JP2013084872A - Wavelength conversion film having pressure sensitive adhesive layer for increasing photovoltaic light collection efficiency - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wavelength conversion film without requiring a special set of tools for applying a wavelength conversion film to a solar cell device.SOLUTION: A wavelength conversion film 10 comprises: a protective layer 100, a wavelength conversion layer 101, an adhesive layer 102, and a removable liner 103. The wavelength conversion layer 101 comprises: a polymer matrix; and at least one optically stable chromophore which is configured so as to convert an incident photon of a first wavelength to a different second wavelength. The adhesive layer 102 includes a pressure-sensitive adhesive.

Description

  The present invention generally relates to wavelength converting films that can be readily applied to solar cells, solar panels or photovoltaic devices using an adhesive layer. The wavelength conversion film of the present invention is useful for improving the sunlight collection efficiency of these types of devices.

  The use of solar energy provides a promising alternative energy source for conventional fossil fuels, and therefore the development of devices that can convert solar energy into electricity, such as photovoltaic devices (which are also solar cells In recent years, it has attracted a great deal of attention. Several different types of fully developed photovoltaic devices include silicon-based devices, III-V and II-VI PN junction devices, copper-indium-gallium-selenium (CIGS) thin films Devices, organic sensitizer devices, organic thin film devices, and cadmium sulfide / cadmium telluride (CdS / CdTe) thin film devices are included. More details on these devices can be found in the literature, for example, Lin et al., “High Photoelectric Convergency Efficiency of Metal Phthalocyanine / Fullerene Heterojunction Photovoltaic Devices” (Inter20). However, many photoelectric conversion efficiencies of these devices still have room for improvement, and developing a technique for improving this efficiency has become an ongoing challenge for many researchers.

  In recent years, one technique that has been developed to improve the efficiency of photovoltaic devices is to utilize wavelength downshift films. Many photovoltaic devices cannot effectively use the entire spectrum of light. This means that the material on the device reaches a photoconductive material layer where this light can pass through a specific wavelength of light (typically a shorter UV wavelength), which can be converted into electricity. Because it absorbs instead of making it possible. By applying a wavelength downshifting film, such shorter wavelength photons are absorbed and re-emitted at a more convenient longer wavelength, in which case this longer wavelength is now caused by the photoconductive layer in the device. Can be absorbed and thus converted to electricity.

  This phenomenon is often observed in CdS / CdTe type and CIGS type thin film solar cells, both of which use CdS as a window layer. The low cost and high efficiency of these thin film solar cells have received great attention in recent years, but typical commercial battery cells have a photoelectric conversion efficiency of 10-16%. However, one problem with these devices is that light at wavelengths below 514 nm is absorbed by CdS, instead of passing light at wavelengths below 514 nm down to a photoconductive layer that can be converted to energy. The energy gap of CdS to cause (approximately 2.41 eV). This inability to use the entire spectrum of light effectively reduces the overall photoelectric conversion efficiency of the device.

  There have been many reports to date that disclose the use of wavelength downshift materials to improve the performance of photovoltaic devices. For example, US Patent Application Publication No. 2009/0151785 discloses a silicon-based solar cell containing an inorganic phosphor material that downshifts the wavelength. US Patent Application Publication No. 2011/0011455 discloses an integrated solar cell that includes a plasmon layer, a wavelength conversion layer, and a photovoltaic layer. US Pat. No. 7,791,157 discloses a solar cell with a wavelength conversion layer containing a quantum dot compound. U.S. Patent Application Publication No. 2010/0294339 discloses an integrated photovoltaic device containing a luminescent downshift material, however, no example embodiments were assembled. US 2010/0012183 discloses a thin film solar cell with a photoluminescent medium that downshifts the wavelength; however, no examples are provided. U.S. Patent Application Publication No. 2008/0236667 discloses an enhanced spectral conversion film made in the form of a thin film polymer comprising an inorganic fluorescent powder. However, each of these patents and patent application publications, which are incorporated herein by reference in their entirety, has a special set of tools for applying such wavelength converting films to solar cell devices. Use time consuming and sometimes complex and expensive techniques that may be required. These techniques include spin coating, drop casting, sedimentation, solvent evaporation, chemical vapor deposition, physical vapor deposition, and the like.

  Accordingly, one aspect of the present invention is to provide a wavelength conversion film that includes an adhesive layer (eg, a pressure sensitive adhesive layer). Such a wavelength conversion film can be easily applied to solar cells, solar panels, and photovoltaic devices, and can increase the efficiency of collecting sunlight when applied to the light incident surface of these devices. In one embodiment, the wavelength conversion film includes a wavelength conversion layer and an adhesive layer. In one embodiment, the wavelength converting layer comprises a polymer matrix and at least one light stable chromophore configured to convert incident photons of a first wavelength to a different second wavelength. In one embodiment, the adhesive layer includes a pressure sensitive adhesive.

  The wavelength conversion film described herein may include additional layers. For example, the wavelength conversion film can include a protective layer configured to prevent oxygen and moisture penetration into the wavelength conversion layer. In one embodiment, the wavelength converting film also includes a removable liner adjacent to the adhesive layer. The wavelength converting film can be applied to solar cells, solar panels or photovoltaic devices by removing the liner and exposing the adhesive layer. The adhesive layer can then be pressed and adhered to the light incident surface of the solar cell, solar panel or photovoltaic device. In one embodiment, application of the wavelength conversion film to a solar cell, solar panel or photovoltaic device improves the solar collection efficiency of the device.

  Another aspect of the present invention is a method for improving the performance of a solar cell, solar panel or photovoltaic device, wherein the wavelength conversion film as described herein is replaced with a solar cell, solar Related to a method comprising applying to a panel or photovoltaic device and adhering an adhesive layer to a light incident surface of a solar cell, solar panel or photovoltaic device. The sunlight collection efficiency of various devices can be improved. For example, silicon-based devices, III-V or II-VI PN junction devices, copper / indium / gallium / selenium (CIGS) thin film devices, organic sensitizer devices, organic thin film devices, or cadmium sulfide Solar light collection efficiency such as / cadmium telluride (CdS / CdTe) thin film devices can be improved.

  The wavelength converting film can be provided in the form of a tape-like roll having various lengths and widths to accommodate smaller individual solar cells or to accommodate the entire solar panel. A roll laminator can be used to apply the wavelength converting film to the device. The wavelength conversion film can be applied to a rigid device, or the wavelength conversion film can be applied to a flexible device. The wavelength converting film can be cut to any desired size using standard cutting methods.

