CN105419782B - As the material for transformation of wave length for improving day light collecting efficiency encapsulated used in solar modules system - Google Patents

As the material for transformation of wave length for improving day light collecting efficiency encapsulated used in solar modules system Download PDF

Info

Publication number
CN105419782B
CN105419782B CN201510744883.1A CN201510744883A CN105419782B CN 105419782 B CN105419782 B CN 105419782B CN 201510744883 A CN201510744883 A CN 201510744883A CN 105419782 B CN105419782 B CN 105419782B
Authority
CN
China
Prior art keywords
optionally substituted
alkyl
optionally
aryl
amino
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510744883.1A
Other languages
Chinese (zh)
Other versions
CN105419782A (en
Inventor
山本道治
张洪喜
斯坦尼斯劳·拉什沃尔
上野馨
蔡洁
胡毓芬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Choshu Industry Co Ltd
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority claimed from CN201280001372.5A external-priority patent/CN103339221B/en
Publication of CN105419782A publication Critical patent/CN105419782A/en
Application granted granted Critical
Publication of CN105419782B publication Critical patent/CN105419782B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

Abstract

The present invention relates to as the material for transformation of wave length for improving day light collecting efficiency encapsulated used in solar modules system.The present invention relates to the encapsulating structure for including luminescent wavelength conversion material at least one solar cell or photovoltaic devices, and it is used for the day light collecting efficiency for improving solar battery apparatus.Luminescent wavelength conversion material includes at least one chromophore and optical clear polymer substrate.Encapsulating structure disclosed herein is applied to the day optical acquisition device including solar cell, solar panel and photovoltaic devices, by widening the spectrum for the incident sunshine that electricity can be effectively converted into by device, so as to improve the day light collecting efficiency of described device.

Description

Turn as the wavelength for improving day light collecting efficiency encapsulated used in solar modules system Conversion materials
The application is the applying date for September in 2012 28 days, entitled " encapsulated as used in solar modules system (the PCT Application No. PCT/ of Chinese patent application 201280001372.5 of the material for transformation of wave length of raising day light collecting efficiency " US2012/058070 divisional application).
The reference of related application
No. 61/567,548 U.S. Provisional Patent Application and 2012 that patent application claims are submitted on December 6th, 2011 The priority for No. 61/662,848 U.S. Provisional Application that on June 21, in submits.All above-mentioned applications are complete by quoting herein Portion is incorporated herein for all purposes.
Background of invention
Technical field
Embodiment of the present invention generally relates to including for solar cell, solar panel or photovoltaic devices and sent out The encapsulating structure of optical wavelength conversion material, the encapsulating structure improve the day light collecting efficiency of these devices.
Description of Related Art
Utilization to solar energy provides the promising alternative energy source of conventional fossil fuel, therefore, it is possible to incite somebody to action The exploitation that solar energy is converted to the device, such as photovoltaic devices (also referred to as solar cell) of electricity causes extensive pass in recent years Note.Developed several different types of photovoltaic devices, including the device based on silicon, III-V and II-VI PN junctions device, Copper-indium-gallium-selenium (CIGS) film apparatus, organic sensitizer (sensitizer) device, organic thin film device and cadmium sulfide/ Cadmium telluride (CdS/CdTe) film apparatus, only enumerates several.More details about these devices can in such as Lin et al., “High Photoelectric Conversion Efficiency of Metal Phthalocyanine/Fullerene Heterojunction Photovoltaic Device”(International Journal of Molecular Sciences 2011) etc. find in document.Improved however, the photoelectric transformation efficiency of many of these devices kind still has Space, and for many researchers, the technology that exploitation improves this efficiency is a continuation challenge.
Recently, a technology for being used for improving photovoltaic devices efficiency for exploitation is to utilize transfer membrane (down- under wavelength shifting film).Many photovoltaic devices can not effectively utilize whole spectrum, because the material on device absorbs some wavelength Light (be usually shorter UV wavelength), rather than these light is reached the light guide material for converting thereof into electricity through the material The bed of material.The application of transfer membrane absorbs the photon of shorter wavelength under wavelength, and is launched them again with more favourable longer wavelength, Then they can be absorbed by the photoconductive layer in device, and be converted into electricity.
This phenomenon often observes that both of which is made using CdS in film CdS/CdTe and CIGS solar cell For Window layer.The low cost and high efficiency of these thin-film solar cells, have been attracted wide attention in recent years, and typical case The photoelectric transformation efficiency of commercial battery be 10-16%.However, a problem of these devices is that CdS energy gap is about 2.41eV, this causes light less than 514nm wavelength to be absorbed by CdS, rather than passes through it and can be converted into the light of energy Conducting shell.Whole spectrum can not be effectively utilized, it reduce the overall photoelectric transformation efficiency of device.
It is many to report the performance for having been disclosed for improving using material for transfer under wavelength photovoltaic devices.For example, the 2009/th No. 0151785 U.S. Patent Application Publication is disclosed containing the solar-electricity based on silicon that inorganic phosphor agent material is shifted under wavelength Pond.No. 2011/0011455 U.S. Patent Application Publication discloses integrated solar cell, and it includes plasma-based layer (plasmonic layer), wavelength conversion layer and photovoltaic layer.No. 7,791,157 disclosed in U.S. Patent to have and contains quantum The solar cell of the wavelength conversion layer of point compound.No. 2010/0294339 U.S. Patent Application Publication is disclosed containing glimmering The integrated photovoltaic device of material for transfer under light, but not constitution and implementation example.No. 2010/0012183 U.S. Patent application public affairs Open and disclose the thin-film solar cells with luminescence generated by light medium is shifted under wavelength；However, embodiment is not provided.2008/th No. 0236667 U.S. Patent Application Publication discloses the spectrum of the enhancing comprising inorganic fluorescent powder prepared in the form of film polymer Change film.However, above-mentioned patents and patent applicationss (they are integrally incorporated herein by quoting) is disclosed will be this extra Wavelength conversion layer directly applies to the top or inside of solar battery apparatus, which increase the cost of manufacture described device, and The thickness of device is added, this can cause the loss in environment of the photon to outside end face to increase.
In addition, solar modules are generally installed on roof or are installed on wide-open space out of doors, wherein they Maximumlly it can be exposed under daylight, referring to No. 2007/0295388 U.S. Patent Application Publication, it is herein by quoting It is incorporated herein by reference with overall situation.The type of this outdoor arrangement causes these devices continuously by weather and moisture Exposure, therefore they must have enough protections to provide steady running for many years.Generally, solar cell is made using glass plate Group resistance to weather proof, but glass plate is expensive, heavy and be rigid, and it also requires some type of edge adhesive tape prevents water Divide infiltration side.No. 7,976,750 U.S. Patent Publication is by the way that solar modules are embedded between two polymeric layers And the method that solar modules are then encapsulated with foaming agent blind.No. 2011/0017268 U.S. Patent Application Publication Disclose the polymeric material of the nanostructured for encapsulating solar modules device.No. 7,943,845 U.S. Patent Publication Utilize the method for poly- (vinyl butyral) composition encapsulation solar modules.These patents and patent applicationss are passed through herein Quote and be incorporated by as reference, however, there is no one to attempt in them for solar energy equipment and meanwhile provide environmental protection and The day light collecting efficiency of raising.
Summary of the invention
Some embodiments of the present invention provide the encapsulating structure for device for converting solar energy.Some realities of the present invention The scheme of applying provides the encapsulation comprising luminescent wavelength conversion material.In some embodiments, luminescent wavelength conversion material includes At least one chromophore and optical clear matrix, wherein luminescent wavelength conversion material are arranged to encapsulate device for converting solar energy simultaneously Suppress moisture and Oxygen permeation into device for converting solar energy.
In some embodiments, encapsulating structure includes luminescent wavelength conversion material and is arranged to suppress moisture and Oxygen permeation Environmental protection cover (environmental protective cover) into luminescent wavelength conversion material.In some embodiment party In case, luminescent wavelength conversion material includes at least one chromophore and optical clear polymer substrate.In some embodiments, Luminescent wavelength conversion material and environmental protection cover are configured to encapsulate device for converting solar energy, so that light reaches the sun Luminescent wavelength conversion material and environmental protection cover can be had to pass through before conversion equipment.
Some embodiments of the present invention provide the method for improving device for converting solar energy performance, including with encapsulating structure Encapsulate described device.In some embodiments, for methods described including the use of encapsulating structure, the encapsulating structure includes luminous ripple Long transition material, the luminescent wavelength conversion material be arranged to encapsulate device for converting solar energy and be arranged to suppress moisture and Oxygen permeation is into device for converting solar energy.In some embodiments, methods described including the use of luminescent wavelength conversion material and Environmental protection cover, wherein environmental protection cover are configured to suppress moisture and Oxygen permeation to luminescent wavelength conversion material.
Brief Description Of Drawings
The embodiment that Fig. 1 shows encapsulating structure, wherein single solar battery apparatus is packaged in emission wavelength conversion In material, and environmental protection cover is used as by the use of glass plate or plastic plate.
The embodiment that Fig. 2 shows encapsulating structure, plurality of solar battery apparatus are packaged in emission wavelength conversion In material, and environmental protection cover is used as by the use of glass plate or plastic plate.
