????
ryan are retarded?
but are you srsly saying this band is better than motW????!!!"
yeah opinions really are a bitch, aren't they? I personally enjoy listening to MotA more than I do motW.fuck me
New album is going to be epic
Digging: Girl Band - Holding Hands With Jamie
Don't worry, you probably shared the song more than intended with the maudlin of the Well confusion.
Great song!
'but are you srsly saying this band is better than motW????!!!!'
yea, we're srsly saying this band is better, way better. i liked the production on the previous version allot more tho, now it sounds a bit messy sometimes.
Digging: The Mire - Volume: II
ITT: people who actually think mouth of the architect is better than maudlin of the well
ITT: people who cant tell the difference between A and W
wacknizzle did fuck it up and while I did notice the difference at first i see where the maudlin boys
are coming from
and all of you comparing two different bands fuck off
I knew this news wasn't about maudlin of the Well and I clicked it anyways.
ITT: people who cant tell the difference between A and W"
This. And there I capitalized the M. Learn to read English. Also, if Maudlin of the Well already had a new song out prior you'd probably have known about it. Get the fuck off your 'jump to conclusions' mat.
motW and MotA are two entirely different bands, both are amazing so shut your fucking pie holes and enjoy the song
Digging: Vanum - Realm of Sacrifice
I love maudlin of the Architect
'and all of you comparing two different bands fuck off'
welcome to a music website!!
feel free to share your opinions with us!
• Brand New release new song as a f..• Tool + Mastodon supergroup• Justin Lowe found dead• Justin Lowe leaves After the Buri..• Cynic break up• Slint guitarist survives suicide ..• Muse unleash new single• Scarlett Johansson forms band• Nickelback get groovy • New Muse song
• Ruhe streams Patriarchs• New Fates Warning album coming• Lindemann debut new video• Earthside stream new track• Koopsta Knicca dead at 40• Aiden premiere new track• Polyenso announce EP1• Cult Leader stream debut LP• Fightstar debut new song• Eulogy stream new music• Rock and Roll Hall of Fame 2016• Evergrey keyboardist's single• Mestis releases new music• Jim Konya dies, age 44• Ramleh announce new album» see all news
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