  Another aspect of the present invention is a method for forming a wavelength conversion film comprising the following steps: a) forming a wavelength conversion layer, b) forming a protective layer, and directly forming the wavelength conversion layer. Laminating on top, and c) laminating an adhesive layer having a removable liner on the wavelength conversion layer on the surface opposite the protective layer.

  For purposes of summarizing the various aspects of the present invention and the advantages achieved over the related art, several objects and advantages of the present invention are described in this disclosure. Of course, it should be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the present invention has an advantage or group of advantages as taught herein for other purposes or that may be taught or suggested herein. It will be appreciated that the advantages may be embodied or implemented in a manner that is achieved or optimized without necessarily achieving.

  These and other embodiments are described in more detail below.

It is a figure which illustrates embodiment of the wavelength conversion film containing a protective layer, a wavelength conversion layer, an adhesive bond layer, and a removable liner. It is a figure which illustrates embodiment of the wavelength conversion film containing a wavelength conversion layer, an adhesive bond layer, and a removable liner. It is a figure which illustrates embodiment by which a wavelength conversion film is applied to a solar module. It is a figure which illustrates embodiment by which a wavelength conversion film is applied to a solar module. It is a figure which illustrates embodiment by which a wavelength conversion film is applied to a solar module. It is a figure which illustrates embodiment which applies a wavelength conversion film to a rigid solar panel using a roll laminator. It is a figure which illustrates embodiment which applies a wavelength conversion film to a flexible solar panel using a roll laminator.

  The present disclosure relates to a wavelength conversion film that, when applied to a light incident surface of a solar cell, solar panel, or photovoltaic device, increases the photoelectric conversion efficiency of the device. The inventors have surprisingly found that the wavelength conversion film comprises a wavelength conversion layer, an adhesive layer, and optionally a protective layer and, optionally, a removal. It has been discovered that this wavelength converting film can be assembled using a removable liner layer (if the removable liner layer is present, the removable liner layer is removed and the adhesive layer is removed from the solar cell). It can be easily applied to a solar cell by pressing it against the light incident surface). By applying a pressure sensitive adhesive type film, the solar light collecting efficiency of the solar cell device is enhanced. Pressure sensitive adhesive type wavelength conversion films are based on silicon-based devices, III-V and II-VI PN junction devices, CIGS thin film devices, organic sensitizer devices, organic thin film devices, CdS / CdTe thin films It can be assembled to be compatible with all different types of solar cells and solar panels, including devices, dye sensitized devices and the like. Devices such as amorphous silicon solar cells, microcrystalline silicon solar cells and crystalline silicon solar cells can also be improved. In addition, the films of the present invention are applicable to new devices or devices that are already in operation over the years and can be cut as needed to fit the device.

  In one embodiment, the wavelength conversion layer of the wavelength conversion film includes at least one chromophore and a polymer matrix. A chromophore compound, sometimes called a luminescent or fluorescent dye, is a compound that absorbs photons of a particular wavelength or wavelength range and re-emits the photons at a different wavelength or wavelength range. The chromophore used in the film media can greatly enhance the performance of solar cells and photovoltaic devices. However, such devices are often exposed to extreme environmental conditions for extended periods (eg, over 20 years). As such, it is important to maintain the stability of the chromophore over a long period of time. In one embodiment, a chromophore having good light stability over a long period of time (eg, 20,000 hours or more of illumination under 1 sun (AM1.5G) irradiation with less than 10% degradation) The compound is preferably used in the wavelength conversion film described herein.

  In one embodiment, the chromophore is configured to convert incident photons of a first wavelength to a different second wavelength. Various chromophores can be used. In one embodiment, the at least one light-stable chromophore is an organic dye selected from the group consisting of perylene derivative dyes, benzotriazole derivative dyes, benzothiadiazole derivative dyes, and combinations thereof.

In one embodiment, the at least one chromophore is a perylene diester derivative represented by the following general formula (I) or general formula (II):
In the above formula, R ₁ and R ₁ ′ in formula (I) are each independently hydrogen, C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₂ -C ₁₀ alkoxyalkyl, C _6- Selected from the group consisting of C ₁₈ aryl and C ₆ -C ₂₀ aralkyl; m and n in formula (I) each independently range from 1 to 5; and R ₂ in formula (II) And R ₂ ′ are each independently selected from the group consisting of C ₆ -C ₁₈ aryl and C ₆ -C ₂₀ aralkyl. In one embodiment, if one of the cyano groups is present at the 4-position of the perylene ring with respect to formula (II), the other cyano group is not present at the 10-position of the perylene ring. In one embodiment, if one of the cyano groups is present at the 10-position of the perylene ring with respect to formula (II), the other cyano group is not present at the 4-position of the perylene ring.

In one embodiment, R ₁ and R ₁ ′ are independently selected from the group consisting of hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkoxyalkyl, and C ₆ -C ₁₈ aryl. In one embodiment, R ₁ and R ₁ ′ are independently selected from the group consisting of isopropyl, isobutyl, isohexyl, isooctyl, 2-ethylhexyl, diphenylmethyl, trityl and diphenyl. In one embodiment, R ₂ and R ₂ ′ are independently selected from the group consisting of diphenylmethyl, trityl and diphenyl. In one embodiment, each m and n in formula (I) is independently in the range of 1-4.

  Perylene diester derivatives represented by general formula (I) or general formula (II) can be prepared by known methods, for example, in US Provisional Patent Application Nos. 61 / 430,053 and 61 / 485,093. (Both of which are hereby incorporated by reference in their entirety).

Benzotriazole derivative dyes and benzothiadiazole derivative dyes are also possible as chromophores in the wavelength conversion layer. In one embodiment, the at least one chromophore is a 2H-benzo [d] [1,2,3] triazole heterocyclic system represented by the following general formula (III):

  In one embodiment, n in formula (III) is an integer in the range of 0-100. In one embodiment, if n is equal to zero, the following conditions may apply: (1) The electron acceptor group at the N-2 position is based on the 2H-benzo [d] [1,2,3] triazole system. And (2) one electron donor group at the C-4 position and two electron donor groups at the C-7 position are the same or different, and at least one of these electron donor groups One is a component that increases the electron density of the 2H-benzo [d] [1,2,3] triazole system, and the other electron donor group is 2H-benzo [d] [1,2,3]. A component that either increases the electron density of the triazole system or has a neutral effect on the electron density of the 2H-benzo [d] [1,2,3] triazole system, or with hydrogen is there.

