The invention relates to the field of photovoltaic devices, more particularly to at least partially transparent photovoltaic devices that incorporate organic or inorganic light harvesting photovoltaic substances.
The direct conversion of sunlight into electricity using energy harvesting devices is key for the provision of renewable energy in the future. Efficient use of existing large surface areas in residential buildings can be made by recently developed transparent photovoltaic technology, which can be integrated into, for instance, window panes. Transparent and flexible energy harvesting tools can also be integrated into for example foldable elements such as curtains, or can be integrated into e.g. screens of portable computers and mobile phones, for providing electrical energy to charge the device. In addition, such transparent devices are interesting for powering invisible electronic circuits that are integrated in, for example, automotive windshields.
The use of inorganic semiconductors, such as silicon, for such energy harvesting applications is limited because of these materials' wide absorption spectra in the visible wavelengths. In contrast, certain photosensitive organic molecules show discrete absorptions spectra in specific narrow spectral regions. Research work has so far shown that it is possible to realize semi-transparent organic solar cells having a residual colored aspect that might find applications, for example, in architectural and design motifs. Organic energy harvesting devices which appear fully transparent to the naked eye require specific organic molecules of which the visible light transmittance is maximized while only the ultraviolet and near-infrared radiation is absorbed by these molecules. Not many organic dyes are available that have these peculiar characteristics and that are highly transparent in the visible part of the spectrum and that are suitable for the mentioned applications, as the organic molecules have to be stable under high temperature conditions as well as under ultraviolet and heat radiation.
Some important steps towards fully transparent solar cells having a high optical-electrical conversation factor were recently reported by several organisations. Early efforts to construct semitransparent devices focused on the use of very thin organic layers having absorption in the visible part of the spectrum and therefore have been limited to either low light energy conversion or too low transmission in the visible part of the spectrum. In recent development work, focus has been on near-infrared absorbing devices with relatively high visible light transmission. Mainly two complementary approaches have been investigated in order to find a compromise between maximizing energy conversion and visible light transparency. The first approach consists of using specific selective near-infrared absorbing donors.
The second approach focuses on the transparent electrodes covered with different types of more or less complex coatings especially designed for improving the near-infra-red (NIR) absorption profile in the solar cell.
In particular US2010/0186623 describes photovoltaic cells incorporating small molecules, such as chloro-aluminium-phthalocyanine as electron donor and C60 as electron acceptor, with which an optical-electrical conversion efficiency of 1.7% is claimed, with a total integrated visible transparency of more than 55%.
In another example, J. Meiss et al. disclose in Applied Physics Letters 99, p. 193307, 2011, solar cells comprising combination of substances such as Ph2-benz-bodipy and C60 that can allegedly reach an energy conversion efficiency of 2.4% and an average transmittance between 400-750 nm of 48%.
There are mainly three problems with the devices disclosed in US 2010/0186623 and J. Meiss et al. The first is that they need complex and expensive vacuum deposition techniques to realize the required layers of the organic photovoltaic cells. The second is that the substrates on which the layers are deposited are solid and expensive materials such as glass sheets (in J. Meiss et al.) or quartz (e.g. in US2010/0186623). Finally, the reported organic photovoltaic devices use dye molecules that have a residual absorption in a portion of the visible spectrum, typically the red part, so that the photovoltaic devices have a residual colored aspect, for example a green-tinted aspect. This is undesirable for instance if the photovoltaic device is integrated into a window pane. The residual colored aspect cannot be modified or corrected easily. Some solutions have been proposed to reduce partially the residual color of the energy harvesting windows. One solution is to incorporate other type of dyes in order to absorb complementary parts of the spectrum, for example green in case of residual red absorption. Other techniques have been proposed such as the deposition of specific designed interference layers. These additional color correction solutions complicate the technology of the organic photovoltaic devices and make it more expensive.
A further alternative to provide solar transparent cells for power window applications is explained in the article of R. Koeppe et al.: “Organic Solar Cells with Semitransparent Metal Back contacts for Power Window Applications”, Chemsuchem, vol. 2, nr.4, 20 Apr. 2009, pp. 309-313. It discloses an organic solar cell comprising a selective anti-reflection layer on the back side of the organic solar cell which is transparent to visible light but reflective to NIR light. This allows the cell to appear transparent and additionally increases the efficiency of the organic solar cell by the increased path length of the incoming light by the reflection of the NIR light on the selective anti-reflection layer. The increased path length and so the electrical conversion efficiency is limited by the single reflection on the selective anti-reflection layer and it would be desirable to further increase the path length and so the electrical conversion efficiency while maintaining a high transparency. Also, the organic solar cell disclosed by R. Koeppe et al. has limited color management possibilities of the transmitted visible light.
