WO2016112200A1 - Films de conversion de longueur d'onde pour régulation thermique incorporant des matériaux à changement de phase - Google Patents

Films de conversion de longueur d'onde pour régulation thermique incorporant des matériaux à changement de phase Download PDF

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Publication number
WO2016112200A1
WO2016112200A1 PCT/US2016/012503 US2016012503W WO2016112200A1 WO 2016112200 A1 WO2016112200 A1 WO 2016112200A1 US 2016012503 W US2016012503 W US 2016012503W WO 2016112200 A1 WO2016112200 A1 WO 2016112200A1
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Prior art keywords
wavelength conversion
conversion film
film
chromophore
thermal regulating
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PCT/US2016/012503
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English (en)
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Yufen HU
Stanislaw Rachwal
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Nitto Denko Corporation
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Publication of WO2016112200A1 publication Critical patent/WO2016112200A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/12—Technologies relating to agriculture, livestock or agroalimentary industries using renewable energies, e.g. solar water pumping

Definitions

  • Embodiments disclosed herein generally relate to wavelength conversion films. Description of the Related Art
  • photovoltaic devices also known as solar cells
  • photovoltaic devices also known as solar cells
  • Several different types of mature photovoltaic devices have been developed, including a silicon-based device, a III-V and II-VI PN junction device, a Copper-Indium-Gallium-Selenium (CIGS) thin film device, an organic dye-sensitized device, an organic thin film device, and a Cadmium Sulfide/Cadmium Telluride (CdS/CdTe) thin film device, to name a few.
  • CIGS Copper-Indium-Gallium-Selenium
  • CdS/CdTe Cadmium Sulfide/Cadmium Telluride
  • wavelength conversion film that can be used to improve the efficiency of solar energy use, including solar energy that is converted to electricity, or put to other uses, such as in a greenhouse, or for heating or lighting a building.
  • some wavelength conversion films comprise: a luminescent chromophore, an optically transparent polymer, an aliphatic ester plasticizer, and an acrylic crosslinking coagent.
  • FIG. 6 shows the normalized absorption of the various embodiments, described herein after about 600 hours exposure to accelerated solar irradiation.
  • FIG. 7 shows the normalized absorption of various embodiments described herein after about 4700 hours exposure to accelerated solar irradiation.
  • FIG. 8 shows the normalized absorption of various embodiments described herein after about 4700 hours exposure to accelerated solar irradiation.
  • FIG. 9 shows the normalized absorption of various embodiments described herein after 2000 hours exposure to accelerated solar irradiation.
  • FIG. 10 shows the normalized absorption of various embodiments described herein after 2000 hours exposure to accelerated solar irradiation. [0014] FIG.
  • FIG. 11 shows the normalized absorption of various embodiments described herein after 850 hours exposure to accelerated solar irradiation.
  • FIG. 12 shows the normalized absorption of various embodiments described herein after 1700 hours exposure to accelerated solar irradiation.
  • FIG. 13 shows the normalized absorption of various embodiments described herein after 1700 hours exposure to accelerated solar irradiation.
  • FIG. 14 shows the normalized absorption of various embodiments described herein after 1700 hours exposure to accelerated solar irradiation.
  • FIG. 15 shows the normalized absorption of various embodiments described herein after 2000 hours exposure to accelerated solar irradiation. [0019] FIG.
  • a wavelength conversion film may help to improve the efficiency of photovoltaic devices.
  • Wavelength conversion film in greenhouse roofing materials may be used to alter the incident solar spectrum plants are exposed to within a greenhouse. Solar cell efficiency is often reduced with exposure to high temperatures. Because the film decreases temperature fluctuations, it is highly suitable to provide solar energy devices with protection from the environment. Additionally, the wavelength conversion film also converts incoming light one wavelength into a different more desirable wavelength which can be more efficiently converted into electricity by the solar energy conversion device.
  • the photoelectric conversion efficiency of these devices can be improved.
  • Solar energy conversion devices include solar cells, solar panels, photovoltaic devices, or any solar module system.
  • Phase change materials can be used to provide thermal regulating and storage properties which helps to improve performance and reliability of solar energy systems, and can help in conserving energy.
  • Embodiments described herein may achieve wavelength conversion of incident light to more desirable wavelengths.
  • Embodiments described herein may achieve improved thermal regulation of solar energy, in a two in one (2-in-1) system.
  • Some embodiments, of the present disclosure relate to a thermal regulating wavelength conversion film that is highly stable under long term solar irradiation.
  • the phase change material acts as a plasticizer to improve the photostability of the film.
  • the wavelength conversion film comprises an aliphatic ester plasticizer.
  • the wavelength conversion film comprises a liquid acrylic material.
  • the liquid acrylic material may comprise a liquid acrylic or acrylic crosslinking coagent.
  • the plasticizer may be the same material as the liquid acrylic material.
  • the wavelength conversion film comprises an (acrylic or acrylate) crosslinking coagent.
  • the wavelength conversion film comprises a (meth)acrylate crosslinking coagent.
  • the acrylic crosslinking coagent may be a (meth)acrylate polymer crosslinking coagent.
  • the wavelength conversion polymerization initiator may comprise an ultraviolet absorbing material. In some embodiments, the wavelength conversion film may comprise a light stabilizer.
  • Some embodiments include a wavelength conversion film comprising an optically transparent polymer; and an aliphatic ester plasticizer and/or a (meth)acrylate polymer crosslinking coagent.
  • the optically transparent polymer may comprise a polyolefin such as polyethylene, polypropylene, etc.; a polyolefins such as ethylene methyl methacrylate (EMMA) copolymer, polyvinyl butyral (PVB), and mixtures thereof.
  • the aliphatic ester plasticizer may be 1,2- cyclohexane dicarboxylic acid diisonoyl ester (DINCH).
  • the acrylic type crosslinking coagent may comprise trimethylolpropane trimethacrylate (TMPTMA).
  • the film of any of the above described embodiments may further comprise a light stabilizer material.
  • the light stabilizer material may be a hindered amine light stabilizer in an additional polymer layer, a glass layer, or a UV absorber material or layer.
  • the film may further comprise an ultraviolet radiation absorber.
  • the film may further comprise an adhesion promoter, a stabilizer, a reducing agent, a crosslinking coagent, or a crosslinking agent.
  • a greenhouse cover material comprises the wavelength conversion film described above.
  • a building or vehicle window comprises the wavelength conversion film described above.
  • Some embodiments include a thermal regulating wavelength conversion film comprising a luminescent chromophore, an optically transparent polymer, and a phase change material.
  • the chromophore acts to absorb incident photons of a particular wavelength range.
  • the phase change material acts to absorb and release heat for improved thermal regulation.
  • the phase change material acts as a plasticizer to improve the photostability of the film.
  • the thermal regulating wavelength conversion film may further comprise an aliphatic ester plasticizer and/or a (meth)acrylate polymer crosslinking coagent.
  • the thermal regulating wavelength conversion film may comprise chromophore and phase change material incorporated into the same polymer layer.
  • the thermal regulating wavelength conversion film may comprise chromophore and phase change material incorporated into separate polymer layers.
  • the optically transparent polymer comprises a host polymer, a copolymer, or multiple polymers.
  • the refractive index of the polymer may be in the range of about 1.4 to about 1.7.
  • the optically transparent polymer may comprise an acrylic polymer material.
  • the acrylic polymer material may be a (meth)acrylic material.
  • the optically transparent polymer may comprise fluoropolymers, polyolefins, polyesters, poly(thiourethane), urethane, polycarbonate (PC), poly(allyl) diglycol carbonate, polyacrylate, esters of a polyacrylic acid, polyacrylic acids, poly(2- hydroxyethylmethacrylate), polyvinylpyrrolidinone (PVP), hexafluoroacetone- tetrafluoroethylene-ethylene (HFA/TFE/E terpolymers), hexafluoropropylene-vinylidene fluoride-tetrafluoroethylene (VDF/HFP/TFE) terpolymer, hexafluoropropylene- vinylidene (HFP/VDF) copolymer, polymethyl methacrylate (PMMA), ethylene methyl methacrylate (EMMA), polyvinyl butyral (PVB), ethylene vinyl acetate (
  • a thermal regulating wavelength conversion film further comprises an additional polymer layer, glass layer, or UV absorber material or layer.
  • a thermal regulating wavelength conversion film further comprises an adhesion promoter, a stabilizer, a reducing agent, a crosslinking coagent, or a crosslinking agent.
  • a wavelength conversion film comprises a chromophore, such as a luminescent chromophore.
  • a wavelength conversion film comprises two or more chromophores.
  • the chromophore may be an organic dye.
  • the chromophore may be selected from perylene derivative dyes, benzotriazole derivative dyes, BODIPY-type chromophores, or benzothiadiazole derivative dyes.
  • the wavelength conversion film may be incorporated into an encapsulation structure for solar energy devices.
  • Some embodiments pertain to an encapsulation structure for a solar energy conversion device comprising a wavelength conversion film as described above, wherein the wavelength conversion film may be configured to encapsulate a solar energy conversion device and inhibit penetration of moisture and oxygen into the solar energy conversion device, and wherein the wavelength conversion film may be configured to encapsulate the solar energy conversion device such that light must pass through the wavelength conversion film prior to reaching the solar energy conversion device.
  • Some embodiments pertain to a method of improving the performance of a solar energy conversion device, comprising encapsulating the device with the encapsulation structure described above.
  • energy requirements for heating and cooling of buildings and vehicles could be reduced by incorporating the thermal regulating wavelength conversion film disclosed herein onto windows.
  • Greenhouse plant growth could also be improved with the disclosed wavelength conversion film which could provide improved wavelengths into the greenhouse for plant growth as well as reducing temperature fluctuations within the greenhouse.
  • Some embodiments include greenhouse roofing or cover material comprising the wavelength conversion film, as disclosed herein.
  • Some embodiments include a building or vehicle window comprising the thermal regulating wavelength conversion film, as disclosed herein.
  • Some embodiments pertain to a greenhouse panel comprising a wavelength conversion film as described above.
  • a greenhouse solar collection panel comprising a wavelength conversion film as described above and a solar energy conversion device.
  • the solar energy conversion device comprises a III-V or II-VI PN junction device, a Copper-Indium-Gallium-Selenium (CIGS) thin film device, an organic sensitizer device (DSC, dye-sensitized solar cell), an organic thin film device, a Cadmium Sulfide/Cadmium Telluride (CdS/CdTe) thin film device, an amorphous silicon solar cell, a microcrystalline silicon solar cell, a polycrystalline silicon solar cell, or a crystalline silicon solar cell.
  • the wavelength conversion film may comprise a chromophore and an optically transparent polymer. In some embodiments, the wavelength conversion film may further comprise a phase change material.
  • the chromophore acts to absorb incident light within a particular wavelength range.
  • the phase change material acts to absorb and release heat for improved thermal regulation.
  • the phase change material acts as plasticizer to improve photostability of the film.
  • the wavelength conversion film described herein may be useful for a variety of applications including window-based building applications, greenhouse roofing or cover materials, vehicle window applications, and solar cell and photovoltaic encapsulation materials.
  • the thermal regulating wavelength conversion film may be incorporated into an encapsulation structure for solar energy devices. Solar cell efficiency is often reduced with exposure to high temperatures. Because the film decreases temperature fluctuations, it is highly suitable to provide solar energy devices with protection from the environment.
  • the thermal regulating wavelength conversion film also converts incoming photons of one wavelength into a different more desirable wavelength which may be more efficiently converted into electricity by the solar energy conversion device. Therefore, by employing the thermal regulating wavelength conversion film to encapsulate solar energy conversion devices, the photoelectric conversion efficiency of these devices may be improved.