The embodiment that Fig. 3 shows encapsulating structure, plurality of solar battery apparatus are packaged in straight polymer encapsulation In, luminescent wavelength conversion material is laminated at the top of polymer encapsulated, and is used as environmental protection cover by the use of glass plate or plastic plate.
The embodiment that Fig. 4 shows encapsulating structure, plurality of solar battery apparatus are packaged in emission wavelength conversion In material, and environmental protection cover is used as by the use of glass plate or plastic plate.
The embodiment that Fig. 5 shows encapsulating structure, plurality of solar battery apparatus are packaged in straight polymer encapsulation In, luminescent wavelength conversion material is laminated at the top of polymer encapsulated, and is used as environmental protection cover by the use of glass plate or plastic plate.
The embodiment that Fig. 6 shows encapsulating structure, plurality of solar battery apparatus are packaged in straight polymer encapsulation In material, luminescent wavelength conversion material is laminated at the top of straight polymer encapsulation, and extra straight polymer film layer is together in luminous ripple The top of long conversion layer, and environmental protection cover is used as by the use of glass plate or plastic plate.
The embodiment that Fig. 7 shows encapsulating structure, wherein single solar battery apparatus is packaged in emission wavelength conversion In material, and luminescent wavelength conversion material also serves as environmental protection device.
The embodiment that Fig. 8 shows encapsulating structure, plurality of solar battery apparatus are packaged in emission wavelength conversion Material, and luminescent wavelength conversion material also serves as environmental protection device.
The embodiment that Fig. 9 shows encapsulating structure, plurality of solar battery apparatus are packaged in straight polymer encapsulation In material, luminescent wavelength conversion material is laminated at the top of straight polymer encapsulation, and luminescent wavelength conversion material also serves as environment Protector.
Figure 10 shows the exemplary of encapsulating structure, wherein the solar-electricity with several solar battery apparatus Pond plate encapsulates solar battery apparatus using luminescent wavelength conversion material, and glass film plates and glass top plate provide environmental protection, Backboard (back sheet) is located under the light incident surface of solar battery apparatus, and solar panel is maintained at by frame Together.
Figure 11 shows the exemplary of encapsulating structure, wherein the solar-electricity with several solar battery apparatus Pond plate encapsulates solar battery apparatus using luminescent wavelength conversion material, and the light that backboard is located at solar battery apparatus enters firing table Under face, glass top plate provides environmental protection, and frame keeps together solar panel.
It is described in detail
Embodiment of the present invention realizes that to protect a battery from harmful environment sudden and violent with killing two birds with one stone in a system Reveal and improve efficiency.Filled with the encapsulating structure encapsulation solar modules disclosed herein comprising luminescent wavelength conversion material Put, improve the day light collecting efficiency of solar battery apparatus, and for the device provides the protection of stable long-range circumstances.Comprising The encapsulating structure of luminescent wavelength conversion material can be formed and all different types of solar cells and solar cell Plate (including it is device based on silicon, III-V and II-VI PN junctions device, CIGS thin film device, organic sensitizer device, organic thin Film device, CdS/CdTe film apparatus, dye sensitization device etc.) it is compatible.By using the construction packages solar modules device, Device for converting solar energy (such as solar cell, photovoltaic devices, solar panel and any solar modules system can be improved System) photoelectric transformation efficiency.
Some embodiments provide is used at least one solar cell or photovoltaic comprising luminescent wavelength conversion material The encapsulating structure of device.Some embodiments provide is used at least one comprising luminescent wavelength conversion material and environmental protection cover The encapsulating structure of kind solar cell or photovoltaic devices.In some embodiments, environmental protection cover is arranged to suppress moisture With Oxygen permeation to luminescent wavelength conversion material and solar cell or photovoltaic devices, and including plastic plate or glass plate.At some In embodiment, band is applied to suppress oxygen and moisture from edge enter around solar panel.Fig. 1-6 is shown Exemplary applied to solar cell or the encapsulating structure of photovoltaic die set.
Some embodiments of the present invention provide is used at least one solar-electricity comprising luminescent wavelength conversion material Pond or the encapsulating structure of photovoltaic devices.In some embodiments, luminescent wavelength conversion material is used as preventing moisture and Oxygen permeation Environmental protection device into solar cell.In one embodiment, luminescent wavelength conversion material is designed to anti-block and water Divide and penetrate into solar cell, so as to no longer need extra environmental protection cover, and the material can also improve the day gloss of battery Collect efficiency.Fig. 7-9 shows the exemplary of the encapsulating structure applied to solar modules device.
Embodiment of the present invention further relates to improve photovoltaic devices, solar cell, solar modules or solar cell The method of the performance of plate, including encapsulate described device with encapsulating structure disclosed herein.In some embodiments, will can seal The luminescent wavelength conversion material of assembling structure is cast on solar battery apparatus, and is cured in situ.In some embodiments, seal The luminescent wavelength conversion material of assembling structure can use the form of film or layer.In some embodiments, film shape will can be used as The luminescent wavelength conversion material layer of rolls of formula is pressed on solar modules device, wherein only front layer (front layer) is laminated at too On positive energy module, or front layer and backing layer (back layer) both of which are laminated on solar modules device.
The luminescent wavelength conversion material of other forms is also possible, and luminescent wavelength conversion material is applied into the sun The other method of energy die set is also possible.Encapsulating structure can be applied to rigid mount, or can be applied to Flexible apparatus.Furthermore, it is possible to improve the performance of multiple solar cells or photovoltaic devices with encapsulating structure.For example, in some realities Apply in scheme, encapsulating structure includes multiple solar cells or photovoltaic devices.
In some embodiments, the environmental protection of enhancing can also be provided using other materials.Glass plate or plastics Plate is commonly used as environmental protection cover, and it can apply to the top of the solar modules device encapsulated with luminescent wavelength conversion material And/or bottom.In some embodiments, band can be applied to around device, so as to which anti-block or moisture pass through Side enters.In some embodiments, can also by backboard be used for solar modules device under, with reflect and reflect not by The incident light that solar cell absorbs.In some embodiments, the solar energy equipment of encapsulation can also be put into frame, such as For formed solar modules or solar energy lamp string (solar strings) those.Figure 10 and 11 shows to be used for solar energy mould The exemplary of encapsulating structure in group device.
Chromophore is also referred to as luminescent dye or fluorescent dye, is to absorb the photon of specific wavelength or wave-length coverage and with not Same wavelength launches the compound of photon again.Because solar cell and photovoltaic devices often long-term (i.e. more than 20 years) exposure Under extreme environmental conditions, therefore, the stability of chromophore is extremely important.In some embodiments, changed in emission wavelength Be used only in material have prolonged good photostability (that is, it is lower luminous more than 20 in 1 times of sunshine (AM1.5G) irradiation, Degraded at 000 hour<10%) chromophore or chromophore compound.In some embodiments of encapsulating structure, two kinds or more Kind chromophore is contained in luminescent wavelength conversion material.
In some embodiments, material for transformation of wave length can be made up of several layers.In some embodiments, two kinds or A variety of chromophores can be located in identical luminescent wavelength conversion material layer, or they can be located in single material layer.Can It is expected having a variety of chromophores or luminescent dye in material for transformation of wave length, this depends on the material solar energy mould to be encapsulated Group.For example, the first chromophore can be used for the photon that wavelength is 400-450nm being converted into the photon that wavelength is 500nm, and Second chromophore can be used for the photon that wave-length coverage is 450-475nm being converted into the photon that wavelength is 500nm, wherein will quilt The solar modules system of material package shows best photoelectric conversion efficiency under 500nm wavelength, so as to which emission wavelength is changed Material package device significantly improves the day light collecting efficiency of solar modules system.
In addition, in some embodiments of encapsulating structure, at least one chromophore is upper shifting dyes or upper transfer dye Material, imply that photon from the chromophore that higher-energy (short wavelength) is converted to compared with low energy (long wavelength).Upper shifting dyes can be with Including having been observed that the photon for absorption IR area (i.e.~975nm) wavelength and launching the light of visual field (400-700nm) wavelength again The rare earth material of son, such as Yb3+、Tm3+、Er3+、Ho3+And NaYF4.Other up-conversions are described in No. 6,654,161 In the 6th, 139, No. 210 United States Patent (USP), and in Indian Journal of Pure and Applied Physics, 33 Volume, the 169-178 pages, in (1995), it is used as reference by quoting to be incorporated by herein.
In some embodiments of encapsulating structure, at least one chromophore is down conversion dyestuff or lower transferred dyes, is anticipated High-energy photon (short wavelength) is converted into the chromophore of the relatively low photon of energy (long wavelength).
In some embodiments of encapsulating structure, material for transformation of wave length includes optically transparent polymer substrate.One In a little embodiments, optically transparent polymer substrate selected from following material by forming：Polyethylene terephthalate, gather It is methyl methacrylate, polyvinyl butyral resin, ethylene-vinyl acetate, ethylene tetrafluoroethylene, polyimides, amorphous poly- Carbonic ester, polystyrene, siloxane sol gel, polyurethane, polyacrylate with and combinations thereof.