Document US 2012/0174980 A1 discloses a solar cell of the dye sensitized and organic type in which a glass window is arranged to the cell comprising a diffraction grating. The diffraction grating allows to selective couple only first order diffractive components into the absorption layer in such a way as to cause multiple excursions of the in-coupled light through the absorption layer. The solar cell disclosed in US 2012/0174980 has limited visible light throughput and has also a very limited choice of the color of the transmitted light.
The object of this invention is to overcome at least partially the limitations of the photovoltaic devices described in the prior art, and thereby to provide a photoelectric conversion device having a greater photoconversion. Furthermore, the color appearance of said photoelectric conversion device to an observer situated to one side of the photoelectric conversion devices can be specified by light management techniques using particular arrangements of gratings arranged in said photoelectric conversion devices.
The object of the invention is more precisely achieved by a photoelectric conversion device which comprises:
The first grating structure is arranged so as to direct a near-infra-red light portion of light incident on said first grating structure into said photoconversion element, and the at least second grating structure is arranged to reflect at least a part of near-infra-red light back into said photoconversion element, enhancing as such the optical path length and improving the photoconversion efficiency. The first grating structure and the second grating structure are optimized to maximize visible light transmission of the photoelectric conversion device.
According to the invention, the grating structures arranged in the photoconversion elements may be reflective grating structures.
The photoconversion element of the photoelectric conversion device may be a single continuous layer and the at least one of said first grating structure and said second grating structure is arranged also as a single continuous layer. Such an arrangement allows maximizing the photoelectric conversion efficiency.
The at least one photoconversion element may comprise a plurality of separate photoconversion elements, all arranged substantially in the same plane, and the at least one of said first grating structures and said second grating structures comprise a plurality of independent grating structures. In that case, the plurality of independent grating structures each face one of the plurality of photoconversion elements. The embodiment comprising a plurality of separate photoconversion elements allows to maximize the visible light transmission through the photoelectric conversion device.
According to the invention further grating structures may be provided in between each of a plurality of independent grating structures, said further grating structures are arranged to direct, by diffraction, near-infrared-light into the said plurality of photoconversion elements. The further grating structures may be arranged also to reflect and/or transmit a portion of the incident visible light. An embodiment comprising further grating structures allows to improve at the same time the near-infra-red photoconversion efficiency and the visible throughput of the photoelectric conversion device.
According to the invention a waveguiding film may be arranged to at least one side of the photoconversion element. This waveguiding film may be arranged to guide visible or near-infrared light. A waveguiding film is a substantially flat film, comprising a first surface and a second surface, which guides incoupled light into said film by multiple reflections on said first surface and said second surface. The waveguiding film is made of a material having a higher index of refraction than the index of refraction of the surrounding medium of the waveguiding film. A waveguiding film is also known in the literature as a light guide, a waveguiding foil, a light waveguiding film or foil, a film optical waveguide, a light waveguide. In combination with the first grating structure arranged to the waveguiding film, at least a portion of the incident visible light on said first grating structure may be directed away from the photoconversion elements and near-infra-red light incident of said first grating structure is directed towards and into the photoconversion element. The cooperation between a first grating structure and a waveguide such as a waveguiding film arranged to the photoconversion element allows a great design flexibility of the visible and near-infra-red light management in the photoelectric conversion device.
The photoelectric conversion device may be further arranged on a transparent substrate layer, which may have waveguiding properties. The transparent substrate may be used to deposit the different layers comprised in the photoconversion elements. The transparent substrate may further have a second grating structure arranged on said transparent substrate. The use of flexible substrates allows for roll-to roll processing techniques, thus for cost effective, mass production.
According to an embodiment of the invention, said first grating structure and said second grating structure may be arranged to reflect a portion of the visible light incident on said first grating structure and/or second grating structure, said portion corresponding to the visible light with a wavelength range complementary to the absorbed wavelength range of the visible spectrum by said photoconversion element. This allows to impose a specific color appearance of the photoelectric conversion device to an observer. The color appearance may be a neutral color, preferably grey, or a well defined color.