  In one embodiment, if n in formula (III) is in the range of 1-100, the following conditions may apply: (1) The electron acceptor group at the N-2 position is independently the same or Selected differently, but in this case, these electron acceptor groups include a component that reduces the electron density of the 2H-benzo [d] [1,2,3] triazole subunit to which it is attached, (2 ) An electron donor linker group connects two 2H-benzo [d] [1,2,3] triazole units at their respective C-4 and C-7 positions, and (3) one electron donor group , At least one of the two electron donor groups or electron donor linker groups increases the electron density of the 2H-benzo [d] [1,2,3] triazole unit to which it is attached. The component or linker and the remaining electron donor group and / or electron donor linker group each increase the electron density of the 2H-benzo [d] [1,2,3] triazole to which they are attached, or Includes a component or linker having a neutral effect on the electron density of the 2H-benzo [d] [1,2,3] triazole to which they are attached, provided that the remaining electron donor group 1 or electron donor group 2 is Hydrogen can be included. In one embodiment, one electron donor group and two electron donor groups are the same or different. In one embodiment, if n in formula (III) is an integer in the range 2-100, the electron donor linker groups are the same or different.

The numbering of atoms in the 2H-benzo [d] [1,2,3] triazole system is defined below:

  Any “electron donor group” increases the electron density of the 2H-benzo [d] [1,2,3] triazole system or 2H-benzo [d] [1,2, 3] Defined as a group having a neutral influence on the electron density of the triazole system. An “electron donor linker” can be any group that connects two 2H-benzo [d] [1,2,3] triazole systems, thereby conjugating their π orbitals. Defined as a group, but this group can also increase the electron density of the 2H-benzo [d] [1,2,3] triazole system to which they are attached, or the 2H-benzo to which they are attached. [D] Can have a neutral effect on the electron density of the [1,2,3] triazole series. An “electron acceptor group” is defined as a group that reduces the electron density of the 2H-benzo [d] [1,2,3] triazole system, whatever the group. Placing an electron acceptor group at the N-2 position of the 2H-benzo [d] [1,2,3] triazole ring system provides unexpected and improved benefits.

Preferably, the electron acceptor significantly reduces the electron density of the triazole ring. In one embodiment of the invention, the electron acceptor group comprises a phenyl ring in which at least one electron withdrawing substituent is present in its ortho or para position, with or without additional substituents. For example, an electron acceptor group can include a component represented by the following formula:

In the electron acceptor component, Y, Y ¹ , Y ² and Y ³ are each independently —NO ₂ , —C≡N, —CH═N—Ar, —N═N—Ar, —N═CH. -Ar, -C (= O) R, -C (= O) OR or -C (= O) NR < ¹ > R < ² >, provided that in these formulas, Ar is an aryl group. In the electron acceptor component, R, R ¹ and R ² are each independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl. Typically, Substituent A, Substituent B, Substituent C and Substituent D are hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl, but they are also either Of electron withdrawing groups or electron donating groups. Furthermore, a pair of substituents, ie A and B, C and D, or B and C, can also be joined together to form one or more fused rings. Some examples of fused rings can include naphthalene, anthracene, phenanthrene, pyrene, and the like.

In one embodiment, the electron acceptor group includes an electron-deficient heterocyclic ring, with or without any additional substituents. A basic example of such a structure is shown below:

In one embodiment, an electron-deficient heterocyclic ring can also be fused with a benzene ring or another heterocyclic ring, as illustrated in the examples shown below. Again, in all of these molecules, the ring may be unsubstituted or may be derivatized with either substituent.

In one embodiment, another option for the electron acceptor in this case involves an electron withdrawing group attached to the N-2 position of the benzotriazole system via a double bond. Possible compounds of this type include the following:

  The disclosed invention involves at least one electron donor group, as given in general formula (III). The position of the second electron donor may be occupied by another electron donor, a hydrogen atom, or another neutral substituent. Typical electron donor groups have been extensively reported in the literature, all of which are suitable for use in the disclosed invention. One electron donor group and two electron donor groups may be the same or different.

In one embodiment, the electron donor component is a phenyl ring in which at least one electron donating heteroatom substituent X (N, O or S) is present in its ortho or para position, as shown below. Is:

In the electron donating component, X, X ¹ , X ² and X ³ are each independently selected from the group consisting of —NR ₂ , —NR ¹ R ² , —NRCOR ¹ , —OR, —OCOR or —SR. In which R, R ¹ and / or R ² are each independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl. In the electron donating component, the substituent A, the substituent B, the substituent C, and the substituent D each contain hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, or a heteroatom. Selected from the group consisting of The group X, group X ¹ , group X ² and group X ³ can also be bonded directly to the benzotriazole core.

In one embodiment, the fused aromatic ring forms another group of electron donor components with or without substituents. Some examples of such rings are shown below:

In another embodiment, the electron donor is a heterocyclic ring, such as an electron-rich heterocyclic ring as shown below. These rings can be optionally substituted.

In one embodiment, for example, when n in formula (III) is 1 or more, two or more benzotriazol-2-yl systems are connected by a linker group, which results in a more complex structure. In this case, the general formula (III) includes an electron-donating linker group. At least one of electron donor 1, electron donor 2, and electron donor linker group must be a group that increases the electron density of the 2H-benzo [d] [1,2,3] triazole system to which it is attached. . Electron donor 1 and electron donor 2 are defined as above except that they can also be hydrogen atoms, or 2H-benzo [d] [1,2,3] triazole to which it is attached. Defined as any other neutral group that has no effect on the electron density of the system. The number n of repeating units can vary from 1 to 100. An electronic linker represents a conjugated electron system, where the conjugated electron system can be neutral or can act as an electron donor itself. A typical structure of a linker assembled exclusively from carbon atoms is shown below. They may or may not contain further linked substituents.

In another embodiment, the electron donating linker can also include a heterocyclic block as shown below. A combination of two carbon-carbon linkers or heterocycle-heterocyclic linkers or carbon-heterocyclic linkers is also possible. R, R ¹ and R ² in these structures represent any substituted or unsubstituted alkyl group or aryl group.