In some embodiments of encapsulating structure, optically transparent polymer substrate includes more than one polymer. In some embodiments, optically transparent polymer substrate include a kind of main polymer, main polymer and copolymer or Multiple polymers.In some embodiments, the ranges of indices of refraction of matrix material is about 1.4 to about 1.7.In some implementations In scheme, the ranges of indices of refraction of matrix material is about 1.45 to about 1.55.
In some embodiments, luminescent dye or chromophore are present in polymerization with about 0.01wt% to about 3wt% amount In thing matrix.In some embodiments, chromophore is present in polymer substrate with about 0.05wt% to about 1wt% amount.
Chromophore represented by formula I-a, I-b, II-a, II-b, III-a, III-b, IV and V can be in various applications In, be included in Wavelength conversion film and be used as fluorescent dye.As shown in formula, dyestuff includes benzoheterocyclic system or perylene spreads out Biology.In the case where not limiting the scope of the present invention, exist for other details of type of compounds and example that can be used It is described below.
" electron donor group " used herein is defined as increasing the electron density of 2H- benzos [d] [1,2,3] triazole system Any group.
" electron donor attachment " is defined as that two 2H- benzos [d] [1,2,3] triazole systems can be connected to provide its π Any group of track conjugation, electron donor attachment can also increase 2H- benzos [d] [1,2,3] triazole for being attached thereto Electron density has neutral influence on it.
" electron accepting groups " are defined as reducing any base of the electron density of 2H- benzos [d] [1,2,3] triazole system Group.The position of electron accepting groups is the N-2 positions of 2H- benzos [d] [1,2,3] triazole member ring systems.
Term " alkyl " refers to side chain or the fully saturated acyclic aliphatic race hydrocarbyl group of straight chain (that is, is made up of not carbon and hydrogen Group containing double bond and three key).Alkyl include but is not limited to methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, Amyl group, hexyl etc..
Terms used herein " cycloalkyl " refers to the representative examples of saturated aliphatic member ring systems group with 3-20 carbon atom, including but not It is limited to cyclopropyl, cyclopenta, cyclohexyl, suberyl etc..
Terms used herein " alkenyl " refers to the group of 2-20 carbon atom of the monovalent straight chain containing carbon double bond or side chain, its Including but not limited to 1- acrylic, 2- acrylic, 2- methyl-1-propylenes base, 1- cyclobutenyls, 2- cyclobutenyls etc..
Terms used herein " alkynyl " refers to the group of 2-20 carbon atom of the monovalent straight chain containing the key of carbon three or side chain, bag Include but be not limited to 1- propinyls, 1- butynyls, 2- butynyls etc..
Terms used herein " aryl " refers to homoatomic ring aromatic group, either a ring or multiple fused rings.Aryl Example include but is not limited to phenyl, naphthyl, phenanthryl, aphthacene base, fluorenyl, pyrenyl etc..Other examples include：
Terms used herein " alkaryl " or " alkylaryl " refer to alkyl-substituted aryl.The example of alkaryl is included but not It is limited to ethylphenyl, 9,9- dihexyl -9H- fluorenes etc..
Terms used herein " aralkyl " or " aryl alkyl " refer to the alkyl of aryl substitution.The example of aralkyl is included but not It is limited to phenylpropyl, phenethyl etc..
It is heteroatomic aromatic ring system group that terms used herein " heteroaryl ", which refers to wherein one or more annular atoms, Either a ring or multiple fused rings.When two or more hetero atoms be present, they can be with identical or different.Condensing In member ring systems, one or more hetero atoms may reside in only one ring.The example of heteroaryl includes but is not limited to benzo thiophene Oxazolyl, benzoxazinyl (benzoxazyl), quinazolyl, quinolyl, isoquinolyl, quinoxalinyl, pyridine radicals, pyridazinyl, Pyrimidine radicals, pyrazinyl, pyrrole radicals, oxazolyls, indyl, thiazolyl etc..Other realities of substitution and unsubstituted heteroaryl ring Example includes：
Terms used herein " alkoxy " refers to by -- O-- connections to be covalently bonded in the straight or branched alkane of parent molecule Base.The example of alkoxy includes but is not limited to methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, n-butoxy, sec- Butoxy, tert-butoxy etc..
Terms used herein " hetero atom " refers to S (sulphur), N (nitrogen) and O (oxygen).
Terms used herein " cyclic amino " refers to secondary amine or tertiary amine in annulus.The example of cyclic amino is included but not It is limited to aziridinyl, piperidyl, N- methyl piperidine bases etc..
Terms used herein " ring-type acylimino " refer to two carbonyl carbons by carbochain and the group that connects in imines. The example of ring-type acylimino includes but is not limited to 1,8- naphthalimides, pyrrolidine-2,5-dione, 1H- pyrroles -2,5- two Ketone etc..
Terms used herein " aryloxy group " refers to by -- O-- connections to be covalently bonded in the aryl of parent molecule.
Terms used herein " acyloxy " refers to group R-C (=O) O-.
Terms used herein " carbamoyl " refers to-NHC (=O) R.
Terms used herein " ketone " and " carbonyl " refer to C=O.
Terms used herein " carboxyl " refers to-COOH.
Terms used herein " ester " refers to C (=O) O.
Terms used herein " acylamino- " refers to-NRC (=O) R '.
Terms used herein " amino " refers to-NR ' R ".
As used herein, substituted radical sources are in unsubstituted precursor structure, wherein with another atom or base Group exchanges one or more hydrogen atoms.When substitution, substituent is that one or more is individually and separately selected from C1-C6Alkyl, C1-C6Alkenyl, C1-C6Alkynyl, C3-C7Cycloalkyl is (optionally with halogen, alkyl, alkoxy, carboxyl, haloalkyl, CN ,-SO2- Alkyl ,-CF3And-OCF3Substitution), the cycloalkyl together with connection, C1-C6Miscellaneous alkyl, C3-C10Heterocyclylalkyl (such as tetrahydrofuran Base) (optionally with halogen, alkyl, alkoxy, carboxyl, CN ,-SO2- alkyl ,-CF3And-OCF3Substitution), aryl (optionally (C is optionally used with halogen, alkyl, aryl in ground1-C6Alkyl substitutes), aralkyl, alkoxy, aryloxy group, carboxyl, amino, acyl it is sub- Amino, acylamino- (carbamoyl), the ring-type acylimino optionally substituted, cyclic amido, CN ,-NH-C (=O)-alkane Base ,-CF3And-OCF3Substitution), aralkyl is (optionally with halogen, alkyl, alkoxy, aryl, carboxyl, CN ,-SO2- alkyl ,- CF3And-OCF3Substitution), heteroaryl (optionally with halogen, alkyl, alkoxy, aryl, heteroaryl, aralkyl, carboxyl, CN、-SO2- alkyl ,-CF3And-OCF3Substitution), halo (such as chloro, bromo, iodo and fluoro), cyano group, hydroxyl, appoint Choose ring-type acylimino, amino, acylimino, the acylamino- ,-CF in generation3、C1-C6Alkoxy, aryloxy group, acyloxy, sulfydryl (sulfydryl (mercapto)), halo (C1-C6) alkyl, C1-C6Alkylthio group, arylthio, single- and di- (C1-C6) alkyl amino, season Ammonium salt, amino (C1-C6) alkoxy, hydroxyl (C1-C6) alkyl amino, amino (C1-C6) alkylthio group, cyanoaminopyrimidine, nitro, amino Formoxyl, ketone (oxygen) base, carbonyl, carboxyl, glycolyl, glycyl, diazanyl, amidino groups, sulfamic, sulfonyl, sulfenyl Base, thiocarbonyl, thiocarboxyl group, sulfonamide, ester, C- acid amides, N- acid amides, N- carbamates, O- carbamates, urea and Its group combined.No matter substituent is somewhere described with " optionally substituting ", then the substituent can be taken with above-mentioned Substitute for base.
Formulas I-a and I-b
Some embodiments provide the chromophore with one of following structures：
Wherein D1And D2It is electron-donating group, LiIt is electron donor attachment, and A0And AiIt is electron accepting groups.One In a little embodiments, if more than the electron donor group of one, then other electron donor groups can be by another electronics Donor, hydrogen atom or another neutral substituents occupy.In some embodiments, D1、D2And LiIn it is at least one be enhancing with Connection 2H- benzos [d] [1,2,3] triazole system electron density group.
In Formulas I-a and I-b, i is 0-100 integer.In some embodiments, i is 0-50,0-30,0-10,0-5 Or 0-3 integer.In some embodiments, i is 0,1,2,3,4,5,6,7,8,9 or 10.
In Formulas I-a and I-b, A0And AiBe each independently selected from the alkyl optionally substituted, the alkenyl optionally substituted, optionally Substituted miscellaneous alkyl, the aryl optionally substituted, the heteroaryl optionally substituted, the amino optionally substituted, the acylamino- optionally substituted, The cyclic amido that optionally substitutes, the ring-type acylimino optionally substituted, the alkoxy optionally substituted and optionally substituted carboxylic Base and the carbonyl optionally substituted.