  • Solar energy conversion devices include solar cells, solar panels, photovoltaic devices, or any solar module system. Also, energy requirements for heating and cooling of buildings and vehicles could be reduced by incorporating the thermal regulating wavelength conversion film disclosed herein onto windows. Greenhouse plant growth could also be improved with the disclosed thermal regulating wavelength conversion film which could provide optimized wavelengths into the greenhouse for plant growth as well as reducing temperature fluctuations within the greenhouse.
  • the chromophore and/or phase change material are incorporated into a polymer layer. In some embodiments of the thermal regulating wavelength conversion film the chromophore and phase change material are incorporated into the same polymer layer. In some embodiments of the thermal regulating wavelength conversion film, the chromophore and phase change material are incorporated into separate polymer layers. [0040] In some embodiments of the thermal regulating wavelength conversion film, the phase change material comprises an organic phase change material. In some embodiments of the thermal regulating wavelength conversion film, the phase change material comprises a paraffin.
  • the phase change material may be formic acid, caprilic acid, glycerin, d-lactic acid, methyl palmitate, camphenilone, docasyl bromide, caprylone, phenol, heptadecanone, 1-cyclohexylooctadecane, 4-heptadecanone, p-joluidine, cyanamide, methyl eicosanate, 3-heptadecanone, 2-heptadecanone, hydrocinnamic acid, cetyl alcohol, 2-naphthylamine, camphene, o-nitroaniline, 9-heptadecanone, thymol, methyl behenate, diphenyl amine, p-dichlorobenzene, oxalate, hypophosphoric acid, o- xylene dichloride, b-chloroacetic acid, chloroacetic acid, nitronaphthalene, trimyristin
  • the phase change material comprises a fatty acid.
  • the phase change material may be acetic acid, polyethylene glycol, capric acid, eladic acid, lauric acid, pentadecanoic acid, tristearin, myristic acid, palmatic acid, stearic acid, acetamide, methyl fumarate, or combinations thereof.
  • the phase change material may be present in the thermal regulating wavelength conversion film in an amount in the range from about 0.01 wt% to about 20.0 wt% of the composition.
  • a second phase change material may be present in the thermal regulating wavelength conversion film.
  • the first and second phase change materials are different, and are independently selected from those listed above.
  • the first phase change material, and if present, a second phase change material are individually present in the thermal regulating wavelength conversion film in an amount in the range from about 0.01 wt% to about 20 wt% or about 0.05 wt% to about 5 wt% of the composition.
  • the first phase change material and, if present, the second phase change material are individually present in the thermal regulating wavelength conversion film in an amount in the range of about 0.05 wt% to about 5 wt%; about 1 wt% to about 10 wt%; about 5 wt% to about 15 wt%; about 1 wt% to about 20 wt%; about 10 wt% to about 20 wt%; about 15 wt% to about 20 wt%; about 0.01 wt% to about 2 wt%; about 2 wt% to about 5 wt%; about 5 wt% to about 10 wt%; about 10 wt% to about 15 wt%; about 15 wt% to about 20 wt%, or any other amoung bound by these ranges of the composition.
  • the wavelength conversion film comprises a chromophore, such as a luminescent chromophore, e.g. a chromophore that emits light by fluorescence or phosphorescence.
  • a luminescent chromophore may absorb light in a wavelength range that is less desirable for use in solar energy (including conversion to electricity, or use as a natural light source), and may then emit light of a different wavelength by fluorescence or phosphorescence.
  • chromophores may be employed in solar cells to convert radiation to useable or more desirable wavelengths.
  • the thermal regulating wavelength conversion film comprises chromophores with photostabilty for long periods of time (i.e., more than 20,000 hours, more than 10,000 hours, more than 5,000 hours, more than 2000 hours, more than 1500 hours, more than 600 hours, or more than 500 hours) of illumination under one sun (AM1.5G) irradiation (with less than about 20%, 10%, 5%, 3%, 2%, 1%, or another other percentage bound by these ranges of degradation).
  • Luminescent materials such as a luminescent chromophore, may be up- converting or down-converting.
  • a chromophore may be an up- conversion luminescent material, meaning a compound that converts light from lower energy (long wavelengths) to higher energy (short wavelengths).
  • Up-conversion dyes may include rare earth materials which have been found to absorb photons of wavelengths in the infrared (IR) region, about 975 nm, and re-emit in the visible region (about 400 nm to about 700 nm), for example, Yb 3+ , Tm 3+ , Er 3+ , Ho 3+ , and NaYF 4 .
  • the luminescent chromophore may be a down-shifting luminescent material, meaning a compound that converts light of high energy (short wavelengths) into lower energy (long wavelengths).
  • the down-shifting luminescent material may be a derivative of perylene, benzotriazole, or benzothiadiazole, as are described in U.S. Provisional Patent Application Nos. 61/430,053 (now U.S. Patent Application No.
  • the luminescent chromophore may be a down-shifting material.
  • the down- shifting luminescent material may be a derivative of BODIPY-type chromophores.
  • the thermal regulating wavelength conversion film comprises both an up-conversion luminescent compound and a down-shifting luminescent compound.
  • at least one of the luminescent materials may be a quantum dot material.
  • the luminescent material may be an organic dye.
  • the luminescent material may be selected from perylene derivative dyes, benzotriazole derivative dyes, diazaborinine derivative dyes, benzothiadiazole derivative dyes, BODIPY-type chromophores, or combinations thereof.
  • the chromophore such as a luminescent chromophore
  • the chromophore may be an organic compound.
  • the chromophore may be selected from perylene derivative dyes, benzotriazole derivative dyes, benzothiadiazole derivative dyes, or combinations thereof.
  • Examples of chromophores, such as luminescent chromophores can be found in U.S. Patent Publication No. 2013/0074927, U.S. Provisional Patent applications 61/865,498 and 61/865,502 (now International Patent Application No. PCT/US2014/050504) which is hereby incorporated by reference in its entirety.
  • the luminescent material efficiency may be independent of angle of incidence, allowing operation over a broad range of incidence angles.
  • a mixture of multiple chromophores which absorb light in the visible spectrum may be used in the thermal regulating wavlength conversion film, wherein the mixture of chromphores produces a neutral color film, similar to that disclosed in U.S. Patent Application No. 61/865502, which is hereby incorporated by references in its entirety.
  • the luminescent chromophore comprises a structure as given by the following formula (I):
  • alkyl refers to a branched or straight fully saturated acyclic aliphatic hydrocarbon group (i.e., composed of carbon and hydrogen containing no double or triple bonds). Alkyls include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, and the like.
  • heteroalkyl used herein refers to an unsaturated moiety having one or more heteroatoms, as well as carbon and hydrogen atoms. When two or more heteroatoms are present, they may be the same or different.
  • cycloalkyl used herein refers to saturated aliphatic ring system having three to twenty-five carbon atoms including, but not limited to, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
  • polycycloalkyl used herein refers to saturated aliphatic ring system having multiple cylcoalkyl ring systems.
  • alkenyl used herein refers to a monovalent straight or branched chain of from two to twenty-five carbon atoms containing at least one carbon double bond including, but not limited to, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1- butenyl, 2-butenyl, and the like.
  • alkynyl used herein refers to a monovalent straight or branched chain of from two to twenty-five carbon atoms containing a carbon triple bond including, but not limited to, 1-propynyl, 1-butynyl, 2-butynyl, and the like.
  • aryl refers to homocyclic aromatic moiety whether one ring or multiple fused rings.
  • aryl groups include, but are not limited to, phenyl, naphthyl, phenanthrenyl, naphthacenyl, fluorenyl, pyrenyl, and the like. Further examples include:
  • aralkyl or“arylalkyl” used herein refers to an aryl-substituted alkyl moiety. Examples of aralkyl include, but are not limited to, phenylpropyl, phenylethyl, and the like.
  • heteroaryl used herein refers to an aromatic group comprising one or more heteroatoms, whether one ring or multiple fused rings. When two or more heteroatoms are present, they may be the same or different. In fused ring systems, the one or more heteroatoms may be present in only one of the rings.
  • heteroaryl groups include, but are not limited to, benzothiazyl, benzoxazyl, quinazolinyl, quinolinyl, isoquinolinyl, quinoxalinyl, pyridinyl, pyrrolyl, oxazolyl, indolyl, thiazyl and the like.
  • substituted and unsubstituted heteroaryl rings include:
  • alkoxy refers to straight or branched chain alkyl covalently bonded to the parent molecule through an -O- linkage.
  • alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, n- butoxy, sec-butoxy, t-butoxy and the like.
  • heteroatom used herein refers to any atom that is not C (carbon) or H (hydrogen). Examples of heteroatoms include S (sulfur), N (nitrogen), and O (oxygen).
  • cyclic imido refers to an imide in which the two carbonyl carbons are connected by a carbon chain.
  • cyclic imide groups include, but are not limited to, 1,8-naphthalimide, pyrrolidine-2,5-dione, 1H-pyrrole-2,5- dione, and the likes.
  • the term“alcohol” used herein refers to a moiety–OH.
  • aryloxy used herein refers to an aryl moiety covalently bonded to the parent molecule through an --O-- linkage.
  • carboxy used herein refers to a moiety–COOR.
  • the term“amino” used herein refers to a moiety–NR’R”.
  • the term“heteroamino” used herein refers to a moiety–NR’R” wherein R’ and/or R” comprises a heteroatom.
  • the term“heterocyclic amino” used herein refers to either secondary or tertiary amines in a cyclic moiety wherein the group further comprises a heteroatom.
  • a substituted group is structurally related to an unsubstituted parent structure in that one or more groups occupy one or more positions that would be occupied by a hydrogen in the parent structure.