According to another embodiment of the invention said first grating structure may be a reflective grating structure arranged to reflect visible light incident on said reflective grating structure, and according to that embodiment said waveguiding film is arranged to guide said reflected visible light, and further gratings may be arranged and optimized to direct near infrared light onto the photoconversion elements, the further gratings being arranged and optimized also to transmit visible light.
Combining a reflecting first grating structure and the waveguide properties of the waveguiding film allows a wide design flexibility of the photoelectric conversion device and in particular a high visible transmission and high photoconversion efficiency of the photoelectric conversion device.
According to another embodiment of the invention the photoelectric conversion device may comprise:
Said first grating structure of the embodiment comprising a reflector is arranged so as to direct a portion of visible light incident on said first grating structure into said waveguiding film, the portion of visible light being at least partially reflected by at least one surface of the waveguide film and subsequently transmitted in between said plurality of photoconversion elements.
According to the invention the photoelectric conversion device comprises at least one organic photoconversion layer that incorporates dyes that are partially transparent in the whole visible part of the spectrum and partially absorbing in the near-infra-red part of the spectrum. These dyes are chosen from the group comprising:
The implementation of the mentioned dyes allows to avoid to have to use very thin layers having absorption in the visible part of the spectrum and therefore avoids to obtain either a low light energy conversion or a too low transmission in the visible part of the spectrum.
In an embodiment said organic photoconverison layer may comprise an inorganic sensitizer. Said inorganic sensitizer may be a quantum dot or a perovskite as further explained.
In an embodiment said photoconversion device may comprise an organic photoconversion layer and at least one quantum dot layer.
In an embodiment said photoconversion device comprises at least one inorganic layer comprising one of the following: quantum dots, perovskites, preferably semiconducting perovskites, more preferably a trihalide perovskite (CH3NH3PbI3), or CH3NH3PbI(3-x)Clx, or CH3NH3SnI3, or a combination of them.
According to the invention the transparent substrate of the photoelectric conversion device is made of a material chosen from the group comprising glass, Polyethylene terephthalate (PET), Polycarbonate (PC), Polyethylene naphthalate (PEN), Polymethyl methacrylate (PMMA), Polyesters, Polyethylene (PE), Polypropylene (PP), Polyethylene furanoate (PEF), polymers based on Poly (bis-cyclopentadiene) condensates, colorless Polyimide (CP), cellulose, Polyether ether ketone (PEEK) and their combination.
The object of the invention is also achieved by a method of generating electrical current. The method comprises the following steps:
In an embodiment of the method of generating electrical current, at least a portion of the visible part of the light incident on the photoelectric conversion device is reflected and wherein another portion of said visible light is transmitted through the photoelectric conversion device.
In a further embodiment of the method of generating current, the reflected portion of the visible part of the light is reflected by means of at least one of a first grating structure arranged on a first side of the photoconversion element and a second grating structure arranged on a second side of the photoconversion element, said reflected portion corresponding to the visible light with a wavelength range complementary to the absorbed wavelength range of the visible spectrum by said photoconversion element.
In a further embodiment of said method of generating electrical current, said reflected portion is arranged such that said photoelectric conversion device appears colorless or grey to an observer situated to one side of said device.
In another embodiment of the method of generating electrical current at least a portion of the light incident on the photoelectric conversion device having a wavelength range corresponding to the absorption wavelength range of the photoconversion element is reflected by at least one of said first grating structure and said second grating structure and wherein at least part of the non-reflected visible light is transmitted through the photoelectric conversion device, such that said photoelectric conversion device appears colorless or grey to an observer situated to one side of said device.
The above described objects and advantages of the present invention will become more readily apparent to those ordinarily skilled in the art after reviewing the following detailed descriptions and accompanying drawings, in which:
The following detailed description illustrates the principles and examples of embodiments according to the invention. It will thus be appreciated that those skilled in the art will be able to devise various arrangements that, although not explicitly described or shown herein, embody the outlined principles of the invention and are included in its scope as defined in the claims. In the description, similar reference signs refer to the same or similar components or structural elements. Also, the term “transparent” as used herein the description encompasses an average visible transparency of a straight through beam of at least 50%, integrated over the whole visible spectrum (V), which is defined as a wavelength range between 400 nm-650 nm.