In some embodiments, A0And AiBe each independently selected from the heteroaryl optionally substituted, the aryl optionally substituted, The ring-type acylimino optionally substituted, the C optionally substituted1-8Alkyl and the C optionally substituted1-8Alkenyl；Wherein optionally substitute The substituent of heteroaryl is selected from alkyl, aryl and halogen；The substituent of the aryl optionally substituted is-NR1- C (=O) R2Or appoint Choose the ring-type acylimino in generation, wherein R1And R2As described above.
In some embodiments, A0And AiIt is each independently by selected from-NR1- C (=O) R2The ring-type optionally substituted The partially substituted phenyl of acylimino, wherein R1And R2As described above.
In some embodiments, A0And AiThe heteroaryl individually optionally substituted or the ring-type acylimino optionally substituted； The substituent of the heteroaryl wherein optionally substituted and the ring-type acylimino optionally substituted is selected from alkyl, aryl and halogen. In some embodiments, A0And AiIn at least one be selected from：The pyridine radicals that optionally substitutes, the pyridazinyl optionally substituted, optionally take The pyrimidine radicals in generation, the pyrazinyl optionally substituted, the triazine radical optionally substituted, the quinolyl optionally substituted, the isoquinoline optionally substituted Quinoline base, the quinazolyl optionally substituted, the phthalazinyl optionally substituted, the quinoxalinyl optionally substituted, the naphthyridines base optionally substituted And the purine radicals optionally substituted.
In other embodiments, A0And AiThe alkyl individually optionally substituted.In other embodiments, A0And AiRespectively The alkenyl optionally substituted naturally.In some embodiments, A0And AiIn at least one be selected from：
Wherein R is the alkyl optionally substituted.
In Formulas I-a and I-b, A2Selected from the alkylidene optionally substituted, the alkenylene optionally substituted, the Asia virtue optionally substituted Base, the heteroarylidene optionally substituted, ketone, ester andWherein Ar be the aryl that optionally substitutes or The heteroaryl optionally substituted.R1Selected from H, alkyl, alkenyl, aryl, heteroaryl, aralkyl, alkaryl；And R2Selected from optional substitution Alkylidene, the alkenylene, the arlydene, the heteroarylidene, ketone and the ester that optionally substitute that optionally substitute that optionally substitute；Or R1With R2It can link together and form ring.
In some embodiments, A2Selected from the arlydene optionally substituted, the heteroarylidene optionally substituted andWherein Ar, R1And R2As described above.
In Formulas I-a and I-b, D1And D2The alkoxy for be each independently selected from hydrogen, optionally substituting, the fragrant oxygen optionally substituted Base, the acyloxy optionally substituted, the alkyl optionally substituted, the aryl optionally substituted, the heteroaryl that optionally substitutes, optionally substitute Amino, acylamino-, cyclic amido and ring-type acylimino, condition are D1And D2Both are not all hydrogen.
In some embodiments, D1And D2The aryl for be each independently selected from hydrogen, optionally substituting, the heteroaryl optionally substituted Base and amino, condition are D1And D2Both are not all hydrogen.In some embodiments, D1And D2It is each independently selected from hydrogen, appoints Aryl, the heteroaryl and diphenyl amino optionally substituted in generation are chosen, condition is D1And D2Both are not all hydrogen.
In some embodiments, D1And D2It is each independently selected from the aryl optionally substituted.In some embodiments, D1And D2It is the phenyl optionally substituted by alkoxy or amino independently of one another.In other embodiments, D1And D2It is each independent Ground is selected from hydrogen, the benzofuranyl optionally substituted, the thienyl optionally substituted, furyl, the dihydro-thiophene dioxy optionally substituted Glutinous rehmannia base (dihydrothienodioxinyl), the benzothienyl optionally substituted and the dibenzothiophenes base optionally substituted, bar Part is D1And D2Both are not all hydrogen.
In some embodiments, the substituent of the aryl optionally substituted and the heteroaryl optionally substituted can be selected from alcoxyl Base, aryloxy group, aryl, heteroaryl and amino.
In Formulas I-a and I-b, LiIndependently selected from the alkylidene optionally substituted, the optionally alkenylene optionally substituted, substitution Alkynylene, the arlydene, the heteroarylidene that optionally substitutes that optionally substitute.In some embodiments, LiSelected from optional substitution Heteroarylidene and the arlydene that optionally substitutes.
In some embodiments, LiIn it is at least one selected from 1,2- ethenylidenes, ethynylene (acetylene), 1,4- phenylenes, 1,1 '-biphenyl -4,4 '-diyl, naphthalene -2,6- diyls, naphthalene -1,4- diyls, 9H- fluorenes -2,7- diyls, dinaphthyl are embedding Benzene -3,9- diyls, perylene -3,10- diyls or pyrene -1,6- diyls, 1H- pyrroles -2,5- diyls, furans -2,5- diyls, thiophene Fen -2,5- diyls, thieno [3,2-b] thiophene -2,5- diyls, benzo [c] thiophene -1,3- diyls, dibenzo [b, d] thiophene - 2,8- diyls, 9H- carbazole -3,6- diyls, 9H- carbazole -2,7- diyls, dibenzo [b, d] furans -2,8- diyls, 10H- fen thiophenes Piperazine -3,7- diyls and 10H- phenthazine -2,8- diyls；Wherein each part optionally substitutes.
Formula II-a and II-b
Some embodiments provide the chromophore with one of following structures：
Wherein i is 0-100 integer.In some embodiments, i is 0-50,0-30,0-10,0-5 or 0-3 integer. In some embodiments, i is 0,1,2,3,4,5,6,7,8,9 or 10.
In Formula II-a and II-b, Ar is the aryl optionally substituted or the heteroaryl optionally substituted.In some embodiments In, carried in the N-2 opening positions of 2H- benzos [d] [1,2,3] triazole member ring systems by the aryl that acylamino- or ring-type acylimino substitute Effect that is unexpected and improving is supplied.
In Formula II-a and II-b, R4It isOr the ring-type acylimino optionally substituted；R1Select independently of one another From H, alkyl, alkenyl, aryl, heteroaryl, aralkyl, alkaryl；R3It is each independently selected from the alkyl optionally substituted, optionally takes The alkenyl in generation, the aryl optionally substituted, the heteroaryl optionally substituted；Or R ' and R " can link together and form ring.
In some embodiments, R4It is to be selected from following optional substituted ring-type acylimino：
And wherein R ' the individually alkyl optionally substituted or the aryl optionally substituted, And X is the miscellaneous alkyl optionally substituted.
In Formula II-a and II-b, R2Selected from the alkylidene optionally substituted, the alkenylene optionally substituted, the Asia optionally substituted Aryl, the heteroarylidene optionally substituted.
In Formula II-a and II-b, D1And D2The alkoxy for be each independently selected from hydrogen, optionally substituting, the virtue optionally substituted Epoxide, the acyloxy optionally substituted, the alkyl optionally substituted, the aryl optionally substituted, the optionally heteroaryl optionally substituted, substitution Amino, acylamino-, cyclic amido and ring-type acylimino, condition is D1And D2Both are not all hydrogen.
In Formula II-a and II-b, LiIndependently selected from the alkylidene optionally substituted, the alkenylene optionally substituted, optionally take The alkynylene in generation, the arlydene optionally substituted, the heteroarylidene optionally substituted.
In some embodiments, LiIn it is at least one selected from 1,2- ethenylidenes, ethynylene, 1,4- phenylenes, 1, 1 '-biphenyl -4,4 '-diyl, naphthalene -2,6- diyls, naphthalene -1,4- diyls, 9H- fluorenes -2,7- diyls, perylene -3,9- diyls, two Rylene -3,10- diyls or pyrene -1,6- diyls, 1H- pyrroles -2,5- diyls, furans -2,5- diyls, thiophene -2,5- diyls, thiophene Fen simultaneously [3,2-b] thiophene -2,5- diyls, benzo [c] thiophene -1,3- diyls, dibenzo [b, d] thiophene -2,8- diyls, 9H- clicks Azoles -3,6- diyls, 9H- carbazole -2,7- diyls, dibenzo [b, d] furans -2,8- diyls, 10H- phenthazine -3,7- diyls and 10H- phenthazine -2,8- diyls；Wherein each part is optionally substituted.
Formula III-a and III-b
Some embodiments provide the chromophore with one of following structures：
The cloth of alkyl in formula (III-a) and (III-b) in 2H- benzos [d] [1,2,3] triazole member ring systems N-2 positions Put and the phenyl that substitutes C-4 and C-7 positions arrangement, there is provided unexpected and improved effect.In formula III-a and In III-b, i is 0-100 integer.In some embodiments, i is 0-50,0-30,0-10,0-5 or 0-3 integer.One In a little embodiments, i is 0,1,2,3,4,5,6,7,8,9 or 10.
In formula III-a and III-b, A0And AiBe each independently selected from the alkyl optionally substituted, the alkenyl optionally substituted, The miscellaneous alkyl that optionally substitutes, the acylamino- optionally substituted, the alkoxy optionally substituted, the carbonyl optionally substituted and optionally substitution Carboxyl.