  • the substituent group(s) is (are) one or more group(s) individually and independently selected from groups having 1-30, 1-20, 1-10, or 1-5 atoms independently selected from C, N, O, S, F, Cl, Br, I, Si, or P, and/or a molecular weight of 15-500 Da, 15-200 Da, 15-100 Da, or 15- 50 Da, such as C 1 -C 25 alkyl, C 2 -C 25 alkenyl, C 2 -C 25 alkynyl, C 3 -C 25 cycloalkyl (optionally substituted with halo, alkyl, alkoxy, alcohol, carboxyl, haloalkyl, CN, OH,– SO 2 -alkyl,–CF 3 , or–OCF 3 ), cycloalkyl geminally attached, C 1 -C 25 heteroalkyl, C 3 -C 25 heterocycloalkyl (e.g., tetrahydrofuryl) (optionally
  • R 3 in formula (I) is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted cycloalkyl, optionally substituted heteroalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxyalkyl, optionally substituted heteroalkenyl, optionally substituted arylalkyl, optionally substituted heteroaryl, optionally substituted cycloalkenyl, optionally substituted cycloheteroalkyl, optionally substituted cycloheteroalkenyl, optionally substituted amino, optionally substituted amido, optionally substituted cyclic amido, optionally substituted cyclic imido, optionally substituted alkoxy, and optionally substituted carboxy, optionally substituted carbonyl, optionally substituted ether, optionally substituted ketone,
  • R 3 in formula (I) is C 1-25 alkyl, C 1-25 heteroalkyl, C 2-25 alkenyl, C 3-25 cycloalkyl, polycycloalkyl, heterocycloalkyl, arylalkyl; and R 3 may be optionally substituted with one or more of any of the following substituents: C 1-25 alkyl, C 1-25 heteroalkyl, C 2-25 alkenyl, C 3-25 cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, heteroaryl, -OH, C m H 2m+1 O ether, C m H 2m+1 CO ketone, C m H 2m+1 CO 2 carboxylic ester, C m H 2m+1 OCO carboxylic ester, ArO aryloxy, ArCO aryl ketone, ArCO 2 ester of aryl- carboxylic acid, ArOCO carboxylic ester of phenol, (C m H 2m
  • R 4 , R 5 , and R 6 in formula (I) are independently C 1-25 alkyl, C 1-25 heteroalkyl, C 2-25 alkenyl, C 3-25 cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, CO 2 C m H 2m+1 carboxylic ester, (C m H 2m+1 )(C p H 2p+1 )NCO amide, c-(CH 2 ) s NCO amide, COC m H 2m+1 ketone, COAr, SO 2 C m H 2m+1 sulfone, SO 2 Ar sulfone, (C m H 2m+1 )(C p H 2p+1 )SO 2 sulfonamide, or c- (CH 2 ) s SO 2 sulfonamide; and R 4 , R 5 , and R 6 are independently optionally
  • L in formula II-b is C 1-25 alkyl, C 1-25 heteroalkyl, or C 2-25 alkenyl; and L may be optionally substituted with one or more of any of the following substituents: C 1-25 alkyl, C 1-25 heteroalkyl, C 2-25 alkenyl, C 3-25 cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, heteroaryl, -OH, C m H 2m+1 O ether, C m H 2m+1 CO ketone, C m H 2m+1 CO 2 carboxylic ester, C m H 2m+1 OCO carboxylic ester, ArO aryloxy, ArCO aryl ketone, ArCO 2 ester of aryl-carboxylic acid, ArOCO carboxylic ester of phenol, amine, c-(CH 2 ) s N amine, (C m H 2m+1 )(C p H 2p+1 )NCO amide, c- (
  • R 3 in formula (I) may be C 1-25 alkyl, C 1-25 heteroalkyl, C 2-25 alkenyl, C 3-25 cycloalkyl, C 5-25 polycycloalkyl, C 1-25 heterocycloalkyl, or C 1-25 arylalkyl; R 4 , R 5 , and R 6 are independently optionally substituted with one or more of any of the following substituents: C 1-25 alkyl, C 1-25 heteroalkyl, C 2-25 alkenyl, C 3-25 cycloalkyl, C 1-25 aryl, and C 1-25 heteroaryl.
  • the luminescent chromophore comprises a structure as given by the following formula (II):
  • the chromophore may be as described in U.S. Patent Provisional Applications 62/100,836 and 62/100,834 which are hereby incorportated by reference in their entireities.
  • D in formula (II) may be a phenyl, substituted phenyl, or an aromatic heterocyclic system, and R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 may be independently phenyl, substituted phenyl, naphthyl, or a heterocyclic system.
  • D in formula (II) may be selected from phenyl, furan, thiophene, pyrrole, benzofuran, benzothiophene, indole, carbazole, dibenzofuran, or dibenzothiophene.
  • D may be
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 in formula (III) are independently selected from:
  • the structure may be any one of the following:
  • the thermal regulating wavelength conversion film may not need to be completely transparent, for instance, for use in greenhouse roofing materials.
  • a greenhouse roofing or cover material may be allowed to have a coloration to the film, i.e. a blue, red, or green film. Therefore, in some embodiments, the chromophore, such as a luminescent chromophore, in the thermal regulating wavelength conversion film may absorb photons in the visible light spectrum.
  • a chromophore such as a luminescent chromophore
  • a chromophore may be present in the polymer matrix of the thermal regulating wavelength conversion film in an amount in the range of about 0.01 wt% to about 10 wt%, about 0.01 wt% to about 3 wt%, about 0.05 wt% to about 2 wt%, about 0.1 wt% to about 1 wt%, or any other weight bound by these ranges of the polymer matrix.
  • the chromophore may be present in the polymer matrix of the wavelength conversion film in an amount in the range of about 0.00001 mmol/g to about 1.0 mmol/g or about 0.00001 mmol/g to about 0.1000 mmol/g of the polymer matrix, e.g., about 0.0006 mmol/gm, about 0.002 mmol/gm, about 0.0004 mmol/g, or any other amount bound by these ranges of polymer matrix (e.g., EMMA and/or PVB).
  • the film comprises two or more chromophores.
  • the film comprises organic chromophores.
  • a first chromophore may be used in the composition to form the thermal regulating wavelength conversion film.
  • an independently selected second chromophore may be used in addition to the first chromophore.
  • 1, 2, 3, 4, 5, or more independently selected additional chromophores are used in combination with the first and second chromophores. It may be desirable to have multiple chromophores in the thermal regulating wavelength conversion film, depending on the solar energy conversion device that the material may be to encapsulate.
  • the first chromophore may act to convert light having a wavelength in a range of about 300-400 nm to a wavelength of about 500 nm
  • the second chromophore may act to convert light having a wavelength in a range of about 400-475 nm to a wavelength of about 500 nm (or vice versa)
  • the solar energy conversion device that may be to be encapsulated by the film exhibits optimum photoelectric conversion efficiency at 500 nm wavelengths, so that the encapsulation of the devices by the thermal regulating wavelength conversion film significantly enhances the solar harvesting efficiency of the solar energy conversion device.
  • a mixture of multiple chromophores may be used in the thermal regulating wavelength conversion film, wherein the mixture of chromophores produces a neutral color film, similar to that disclosed in U.S. Patent Application No.61/865502.
  • the above-mentioned combination of chromophores may be especially suitable for use in the solar cells and agriculture (greenhouse) applications because they are surprisingly more stable in harsh environmental conditions than currently available wavelength converting chromophores. This stability makes these chromophores advantageous in their use as wavelength conversion materials for solar cells and agriculture applications. Without such photostability, these chromophores would degrade and lose efficiency.
  • the photostability of chromophores may be measured by fabricating a thermal regulating wavelength conversion film containing the chromophore compound and then measuring the absorption peak prior to exposure and after exposure to continuous one sun (AM1.5G) irradiation at ambient temperature.
  • A1.5G continuous one sun
  • the preparation of such a wavelength conversion film is described in the Examples section below.
  • the amount of remaining chromophore after irradiation may be measured using the maximum absorption of the chromophore before and after irradiation using the following equation:
  • the % degradation can be measured using the following equation:
  • a photostable chromophore shows less than about 30%, 20%, 15%, 10%, 5%, 2.5%, 1.0%, or 0.5% degradation in maximum absorption peak intensity after 24 hours of continuous one sun (AM1.5G) irradiation at ambient temperature.
  • a photostable chromophore has greater than about 70%, 80%, 85%, 90%, 95%, 97.5%, 99.0%, 99.5%, or any percentage bound by these values of the chromophore remaining (as measured by maximum absorption peak intensity) after 24 hours of continuous one sun (AM1.5G) irradiation at ambient temperature.
  • the total amount of the chromophore(s) in the thermal regulating wavelength conversion film may be in the range of about 0.01% to about 3.0%, about 0.05% to about 1.0%, about 0.01% to about 3.0%, or about 0.05% to about 1.0% by weight, , or any percentage bound by these values of the thermal regulating wavelength conversion film.
  • the second chromophore or additional chromophores may be any of the chromophores defined above and may be in any combination independently selected from the other chromophores present in the composition.
  • the first chromophore and, if present, the second chromophore are individually present in the thermal regulating wavelength conversion film in an amount in the range from about 0.01 wt% to about 3.0 wt% or 0.05 wt% to about 1.0 wt% of the composition.
  • the first chromophore and, if present, the second chromophore are individually present in the thermal regulating wavelength conversion film in an amount in the range of about 0.05 wt% to about 0.1 wt%, about 0.1 wt% to about 0.2 wt%, about 0.2 wt% to about 0.3 wt%, about 0.3 wt% to about 0.4 wt%, about 0.5 wt% to about 0.6 wt%, about 0.6 wt% to about 0.7 wt%, about 0.7 wt% to about 0.8 wt%, about 0.8 wt% to about 0.9 wt%, about 0.9 wt% to about 1.0 wt%, about 1.0 wt% to about 2.0 wt%, about 2.0 wt% to about 3.0 wt%, or any other wt% bound by these values of the composition.
  • the first chromophore and, if present, the second chromophore are individually present in the wavelength conversion film in an amount in the range from about 0.00001 mmol/gm to about 1.0 mmol/gm, or about 0.0002 mmol/gm, about 0.0004 mmol/g, or about 0.0006 mmol/gm polymer matrix material (PVB and/or EMMA).
  • the total amount of all the chromophores present in the thermal regulating wavelength conversion film may be in the range of about 0.05% to about 0.1%, about 0.1% to about 0.2%, about 0.2% to about 0.3%, about 0.3% to about 0.4%, about 0.4% to about 0.5%, about 0.5% to about 0.6%, about 0.6% to about 0.7%, about 0.7% to about 0.8%, about 0.8% to about 0.9%, about 0.9% to about 1.0%, about 1.0% to about 2.0%, about 2.0% to about 3.0%, about 3.0% to about 5.0%, about 5.0% to about 7.5%, about 7.5% to about 10.0%, or any percentage bound by these values of the total weight of the composition.
  • the wavelength conversion film comprises an optically transparent polymer.
  • the optically transparent polymer comprises one host polymer, a host polymer and a copolymer, or multiple polymers.
  • the refractive index of the optically transparent polymer may vary. In some embodiments of the thermal regulating wavelength conversion film the refractive index of the polymer may be in the range of about 1.4 to about 1.7 or about 1.45 to about 1.55.
  • the optically transparent polymer comprises a material selected from fluoropolymers, polyolefins, polyesters, thiourethane, polycarbonate (PC), allyl diglycol carbonate, polyacrylate, esters of a polyacrylic acid or a polyacrylic acid, 2- hydroxyethylmethacrylate, polyvinylpyrrolidinone, hexafluoroacetone- tetrafluoroethylene-ethylene (HFA/TFE/E terpolymers), hexafluoropropylene-vinylidene fluoride-tetrafluoroethylene (VDF/HFP/TFE) terpolymer, hexafluoropropylene- vinylidene (HFP/VDF) copolymer, polymethyl methacrylate (PMMA), ethylene methyl methacrylate (EMMA), polyvinyl butyral (PVB), ethylene vinyl acetate (EV).
  • fluoropolymers polyolefins
  • the optically transparent polymer may be a crosslinkable polymer such as ionomer, thermoplastic polyurethane (TPU), thermoplastic polyurethanethermoplastic polyolefin (TPO), polymethyl methacrylate (PMMA), polyvinyl butyral (PVB), polydimethyl silicone (PDMS), ethylene-methyl methacrylate (EMMA), and ethylene vinyl acetate (EVA).
  • an optically transparent crosslinkable polymer may be a polymer that is optically transparent after crosslinking.
  • optically transparent refers to a material that provides at least 50%, at least 70%, at least 90% total transmittance of visible light.
  • the film may comprise second polymer matrixes in combination with the first optically transparent polymer.
  • the second additional optically transparent polymer is as defined above.
  • the second optically transparent polymer may be ionomer, thermoplastic polyurethane (TPU), thermoplastic polyurethanethermoplastic polyolefin (TPO), polymethyl methacrylate (PMMA), polyvinyl butyral (PVB), polydimethyl silicone (PDMS), ethylene-methyl methacrylate (EMMA), ethylene vinyl acetate (EVA), or combinations thereof.
  • the first and second optically transparent polymers are independently selected from the above polymer and may be in any combination.
  • the composition comprises 1, 2, 3, 4, 5, 6, or more additional optically transparent polymers.
  • the optically transparent polymers may be as defined above or otherwise and may be in any combination.