  The benzotriazole derivative represented by the general formula (III) can be prepared by a known method, for example, the method described in US Provisional Patent Application No. 61 / 539,392 (the content of which is Incorporated herein by reference in its entirety).

  Preferably, the at least one light-stable chromophore ranges from about 0.01 wt% to about 10.0 wt% in the weight ratio of the polymer matrix in any wavelength conversion layer (or wavelength conversion sublayer) polymer matrix. Present in the amount. In one embodiment, the at least one light-stable chromophore is about 0.01 wt% to about 3.0 wt% by weight ratio of the polymer matrix in the polymer matrix of any wavelength conversion layer (or wavelength conversion sublayer). Present in an amount in the range of%. In one embodiment, the at least one light-stable chromophore is about 0.05 wt% to about 2.0 wt% by weight of the polymer matrix in the polymer matrix of any wavelength conversion layer (or wavelength conversion sublayer). Present in an amount in the range of%. In one embodiment, the at least one light-stable chromophore is about 0.1 wt% to about 1.0 wt% by weight of the polymer matrix in the polymer matrix of any wavelength conversion layer (or wavelength conversion sublayer). Present in an amount in the range of%.

  In one embodiment, the wavelength converting layer includes two or more chromophores, such as at least two different light stable chromophores. Depending on the solar module to which the film is to be attached, it may be desirable to have multiple light stable chromophores in the wavelength conversion layer. For example, in a solar module system having optimal photoelectric conversion at a wavelength of about 500 nm, the efficiency of such a system can be improved by converting photons of other wavelengths to a wavelength of 500 nm. In such cases, the first light-stable chromophore can act to convert photons having a wavelength in the range of about 400 nm to about 450 nm to photons with a wavelength of about 500 nm. Such chromophores can act to convert photons having wavelengths in the range of about 450 nm to about 475 nm to photons with a wavelength of about 500 nm. A particular wavelength control can be selected based on the chromophore utilized.

  In one embodiment, two or more chromophores are mixed together in the same layer. In one embodiment, two or more chromophores are placed in separate sublayers within the wavelength converting film. For example, the first wavelength conversion sublayer can include a first chromophore and the second wavelength conversion sublayer can include a second chromophore.

  In one embodiment, when more than one chromophore is present in the wavelength converting layer, at least one of these chromophores is an upconversion chromophore. Upconversion chromophores are chromophores that convert photons from lower energy (long wavelength) to higher energy (short wavelength). In one embodiment, when more than one chromophore is present in the wavelength converting layer, at least one of these chromophores is a downshift chromophore. Downshift chromophores are chromophores that convert high energy (short wavelength) photons to lower energy (long wavelength). Thus, the wavelength conversion film can include an upconversion chromophore and a downshift chromophore.

  The wavelength converting layer can also be divided into two or more sub-layers such that the wavelength converting film includes at least two layers each containing one or more chromophores. In one embodiment, the wavelength conversion layer includes a first wavelength conversion sublayer and a second wavelength conversion sublayer. In one embodiment, the first wavelength conversion sublayer and the second wavelength conversion sublayer comprise the same light stable chromophore or different light stable chromophores. The first wavelength conversion sublayer can include a first chromophore and the second wavelength conversion sublayer can include a second chromophore.

  The wavelength conversion layer preferably comprises a polymer matrix. A variety of polymers can be used. In one embodiment, the protective layer polymer matrix comprises polyethylene terephthalate, polymethyl methacrylate, polyvinyl butyral, ethylene vinyl acetate, ethylene tetrafluoroethylene, polyimide, amorphous polycarbonate, polystyrene, siloxane sol gel, polyurethane, poly Including a material selected from the group consisting of acrylates and combinations thereof.

  The thickness of the wavelength conversion layer (or wavelength conversion sublayer in combination) may vary. In one embodiment, the thickness of the wavelength converting layer ranges from about 10 μm to about 2 mm. In one embodiment, the thickness of the wavelength conversion layer ranges from about 25 μm to about 1.5 mm. In one embodiment, the thickness of the wavelength conversion layer ranges from about 50 μm to about 1 mm. The thickness can be controlled by those skilled in the art using known film deposition techniques, as indicated by the disclosure herein.

  In one embodiment, the wavelength conversion film further includes a protective layer configured to maintain chromophore stability in the wavelength conversion layer. For example, the protective layer can prevent oxygen and moisture from penetrating into the wavelength conversion layer. In one embodiment, the protective layer includes a polymer matrix. In one embodiment, the protective layer polymer matrix comprises polyethylene terephthalate, polymethyl methacrylate, polyvinyl butyral, ethylene vinyl acetate, ethylene tetrafluoroethylene, polyimide, amorphous polycarbonate, polystyrene, siloxane sol gel, polyurethane, poly Including a material selected from the group consisting of acrylates and combinations thereof. As with the wavelength conversion layer, the thickness of the protective layer can vary. In one embodiment, the thickness of the protective layer ranges from about 10 μm to about 2 mm. In one embodiment, the thickness of the protective layer ranges from about 25 μm to about 1.5 mm. In one embodiment, the thickness of the protective layer ranges from about 50 μm to about 1 mm.

  Preferably, the polymer matrix used in either the wavelength converting layer or the protective layer, or both, has a refractive index in the range of about 1.400 to about 1.700. In one embodiment, the refractive index of the polymer matrix material in the wavelength converting layer or the protective layer or both ranges from about 1.450 to about 1.550.

  Various types of adhesives can be used in the adhesive layer. Preferably, the adhesive layer includes a pressure sensitive adhesive. The pressure sensitive adhesive can be permanent or non-permanent or a combination of both. Preferably, the pressure sensitive adhesive is compatible with the light incident surface of a solar cell, solar panel or photovoltaic device. Such a light incident surface can include, for example, glass or a polymer. In one embodiment, the adhesive layer comprises a material selected from the group consisting of acrylic, ethylene vinyl acetate, polyurethane, and combinations thereof. The thickness of the adhesive layer can vary. In one embodiment, the thickness of the adhesive film ranges from about 0.5 μm to about 1 mm. In one embodiment, the thickness of the adhesive film ranges from about 1 μm to about 100 mm.

  A removable liner can be present in the wavelength converting film. The removable liner can be placed adjacent to the adhesive layer such that the removable liner prevents the adhesive layer from bonding to other objects until the liner is removed. The removable liner can include known materials. For example, the removable liner can include a material selected from a fluoropolymer or polyethylene terephthalate (PET). In one embodiment, the removable liner thickness ranges from about 10 μm to about 100 μm.