In some embodiments, A0And AiIt is unsubstituted alkyl independently of one another or is substituted selected from following part Alkyl：- NRR " ,-OR ,-COOR ,-COR ,-CONHR ,-CONRR ", halogen and-CN；Wherein R is C1-C20Alkyl, and R " It is hydrogen or C1-C20Alkyl.In some embodiments, the alkyl optionally substituted can be the C optionally substituted1-C40Alkyl.One In a little embodiments, A0And AiIt is C independently of one another1-C40Alkyl or C1-C20Haloalkyl.
In some embodiments, A0And AiIt is C independently of one another1-C20Haloalkyl, C1-C40Aralkyl or C1-C20Alkene Base.
In formula III-a and III-b, each R5The fragrant oxygen for be independently selected from the alkoxy optionally substituted, optionally substituting Base, the acyloxy optionally substituted and amino.In some embodiments, R5Benzyl ring can be connected at ortho position or contraposition. In some embodiments, R5Independently selected from C1-C40Alkoxy.
In formula III-a and III-b, A2Selected from the alkylidene optionally substituted, the alkenylene optionally substituted, optionally substitute Arlydene, the heteroarylidene optionally substituted, ketone, ester andWherein Ar is the virtue optionally substituted Base or the heteroaryl optionally substituted, R1Selected from H, alkyl, alkenyl, aryl, heteroaryl, aralkyl, alkaryl；And R2Selected from optional Substituted alkylidene, the alkenylene optionally substituted, the arlydene optionally substituted, heteroarylidene, ketone and the ester optionally substituted；Or R1And R2It can link together and form ring.
In formula III-a and III-b, LiIndependently selected from the alkylidene optionally substituted, the alkenylene optionally substituted, optionally Substituted alkynylene, the arlydene optionally substituted, the heteroarylidene optionally substituted.
In some embodiments, LiIn it is at least one selected from 1,2- ethenylidenes, ethynylene, 1,4- phenylenes, 1, 1 '-biphenyl -4,4 '-diyl, naphthalene -2,6- diyls, naphthalene -1,4- diyls, 9H- fluorenes -2,7- diyls, perylene -3,9- diyls, two Rylene -3,10- diyls or pyrene -1,6- diyls, 1H- pyrroles -2,5- diyls, furans -2,5- diyls, thiophene -2,5- diyls, thiophene Fen simultaneously [3,2-b] thiophene -2,5- diyls, benzo [c] thiophene -1,3- diyls, dibenzo [b, d] thiophene -2,8- diyls, 9H- clicks Azoles -3,6- diyls, 9H- carbazole -2,7- diyls, dibenzo [b, d] furans -2,8- diyls, 10H- phenthazine -3,7- diyls and 10H- phenthazine -2,8- diyls；Each of which part all optionally substitutes.
Formula IV
Some embodiments provide the chromophore with following structures：
Wherein i is 0-100 integer.In some embodiments, i is 0-50,0-30,0-10,0-5 or 0-3 integer. In some embodiments, i is 0,1,2,3,4,5,6,7,8,9 or 10.
In formula IV, Z and ZiBe each independently selected from-O-,-S-,-Se-,-Te-,-NR6–、–CR6=CR6- and-CR6 =N-, wherein R6It is hydrogen, the C that optionally substitutes1-C6Alkyl or the C optionally substituted1-C10Aryl；And
In formula IV, D1And D2Independently selected from the alkoxy optionally substituted, the aryloxy group optionally substituted, optionally substitute Acyloxy, the alkyl optionally substituted, the aryl optionally substituted, the heteroaryl optionally substituted, the amino optionally substituted, acylamino-, Cyclic amido and ring-type acylimino；J is 0,1 or 2, and k is 0,1 or 2.In some embodiments ,-C (=O) Y1 With-C (=O) Y2Group can be connected to D1And D2Optionally substituted part substituent.
In formula IV, Y1And Y2Independently selected from the aryl optionally substituted, the alkyl optionally substituted, the cycloalkanes optionally substituted Base, the alkoxy optionally substituted and the amino optionally substituted；And
In formula IV, LiIndependently selected from the alkylidene optionally substituted, the alkenylene optionally substituted, the sub- alkynes optionally substituted Base, the arlydene optionally substituted, the heteroarylidene optionally substituted.
In some embodiments, LiIn it is at least one selected from 1,2- ethenylidenes, ethynylene, 1,4- phenylenes, 1, 1 '-biphenyl -4,4 '-diyl, naphthalene -2,6- diyls, naphthalene -1,4- diyls, 9H- fluorenes -2,7- diyls, perylene -3,9- diyls, two Rylene -3,10- diyls or pyrene -1,6- diyls, 1H- pyrroles -2,5- diyls, furans -2,5- diyls, thiophene -2,5- diyls, thiophene Fen simultaneously [3,2-b] thiophene -2,5- diyls, benzo [c] thiophene -1,3- diyls, dibenzo [b, d] thiophene -2,8- diyls, 9H- clicks Azoles -3,6- diyls, 9H- carbazole -2,7- diyls, dibenzo [b, d] furans -2,8- diyls, 10H- phenthazine -3,7- diyls and 10H- phenthazine -2,8- diyls；Each of which part all optionally substitutes.
For the L in any of the above described formulai, the electron system of electronics attachment expression conjugation, it can be neutral or oneself Body serves as electron donor.In some embodiments, provided hereinafter some examples, it, which can contain or can be free of, other companies The substituent connect.
Deng.
Deng.
Formula V-a and V-b
Some embodiments provide following formulas (V-a) or the perylene diester deriv shown in formula (V-b)：
R wherein in formula (I)1And R1' it is each independently selected from hydrogen, C1-C10Alkyl, C3-C10Cycloalkyl, C2-C10Alkoxy Alkyl, C6-C18Aryl and C6-C20Aralkyl；M and n in formula (I) are each independently 1-5；And the R in formula (II)2And R2’ It is each independently selected from C6-C18Aryl and C6-C20Aralkyl.In one embodiment, if a cyano group in formula (II) It is present on 4 of perylene ring, then other cyano group are not present on 10 of perylene ring.In an embodiment In, if a cyano group in formula (II) is present on 10 of perylene ring, other cyano group are not present in perylene On 4 of ring.
In one embodiment, R1And R1' independently selected from hydrogen, C1–C6Alkyl, C2–C6Alkoxyalkyl and C6–C18 Aryl.In one embodiment, R1And R1' be each independently selected from isopropyl, isobutyl group, isohesyl, iso-octyl, 2- ethyls- Hexyl, diphenyl methyl, trityl and diphenyl.In one embodiment, R2And R2' independently selected from diphenylmethyl Base, trityl and diphenyl.In one embodiment, each m and n in formula (I) independently are 1-4.
In some embodiments, the luminescent wavelength conversion material of encapsulating structure also includes one or more sensitizers. In some embodiments, sensitizer includes nano particle, nano metal, nano wire or CNT.In some embodiments, Sensitizer includes fullerene.In some embodiments, fullerene is selected from the C optionally substituted60, the optionally C that substitutes70, optionally take The C in generation84, the optionally single-walled carbon nanotube that substitutes and the multi-walled carbon nanotube optionally substituted.In some embodiments, fowler Alkene is selected from [6,6]-phenyl-C61- butyric acid-methyl esters, [6,6]-phenyl-C71- butyric acid-methyl esters and [6,6]-phenyl-C85- butyric acid- Methyl esters.In some embodiments, sensitizer is selected from the phthalocyanine optionally substituted, the perylene optionally substituted, optionally substituted Porphyrin and three rylenes (terrylene) optionally substituted.In some embodiments, the emission wavelength conversion of encapsulating structure Material also includes the combination of sensitizer, and the combination of wherein sensitizer is selected from the fullerene optionally substituted, the phthalocyanine optionally substituted, appointed Choose perylene, the porphyrin optionally substituted and three rylenes optionally substituted in generation.
In some embodiments, the amount for the sensitizer that the luminescent wavelength conversion material of encapsulating structure is included is based on combination The gross weight of thing is about 0.01% to about 5% weight ratio.
In some embodiments, the luminescent wavelength conversion material of encapsulating structure also includes one or more plasticizer. In some embodiments, plasticizer is selected from N- alkyl carbazoles derivative and triphenylamine derivative.
In some embodiments, the composition of luminescent wavelength conversion material also includes UV stabilizer, antioxidant or suction Receive agent.In some embodiments, the composition of straight polymer encapsulation also includes UV stabilizer, antioxidant or absorbent.
In some embodiments, glass plate or plastic plate as environment cover can also include strong UV absorbents to prevent Harmful high-energy radiation.In some embodiments, other materials or layer can be used in structure, such as glass plate, reflection Backboard, edge seal band, frame material, polymeric material or the adhesion layer that other layers are adhered to system.
Another aspect of the present invention, which is related to, improves solar cell, solar energy lamp string, solar panel or photovoltaic devices Performance method, methods described include with encapsulating structure disclosed herein encapsulation described device.