  • the refractive index of the one or more additional optically transparent polymers may vary. In some embodiments the refractive index of each of the first, second, or more additional optically transparent polymers may be in the range of about 1.4 to about 1.7 or about 1.45 to about 1.55. In some embodiments, the refractive index of the first, second, and/or more additional optically transparent polymers, together, may be in the range of about 1.4 to about 1.7, or about 1.45 to about 1.55.
  • the optically transparent polymer comprises a host polymer, a copolymer, or multiple polymers. Those skilled in the art will appreciate that the use of the term“polymer” herein includes copolymers.
  • monomer precursors that polymerize to form optically transparent polymers may be used to form the composition. These monomers may be substituted for or used in combination with the optically transparent polymers in the thermal regulating wavelength conversion film. The monomers for forming such polymers are appreciated by those of ordinary skill in the art. The monomers include, for example, monomers capable of forming the optically transparent polymers described above.
  • the film further comprises an antioxidant.
  • additives such as those described in U.S. Patent Application No. 61/831,074, which is hereby incorporated by reference in its entirety, may be incorporated into the thermal regulating wavelength conversion film.
  • some embodiments of the disclosed polymer matrices of the thermal regulating wavelength conversion film are optically transparent. Optical transparency improves the transmittance of light through the thermal regulating wavelength conversion film allowing more energy to be captured from the light. Additionally, when used as, for example, a window, the additional light that travels through the thermal regulating wavelength conversion film results enhanced brightness through the window.
  • an optically transparent polymer matrix allows transmission of greater than about 80%, 90%, 95%, 97.5%, 99.0%, 99.5%, 99.9%, or any percentage bound by these values of the visible light spectrum.
  • the thermal regulating wavelength conversion film further comprises one or more of IR reflectors, IR absorbers, anti-fog agents, anti-mist agents, anti-drop agents, anti-dust agents, lubricants, modifiers, inorganic fillers, anti- static agents, or combinations thereof.
  • Anti-fog or anti-mist agents are generally non- ionic surfactants.
  • the methyl methacrylate (MMA) content in the EMMA may be in the range of about 5 to about 32 or about 10 to about 25 parts by weight, based on 100 parts by weight, or any amount in a range bound by these values of EMMA.
  • the wavelength conversion film comprises a light stabilizer.
  • the light stabilizer may be a hindered amine light stabilizer.
  • the thermal regulating wavelength conversion film comprises the stabilizer tetrakis(,2,2,6,6-pentamethyl-4-piperidinyl)1,2,3,4- butanetetracarboxylate (Stab LA-57) from Adeka Palmarole (Mulhouse, FR).
  • the thermal regulating wavelength conversion film comprises UV absorbers such as 2-Hydroxy-4-(octyloxy)benzophenone (CHIMASSORB® 81), 2-(2H-Benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (TINUVIN® 234 or TINUVIN® 900), and 2,2 ⁇ -Methylenebis[6-(2H-benzotriazol-2-yl)- 4-(1,1,3,3-tetramethylbutyl)phenol] TINUVIN® 360 all from BASF (Ludwigshafen, DE).
  • the wavelength conversion film comprises a non- phthalate plasticizer.
  • Some aliphatic ester plasticizers may be a dialkylester of cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, or combinations thereof, wherein each alkyl group of the dialkylester is independently C 4-14 alkyl.
  • each alkyl group of a dialkylester of a dicarboxylic acid of a cycloalkyl is independently C 4-14 alkyl, such as C 4 alkyl (e.g.
  • each alkyl group of the dialkylester is C 6-12 alkyl. In some embodiments, each alkyl group of the dialkylester is C 8-10 alkyl.
  • the aliphatic ester plasticizer may be 1,2-cyclohexane dicarboxylic acid diisonoyl ester (DINCH).
  • the non-phthalate plasticizer and/or aliphatic ester plasticizer may be 1,2-cyclohexane dicarboxylic acid diisononyl ester (DINCH).
  • a non-phthalate plasticizer such as an aliphatic ester plasticizer including an ester of cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, e.g.
  • the wavelength conversion film comprises a crosslinker and/or crosslinking coagent.
  • the crosslinker and/or crosslinking coagent may be an acrylic coagent.
  • the acrylic coagent may be a trifunctional (meth)acrylate ester or a metallic (meth)acrylate.
  • the acrylic coagent may be TMPTMA.
  • the crosslinking coagent may be a plasticizer.
  • the plasticizer and crosslinking coagent may be the same material. [0116] In some embodiments, the crosslinking coagent may be an acrylic crosslinker.
  • Typical acrylic crosslinkers include acrylate or alkacrylate (e.g., methacrylate) esters of polyols, including diols such as glycols (e.g., ethylene glycol, propylene glycol, butylene glycol, etc.); triols (e.g., glycerine, trimethylol propane, etc.); or acrylate or alkacrylate (e.g., methacrylate) esters of other polyols.
  • the crosslinking coagent may be an acrylic type coagent selected from trifunational (meth)acrylate esters, metallic (meth)acrylates.
  • the acrylic crosslinker may be ethylene glycol dimethacrylate (EGDMA) or trimethylolpropane trimethacrylate (TMPTMA), triallyl isocyanurate (TAIC), or combinations thereof.
  • the acrylic type coagent may be ethylene glycol dimethacrylate and/or trimethol propane tri(meth)acrylate.
  • An acrylic cosslinking coagent such as an acrylate or alkacrylate ester of a diol or triol, e.g.
  • TMPTMA may be present in any useful amount, such as about 1% to about 40%, about 5% to about 30%, about 1% to about 10%, about 5% to about 20%, about 10% to about 20%, about 20% to about 30%, about 30 to about 40%, about 1%, about 2.5%, about 5%, about 7%, about 10%, about 15%, about 20%, about 25%, or any other percentage bound by these ranges of the weight of the film.
  • a wavelength conversion material or layer may be formed by curing a layer of the above described compositions. This cured material or layer may be used for forming a thermal regulating wavelength conversion film.
  • the layer may be cured at a temperature of between about 130 °C to about 180 °C; about 140 to about 160 °C; about 130 °C to about 145 °C, about 145 °C to about 160 °C, about 160 °C to about 180 °C, or any other temperature bound by these ranges.
  • the curing time for the wavelength conversion layer depends on the temperature. When the cure temperature is high, the cure time is low, while lower cure temperatures require longer curing times.
  • the wavelength conversion layer may be cured for a time of about 5 minutes to about 100 minutes; about 10 minutes to about 50 minutes; about 10 to about 45 minutes; about 5 minutes to about 10 minutes; about 10 minutes to about 20 minutes; about 20 minutes to about 30 minutes; about 30 minutes to about 40 minutes; about 40 to about 50 minutes; about 50 to about 60 minutes; about 60 minutes to about 70 minutes; about 70 minutes to about 80 minutes; about 80 minutes to about 90 minutes; or any other duration bound by these values.
  • the thermal regulating wavelength conversion film described herein may be prepared in various ways, such as by polymerization or crosslinking of the corresponding component monomers or precursors thereof. Polymerization may be carried out by methods known to a skilled artisan, as informed by the guidance provided herein.
  • the thermal regulating wavelength conversion film for a solar energy conversion device may be prepared in a conventional manner by free- radical copolymerization with the monomers in suitable solvents, such as, hydrocarbons, (e.g., n-hexane); aromatic hydrocarbons (e.g., toluene or xylene), halogenated aromatic hydrocarbons (e.g., chlorobenzene); ethers (e.g., tetrahydrofuran and dioxane); ketones (e.g., acetone and cyclohexanone, and dimethylformamide), alcohols, or combinations thereof, at elevated temperatures, in general in the range from about 30 °C to about 100 °C; about 40 °C to about 60 °C; about 50 °C to about 80 °C, or any other temperature bound by these values.
  • suitable solvents such as, hydrocarbons, (e.g., n-hexane); aromatic hydrocarbons (e.g., toluen
  • the reaction may be performed in the absence of water and air.
  • Various methods may be used to incorporate the chromophore into the thermal regulating wavelength conversion film.
  • the chromophore may be attached to the optically transparent polymer in one or more side chains.
  • the chromophore may be incorporated into the thermal regulating wavelength conversion film as a separate compound.
  • the chromophore may be doped into the film such that the polymer and the chromophore are not chemically bonded.
  • one or more of the chromophores may be covalently bonded to the optically transparent polymer.
  • chromophore may be covalently bond into to the polymer matrix of the film.
  • free radical polymerization may be used to covalently bond the optically transparent polymer matrix and the chromophore together.
  • the chromophore may be attached to the polymer backbone in one or more side chains.
  • the chromophore may be incorporated into the thermal regulating wavelength conversion film as a separate compound.
  • Various methods may be used to incorporate the phase change material into the thermal regulating wavelength conversion film. In some embodiments, the phase change material may be incorporated into the thermal regulating wavelength conversion film as a separate compound.
  • the phase change material may be incorporated into the thermal regulating wavelength conversion film such that the polymer and the phase change material are not chemically bonded. In some embodiments of the thermal regulating wavelength conversion film, the phase change material may be dispersed within the thermal regulating wavelength conversion film. [0126] In some embodiments, the thermal regulating wavelength conversion film may be formed into self-supporting films or layers. However, in some embodiments, the thermal regulating wavelength conversion film may be formed into films or layers that are applied to support materials. This may be carried out by various techniques known in the art. In some embodiments, the method being selected depending on whether a thick or thin film may be desired.
  • Thin films may be produced, for example, by spin coating or casting from solutions or melts, while thicker coatings may be produced from prefabricated cells, by hot pressing, extruding or injection molding.
  • the thermal regulating wavelength conversion film is formed into a thin film or layer.
  • the method for forming the thermal regulating wavelength conversion film into a thin film may be appropriately selected from known methods used to produce thin films. Specific examples thereof include cast- and calendar-film extrusion, injection molding, roll coating, kiss roll coating, gravure coating, reverse coating, roll brush coating, spray coating, dip roll coating, bar coating, knife coating, and air knife coating.
  • the thermal regulating wavelength conversion film may be coated onto an optically transparent substrate.
  • the optically transparent substrate may be plastic (sheet), polymer film, or glass.
  • An embodiment of a thermal regulating wavelength conversion film 100 is illustrated in FIG. 1, comprising a chromophore 101, an optically transparent polymer, and a phase change material 102. Glass or plastic films may be used as substrates or protective covers 103.
  • An embodiment of a thermal regulating wavelength conversion film 100 is illustrated in FIG. 2, comprising a chromophore 101, an optically transparent polymer, and a phase change material 102, wherein the chromophore and the phase change material are incorporated into separate layers. Glass or plastic films may be used as substrates or protective covers 103.
  • FIG.3 An embodiment of a thermal regulating wavelength conversion film 100 is illustrated in FIG.3, comprising a first chromophore 101 and a second chromophore 104, an optically transparent polymer, and a phase change material 102, wherein the chromophore and the phase change material are incorporated into separate layers. Glass or plastic films may be used as substrates or protective covers 103.
  • Synthetic methods for the thermal regulating wavelength conversion layer are not restricted, but may follow the example synthetic procedures described as Scheme 1 and Scheme 2 detailed below.
  • Scheme 1 Wet processing general procedure for forming the thermal regulating WLC layer
  • a thermal regulating wavelength conversion layer which comprises a chromophore, an optically transparent polymer, and a phase change material, is fabricated into a film structure.