According to a generic embodiment of the invention, illustrated in
The layers of the photoconversion element 10 may be separated between each other by an intermediate layer. An example of an intermediate layer is a hole extraction layer 13 and an electron extraction layer 17.
The function of said at least one organic photoconversion layer 15 of the photoconversion element 10 is to separate the excitons that are formed by absorbed light into charges in said organic photoconversion layers. It should be noted that photoconversion elements are also known as light conversion elements, or light harvesting elements. The organic photoconversion layer considered in the invention have preferably strong absorption features outside the visible light spectrum, e.g. in the ultraviolet and particularly in the near-infrared part of the spectrum, said near infra-red part being defined as light between 670 nm to 1400 nm
Said organic photoconversion layer(s) 15 may comprise, for instance, dyes chosen from the group comprising:
In an embodiment said organic photoconversion layer may comprise an inorganic sensitizer. A sensitizer is defined as a photoactive material that is added into the organic photoconversion layer, typically in small quantities (i.e. smaller quantities than the default photoactive material), in order to broaden the absorption spectrum to have a better overlap with the solar spectrum. Said sensitizers typically have much higher absorption coefficients than the default photoactive material, but in limited region of wavelengths. Said sensitizer may be nanocrystal quantum dots or may be perovskites nanocrystals that are embedded in said organic layer, quantum dots being described further in par. [0051].
In an embodiment said photoelectric conversion device 1 may comprise an inorganic photoconversion layer comprising at least perovskite, preferably a semiconducting perovskite, such as BaSnO, but not limited to BaSnO. Said semiconducting perovskite may be a synthetic perovskite. In a variant said perovskite material may be a hybrid inorganic-organic perovskite, preferably a trihalide perovskite (CH3NH3PbI3). Said perovskite may also be CH3NH3PBI(3-x)Clx or CH3NH3SnI3.
It should be noted here that said hybrid inorganic-organic perovskite being imbedded in said inorganic photoconversion layer is a hybrid inorganic-organic material, and comprises at least an organic part, for example CH3NH3, and an inorganic part, for example PBI3 or SnI3.
In an embodiment said organic photoconversion layer 15 may comprise one of said perovskite types and at least one of the dyes mentioned in [0041].
In an embodiment said photoconversion device 1 may comprise a perovskite layer, defined as a layer comprising at least one of the perovskite types described above.
In another embodiment, said photoconversion device 1 may comprise at least one quantum dot layer, said quantum dot layer being a layer comprising quantum dots as further described in par. [0050].
It should be noted that said perovskite layer or said quantum dot layer may be arranged to each side of said organic photoconversion layer 15. In a variant said photoconversion device 1 may comprise said organic photoconversion layer 15 and at least a quantum dot layer and a perovskite layer, said perovskite layer or said quantum dot layer may each be arranged to any side of said organic photoconversion layer 15. Any combination of stacking can be considered. In still another variant said photoconversion device 1 may comprise a photoconversion stack comprising a plurality of organic photoconveriosn layers and/or a plurality of said quantum dot layers and/or a plurality of said perovskite layers, each layer of said photoconversion stack may be arranged in any position in said stack.
In an embodiment, said organic photoconversion layer 15 may comprise different types of said quantum dots and at least one of the dyes mentioned in par. [0041]. In another embodiment said organic photoconversion layer 15 may comprise different types of perovskites.
In the context of the present invention a quantum dot layer is defined as a layer comprising quantum dots. Quantum dots are semiconductor particles that have been reduced below the size of the Exciton Bohr-radius, and due to quantum-mechanic considerations and the electron energies that can exist within them become finite, much alike energies in an atom. Quantum dots may be referred to as “articifial atoms”. Their energy levels are tunable by changing their size, which in turn defines the bandgap. Quantum dots may produce more than one exciton from one high energy photon via the process of carrier multiplication or multiple exciton generation (MEG). This is very favorable compared with photoconversion layers which can manage one exciton per high-energy photon, with high energy carriers losing their energy as heat. Quantum dots may be realized in a cheap manner as they can be made using simple chemical reactions. Wet chemistry and improved cheap molecular beam epitaxy processes are an example of the way how to fabricate quantum dot layers. Quantum dots may be grown over a range of sizes, allowing them to express a wide variety of bandgaps without changing the underlying material or construction techniques. In typical wet chemistry preparations, said tuning is realized by varying the synthesis duration or temperature. The ability to tune the bandgap makes quantum dots desirable for solar cells. The combination of quantum dots with dyes as listed above may further increase the design possibilities of the photoconversion device 1 of the invention.