In methods described some embodiments, solar panel includes at least one photovoltaic devices or solar-electricity Pond, it includes cadmium sulfide/cadmium telluride solar cell.In some embodiments, photovoltaic devices or solar cell include connection Copper indium gallium selenide solar cell.In some embodiments, photovoltaic cell or solar cell include III-V or II-VI PN Tie device.In some embodiments, photovoltaic cell or solar cell include alert and resourceful agent device.In some embodiments In, photovoltaic cell or solar cell include organic thin film device.In some embodiments, photovoltaic devices or solar cell Including non-crystalline silicon (a-Si) solar cell.In some embodiments, photovoltaic devices or solar cell include microcrystal silicon (μ C-Si) solar cell.In some embodiments, photovoltaic devices or solar cell include crystalline silicon (c-Si) solar-electricity Pond.
In methods described some embodiments, extra material layer can also be used in encapsulating structure.For example, can be with Extra environmental protection is provided with glass plate or plastic plate.Backboard may be used to provide the photon not absorbed by solar cell Reflection and/or refraction.Adhesion layer may be also what is needed.For example, the adhesion between luminescent wavelength conversion material and glass plate Layer, for this two layers to be adhered to each other.Other layers can also be included further to improve the photoelectricity of solar modules to turn Change efficiency.For example, microstructured layers can be provided in on the top of encapsulating structure or be provided in luminescent wavelength conversion material and glass Between glass plate, the micro-structural is designed to further improve the day of solar modules by reducing photon to the loss of environment Light collecting efficiency, the photon absorb and wavelength convert after, to leave the light of solar modules device generally from chromophore Launch again in the direction of electric conversion layer.The layer with various micro-structurals (i.e. pyramid or cone) can increase photon and arrive on surface The internal reflection and refraction of the photoelectric conversion layer of solar battery apparatus, so as to further improve the day light collection effect of described device Rate.
Day optical acquisition device can also be rigid or flexible.For example, rigid mount includes the solar-electricity based on silicon Pond.Flexible solar device is often made up of organic film, and can be used on clothes, tent or other flexible parent metals.Cause This, in some embodiments, can be applied to rigid mount or flexible apparatus by encapsulating structure.
Fig. 1 shows an embodiment of encapsulating structure, and it is included by changing material in the laminated emission wavelength in battery both sides The single solar battery apparatus 100 expected 101 film and encapsulated, luminescent wavelength conversion material include optically transparent polymer matrix Matter and at least one chromophore 102.Glass or plastic foil may be used as environmental protection cover 103, and be sealed side with band 104 Firmly to prevent the entrance of block and moisture.
Fig. 2 shows the another embodiment of encapsulating structure, and which show by being changed in the laminated emission wavelength in battery both sides The film of material 101 and the multiple solar battery apparatus 100 encapsulated, luminescent wavelength conversion material include optically transparent polymer Matrix and at least one chromophore 102, wherein glass or plastic foil are used as environmental protection cover 103, and with band 104 by side Seal to prevent block and moisture entrance.
Fig. 3 shows the another embodiment of encapsulating structure, and which show by being encapsulated in the laminated straight polymer in battery both sides The 105th, luminescent wavelength conversion material 101 is then laminated in the multiple solar cells encapsulated on the top of straight polymer encapsulation Device 100.Luminescent wavelength conversion material 101 includes optically transparent polymer substrate and at least one chromophore 102, and its Middle glass or plastic foil are used as environmental protection cover 103, and seal side with band 104 and enter to prevent block and moisture.
Fig. 4 shows the another embodiment of encapsulating structure, and which show laminated luminous by the light incident surface in battery The film of material for transformation of wave length 101 and the multiple solar battery apparatus 100 encapsulated, luminescent wavelength conversion material include optical clear Polymer substrate and at least one chromophore 102.Backboard 106 is used under solar cell, and glass or plastic foil are used as ring Border protective cover 103, and side is sealed with band 104 and entered to prevent block and moisture.
Fig. 5 shows the another embodiment of encapsulating structure, and which show by being encapsulated in the laminated straight polymer in battery both sides The 105th, luminescent wavelength conversion material 101 is then laminated in the multiple solar cells encapsulated on the top of straight polymer encapsulation Device 100.Luminescent wavelength conversion material includes optically transparent polymer substrate and at least one chromophore 102.Backboard 106 is used Under solar cell, glass or plastic foil are used as environmental protection cover 103, and are sealed side to prevent with band 104 Oxygen and moisture enter.
Fig. 6 shows the another embodiment of encapsulating structure, and which show by being encapsulated in the laminated straight polymer in battery side The 105th, luminescent wavelength conversion material 101 is then laminated in the multiple solar cells encapsulated on the top of straight polymer encapsulation Device 100.Luminescent wavelength conversion material 101 includes optically transparent polymer substrate and at least one chromophore 102.Contain resistance The extra straight polymer encapsulated layer 105 for being only harmful to the UV absorbents of high-energy radiation is laminated in the top of luminescent wavelength conversion material In portion, and glass or plastic foil are used as environmental protection cover 103, and are sealed side to prevent block and moisture with band 104 Into.
Fig. 7 shows the another embodiment of encapsulating structure, and which show the list being encapsulated in luminescent wavelength conversion material 101 Individual solar battery apparatus 100, luminescent wavelength conversion material include optically transparent polymer substrate and at least one chromophore 102, and wherein luminescent wavelength conversion material also plays anti-block and moisture penetration to the Environmental Role of battery.
Fig. 8 shows the another embodiment of encapsulating structure, more in luminescent wavelength conversion material 101 which show being encapsulated in Individual solar battery apparatus 100, luminescent wavelength conversion material include optically transparent polymer substrate and at least one chromophore 102, and wherein luminescent wavelength conversion material also plays anti-block and moisture penetration to the Environmental Role of battery.
Fig. 9 shows the another embodiment of encapsulating structure, and which show pass through the laminated simple polymerisation of light incident side in battery Thing encapsulation 105, luminescent wavelength conversion material 101 is then laminated in the multiple sun encapsulated on the top of straight polymer encapsulation Can cell apparatus 100.Luminescent wavelength conversion material 101 includes optically transparent polymer substrate and at least one chromophore 102, And wherein luminescent wavelength conversion material also plays anti-block and moisture penetration to the Environmental Role of battery.Glass or plastics Film is used as bottom environment protective cover 103, and seals side with band 104 and enter to prevent block and moisture.
Figure 10 shows the another embodiment of encapsulating structure, and which show what is constructed with multiple solar battery apparatus 100 Solar panel, luminescent wavelength conversion material 101 encapsulate solar battery apparatus, and glass film plates 103 and glass top plate 103 are used Make environmental protection cover 103, backboard 106 is located under bottom glass plate, and frame 107 keeps together module.
Figure 11 shows the another embodiment of encapsulating structure, and which show what is constructed with multiple solar battery apparatus 100 Solar panel, luminescent wavelength conversion material 101 encapsulate solar battery apparatus, and backboard 106 is located at solar battery apparatus Light incident surface under, glass top plate 103 is adhered to the top of module, and frame 107 keeps together module.
In some embodiments, at least one chromophore and optical clear polymer substrate will be included in the following manner Luminescent wavelength conversion material be applied to solar battery apparatus：Dyestuff/polymer of synthetic fluid or gel form first is molten Liquid, using the standard method of the application, such as rotary coating or stamping die casting, dyestuff/polymer solution is applied to be arranged in can Tear the solar cell matrix on substrate open, dyestuff/polymer solution then is solidified into solid form, and (i.e. heat treatment, UV expose Deng), as determined by can be by formula design.
In another embodiment, at least one chromophore and optical clear polymer substrate will be included in the following manner Luminescent wavelength conversion material be applied to solar battery apparatus：Synthetic dyestuffs/thin polymer film first, followed by optical lens Dyestuff/thin polymer film is adhered to solar battery apparatus by the stable adhesive of bright and light and/or laminated dose.It will can contaminate Material/thin polymer film is initially applied on the top of solar cell, then applied on the bottom of solar cell, so as to complete Full encapsulation battery.Dyestuff/thin polymer film can also be only applied to top surface, wherein, the basal surface of solar cell is fixed on Substrate, such as backboard, dyestuff/thin polymer film are applied to the top surface of solar cell and are connected thereto solar cell Substrate portion.
The synthetic method of formation encapsulating structure is simultaneously unrestricted.The synthetic method of luminescent wavelength conversion material is simultaneously unrestricted, but It is that can follow the illustrative steps described in the scheme 1 and scheme 2 being detailed below.
Scheme 1：Form the wet-milling product general step of WLC materials
In some embodiments, the luminous ripple of at least one chromophore 102 and optical clear polymer substrate will be included Long transition material 101 is manufactured into membrane structure.Wavelength conversion layer manufactures in the following manner：(i) polymer solution is prepared, wherein poly- Compound powder is dissolved in such as tetrachloro-ethylene (TCE), cyclopentanone, dioxane equal solvent with predetermined ratio；(ii) pass through by Polymer solution is mixed with chromophore's solution containing polymeric blends to be contained with chromophore with predetermined weight ratio The polymer solution of dyestuff, (iii) directly cast the polymer solution containing dyestuff on the glass substrate, then at 2 hours It is interior to be heat-treated the base materials from room temperature to up to 100 DEG C, removed completely by 130 DEG C of further overnight vacuums heating remaining molten Agent, so as to form dyestuff/polymer film, and (iv) is before the use, and dyestuff/polymer film is peeled off in water, is then dried The polymer film of self-support (free-standing)；(v) by changing dyestuff/polymer solution concentration and evaporation rate, can incite somebody to action Film thickness is controlled at 1 μm to 1mm.