  • the thermal regulating wavelength conversion layer may be fabricated by: (i) preparing a polymer solution by dissolving polymer powder or pellets in a soluble solvent such as hydrocarbons, aromatic hydrocarbons, or alcohols, such as cyclopentanone, dioxane, etc., at a predetermined ratio; (ii) preparing a chromophore solution by dissolving the chromophore in the same solvent as the polymer solution at a predetermined concentration; (iii) preparing a phase change material solution by dissolving a phase change material in the same solvent as the polymer solution at a predetermined concentration; (iv) preparing a thermal regulating wavelength conversion solution by mixing the polymer solution with the chromophore solution and the phase change material solution, and then adding any other components as needed
  • a thermal regulating wavelength conversion layer which comprises a chromophore, and an optically transparent polymer, may be fabricated into a film structure.
  • the wavelength conversion layer may comprise a phase change material.
  • the thermal regulating wavelength conversion layer may be fabricated by: (i) mixing polymer powders or pellets, the chromophore and/or the phase change material, together at a predetermined ratio by a mixer at a temperature below the half decay temperature of the peroxide for a certain time, then adding the adhesion promoter, the coagent, and the peroxide, together at a predetermined ratio to the mixture and further mixing for a certain time as determined by the extent of desired crosslinking for the particular composition; (ii) then hot pressing the mixture under vacuum at about 80 °C to about 140 °C for about 3 minutes to about10 minutes to a predetermined thickness; (vi) the film thickness may be adjusted as desired during hot pressing.
  • the thermal regulating wavelength conversion layer may be formed it needs to be cured at an elevated temperature to induce crosslinking.
  • the curing temperature may be from about 130 °C to about 180 °C.
  • the curing time ranges from about 5 minutes to about 90 minutes.
  • Encapsulation Structure for Solar Energy Conversion Device [0136] Some embodiments include an encapsulation structure for a solar energy conversion device. In some embodiments, the encapsulation structure comprises the thermal regulating wavelength conversion film as described above. In some embodiments the thermal regulating wavelength conversion may be configured to encapsulate the solar energy conversion device and inhibit penetration of moisture and oxygen into the solar energy conversion device.
  • the thermal regulating wavelength conversion film may be configured to encapsulate the solar energy conversion device such that light must pass through the thermal regulating wavelength conversion film prior to reaching the solar energy conversion device.
  • Some embodiments include an encapsulation structure for a solar energy conversion device comprising a thermal regulating wavelength conversion film.
  • the thermal regulating wavelength conversion film may be configured to inhibit penetration of moisture and oxygen into the solar energy conversion device.
  • the thermal regulating wavelength conversion film may be configured to improve the thermal regulation of the solar energy conversion device.
  • Additional forms of the thermal regulating wavelength conversion film are also possible, as well as additional methods of applying the thermal regulating wavelength conversion film to the solar energy conversion devices.
  • the encapsulation structure may be applied to rigid devices or it may be applied to flexible devices. Furthermore, the encapsulation structure may be used to improve the performance of multiple solar cells or photovoltaic devices. For example, in an embodiment, the encapsulation structure comprises a plurality of solar cells or photovoltaic devices.
  • Additional materials may also be utilized to provide increased environmental protection. Glass or plastic sheets are often used as an environmental protective cover and may be applied both on top of and/or underneath the solar energy conversion devices once encapsulated with the thermal regulating wavelength conversion film.
  • a sealing tape may be applied to the perimeter of the device to prevent ingress of oxygen or moisture through the sides. In some embodiments, an edge seal may be applied to the perimeter of the device to prevent ingress of oxygen or moisture through the sides.
  • a back sheet may also be used underneath the solar module devices to reflect and refract incident light that was not absorbed by the solar cell.
  • the encapsulated solar energy conversion devices may also be put in a frame, such as those utilized to form solar panels or solar strings.
  • the encapsulation structure further comprises additional layers which may contain light stabilizers, antioxidants, UV absorbers, or combinations thereof.
  • an additional polymer layer may be used in the encapsulation structure which may further comprise light stabilizers, antioxidants, UV absorbers, or combinations thereof.
  • the glass or polymer sheets used as an environmental cover may also further comprise a strong UV absorber to block harmful high energy radiation.
  • additional materials or layers may be used in the structure such as glass sheets, reflective and/or thermally conductive backsheets, edge seals, frame materials, polymer materials, or adhesive layers to adhere additional layers to the system.
  • the edge seals may comprise a butyl material.
  • the frame materials comprise a metal.
  • Solar harvesting devices may be rigid or flexible. Rigid devices include silicon-based solar cells. Flexible solar devices are often made out of organic thin films and may be used on clothing, tents, or other flexible substrates. In other embodiments, the encapsulation structure may be applied to rigid devices or flexible devices. [0143] An embodiment of an encapsulation structure is illustrated in FIG.
  • the encapsulation structure may also comprise a phase change material 102. Glass or plastic films may be used as an environmental protective cover 103.
  • Some embodiments include a method of improving the performance of a solar energy conversion device.
  • Solar energy conversion devices include any type of photovoltaic device, solar cell, solar module, or solar panel.
  • the method of improving the performance of a solar energy conversion device comprises encapsulating the device with the encapsulation structure disclosed herein.
  • the encapsulation structure comprises the thermal regulating wavelength conversion film.
  • the solar energy conversion device comprises a III-V or II-VI PN junction device, a Copper-Indium-Gallium-Selenium (CIGS) thin film device, an organic sensitizer device, an organic thin film device, or a Cadmium Sulfide/Cadmium Telluride (CdS/CdTe) thin film device, an amorphous silicon solar cell, a microcrystalline silicon solar cell, a crystalline silicon solar cell, or a polycrystalline silicon solar cell.
  • the thermal regulating wavelength conversion film of the encapsulation structure may be cast onto the solar energy conversion device and cured in place.
  • the thermal regulating wavelength conversion film of the encapsulation structure may be in the form of film(s) or layer(s).
  • the thermal regulating wavelength conversion film in the form of a thin film, may be roll laminated onto the solar energy conversion devices, wherein only a front layer may be laminated onto the solar energy conversion devices, or both a front and back layer are laminated onto the solar energy conversion devices.
  • additional material layers may also be used in the encapsulation structure. For example, glass or plastic sheets may be used to provide additional environmental protection. Back sheets may be used to provide reflection and/or refraction of photons not absorbed by the solar cells. Adhesive layers may also be needed.
  • an adhesive layer in between the thermal regulating wavelength conversion film and the glass sheets which may be used to adhere these two layers together.
  • Other layers may also be included to further enhance the photoelectric conversion efficiency of solar modules.
  • a microstructured layer may also be provided on top of the encapsulation structure or in between the thermal regulating wavelength conversion film and a glass sheet, which may be designed to further enhance the solar harvesting efficiency of solar modules by decreasing the loss of photons to the environment which are often re-emitted from the chromophore after absorption and wavelength conversion in a direction that may be away from the photoelectric conversion layer of the solar module device.
  • the thermal regulating wavelength conversion film comprising a chromophore, an optically transparent polymer, and/or an optional phase change material
  • a suitable solvent e.g., toluene, cyclopentanone, etc.
  • the mixture may be applied to solar cell devices by first mixing the components of the thermal regulating wavelength conversion film in a suitable solvent (e.g., toluene, cyclopentanone, etc.) to form a liquid or gel, applying the mixture to a solar cell matrix arranged on a removable substrate using standard methods of application, such as spin coating or drop casting, then curing the mixture to a solid form (e.g., heat treating, UV exposure, etc.) as may be determined by the formulation design.
  • a suitable solvent e.g., toluene, cyclopentanone, etc.
  • the thermal regulating wavelength conversion film comprising a chromophore, an optically transparent polymer, and/or an optional phase change material
  • the thermal regulating wavelength conversion film may be applied to solar cell devices by first synthesizing a thermal regulating wavelength conversion thin film or layer, and then adhering the thermal regulating wavelength conversion layer to the solar cell devices using an optically transparent and photostable adhesive and/or laminator.
  • the thermal regulating wavelength conversion layer may be applied first on top of and then on bottom of the solar cells, to completely encapsulate the cells.
  • the thermal regulating wavelength conversion layer may also be applied to just the top surface, wherein the bottom surface of the solar cells are secured to a substrate, such as a back sheet, and the thermal regulating wavelength conversion layer may be applied to the top surface of the solar cells and the portion of the substrate that does not have solar cells attached to it.
  • Synthetic methods for forming the encapsulation structure are not restricted.
  • the thermal regulating wavelength conversion film, once formed, may be easily attached to the light incident surface of a solar energy conversion device by pressing or laminating.
  • an adhesive may be needed to attach the thermal regulating wavelength conversion film to the solar energy conversion device.
  • thermo regulating wavelength conversion film once the thermal regulating wavelength conversion film is formed it is adhered to the solar module devices using an optically transparent and photostable adhesive.
  • Greenhouse Panel Additional uses for the thermal regulating wavelength conversion film include greenhouse roofing or greenhouse cover materials. Plants use the energy in sunlight to convert carbon dioxide from the atmosphere and water into simple sugars. Plants then use these sugars as structural building blocks. Sugars form the main structural component of the plant. It is understood that plants react differently to the intensity and wavelengths of the light during their development. Improved plant growth is achieved using light in the violet-blue region and in the orange-red region. Light in the green region is usually not used by the plant (and is often reflected by the leaves).
  • photovoltaic devices e.g., solar cells
  • solar cells have been incorporated into greenhouse roofing materials to convert incident solar radiation to electricity. This electricity is then used for other applications within the greenhouse system. While the utilization of solar energy offers a promising alternative energy source, the use of photovoltaic modules lowers the amount of available light for the plant species.
  • a significant amount of development effort is ongoing to find greenhouse cover materials with photovoltaic devices which provide sufficient electrical generation efficiency and the desired plant growth for an acceptable cost. For instance, a polymer sheeting comprising an inorganic luminescent material, yttrium-europium, is described for use in greenhouses.
  • UV portion of the spectrum is not only used by most plant species, but is usually quite harmful to the plant. Elimination of the UV portion of light is often done by incorporating a UV absorber into the covermaterial to absorb all of the UV radiation, effectively removing it from the spectrum that reaches the plant inside the greenhouse. Because UV is so harmful to plant species, blocking the UV portion of light may enhance plant growth. However, this solar energy is then lost to the environment as heat. Previous attempts to further enhance plant growth have incorporated a luminescent dye into greenhouse cover panels which converts green light into red light, basically increasing the useable solar energy that is directed to the plant. The conversion and use of the UV wavelengths of light for greenhouses has not been reported.
  • organic photostable chromophores that may convert UV energy into blue light have been found to further enhance plant growth by further increasing the amount of useable light available to the plant.
  • Some embodiments include a greenhouse panel.
  • the greenhouse panel comprises a thermal regulating wavelength conversion layer, wherein the thermal regulating wavelength conversion layer is formed as described above.
  • the greenhouse panel is useful as a greenhouse cover to provide improved wavelength profiles and improved thermal regulation of the greenhouse which accelerates plant growth.
  • the greenhouse panel comprises an organic photostable chromophore compound.
  • the greenhouse panel comprises at least two organic photostable chromophore compounds.
  • the chromophore compounds comprise an organic photostable chromophore (A), which has an wavelength absorbance maximum in the UV wavelength range and has an wavelength emission maximum in the blue wavelength range, and another organic photostable chromophore (B), which has an wavelength absorbance maximum in the green wavelength range and has an wavelength emission maximum in the red wavelength range.
  • the two chromophores may be mixed in the same wavelength conversion layer. In some embodiments, when more than one wavelength conversion layer is present, the two chromophores may be in different wavelength conversion layers.
  • the thermal regulating wavelength conversion film further comprises an optically transparent polymer, and a phase change material.