  The overall thickness of the wavelength converting film can be expressed by adding the thickness of each individual film described herein. In one embodiment, the thickness of the wavelength converting film ranges from about 10 μm to about 2 mm. In one embodiment, the thickness of the wavelength conversion film ranges from about 1 μm to about 5 mm. In one embodiment, the thickness of the wavelength conversion film ranges from about 50 μm to about 1 mm.

  The wavelength converting film can also include additional layers. For example, an additional adhesive layer can be included. In one embodiment, an adhesive layer is present to integrally bond the two layers between the protective layer and the wavelength converting layer. Other layers can also be included to further increase the photovoltaic conversion efficiency of the solar module. For example, the wavelength conversion film can have a microstructure layer on top of the protective layer or between the protective layer and the wavelength conversion layer. The microstructure layer is the solar module solar by reducing the loss of photons to the environment that is often re-emitted from the chromophore after absorption and wavelength conversion away from the photoelectric conversion layer of the solar module device. It can be designed to further increase the light collection efficiency. Layers with various microstructures (ie pyramids or cones) on the surface can increase the internal reflection and internal refraction of photons into the photoelectric conversion layer of the device, thereby increasing the solar concentration of the device. Efficiency can be further increased. Additional layers can also be incorporated into the pressure sensitive adhesive type wavelength converting film.

  Methods for improving the performance of solar cells, solar panels or photovoltaic devices can be performed using the wavelength conversion films described herein. For example, the wavelength converting film can be applied to a solar cell, solar panel or photovoltaic device using the adhesive layer of the film. In one embodiment, the film can be applied to a solar cell, solar panel or photovoltaic device using a roll laminator. Silicon-based devices, III-V or II-VI PN junction devices, copper / indium / gallium / selenium (CIGS) thin film devices, organic sensitizer devices, organic thin film devices or cadmium sulfide / cadmium telluride Devices such as (CdS / CdTe) thin film devices can be improved. Such devices can include a light incident surface comprising glass or polymer. In one embodiment, the polymer of the device is polyethylene terephthalate, polymethyl methacrylate, polyvinyl butyral, ethylene vinyl acetate, ethylene tetrafluoroethylene, polyimide, polycarbonate, polystyrene, siloxane sol gel, polyurethane, polyacrylate, and combinations thereof Can be selected from the group consisting of

  The solar concentrating device may also be rigid or flexible. For example, rigid devices include silicon-based solar cells. Flexible solar devices are often made from organic thin films and may be used on the surface of a covering, tent or other flexible substrate. Thus, in one embodiment, the wavelength conversion film can be applied to a rigid device or a flexible device.

  The wavelength conversion film can be manufactured according to several different methods. In one embodiment, the method comprises: a) forming a wavelength conversion layer, b) forming a protective layer and laminating it directly on the wavelength conversion layer, and c) a removable liner. A step of laminating an adhesive layer having a wavelength conversion layer on the surface opposite to the protective layer. In one embodiment, the method includes a) forming a wavelength conversion layer, and b) laminating an adhesive layer having a removable liner on the wavelength conversion layer.

  In some embodiments as shown in FIG. 1, the wavelength conversion film 10 includes a protective layer 100, a wavelength conversion layer 101, an adhesive layer 102, and a removable liner 103. In some embodiments as shown in FIG. 2, the wavelength conversion film 11 includes a wavelength conversion layer 104, an adhesive layer 102 and a removable liner 103.

  As shown in FIG. 3A, the wavelength converting film 10 comprising the protective layer 100, the wavelength converting layer 101, the adhesive layer 102 and the removable liner 103 is obtained by first removing the liner 103 and exposing the adhesive layer 102. It can be applied to solar panels. As shown in FIG. 3B, the adhesive layer 102 can then be applied against the light incident surface 106 of the solar panel 105 in order to adhere the wavelength conversion film to the solar panel 105. As shown in FIG. 3C, this forms a solar panel 20 with improved sunlight collection efficiency. In some embodiments, the protective layer 100 shown in FIGS. 3A-3C is not required and is present as needed.

  As shown in FIG. 4, the wavelength converting film can be applied to a rigid solar panel using a roll laminator to peel off the liner, spread the film from the roll, and then press the film against the solar panel. it can. As shown in FIG. 5, the wavelength converting film is applied to a flexible solar panel device using a roll laminator to peel the liner, spread the film from the roll, and then press the film against the solar panel. Can do.

  The synthesis method for the pressure sensitive adhesive type wavelength conversion film is not limited, but can follow the synthesis procedure as an example described as scheme 1 to scheme 2 detailed below.

Scheme 1: General Procedure for Wet Processing to Form Wavelength Conversion Films Wavelength conversion films can be processed into film structures using wet processing techniques. The wavelength conversion layer (i) preparing a polymer solution in which the polymer powder is dissolved in a solvent (for example, tetrachloroethylene (TCE), cyclopentanone, dioxane, etc.) in a predetermined ratio; (ii) containing a polymer mixture A chromophore solution is prepared by mixing the polymer solution with a chromophore in a predetermined weight ratio to obtain a chromophore-containing polymer solution; (iii) a chromophore / polymer layer is prepared by adding a chromophore-containing polymer solution; Flowing directly onto the glass substrate, after which the substrate is heat treated from room temperature to 100 ° C. in 2 hours, and the residual solvent is completely removed by further vacuum heating at 130 ° C. overnight, and (Iv) peeling off the chromophore / polymer layer below the surface of the water and then completely drying the unsupported polymer layer before use. It is prepared me; thickness (v) layer can be controlled from about 1μm to about 1mm by varying the concentration and evaporation rate of the chromophore / polymer solution.

  When the wavelength conversion layer is formed, a protective layer is formed if necessary. When the protective layer is present, the protective layer is produced by an extruder and then laminated on the wavelength conversion layer by a laminator. An adhesive layer with an optional removable liner is then applied to the exposed wavelength converting layer using a laminator. The film can be wound up like a roll of tape.

Scheme 2: General Procedure for Dry Processing to Form Wavelength Conversion Film In one embodiment, the wavelength conversion layer comprises (i) a polymer powder or polymer pellet and a luminescent dye powder together at a specific temperature. Mixing in a predetermined ratio by means of a mixer, (ii) degassing the mixture at a specific temperature for between 1 and 8 hours, (iii) then forming a layer using an extruder (V) The thickness of the layer is controlled from about 1 μm to about 1 mm by the extruder.