Scheme 2：For forming the dry processing general step of WLC materials
In some embodiments, the luminous ripple of at least one chromophore 102 and optical clear polymer substrate will be included Long transition material 101 is manufactured into membrane structure.Wavelength conversion layer manufactures in the following manner：(i) at a certain temperature, mixing is utilized Device is mixed polymer powder or particle with chromophore powder with predetermined ratio；(ii) at a certain temperature, mixture is deaerated 1-8 hours；(iii) followed by extruder forming layer；(v) extruder by layer thickness control at 1 μm to 1mm.
Once forming emission wavelength conversion encapsulation film, then using optical clear and the adhesive of light stabilization, adhered to In solar modules device.
The advantages of in order to summarize each aspect of the present invention and be realized relative to correlation technique, the present disclosure describes the present invention Some targets and advantage.It should, of course, be understood that the present invention any specific embodiment can not necessarily realize it is all this Class target or advantage.Thus, for example, it should be recognized by those skilled in the art that the present invention can be to realize or optimize this paper institutes A kind of advantage of teaching or the mode of one group of advantage embody or performed, without realizing other targets teaching herein or propose Or advantage.
According to example detailed below, other aspects of the present invention, feature and advantage will be apparent.
Embodiment
Following embodiments are not intended to the limitation present invention.In the disclosure, unless otherwise indicated, listed substituent bag Include group be further substituted with and unsubstituted.In addition, in the disclosure, such as not specified condition and/or structure, then this area Technical staff can should easily provide this kind of condition and/or structure according to teaching herein.
The synthesis of chromophore
Compound 1 and 2
According to following proposal, the synthesis of chromophore is carried out：
4,7- dibromos benzo [2,1,3] thiadiazoles (13.2g, 45mmol), 4- (N, N- diphenylamines) benzene are stirred in argon gas Water (80mL) solution, the tetrakis triphenylphosphine palladium (0) of ylboronic acid (30.0g, 104mmol), sodium carbonate (21.2g, 200mmol) (5.0g, 4.3mmol), n-butanol (800mL) and toluene (400mL) mixture, and heated 20 hours at 100 DEG C. After being cooled to room temperature, with water (600mL) diluted mixture, and stir 2 hours.Toluene (2L) extractive reaction mixture is finally used, And volatile matter is removed at reduced pressure conditions.Hexanes/ch (1 by the use of silica gel and as eluant, eluent:1), residue is carried out Chromatography, so as to obtain double [(N, N- diphenyl amino) the phenyl)] benzos [2,1,3] of 26.96g (43.3mmol, 96%) 4,7- Thiadiazoles (intermediate A).
To the dichloromethane for the intermediate A (22.0g, 35.3mmol) for stirring and being cooled down in ice water bath under argon gas The diethyl ether of (800mL) solution by portions addition 4- tert-butyl benzoyl chlorides (97.4mL, 500mmol) and zinc chloride (700mL, 1M solution 700mmol).The mixture of acquisition is stirred and heated 68 hours by 44 DEG C.Reactant mixture is poured into trash ice (2kg) In, stirring, handled to pH 8 with saturated sodium carbonate, diluted with dichloromethane (2L), and at atmosheric pressure by sintering glass Glass funnel filters.Dichloromethane layer is separated, is dried with magnesium sulfate, and evaporation solvent.Residue column chromatography (silica gel, hexane/bis- Chloromethanes/ethyl acetate, 48:50:2) the pure luminescent dye compound 1 as the first fraction then, is obtained from ethanol recrystallization, 7.72g (28%).1H NMR(400MHz,CDCl3)：δ 7.94 (d, 2H, J=7.3Hz), 7.87 (d, 2H, J=7.7Hz), 7.74 (m, 6H), 7.47 (d, 2H, J=7.3Hz), 7.36 (t, 2H, J=7.3Hz), 7.31 (d, 2H, J=7.3Hz), 7.27 (m, 6H), 7.19 (m, 7H), 7.13 (d, 2H, J=7.7Hz), 7.06 (t, 2H, J=7.3Hz), 1.35 (s, 9H) .UV-vis spectrum： λmax=448nm (dichloromethane), 456nm (PVB films).Fluoremetry：λmax=618nm (dichloromethane), 562nm (PVB films).
Second fraction produces chromophore compound 2,12.35g (37% yield).1H NMR(400MHz,CDCl3)：δ7.95 (d, 4H, J=8.4Hz), 7.79-7.73 (m, 10H), 7.48 (d, 4H, J=7.7Hz), 7.36 (t, 4H, J=7.7Hz), 7.31 (d, 4H, J=8.4Hz), 7.25 (d, 4H, J=7.7Hz), 7.18 (t, J=7.3,2H, Ph), 7.14 (d, 4H, J=8.8Hz), 1.35(s,18H).UV-vis spectrum：λmax=437nm (dichloromethane), 455nm (PVB films).Fluoremetry：λmax=607nm (dichloromethane), 547nm (PVB films).
Intermediate B
With two-step method synthesis common intermediate B.
Step 1：The synthesis of 2- (4- nitrobenzophenones) -2H- benzos [d] [1,2,3] triazole
Under argon gas by 4- nitro-chlorobenzenes (55.0g, 349mmol), BTA (50.0g, 420mmol), potassium carbonate (200g, 500mmol) and NMP (500mL) mixture are stirred and heated 5 hours at 130 DEG C.Utilize thin-layer chromatography, monitoring Reaction process.Reactant mixture is poured into trash ice (2kg).After all ice-outs, solid is filtered out, and use water (200mL) is washed.Product is suspended in methanol (1.5L), stirred 30 minutes.Filter out crystal and done in vacuum drying chamber It is dry.Column chromatography is carried out using silica gel and as the toluene hot solution of the ethyl acetate (1%) of eluant, eluent, obtains 2- (4- nitrobenzene Base) -2H- benzos [d] [1,2,3] triazole (24.24g, 30% yield).1H NMR(400MHz,CDCl3)：δ 8.57 (d, J= 9.2Hz, 2H, 4- nitrobenzophenone), 8.44 (d, J=9.2Hz, 2H, 4- nitrobenzophenones), 7.93 (m, 2H, BTAs), 7.47 (m, 2H, BTA).
Step 2：The synthesis of 4,7- bis- bromo- 2- (4- nitrobenzophenones) -2H- benzos [d] [1,2,3] triazoles (intermediate B)
In the reflux condenser being connected with Hbr traps, by 2- (4- nitrobenzophenones) -2H- benzos [d] [1,2,3] triazole (7.70g, 31.2mmol), bromine (4.8mL, 94mmol) and 48%HBr (120mL) mixture heat 20 hours in 130 DEG C.Will Reactant mixture is poured on trash ice (800g), with 5% Na2SO3Solution decolourizes, and stands 2 hours at room temperature.Filtering precipitation, And washed with water (200mL), then use 2%NaHCO3(200mL) is washed, and is then washed again with water (200mL).It is being dried in vacuo Drying material in case, so as to obtain 4,7- bis- bromo- 2- (4- nitrobenzophenones) -2H- benzos [d] [1,2,3] triazole (intermediate B, 13.47g), its purity is 90%.Yield is 97%.1H NMR(400MHz,CDCl3)：δ 8.65 (m, 2H, 4- nitrobenzophenone), 8.44 (m, 2H, 4- nitrobenzophenones), 7.54 (s, 2H, BTAs).
Intermediate C
Utilize following reaction scheme synthetic intermediate C.
By intermediate B (3.98g, 10.0mmol), 4- isobutyl phenyl ethers ylboronic acid (5.00g, 25.7mmol), sodium carbonate (5.30g, 50mmol) water (40mL) solution, tetrakis triphenylphosphine palladium (0) (2.00g), n-butanol (60mL) and toluene The mixture of (30mL) is stirred and heated 4 hours at 100 DEG C under argon gas.Reactant mixture is poured into water (200mL), stirred Mix 30 minutes, and extracted with toluene (500mL).Extract is washed with water (200mL), is concentrated into 100mL volumes, and uses dichloro Methane (200mL) and methanol (200mL) dilution.Solution hydrogenated 20 minutes of acquisition are passed through with 10%Pd/C (2g) with 50psi Celite layers filter, and remove solvent at reduced pressure conditions.(silica gel, hexanes/ch/acetic acid are chromatographed to residue Ethyl ester, 35:50:5), so as to obtaining double (4- isobutoxy phenyls) -2- (4- the aminophenyls) -2H- benzos [d] [1,2,3] of 4,7- Triazole (intermediate C) (3.80g, 75%).1H NMR(400MHz,CDCl3)：(d, J=8.4Hz, 2H, the 4- aminobenzenes of δ 8.22 Base), 8.09 (d, J=8.7Hz, 4H, 4-i-BuOC6H4), 7.57 (s, 2H, BTAs), 7.06 (d, J=8.7Hz, 4H, 4- i-BuOC6H4), 6.79 (d, J=8.5Hz, 2H, 4- aminophenyls), 3.90 (bs, 2H, NH2), 3.81 (d, J=6.6Hz, 4H, ), i-BuO 2.14 (m, 2H, i-BuO), 1.06 (d, J=7.0Hz, 12H, i-BuO).