  • the emission spectrum of (A) and the absorption spectrum of (B) have minimal overlap.
  • minimal overlap may be an overlap ranging from about 0% to about 3%; about 3% to about 5%; about 5% to about 10%; about 10% to about 15%; about 15% to about 25%; about 25% to about 35%, or any other percentage bound within these ranges, where the percent overlap is a measure of the area under the portion of over lapping spectra divided by the area under either the emission or absorption curve.
  • the chromophores utilized in the greenhouse panel may be tailored to provide specific emission spectrums which are optimal to the specific plant species that is to be grown within the greenhouse.
  • the wavelength conversion layer(s) of the film comprises three or more chromophores.
  • the wavelength conversion layer(s) comprises four or more chromophores.
  • the wavelength conversion layer(s) comprises five or more chromophores.
  • chromophore (A) may be in a wavelength conversion layer that receives the incident solar energy before the wavelength conversion layer comprising chromophore (B).
  • chromophore (B) may be in a wavelength conversion layer that receives the incident solar energy before the wavelength conversion layer comprising chromophore (A). In some embodiments, it may be desirable to have the wavelength conversion layer comprising chromophore (A) receive the solar energy first. In some embodiments, chromophore (A) acts to convert UV wavelengths to blue wavelengths. Chromophore compounds often degrade much faster when exposed to UV wavelengths. Therefore, by having the wavelength conversion layer comprising chromophore (A) exposed to the incident solar radiation first, much of the UV light may be converted to blue light, and the underlying layers will not be exposed to the UV light.
  • the wavelength conversion layers are placed in ascending order of their wavelength absorption properties.
  • the greenhouse panel may further comprise glass or polymer layers.
  • the glass or polymer layers may act to protect the wavelength conversion layer or layers.
  • the glass or polymer layers may also act as a substrate to adhere to the wavelength conversion layer or layers.
  • the wavelength conversion layer or layers may be in between glass or polymer plates, wherein the glass or polymer plates may act to protect the wavelength conversion layer or layers from moisture or oxygen penetration.
  • additional materials may be used in the greenhouse panel, such as glass plates, polymer layers, or reflective mirror layers.
  • the materials may be used to encapsulate the wavelength conversion layer or layers, or they may be used to protect or encapsulate the wavelength conversion layer(s).
  • glass plates selected from low iron glass, borosilicate glass, or soda-lime glass, may be used in the greenhouse panel.
  • the composition of the glass plate or polymer layers may also further comprise a strong UV absorber to block harmful high energy radiation into the panel. The UV absorber in the glass plates or polymer layers may also block harmful high energy radiation from the wavelength conversion layer, thus improving the lifetime of the wavelength conversion layer(s).
  • the greenhouse solar collection panel comprises the greenhouse panel, as disclosed herein, and a solar energy conversion device.
  • the greenhouse solar collection panel is useful as a greenhouse roof or cover to simultaneously provide improved plant growth and solar harvesting ability which is photostable for long periods of time.
  • the solar energy conversion device is encapsulated within the greenhouse solar collection panel such that the device is not exposed to the outside environment, and wherein the solar energy conversion device receives a portion of the solar energy and converts that energy into electricity.
  • Some embodiments include a greenhouse solar collection panel.
  • the greenhouse solar collection panel comprises the thermal regulating wavelength conversion film, wherein the thermal regulating wavelength conversion film as described above.
  • the greenhouse panel and the greenhouse solar collection panel may have numerous configurations.
  • the panel may comprise only a single thermal regulating wavelength conversion film. In some embodiments, multiple thermal regulating wavelength conversion films may be present. Additional polymer layers or glass sheets may also be incorporated into the greenhouse panel and the greenhouse solar collection panel. Various structures for the greenhouse panel and the greenhouse solar collection panel may be similar to those shown in U.S. Provisional Patent Application Nos. 61/923,559 and 61/805,430, and International Application No. PCT/US2014/031722, which are hereby incorporated by reference in their entireties. [0166] In some embodiments of the greenhouse panel, additional materials or layers may be used such as edge sealing tape, frame materials, polymer materials, or adhesive layers to adhere additional layers to the system.
  • the greenhouse panel further comprises an additional polymer layer containing a UV absorber.
  • the UV absorber may be selected to absorb UV wavelengths that are not absorbed by the chromophore (A). By doing this, the UV wavelengths which may be converted to useable blue light by the chromophore (A) will be converted, while the UV wavelengths that cannot be converted by chromophore (A) will be absorbed by the UV absorber, so that these harmful wavelengths do not reach the plants inside the greenhouse.
  • the greenhouse solar collection panel comprises the solar energy conversion device. The greenhouse solar collection panel is useful as a greenhouse roof to simultaneously provide improved plant growth, thermal regulating, and to allow solar energy harvesting.
  • the solar energy conversion device is encapsulated within the greenhouse panel such that the device is not exposed to the outside environment, and wherein the solar energy conversion device receives a portion of the solar energy and converts that energy into electricity.
  • the solar energy conversion device receives a portion of the solar energy and converts that energy into electricity.
  • solar energy conversion devices into the greenhouse cover panels that have luminescent materials
  • the incorporation of solar energy conversion devices into the panel provides sufficient electricity generation by converting a portion of the solar energy into electricity.
  • Various designs may be used to incorporate solar cells into the greenhouse panel to form a greenhouse solar collection panel, depending on the electricity generation that is desired and the amount of photons that are needed to reach the plant species.
  • solar energy conversion devices When solar energy conversion devices are incorporated into greenhouse cover panels, the solar energy conversion device competes with the plants for the incident solar radiation. The solar energy conversion device is opaque, and will block the incident solar radiation.
  • the amount of solar energy conversion devices incorporated into the greenhouse solar collection panel may be tailored to meet the solar radiation requirements of the plants within the greenhouse.
  • different portions of the greenhouse may comprise different densities of solar energy conversion devices within the greenhouse solar collection panels. For instance, the north side of a greenhouse cover may incorporate more solar energy conversion devices in the greenhouse solar collection panels compared to the south side of the greenhouse. Adjustments may be made based on the location of the greenhouse. [0170] There is no restriction on the placement of the solar energy conversion device within the greenhouse panel.
  • the solar energy conversion device may be incorporated into the thermal regulating wavelength conversion film of the greenhouse panel. In some embodiments, the solar energy conversion device may be incorporated in between the wavelength conversion layer or layers and another polymer or glass layer of the greenhouse panel. In some embodiments, the placement of the solar energy conversion device in the greenhouse panel may be designated based on the type of solar energy conversion device.
  • the solar energy conversion device may also be placed within the thermal regulating wavelength conversion film that re-emits radiation at the optimal wavelength for the solar energy conversion device to convert photons into electricity.
  • silicon-based solar cells which exhibit their maximum electrical conversion rates with blue photons, would be placed in the greenhouse panel at a position that would allow the silicon solar cell to capture mostly blue photons.
  • the optimal electrical conversion rates vary with different types of solar cells. Therefore, in some embodiments, the solar energy conversion device may be placed within the greenhouse panel at a position that maximizes the capture of the optimal wavelength photons for that particular solar energy conversion device.
  • the greenhouse solar collection panel is compatible with all different types of solar energy conversion devices.
  • the greenhouse solar collection panel may be constructed to be compatible with all different types and sizes of solar cells and solar panels, including 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 film devices, dye sensitized devices, etc.
  • Devices such as an amorphous silicon solar cell (a-Si), a microcrystalline silicon solar cell (mc-Si), and a crystalline silicon solar cell (c-Si), may also be utilized.
  • the solar energy conversion device comprises a photovoltaic device or solar cell comprising a Cadmium Sulfide/Cadmium Telluride solar cell.
  • the solar energy conversion device comprises a Copper Indium Gallium Diselenide solar cell. In some embodiments, the solar energy conversion device comprises a III-V or II-VI PN junction device. In some embodiments, the solar energy conversion device comprises an organic sensitizer device. In some embodiments, the solar energy conversion device comprising an organic thin film device. [0173] In some embodiments of the greenhouse solar collection panel, multiple types of photovoltaic devices may be used within the panel and may be independently selected and incorporated into the greenhouse panel according to the emission wavelength of the wavelength conversion layer, to provide the highest possible photoelectric conversion efficiency.
  • the greenhouse solar collection panel further comprises a refractive index matching liquid that is used to attach the layers within the greenhouse panel to the light incident surface of the photovoltaic device or solar cell.
  • the refractive index matching liquid used is a Series A mineral oil comprising aliphatic and alicyclic hydrocarbons, and hydrogenated terphenyl from Cargille-Sacher Labratories, Inc (Cedar Grove, NJ).
  • Solar energy conversion devices utilizing different types of light incident surfaces may be used. For instance, some solar energy conversion devices are dual sided, and may receive radiation from two sides. Some solar energy conversion devices may only receive radiation on one side. In some embodiments of the greenhouse solar collection panel, a dual sided solar energy conversion device is used such that it may receive direct incident solar radiation on one of its sides, and it may also receive indirect radiation from internal reflection within the greenhouse panel on two of its sides. In some embodiments of the greenhouse solar collection panel, a single sided solar energy conversion device is used and is positioned within the greenhouse solar collection panel such that it receives direct incident solar radiation on its one side, and may also receive indirect radiation from internal reflection within the greenhouse panel on its one side.
  • the solar energy conversion device may be desirable to position the solar energy conversion device upside down, such that the light incident side of the solar energy conversion device is facing away from the sun.
  • the solar energy conversion device cannot receive direct solar radiation, which limits the radiation that will be converted into energy to that of the photons which become trapped within the greenhouse panel and are internally reflected and refracted until they reach the solar energy conversion device. This helps to alleviate the competition between the plants and the solar cells. It also protects the solar cells from direct sunlight, which may increase their lifetime by decreasing the amount of UV radiation exposure.
  • Embodiment 3 The wavelength conversion film of Embodiment 1 or 2, wherein the aliphatic ester plasticizer is an ester of cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, or cycloheptanedicarboxylic acid.
  • Embodiment 4 The wavelength conversion film of Embodiment 3, wherein the aliphatic ester plasticizer is an ester of cyclohexanedicarboxylic acid.
  • the wavelength conversion film of Embodiment 3 or 4 wherein the aliphatic ester plasticizer is a dialkylester of cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, or cycloheptanedicarboxylic acid, wherein each alkyl group of the dialkylester is independently C 4-14 alkyl.
  • Embodiment 6 The wavelength conversion film of Embodiment 5, wherein the aliphatic ester plasticizer is 1,2-cyclohexane dicarboxylic acid diisonoyl ester (DINCH).
  • DINCH 1,2-cyclohexane dicarboxylic acid diisonoyl ester
  • Embodiment 1 The wavelength conversion film of Embodiment 1, 2, 3, 4, 5, or 6, wherein the aliphatic ester plasticizer is about 5% to about 20% of the weight of the film.
  • Embodiment 8. The wavelength conversion film of Embodiment 1, 2, 3, 4, 5, 6, or 7, wherein the acrylic crosslinking coagent comprises an acrylate or alkacrylate ester of a diol or a triol.
  • Embodiment 9. The wavelength conversion film of Embodiment 8, wherein the acrylic crosslinking coagent comprises trimethylolpropane trimethacrylate (TMPTMA).
  • TMPTMA trimethylolpropane trimethacrylate
  • Embodiment 10 The wavelength conversion film of Embodiment 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the acrylic crosslinking coagent is about 5% to about 20% of the weight of the film.
  • Embodiment 11 The wavelength conversion film of Embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, further comprising a light stabilizer material.