Quantum dots may be based on perovskites, for example perovskite nanocrystals. Quantum dots may also be PbS quantum dots, defined as quantum dots made of PbS molecules.
In an embodiment the quantum dot layer may comprise a plurality of layers of different types of quantum dots.
The layers of the photoconversion element 10 shown in
The design and realisation of the photoconversion element 10 itself, comprising at least one organic photoconversion layer 15, is well known in the literature, and need not be described further in more detail. Some publications on this subject are cited:
Photoconversion elements comprising organic photoconversion layers using said dyes are very transparent in the visible range of the spectrum but they are not completely color free due to an unbalanced transmittance in the visible range. The graph of
To improve the near-infra-red light conversion efficiency and to carry out a color correction of the appearance of the photoelectric conversion device due to the partial absorption of a part of the visible spectrum by the photoconversion element, the photoelectric conversion device further comprises a first grating structure and a second grating structure arranged adjacent to the organic photoconversion element.
In the generic embodiment illustrated in
The first grating structure 20 is designed to transmit a portion of the visible part 80 of the spectrum of the incident light on said first grating structure 20 and to direct the near-infra-red part 60 of the incoming light incident on said first grating structure 20 into said organic photoconversion layer 15. The angle of the diffracted near-infra-red light 60 by said first grating structure, i.e. the angle to the normal to said first grating structure 20 after diffraction by said first grating structure, is chosen to make the path length of the incoupled near-infra-red as long as possible in order to improve the photoconversion efficiency. The diffraction angle of the incoupled near-infra-red light 61 will preferably be chosen greater than 10°, preferably greater than 30°, and even more preferably greater than 60°.
Besides coupling near-infra-red light into said photoconversion element, said first grating structure 20 is also designed as a color correction grating and reflects, to the side of the light source, as shown in
There are different ways to realize the first grating structure 20. Said first grating structure can be made for instance by embossing a Polyethylene carbonate (PEC) plastic waveguiding film, on which a ZnS diffraction enhancement layer is deposited. The transmission and reflection properties of an exemplary first grating structure 20 are shown in
The first grating structure 20 may comprise at least two superposed grating structures as taught in PCT/EP2013/065631. In a variant, one of the at least two grating structures is a color correction grating, while the second of the at least two grating structures diffracts near-infra-red light towards and into said organic photoconversion layer, as illustrated in
The photoelectric conversion element 1 comprises further a substrate layer 50 comprising a second grating structure 30 arranged on one of the surfaces of said substrate layer 50. The substrate layer 50 is a layer on which the photoconversion elements 10 may be arranged. Said photoconversion elements 10 may be deposited on said substrate layer 50 or they may be connected to the substrate layer by any intermediate layer, such as a glue layer or any transparent layer. Said substrate layer 50 may have waveguiding properties. The material of the substrate layer may be chosen from similar materials as the materials mentioned for the waveguiding film 40.
The second grating structure 30 is designed and arranged to transmit visible light and also to reflect at least a part 62 of the near-infra-red portion 61 that is coupled into the photoconversion element by said first grating structure 20, thereby trapping said near-infra-red portion into said photoconversion element 10.
The photoelectric conversion device 1 according to the generic embodiment illustrated in
A wide variety of applications of the photoelectric conversion device 1 are possible. For example, light emitting displays may be integrated into screens such as windshields of cars or other vehicles. In the case of car windows for instance tinted glass is a desired feature, and on some car front windows a colored sign or bar may be arranged. The photoelectric conversion device may be integrated as a design feature for expensive cars: the color of the sign or the bar or the window could change so that the apparent tint may change in function of the angle of incidence of the light source.
Another field of application is where semi-transparent light harvesting window shades are needed, possibly vertical or horizontal shades. Users may for instance tune the transmission intensity and color by changing the angle of the lamellae of the shades or shutters. The market may demand different degrees of transparency, but also different colors to match interior designs. Also, in different factories windows are needed where a portion of the spectrum of the incident light has to be filtered such as waferfabs requiring a yellow over-all illumination. Architectural designs of buildings are also an application, requiring a control of the color of the photoelectric conversion elements. Another application is the design of films having the shape of particular objects, such as artificial light-harvesting trees appearing green.