  When the wavelength conversion layer is formed, a protective layer is formed if necessary. A protective layer is produced by an extruder and then laminated on the wavelength conversion layer by a laminator. An adhesive layer with an optional removable liner is then applied to the exposed wavelength converting layer using a laminator. The film can be wound up like a roll of tape.

  Further aspects, features and advantages of the present invention will become apparent from the detailed examples below.

  Embodiments of the present invention are described with reference to preferred embodiments that are not intended to limit the present invention. In this disclosure, the listed substituents include both further substituted and unsubstituted groups, unless otherwise specified. Further, in the present disclosure where conditions and / or structures are not specified, one of ordinary skill in the art can readily provide such conditions and / or structures as routine experimentation in light of the present disclosure. .

Example 1
a) Synthesis of chromophore compounds
Intermediate A
A common intermediate A is synthesized in a two-step process.

Step 1: Synthesis of 4,7-dibromo-2H-benzo [d] [1,2,3] triazole Benzotriazole (5.96 g, 50 mmol), bromine (7.7 mL, 150 mmol) and 48% HBr (30 mL) The mixture was heated at 120 ° C. for 24 hours. The reaction mixture was poured into ice / water (200 mL), neutralized with 5N NaOH, and excess bromine was removed by adding 1M sodium thiosulfate (test with KI / starch paper). After stirring for 30 minutes, the solid was filtered off, washed with water and dried in a vacuum oven. The crude product was purified by column chromatography (silica gel; dichloromethane / ethyl acetate, 75:25) and washing with ethyl acetate (50 mL) to give 4,7-dibromo-2H-benzo [d] [1,2,3 Triazole was obtained (2.65 g, 19%).

Step 2: Synthesis of Intermediate A, ie 4,7-bis (4- (N, N-diphenylamino) phenyl) -2H -benzo [d] [1,2,3] triazole 4,7-dibromo- 2H-benzo [d] [1,2,3] triazole (1.37 g, 5.5 mmol), 4- (diphenylamino) phenylboronic acid (3.47 g, 12 mmol), sodium carbonate (5 mL) in water (10 mL) .30 g, 50 mmol), a mixture of tetrakis (triphenylphosphine) palladium (0) (1.15 g, 1.0 mmol), n-butanol (80 mL) and toluene (10 mL) was stirred at 120 ° C. for 4 days under argon. And heated. The reaction mixture was poured into water (300 mL), stirred for 15 minutes and extracted with dichloromethane (2 x 300 mL). The solution is dried over anhydrous sodium sulfate, the solvent is removed under reduced pressure, and the residue is chromatographed (silica gel; dichloromethane / ethyl acetate, 95: 5) to give 4,7-bis (4- (N, N- Diphenylamino) phenyl) -2H-benzo [d] [1,2,3] triazole (Intermediate A) was obtained (1.85 g, 56%). ¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.58 (s, 2H, benzotriazole), 7.16 to 7.23 (m, 16H, p-phenylene and Ph), 7.07 (t, J = 7.3, 4H, Ph), 7.02 (bs, 1H, NH).

A mixture of Intermediate A (500 mg, 0.82 mmol), 2-chloropyrimidine (343 mg, 3.0 mmol), 60% NaH (60 mg, 1.5 mmol) and dimethylformamide (10 mL) was stirred under argon, 120 ° C. For 20 hours. The reaction mixture was poured into water (100 mL) and extracted with dichloromethane (4 × 100 mL). The extract was dried over anhydrous sodium sulfate, the volatiles were removed under reduced pressure, and the residue was chromatographed using silica gel and dichloromethane / ethyl acetate (95: 5) as eluent. The resulting product was recrystallized from ethanol to give 4,7-bis (4- (N, N-diphenylamino) phenyl) -2- (pyrimidin-2-yl) -2H-benzo [d] [1 , 2,3] triazole (compound 1) was obtained (orange crystals; 340 mg, 61%). ¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.99 (d, J = 5.1 Hz, 2H, pyrimidine), 8.02 (d, J = 8.8 Hz, 4H, p-phenylene), 7.66 (S, 2H, benzotriazole), 7.47 (t, J = 4.8Hz, 1H, pyrimidine), 7.28 (m, 8H, Ph), 7.21 (d, J = 8.4Hz, 4H , P-phenylene), 7.18 (m, 8H, Ph), 7.05 (tt, J = 7.3 Hz and 1.1 Hz, 4H, Ph). UV-vis spectrum (dichloromethane): λ _max = 451 nm. Fluorescence measurement method (dichloromethane): λ _max = 600 nm.

Compound 2 and Compound 3
Perylene diester derivatives, which are preferred but non-limiting embodiments of the invention as disclosed herein, are synthesized using a two-step process.

Step 1: Synthesis of diisobutyl 4,10-dibromoperylene-3,9-dicarboxylate
To synthesize 4,10-dibromoperylene-3,9-dicarboxylate diisobutyl ("Compound 2"), N-bromosuccinimide (7.85 g, 44 mol) was added to a solution of perylene dicarboxylic acid diisobutyl ester (perylene). Dicarboxylic acid diisobutyl ester can be purchased from Aldrich Chemical Co.). Perylene dicarboxylic acid diisobutyl ester is also prepared by performing esterification with isobutyl alcohol in DMF (50 ml) under heating at 65 ° C. for 3 hours (until the initial suspension changes to a clear solution). Synthesized from acid derivatives. After cooling, methanol (500 ml) was added to the stirred reaction mixture. A heavy precipitate formed immediately, which was separated by filtration, washed with a small amount of cold methanol and dried in a vacuum oven to give compound 2 as a yellow solid (which was purified by ¹ H-NMR. 9.6 g, 78%).