  • Embodiment 12. The wavelength conversion film of Embodiment 11, wherein the light stabilizer material is a hindered amine light stabilizer, an additional polymer layer, a glass layer, or a UV absorber material or layer.
  • Embodiment 13 The wavelength conversion film of Embodiment 11, wherein the light stabilizer material is a UV absorber.
  • Embodiment 14 The wavelength conversion film of Embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13, further comprising an adhesion promoter, a stabilizer, a reducing agent, a crosslinking coagent, or a crosslinking agent.
  • Embodiment 15. The wavelength conversion film of Embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13, further comprising an adhesion promoter, a stabilizer, a reducing agent, a crosslinking coagent, or a
  • a greenhouse cover material comprising the wavelength conversion film of Embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, or 37.
  • Embodiment 16 A building or vehicle window comprising the wavelength conversion film of Embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, or 37.
  • a thermal regulating wavelength conversion film comprising: a chromophore and an optically transparent polymer, wherein said chromophore acts to absorb a portion of incident photons of a particular wavelength range and re-emit those photons at a different wavelength range, and wherein said phase change material acts to absorb and release heat for improved thermal regulation.
  • Embodiment 18 The film of Embodiment 17, further comprising a phase changing material, wherein said phase change material acts to absorb and release heat for improved thermal regulation.
  • Embodiment 19 The film of Embodiment 17, wherein the chromophore and phase change material are incorporated into the same polymer layer.
  • Embodiment 20 The film of Embodiment 17.
  • Embodiment 17 wherein the chromophore and phase change material are incorporated into separate polymer layers.
  • Embodiment 21 The film of Embodiment 17, 18, or 19, wherein the phase change material comprises an organic phase change material.
  • Embodiment 22 The film of Embodiment 21, wherein the phase change material comprises a paraffin.
  • Embodiment 23 The film of Embodiment 17, wherein the chromophore and phase change material are incorporated into separate polymer layers.
  • Embodiment 21 The film of Embodiment 17, 18, or 19, wherein the phase change material comprises an organic phase change material.
  • Embodiment 22 The film of Embodiment 21, wherein the phase change material comprises a paraffin.
  • Embodiment 23 Embodiment 23.
  • phase change material is formic acid, caprilic acid, glycerin, d-lattic acid, methyl palmitate, camphenilone, docasyl bromide, caprylone, phenol, heptadecanone, 1- cyclohexylooctadecane, 4-heptadecanone, p-joluidine, cyanamide, methyl eicosanate, 3- heptadecanone, 2-heptadecanone, hydrocinnamic acid, cetyl alcohol,, a-nepthylamine, camphene, O-nitroaniline, 9-heptadecanone, thymol, methyl behenate, diphenyl amine, p- dichlorobenzene, oxalate, hypophosphoric acid, o-xylene dichloride, b-chloroacetic acid, chloroacetic acid, nitro naphthalene, trimyristin
  • Embodiment 24 The film of Embodiment 21, wherein the phase change material comprises a fatty acid.
  • the film of Embodiment 24, wherein the phase change material is acetic acid, polyethylene glycol, capric acid, eladic acid, lauric acid, pentadecanoic acid, tristearin, myristic acid, palmatic acid, stearic acid, acetamide, or methyl fumarate.
  • Embodiment 26 The film of Embodiment 17, 18, 19, 20, 21, 22, 23, 24, or 25, wherein the optically transparent polymer comprises one host polymer, a host polymer and a copolymer, or multiple polymers.
  • the film of Embodiment 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, or 27, wherein the optically transparent polymer comprises a material selected from fluoropolymers, polyolefins, polyesters, thiourethane, polycarbonate (PC), allyl diglycol carbonate, polyacrylate, esters of a polyacrylic acid or a polyacrylic acid, 2- hydroxyethylmethacrylate, polyvinylpyrrolidinone, hexafluoroacetone- tetrafluoroethylene-ethylene (HFA/TFE/E terpolymers), hexafluoropropylene-vinylidene fluoride-tetrafluoroethylene (VDF/HFP/TFE) terpolymer, hexafluoropropylene- vinylidene
  • Embodiment 29 The film of Embodiment 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, or 28, further comprising an additional polymer layer, a glass layer, or a UV absorber material or layer.
  • Embodiment 30 The film of Embodiment 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or 29, further comprising an adhesion promoter, a stabilizer, a reducing agent, a crosslinking coagent, or a crosslinking agent.
  • Embodiment 31 The film of Embodiment 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, further comprising an antioxidant.
  • Embodiment 32 The film of Embodiment 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, or 31, wherein the film comprises two or more chromophores.
  • Embodiment 33 The film of Embodiment 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, or 32, wherein the chromophore is an organic dye.
  • Embodiment 34 The film of Embodiment 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, or 33, wherein the chromophore is selected from perylene derivative dyes, benzotriazole derivative dyes, benzothiadiazole derivative dyes, or BODIPY-type chromophores.
  • Embodiment 35 Embodiment 35.
  • An encapsulation structure for a solar energy conversion device comprising; the wavelength conversion film of Embodiment 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, or 34; wherein the wavelength conversion film is configured to encapsulate the solar energy conversion device and inhibit penetration of moisture and oxygen into the solar energy conversion device; and wherein the wavelength conversion film is configured to encapsulate the solar energy conversion device such that light must pass through the wavelength conversion film prior to reaching the solar energy conversion device.
  • Embodiment 36 A method of improving the performance of a solar energy conversion device, comprising encapsulating the device with the encapsulation structure of Embodiment 35.
  • Embodiment 37 A method of improving the performance of a solar energy conversion device, comprising encapsulating the device with the encapsulation structure of Embodiment 35.
  • the solar energy conversion device comprises a III-V or II-VI PN junction device, a Copper- Indium-Gallium-Selenium (CIGS) thin film device, an organic sensitizer device, an organic thin film device, or a Cadmium Sulfide/Cadmium Telluride (CdS/CdTe) thin film device, an amorphous silicon solar cell, a microcrystalline silicon solar cell, a polycrystalline silicon solar cell, or a crystalline silicon solar cell.
  • CdS/CdTe Cadmium Sulfide/Cadmium Telluride
  • Embodiment 38 A solar energy conversion system comprising the wavelength conversion film of Claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, or 34.
  • Step 2 A mixture of Compound a (13.4 g, 42 mmol), 4-methoxybenzyl alcohol (17.5 g, 126 mmol, 3 eq.) and 4-toluenesulfonic acid (200 mg) in toluene was heated at reflux under Dean-Stark trap for 16 hours. After cooling, the toluene solution was decanted from an oily layer formed on the flask bottom.
  • the oily layer was triturated first with hexane and then with methanol to wash out an excess of benzyl alcohol.
  • the brown solid obtained was separated, washed with methanol and dissolved in dichloromethane (DCM) (as little as possible to get clear solution). Diethyl ether was then added portion wise, while stirring, until crystals started to form, and the mixture was left for crystallization.
  • DCM dichloromethane
  • Step 3 Compound b (6.7 g, 12 mmol) was placed in a mixture of solvents (toluene/EtOH/2M-Na 2 CO 3 , 3:2:1 by volume, total volume 150 mL) was treated with 4- (diphenylamino)phenylboronic acid (10.4 g, 35 mmol) and tetrakis-triphenylphosphine- Pd(0) (2.00 g, 1.75 mmol) and heated with stirring at 100 °C. Progress of the reaction was monitored by TLC. When all the starting material was consumed (about 2 h), the mixture was cooled down to room temperature and transferred to a separatory funnel.
  • solvents toluene/EtOH/2M-Na 2 CO 3 , 3:2:1 by volume, total volume 150 mL
  • 4- (diphenylamino)phenylboronic acid (10.4 g, 35 mmol)
  • CE-8 was made as described in International Patent Publication No. WO2015/150120.
  • Optically transparent polymer Material [0210] Polyvinyl butyral (PVB) was obtained from Kuraray Co., Ltd. (Tokyo, JP) (MOWITAL® B 60T and/or MOWITAL® BX860) and used as received. Ethylene methyl methacrylate (EMMA) was obtained from Sumitomo Chemicals (Tokyo, JP) (ACRYFT® WK307) and used as received.
  • Adhesion promoter As the adhesion promoter, a silane coupling agent 3- methacryloxypropyltrimethoxysilane (KBM-503) was obtained from Shin-Etsu Chemical Co., Ltd. (Tokyo, JP) and used as received.
  • Stabilizer [0212] The stabilizer tetrakis(2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4- tetracarboxylate ADK Stab LA-57 was obtained from Adeka Palmarole (Mulhouse, FR) and used as received.
  • UV absorber [0213] The UV absorber 2,2’-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3- tetramethylbutyl))phenol (TINUVIN® 360) was obtained from BASF (Ludwigshafen, DE) and used as received.
  • Crosslinking Coagent [0214] The crosslinking coagent trimethylolpropane trimethacrylate (TMPTMA) was purchased from Sigma-Aldrich (St. Louis, MO) and used as received.
  • Crosslinking Agent/Initiator The organic peroxides t-butylperoxy-2-ethylhexylmonocarbonate (PERBUTYL® E) was used as crosslinking agents, and were obtained from NOF Co. (Tokyo, JP) and used as received.
  • Phase Change Material [0216] The phase change material paraffin wax (PCM24) was obtained from Microtek Laboratories Inc. (Moraine, OH) and used as received.
  • Plasticizer [0217] The plasticizer HEXAMOLL® DINCH was obtained from BASF and used as received. [0218] The plasticizer may be characterized by the following structure:
  • the plasticizer 3G8 was obtained from Sigma Aldrich and used as received.
  • the plasticizer PLASTOMOLL® DOA was obtained from BASF (Ludwigshafen, DE) and used as received.
  • Example 1 - Preparation of Wavlength Conversion Layer [0220] A thermal regulating wavelength conversion film was prepared. The components of the film were as shown in Table 1. Table 1
  • a thermal regulating wavelength conversion film comprising the components listed above was fabricated into a film structure following the wet processing procedure.
  • the thermal regulating wavelength conversion film is fabricated by (i) preparing a polymer solution by dissolving the EMMA resin pellets in a soluble solvent such as toluene, at a predetermined ratio; (ii) preparing a chromophore solution by dissolving the chromophore in the same solvent as the polymer solution at the predetermined concentration; (iii) preparing a phase change material solution by dissolving a phase change material in the same solvent as the polymer solution at the predetermined concentration; (iv) preparing a thermal regulating wavelength conversion solution by mixing the polymer solution with the chromophore solution and the phase change material solution, and then adding the other components (adhesion promoter, the coagent(s), and the peroxide), independently and at the predetermined weight ratio; and (v) forming the thermal regulating wavelength conversion film by directly
  • the thermal regulating wavelength conversion film was then laminated between two pieces of clear low-iron glass that were 2 mm thick and approximately 5 cm x 5 cm in dimension. Following lamination, the testing device was then cured to induce crosslinking. The curing temperature for the Example 1 testing device was 160 °C with a curing time of 15 min. Measurement of the Photostability [0222] An indoor WEATHEROMETERTM chamber model SUNTEST XXL+TM from Atlas Material Testing Technology (Mount Prospect, IL) was used to provide accelerated radiation aging of the test samples. The conditions were as follows: UV exposure of 60 W/m 2 at 63 °C and 60% relative humidity.
  • Example 2 For each testing sample, the absorption of the film was measured and used to determine the degradation of the chromophore within the layer. The absorption of the wavelength conversion films were measured using a UV- Vis-NIR spectrophotometer model UV-3600 from Shimadzu Corporation (Kyoto, JP). For each example composition, the absorption was measured after various irradiation exposure times in the chamber, and the normalized absorption was calculated to determine the photostability of the composition. [0223] FIG. 5 shows the normalized absorption of the Example 1 testing device after 1200 hours of exposure time with different concentrations of the phase change material (PCM). This data shows that increased concentration of PCM increases the photostability of the film.