It will be understood that other color correction arrangements can be realized with the embodiment of
Said waveguiding film 40 and substrate layer 50 may further comprise each at least an anti-reflection layer. On at least one of the surfaces of said waveguiding film and/or said substrate layer, a dielectric coating may be applied. The dielectric coating may be a multilayer interference filter coating. The surface of the waveguiding film 40 opposite to said first grating structure 20 may comprise microlens arrays, or microprism arrays or diffractive gratings, or a combination of them, allowing for instance to change the angle and/or the aperture of the incident light beam on said first grating structure 40. The surface of the substrate layer 50 opposite to said second grating structure 30 may comprise microlens arrays, or microprism arrays or diffractive gratings, or a combination of them, to change the angle and/or the aperture of the incident light beam on said second grating structure.
Said waveguiding film 40 and/or said substrate layer 50 may be separated from the photoconversion element 10 by a spacer or by a transparent layer, for example a dielectric layer. Said layer may comprise several different transparent layers.
In the embodiment of the photoelectric conversion device 1, shown in
For example, the embodiment of
The typical situation in which the photoelectric conversion device 1 of
An observer positioned to the side of the photoelectric conversion device opposite to the artificial light source, i.e. typically an observer being outdoors looking to a window illuminated by an inside artificial light, will see the photoelectric conversion device 1 as having a greenish-blue tint. The embodiment of
The embodiment represented in
The embodiment represented in
In another embodiment, similar to the embodiment represented in
In another embodiment, shown in
In another variant, at least a portion 120 of the near-infra-red light incident on said further gratings 22 could additionally be reflected by said further gratings 22, this portion 120 guided by the waveguide film 40 being subsequently coupled into the photoconversion elements by said first grating structures 20 as illustrated in
The further grating structure 22 may be arranged on any side of the waveguiding film 20, or at both sides. Further gratings structures 22 may at the same time transmit near-infra-red light, diffract near-infra-red light and reflect near-infra-red light.
The embodiment shown in
In another embodiment similar to the one of
The possible arrangements of the photoelectric conversion elements are not limited to the previously described embodiments. Additional features may be added to the described structural elements of the embodiments. For example, additional optical elements may be arranged to or into the photoelectric conversion device. As an example, microlens arrays, or coatings, or microprisms may be adapted on any of the surfaces of the waveguiding film and/or substrate layer. Additional layers may be disposed on the surfaces of the waveguiding film and/or the substrate layer. Said additional layers may be protection layers. Additional optical scattering microstructures may be imbedded in the waveguiding film and/or substrate layer and/or any layers of the photoelectric conversion device 1.
The invention is not limited to embodiments wherein the light source is to the side of the first grating structure 20 of the photoelectric conversion device 1. Similar embodiments may be devised wherein the light source is to the side of the second grating structure 30. In such a variant the first grating structure 20 may be designed as a reflection grating and arranged so as to reflect a portion of the transmitted visible light by the second grating structure 30, as illustrated in
In particular situations, according to the invention, the photoelectric conversion device 1 may be arranged to cope with the presence of at least two light sources, at least one light source being positioned to each side of the photoelectric conversion device 1.
According to another aspect of the invention, photoelectric conversion elements 10 may comprise at least two different photoelectric conversion elements, of which at least two photoelectric conversion elements are designed and arranged according to a different embodiment of the invention, and wherein said different photoelectric conversion elements 10 are connected so as to form a single photoelectric conversion element. Said at least two photoconversion elements 10 must not be arranged in a single plane and may be arranged and connected in different planes.
Also, the photoelectric conversion device 1 may be arranged for particular light sources, such as, but not limited to, high efficiency lighting sources such as solid state lighting sources.
The invention relates also to a method to generate electrical current, which will be directly understood by the skilled person from the description of the photoelectric conversion device 1 describes above.
Number | Date | Country | Kind |
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13180514.5 | Aug 2013 | EP | regional |
Filing Document | Filing Date | Country | Kind |
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PCT/EP2014/067497 | 8/15/2014 | WO | 00 |