Step 2: Synthesis of diisobutyl 4,10-bis (4- (trifluoromethyl) phenyl) perylene-3,9-dicarboxylate
To synthesize diisobutyl 4,10-bis (4- (trifluoromethyl) phenyl) perylene-3,9-dicarboxylate (“Compound 3”), tetrakis (triphenylphosphine) palladium (0) (500 mg, 0 .43 mmol) under argon atmosphere, Compound 2 (3.05 g, 5 mmol), 4-trifluoromethylphenylboronic acid (2.09 g, 11.0 mmol) in toluene (50 mL), 2M Na ₂ CO ₃ in water. (20 mL) and ethanol (30 mL) were added to the solution in a mixture. The reaction mixture was heated at 90 ° C. for 1 hour (until a clear separation of organic layer, water and solid was observed). The organic layer was separated and filtered through celite to remove the palladium catalyst, and then the solvent was partially removed under vacuum. The product was precipitated from methanol, filtered off, washed with cold methanol and dried in a vacuum oven to give pure compound 3 (by ¹ H-NMR) as a yellow solid (3.30 g, 89% ). Alternative purification was performed by column chromatography (silica gel and a mixture of hexane-ethyl acetate (4: 1) as mobile phase).

b) Wet process synthesis wavelength conversion film of wavelength conversion film, which includes a protective layer 100, a wavelength conversion layer 101, an adhesive layer 102 and a removable liner 103 as illustrated in FIG. Processed into a structure. First, the wavelength conversion layer is used to (i) polyvinyl butyral (PVB) polymer solution, PVB powder (obtained from Aldrich and used as received) TCE (obtained from Aldrich and used as received) And (ii) a chromophore containing a PVB matrix, compound 1 (Example 1a) or compound 3 (Example) from which a PVB polymer solution was synthesized. 1b) and mixing at a weight ratio of 0.3 wt% (chromophore compound / PVB) to obtain a chromophore-containing polymer solution, (iii) a chromophore / polymer layer comprising a chromophore-containing polymer solution Is poured directly onto the glass substrate, after which the substrate is heat-treated from room temperature to 100 ° C. in 2 hours, and the residual solvent is left at 130 ° C. overnight. And (iv) by peeling off the chromophore / polymer layer under the surface of the water and then completely drying the freestanding polymer layer; (v ) Layer thickness was 250 μm. This was obtained by varying the concentration of the chromophore / polymer solution and the evaporation rate.

  When the wavelength conversion layer is formed, a protective layer is formed. A protective layer is produced by an extruder and then laminated on the wavelength conversion layer by a laminator. Thereafter, an adhesive layer having a removable liner is applied to the exposed wavelength converting layer using a laminator. The thickness of the wavelength conversion film is about 400 μm.

c) Application of film to solar cell The film is cut to fit the light incident surface of the CdS / CdTe solar cell. The removable liner is removed and the exposed adhesive layer is pressed against the light incident effective window of the CdS / CdTe battery cell to adhere the film to the device.

d) Measurement of efficiency enhancement The photoelectric conversion efficiency of the solar cell was measured by a Newport 400W full spectrum solar simulator system. The light intensity was adjusted to 1 sun (AM1.5G) with a calibrated reference single crystal silicon solar cell measuring 2 cm × 2 cm. Thereafter, IV characterization of CdS / CdTe solar cells was performed under the same irradiation. Its efficiency is calculated by the Newport software program installed in the simulator. After determining the efficiency of the battery cell alone, the efficiency enhancement of the battery cell having a pressure sensitive adhesive type wavelength conversion film is measured. The film was cut into the same shape and size of the light incident effective window of the CdS / CdTe battery cell and applied to the light incident front glass substrate of the CdS / CdTe battery cell using the method described above.

The efficiency enhancement of the solar cell with the film applied was determined using the following formula:
Efficiency enhancement = (η _{battery cell + film} −η _{battery cell} ) / η _{battery cell} ^* 100%

  The relative efficiency enhancement for the CdTe solar cell was 14.0% for Example 1a containing Compound 1 and 15.2% for Example 1b containing Compound 3.

Example 2
Example 2 is the same procedure as shown in step a to step d of Example 1, except that dry processing techniques were used to produce the wavelength conversion layer as will be demonstrated below. Followed.

  The wavelength converting layer is (i) mixing the powder of PVB (Example 2a) or EVA (Example 2b) in a mixer at 170 ° C. in a predetermined ratio of 0.3% with (ii) this mixture. (Iii) is then produced by forming the layer using an extruder or hot press at 120 ° C .; (v) The layer thickness was 250 μm. This was controlled by an extruder. When the wavelength conversion layer is formed, a protective layer is formed. A protective layer is produced by an extruder and then laminated on the wavelength conversion layer by a laminator. Thereafter, an adhesive layer having a removable liner is applied to the exposed wavelength converting layer using a laminator. The thickness of the wavelength conversion film is about 400 μm.

  The relative efficiency enhancement for CdTe solar cells is 15.0% for Example 2a containing PVB and 14.3% for Example 2b containing EVA.

Comparative Example 3
This example shows that Lumogen F Yellow Y083 (purchased from BASF and used as received) (perylene derivative luminescent dye blend mixture) was used in place of Compound 1 or Compound 3, The same procedure outlined in Example 1 and Example 2 was followed.

  The relative efficiency enhancement is 11%, 11.2% and 10% for wet processed PVB, dry processed PVB and dry processed EVA, respectively.

The above description discloses several methods and materials of the preferred embodiments. The present invention is amenable to modifications in methods and materials, as well as changes in manufacturing methods and equipment. Such modifications will be apparent to those skilled in the art from consideration of the present disclosure or from practice of the invention disclosed herein. Therefore, it is not intended that the invention be limited to the specific embodiments disclosed herein, but the invention be as embodied in the appended claims. It is intended to encompass all modifications and variations that fall within the true scope and spirit of the present invention.

Claims (27)