  • Example 2 An Example 2 testing sample is synthesized using the same method as given in Example 1, except the wavelength conversion composition comprises the following composition as shown in Table 2: Table 2
  • FIG. 6 shows the normalized absorption of the Example 2 testing device after 600 hours of exposure time Comparative Example 3
  • An Example 3 testing sample is synthesized using the same method as given in Example 2, except the wavelength conversion composition comprises a plasticizer instead of a phase change material, as shown in Table 3: Table 3
  • FIG.6 shows the normalized absorption of the Comparative Example 3 testing device after 600 hours of exposure time.
  • Comparative Example 4 [0228] An Example 4 testing sample is synthesized using the same method as given in Example 2, except the wavelength conversion composition comprises a plasticizer instead of a phase change material, as shown in Table 4: Table 4
  • FIG.6 shows the normalized absorption of the Comparative Example 4 testing device after 600 hours of exposure time.
  • Comparative Example 5 [0230] An Example 5 testing sample is synthesized using the same method as given in Example 2, except the wavelength conversion composition comprises a plasticizer instead of a phase change material as shown in Table 5: Table 5
  • FIG.6 shows the normalized absorption of the Comparative Example 5 testing device after 600 hours of exposure time.
  • Comparative Example 6 [0232] An Example 6 testing sample is synthesized using the same method as given in Example 2, except the wavelength conversion composition does not comprise a phase change material as shown in Table 6: Table 6
  • FIG. 7 shows the normalized absorption of chromophores CE-7, CE-8, Compound 5, and Compound 6 in PVB composition testing devices (100 wt% PVB, 0.00065 mmol/g PVB of the chromophores, 7 wt% TMPTMA; 0.9 wt% TM360; 0.1 wt% KBM503, 0.3 wt% L-57 and 0.1 wt% PO-E, as described in Table 7), over about 4700 hours.
  • FIG. 8 shows the normalized absorption of chromophores CE-7, CE-8, Compound 5 and Compound 6 in EMMA composition testing devices (100% EMMA, 0.00065 mmol/g EMMA of chromophore, 7% TMPTMA; 0.9% TM360; 0.1 wt% KBM503, 0.3 wt% L-57 and 0.1 wt% PO-E as described in Table 8), over about 4700 hours.
  • FIG. 9 shows the normalized absorption of chromophore Compounds 5, 6, 7 and 8 in PVB compositioned testing devices (100% PVB, 0.0006 mmol/g PVB of chromophore, 10% TMPTMA; 0.9% TM360; 10.0 wt% DINCH, and 0.3 wt% LA-57, as described in Table 9) over about 2000 hours.
  • Table 9 shows the normalized absorption of chromophore Compounds 5, 6, 7 and 8 in PVB compositioned testing devices (100% PVB, 0.0006 mmol/g PVB of chromophore, 10% TMPTMA; 0.9% TM360; 10.0 wt% DINCH, and 0.3 wt% LA-57, as described in Table 9) over about 2000 hours.
  • Table 9 shows the normalized absorption of chromophore Compounds 5, 6, 7 and 8 in PVB compositioned testing devices (100% PVB, 0.0006 mmol/g PVB of chromophore, 10%
  • FIG. 11 shows the normalized absorption of chromophores Compound 5 PVB compositioned testing devices (100% PVB, 0.002 mmol/g PVB of chromophore, [0 wt% TMPTMA/20 wt% DINCH, 5%wt TMPTMA/15 wt% DINCH, 10%TMPTMA/10wt% DINCH; or 15% TMPTMA/5 wt% DINCH]; 0.9% TM360; and 0.3 wt% LA-57, as described in Table 11) over about 850 hours.
  • Table 11 shows the normalized absorption of chromophores Compound 5 PVB compositioned testing devices (100% PVB, 0.002 mmol/g PVB of chromophore, [0 wt% TMPTMA/20 wt% DINCH, 5%wt TMPTMA/15 wt% DINCH, 10%TMPTMA/10wt% DINCH; or 15% TMPTMA/5 wt% DINCH]; 0.9% TM360; and
  • FIG. 12 shows the normalized absorption of chromophores Compound 5 PVB compositioned testing devices (100% PVB, 0.0006 mmol/g PVB of Compound 6, [10 wt% TMPTMA/10 wt% DINCH, 10%wt TMPTMA/15 wt% DINCH]; 0.9% TM360; and 0.3 wt% LA-57, as described in Table 12) over about 1700 hours.
  • Table 12 shows the normalized absorption of chromophores Compound 5 PVB compositioned testing devices (100% PVB, 0.0006 mmol/g PVB of Compound 6, [10 wt% TMPTMA/10 wt% DINCH, 10%wt TMPTMA/15 wt% DINCH]; 0.9% TM360; and 0.3 wt% LA-57, as described in Table 12) over about 1700 hours.
  • Table 12 shows the normalized absorption of chromophores Compound 5 PVB compositioned testing devices (100% PVB, 0.0006 mmol/g
  • FIG. 13 shows the normalized absorption of chromophores Compound 6 PVB compositioned testing devices (100% PVB, 0.0006 mmol/g PVB of Compound 16, [10 wt% TMPTMA/10 wt% DINCH, 15%wt TMPTMA/10 wt% DINCH, 20%wt TMPTMA/10 wt% DINCH]; 0.9% TM360; and 0.3 wt% LA-57, as described in Table 13) over about 1700 hours.
  • Table 13 shows the normalized absorption of chromophores Compound 6 PVB compositioned testing devices (100% PVB, 0.0006 mmol/g PVB of Compound 16, [10 wt% TMPTMA/10 wt% DINCH, 15%wt TMPTMA/10 wt% DINCH, 20%wt TMPTMA/10 wt% DINCH]; 0.9% TM360; and 0.3 wt% LA-57, as described in Table 13
  • FIG. 14 shows the normalized absorption of chromophores Compound 6 PVB compositioned testing devices (100% PVB, 0.0006 mmol/g PVB of Compound 16, [10 wt% TMPTMA/10 wt% DINCH, 15%wt TMPTMA/15 wt% DINCH]; 0.9% TM360; and 0.3 wt% LA-57, as described in Table 14) over about 1700 hours.
  • Table 14 shows the normalized absorption of chromophores Compound 6 PVB compositioned testing devices (100% PVB, 0.0006 mmol/g PVB of Compound 16, [10 wt% TMPTMA/10 wt% DINCH, 15%wt TMPTMA/15 wt% DINCH]; 0.9% TM360; and 0.3 wt% LA-57, as described in Table 14) over about 1700 hours.
  • FIG. 15 shows the normalized absorption of chromophores Compound 6 PVB composition testing devices (100% BX860 PVB, 0.0004 mmol/g PVB of Compound 6, [0 wt% PCM, 1 wt% PCM, 3 wt% PCM, 5 wt% PCM]; 0.9% TM360; and 0.3 wt% LA-57, 10 wt%, DINCH, 10 wt% TMPTMA, as described in Table 15) over about 2000 hours.
  • Table 15 shows the normalized absorption of chromophores Compound 6 PVB composition testing devices (100% BX860 PVB, 0.0004 mmol/g PVB of Compound 6, [0 wt% PCM, 1 wt% PCM, 3 wt% PCM, 5 wt% PCM]; 0.9% TM360; and 0.3 wt% LA-57, 10 wt%, DINCH, 10 wt% TMPTMA, as described in Table 15) over about 2000 hours
  • FIG.16 shows shows the normalized absorption of chromophores Compounds 5, 9, 10, and 11 PVB composition testing devices (100% PVB, 0.0004 mmol/g PVB of Compounds 5, 9, 10, and 11; 0.9% TM360; and 0.3 wt% LA-57, 10 wt% DINCH, 10 wt% TMPTMA, as described in Table 16) over about 2000 hours.
  • Table 16 shows the normalized absorption of chromophores Compounds 5, 9, 10, and 11 PVB composition testing devices (100% PVB, 0.0004 mmol/g PVB of Compounds 5, 9, 10, and 11; 0.9% TM360; and 0.3 wt% LA-57, 10 wt% DINCH, 10 wt% TMPTMA, as described in Table 16
  • Example 2 thermal regulating wavelength conversion film has very high photostability, with hardly any degradation of the chromophore in the layer, as indicated by the very little change in the normalized absorption of the film after 600 hours of exposure time.
  • An object is to provide a thermal regulating wavelength conversion film that is photostable for long periods of time with exposure to solar radiation.
  • the film may be useful to encapsulate solar energy conversion devices and/or as a greenhouse roofing material. As illustrated by the above examples, the film is very stable after exposure to solar radiation for long periods of time.
  • this film to encapsulate solar cells, solar modules, photovoltaic devices, or entire solar panels, will provide stable enhancement of the photoelectric conversion efficiency for the lifetime of the solar energy harvesting device. Also, the use of this film may provide enhanced plant growth when used as a greenhouse roofing material.

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Abstract

La présente invention concerne un film de conversion de longueur d'onde pour régulation thermique comprenant un chromophore, un polymère optiquement transparent, et un matériau à changement de phase. Dans certains modes de réalisation, le chromophore et le matériau à changement de phase sont incorporés dans la même couche polymère. Dans certains modes de réalisation, le chromophore et le matériau à changement de phase sont incorporés dans des couches polymères distinctes. Le film de conversion de longueur d'onde pour régulation thermique est utile pour convertir des longueurs d'onde incidentes en longueurs d'onde plus souhaitables, tout en absorbant et en libérant la chaleur pour fournir une régulation thermique. Le film de conversion de longueur d'onde pour régulation thermique peut être utilisé comme encapsulation pour dispositifs de collecte d'énergie solaire, un film de fenêtre pour bâtiments ou véhicules, ou peut être utilisé comme couvercle ou matériau de toiture pour applications agricoles.
PCT/US2016/012503 2015-01-07 2016-01-07 Films de conversion de longueur d'onde pour régulation thermique incorporant des matériaux à changement de phase WO2016112200A1 (fr)

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KR20200054894A (ko) * 2018-11-12 2020-05-20 주식회사 엘지화학 색변환 필름, 이를 포함하는 백라이트 유닛 및 디스플레이 장치
CN113278177A (zh) * 2021-05-24 2021-08-20 重庆禾维科技有限公司 一种可逆热致变色阳光温室材料及其制备方法和应用
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CN114479770B (zh) * 2021-12-31 2024-05-03 苏州荣格君新材料有限公司 一种光热相变储能材料及其制备方法和应用
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KR102404987B1 (ko) * 2018-11-12 2022-06-07 주식회사 엘지화학 색변환 필름, 이를 포함하는 백라이트 유닛 및 디스플레이 장치
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CN110093064A (zh) * 2018-11-14 2019-08-06 重庆理工大学 一种长余辉发光墨水的制备方法及其应用
US20220264805A1 (en) * 2019-07-24 2022-08-25 Clearvue Technologies Ltd Method of and building for growing plants
WO2022112459A1 (fr) * 2020-11-30 2022-06-02 Merck Patent Gmbh Particule de matériau polymère électroluminescent
CN113278177A (zh) * 2021-05-24 2021-08-20 重庆禾维科技有限公司 一种可逆热致变色阳光温室材料及其制备方法和应用
CN114479770B (zh) * 2021-12-31 2024-05-03 苏州荣格君新材料有限公司 一种光热相变储能材料及其制备方法和应用

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