A wavelength conversion film including a wavelength conversion layer and an adhesive layer,
The wavelength converting layer comprises a polymer matrix and at least one light stable chromophore configured to convert incident photons of a first wavelength to a different second wavelength, and the adhesive layer is sensitive A wavelength conversion film containing a pressure-sensitive adhesive.   The wavelength conversion film according to claim 1, further comprising a protective layer configured to prevent oxygen and moisture from penetrating into the wavelength conversion layer.   The wavelength conversion film according to claim 1, further comprising a removable liner adjacent to the adhesive layer.   The wavelength conversion film according to claim 1, wherein the wavelength conversion layer contains at least two different light-stable chromophores.   The wavelength conversion film according to claim 1, wherein at least one light-stable chromophore is an up-conversion chromophore.   The wavelength conversion film according to claim 1, wherein at least one light-stable chromophore is a downshift chromophore.   The wavelength conversion layer includes a first wavelength conversion sublayer and a second wavelength conversion sublayer, and the first wavelength conversion sublayer and the second wavelength conversion sublayer are the same or different from each other. The wavelength conversion film in any one of Claims 1-6 containing these.   The wavelength conversion film in any one of Claims 2-7 in which the said protective layer contains a polymer matrix.   The polymer matrix of the protective layer is polyethylene terephthalate, polymethyl methacrylate, polyvinyl butyral, ethylene vinyl acetate, ethylene tetrafluoroethylene, polyimide, amorphous polycarbonate, polystyrene, siloxane sol-gel, polyurethane, polyacrylate, and their The wavelength conversion film according to claim 8, comprising a substance selected from the group consisting of combinations.   The polymer matrix of the wavelength conversion layer is made of polyethylene terephthalate, polymethyl methacrylate, polyvinyl butyral, ethylene vinyl acetate, ethylene tetrafluoroethylene, polyimide, amorphous polycarbonate, polystyrene, siloxane sol-gel, polyurethane, polyacrylate and the like The wavelength conversion film in any one of Claims 1-9 containing the substance selected from the group which consists of these.   11. The at least one light stable chromophore is present in the polymer matrix of the wavelength converting layer in an amount in the range of about 0.01 wt% to about 3.0 wt% by weight ratio of the polymer matrix. The wavelength conversion film in any one of.   12. The at least one light-stable chromophore is an organic dye selected from the group consisting of perylene derivative dyes, benzotriazole derivative dyes, benzothiadiazole derivative dyes, and combinations thereof. Wavelength conversion film. Said at least one light-stable chromophore is represented by the following general formula (I) or general formula (II):
(In the above formula, R ₁ and R ₁ ′ in formula (I) are each independently hydrogen, C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₁ -C ₁₀ alkoxy, C _6- Selected from the group consisting of C ₁₈ aryl and C ₆ -C ₂₀ aralkyl; m and n in formula (I) each independently range from 1 to 5; and R ₂ in formula (II) And R ₂ ′ are each independently selected from the group consisting of C ₆ -C ₁₈ aryl and C ₆ -C ₂₀ aralkyl)
The wavelength conversion film in any one of Claims 1-12 which is the perylene diester derivative represented by these. Said at least one light-stable chromophore is represented by the following general formula (III):
(In the above formula,
n is an integer in the range of 0-100;
If n is equal to zero,
The electron acceptor group at the N-2 position is a component that lowers the electron density of the 2H-benzo [d] [1,2,3] triazole system; and an electron donor group at the C-4 position and the C-7 position The two electron donor groups in are the same or different and at least one of these electron donor groups is a component that increases the electron density of the 2H-benzo [d] [1,2,3] triazole system, and The other electron donor group increases the electron density of the 2H-benzo [d] [1,2,3] triazole system or the electron of the 2H-benzo [d] [1,2,3] triazole system. Is either a component that has a neutral effect on density, or is hydrogen;
If n is in the range of 1-100,
The electron acceptor groups at the N-2 position are independently selected to be the same or different, provided that these electron acceptor groups are the 2H-benzo [d] [1,2,3 to which they are attached. A component that reduces the electron density of the triazole subunit;
An electron donor linker group connects two 2H-benzo [d] [1,2,3] triazole units at their respective C-4 and C-7 positions; and one electron donor group, two electron donor groups Or at least one of the electron donor linker groups is a component or linker that increases the electron density of the 2H-benzo [d] [1,2,3] triazole unit to which it is attached, and the remaining electron donor group And / or each electron donor linker group increases the electron density of the 2H-benzo [d] [1,2,3] triazole to which they are attached, or 2H-benzo [d] [1 to which they are attached. , 2, 3] a component or linker having a neutral influence on the electron density of the triazole, provided that in this case the remaining electron donor group 1 or The electron donor group 2 can comprise hydrogen;
1 electron donor group and 2 electron donor groups are the same or different; and if n is an integer in the range of 2-100, the electron donor linker group is the same or different)
The wavelength conversion film according to claim 1, which is a derivative containing a 2H-benzo [d] [1,2,3] triazole heterocyclic system represented by:   The wavelength conversion film according to claim 1, wherein the wavelength conversion film has a thickness in a range of about 10 μm to about 2 mm.   The wavelength conversion film according to claim 1, wherein the adhesive layer contains a substance selected from the group consisting of acrylic, ethylene vinyl acetate, polyurethane, and combinations thereof.   The wavelength conversion film according to claim 1, wherein the adhesive layer has a thickness in a range of about 1 μm to about 100 μm.   The wavelength conversion film according to claim 3, wherein the removable liner comprises a material selected from fluoropolymer or polyethylene terephthalate (PET).   The wavelength conversion film according to any one of claims 3 to 18, wherein the thickness of the removable liner is in the range of about 10 m to about 100 m.   The wavelength conversion film according to claim 2, wherein the protective layer has a thickness in a range of about 50 μm to about 1 mm.   The wavelength conversion film according to any one of claims 1 to 20, wherein the wavelength conversion layer has a thickness in the range of about 50 µm to about 1 mm.   A method for improving the performance of a solar cell, a solar panel or a photovoltaic device, wherein the wavelength conversion film according to claim 1 is used as the solar cell, the solar panel or the photovoltaic property. Applying to a device and adhering the adhesive layer to a light incident surface of the solar cell, the solar panel or the photovoltaic device.   23. The method of claim 22, wherein the wavelength conversion film is applied to the solar cell, the solar panel or the photovoltaic device using a roll laminator.   The solar panel, the solar cell or the photovoltaic device is a silicon-based device, a III-V group or II-VI group PN junction device, a copper-indium-gallium-selenium (CIGS) thin film device, 24. The organic sensitizer device, the organic thin film device, or at least one device selected from the group consisting of a cadmium sulfide / cadmium telluride (CdS / CdTe) thin film device. Method.   The solar panel, the solar cell or the photovoltaic device comprises at least one device selected from the group consisting of an amorphous silicon solar cell, a microcrystalline silicon solar cell or a crystalline silicon solar cell. The method according to any one of 22 to 23.   The method according to any one of claims 22 to 25, wherein the light incident surface of the solar cell, the solar panel or the photovoltaic device is a substance containing glass or polymer. A method for forming the wavelength conversion film according to any one of claims 3 to 21,
a) forming a wavelength conversion layer;
b) forming a protective layer and laminating it directly on the wavelength conversion layer; and c) converting the adhesive layer having a removable liner on the surface opposite the protective layer to the wavelength conversion. A method comprising the step of laminating on a layer.