Compound 3
Compound 3 is synthesized according to following reaction schemes：
Intermediate C (0.92g, 1.82mmol), 3,3- dimethylated pentanedioic acids acid anhydride (284mg, 2.0mmol) chloroethenes of 1,2- bis- Alkane (20mL) solution heats 20 hours in reflux condenser in 80 DEG C.After cooling to room temperature, add chloroacetic chloride (0.28mL, 4.0mmol), and by mixture in 80 DEG C heat 1 hour.With dichloromethane (200mL) diluted reaction mixture, and use saturation NaHCO3(100mL) is washed.Use MgSO4Solution is dried, and removes volatile matter at reduced pressure conditions.Using column chromatography (silica gel, oneself Alkane/dichloromethane/ethyl acetate, 37:60:3) purification of crude product, and crystallized from ethanol, so as to obtain the 1- of yellow fine acicular (4- (double (4- isobutoxy phenyls) -2H- benzos [d] [1,2,3] triazole -2- bases of 4,7-) phenyl) -4,4- lupetidine -2, 6- diketone (compound 3,551mg, 48% yield).1H NMR(400MHz,CDCl3)：(d, J=8.8Hz, 2H, 4- acyl are sub- by δ 8.53 Aminophenyl), 8.08 (d, J=8.8Hz, 4H, 4-i-BuOC6H4), 7.61 (s, 2H, BTAs), 7.26 (d, J=8.8Hz, 2H, 4- acylimino phenyl), 7.07 (d, J=8.8Hz, 4H, 4-i-BuOC6H4), 3.82 (d, J=6.6Hz, 4H, i-BuO), 2.72 (s, 4H, 4,4- lupetidine -2,6- diketone), 2.14 (m, 2H, i-BuO), 1.24 (s, 6H, 4,4- lupetidine - 2,6- diketone), 1.06 (d, J=7.0Hz, 12H, i-BuO).UV-vis spectrum (PVB)：λmax=388nm.Fluoremetry (PVB)：λmax=478nm.
Embodiment 1
Wavelength conversion layer is manufactured in the following manner：(i) polyvinyl butyral resin (PVB) for preparing 20wt% (comes from Aldrich, and by using as former state when receiving) polymer solution, it has the polymer powder dissolved in cyclopentanone；(ii) By the way that PVB polymer solutions are mixed to prepare with the compound 1 synthesized with 0.3wt% weight ratio (with compound 1/PVB) PVB matrix containing chromophore, to obtain the polymer solution containing chromophore；(iii) by directly will be containing dyestuff it is poly- Polymer solution is cast on the glass substrate, then in room temperature up to 100 DEG C of heat treatment substrates 2 hours, by entering one in 130 DEG C Overnight vacuum heating is walked, the solvent of residual is removed completely, so as to form dyestuff/polymer film；And (iv) is before the use, Dyestuff/polymer film is peeled off in water, then dries the polymer film supported oneself.After film is dried, thickness can be hot pressed into The emission wavelength conversion sheet material that degree is about 500 μm.
So, in some embodiments, under vacuo, emission wavelength is changed into sheet material, commercial 5 inches of lists in 130 DEG C Crystal silicon solar batteries and pure PVB polymer encapsulateds material are laminated on the glass plate of about 3mm thickness, with emission wavelength conversion sheet For material as preceding surface, this is similar to the structure shown in Fig. 8.Before lamination and afterwards, the output of solar cell is measured, institute is real Existing rises to about 12.5% relatively.
Embodiment 2
Using the method identical method synthetic example 2 with being provided in embodiment 1, but difference is to use chemical combination Thing 2 rather than compound 1, and sealed using pure ethylene-vinylacetate (EVA) polymer encapsulated material rather than pure PVB polymer Fill material.Before lamination and afterwards, the output of solar cell is measured, it was observed that relative rise to about 8.9%.
Embodiment 3
Ground similar to Example 2 synthetic example 3, but difference is that the structure tegillum is thick together in two about 3mm Glass plate between, this is similar to the structure shown in Fig. 3, and the order in its middle level is as follows：Push up glass plate, emission wavelength conversion sheet Material, the solar cell being packaged in pure EVA polymer and bottom glass plate.Before lamination and afterwards, solar energy is measured The output of battery, it was observed that relative rise to about 7.5%.
Embodiment 4
Ground similar to Example 2 synthetic example 4, but difference is the structure sheaf together in glass thick about 3mm Glass plate and the backboard (Madico of 254 μ m-thicksTFB PV backboards, manufactured by Madico, Inc.), this and Fig. 5 institutes Show that structure is similar, the order in its middle level is：Top glass plate, emission wavelength conversion sheet material, the sun being packaged in pure EVA polymer Can battery and backboard.Before lamination and afterwards, the output of solar cell is measured, it was observed that relative rise to about 7.8%.
Embodiment 5
Ground similar to Example 3 synthetic example 5, but difference is with 0.1% weight ratio (to change compound 3 Compound 3/EVA) it is used in wavelength conversion layer, and replace 5 inches × 5 English using 1 inch × 1 inch of crystal silicon solar energy battery Very little monocrystaline silicon solar cell.By the structure sheaf together between glass plate thick two about 3mm, this and the knot described in Fig. 3 Structure is similar, and the order in its middle level is as follows：Push up glass plate, emission wavelength change-over panel, the solar-electricity being packaged in pure EVA polymer Pond and bottom glass plate.Before lamination and afterwards, the output of solar cell is measured, it was observed that relative rise to about 2.6%.
Embodiment 6
Ground similar to Example 5 synthetic example 6, but difference is with 0.2% weight ratio (to change compound 3 Compound 3/EVA) it is used in wavelength conversion layer.Before lamination and afterwards, the output of solar cell is measured, it was observed that relative carry A height of about 2.8%.
Embodiment 7
Ground similar to Example 5 synthetic example 7, but difference is with 0.3% weight ratio (to change compound 3 Compound 3/EVA) it is used in wavelength conversion layer.Before lamination and afterwards, the output of solar cell is measured, it was observed that relative carry A height of about 1.6%.
Comparing embodiment 8
Ground similar to Example 5 synthetic example 8, but luminophor is not used, the order in its middle level is as follows：Push up glass Plate, pure EVA sheet, the solar cell being packaged in EVA polymer and bottom glass plate.Before lamination and afterwards, survey The output of solar cell is measured, it was observed that relative rise to about 0.7%.
It is an object of the present invention to provide suitable encapsulation solar cell, photovoltaic devices, solar modules and solar-electricity The encapsulating structure for including luminescent wavelength conversion material of pond plate.As described in the above-described embodiment, the use of the material improves Solar cell light conversion efficiency.
The advantages of in order to summarize each aspect of the present invention and be realized relative to correlation technique, the present disclosure describes the present invention Some targets and advantage.It should, of course, be understood that the present invention any specific embodiment differ surely realize it is all such Target or advantage.Thus, for example, it should be recognized by those skilled in the art that the present invention can be taught herein with realizing or optimizing The mode of a kind of advantage led or one group of advantage embodies or performed, without realize it is teaching herein or propose other targets or Advantage.It should be recognized by those skilled in the art that in the case of without departing from spirit of the invention, many different repair can be carried out Decorations.It is therefore apparent that ground is recognized, form of the invention is only exemplary, and is not intended to the model of the limitation present invention Enclose.

Claims (18)

1. for the encapsulating structure of device for converting solar energy, it includes：
Luminescent wavelength conversion material, it includes at least one chromophore and optically transparent polymer substrate；And
Wherein described luminescent wavelength conversion material is arranged to encapsulate the device for converting solar energy and suppresses moisture and Oxygen permeation To the device for converting solar energy,
At least one of wherein described chromophore is represented by formula (I-a) or (I-b)：
Wherein
I is 0~100；
LiIndependently selected from the alkylidene optionally substituted, the alkenylene optionally substituted, the alkynylene optionally substituted, optionally substitute Arlydene, the heteroarylidene optionally substituted, also, LiFor be optionally substituted heteroarylidene when, be not optionally substituted Thienyl and the carbazyl that is optionally substituted；
A0It is each independently selected from the alkyl being optionally substituted, the alkenyl being optionally substituted, the miscellaneous alkane being optionally substituted Base, the aryl being optionally substituted, the heteroaryl being optionally substituted, the amino that is optionally substituted, it is optionally substituted Acylamino-, the cyclic amido being optionally substituted, the ring-type acylimino being optionally substituted, the alcoxyl being optionally substituted Base, the carboxyl being optionally substituted and the carbonyl being optionally substituted；
A2Selected from the alkylidene being optionally substituted, the alkenylene being optionally substituted, the arlydene being optionally substituted, optionally Heteroarylidene that ground is substituted, ketone, ester and
Wherein Ar is the aryl being optionally substituted or the heteroaryl being optionally substituted；R1Selected from H, alkyl, alkenyl, aryl, miscellaneous Aryl, aralkyl and alkaryl；R2Selected from the alkylidene being optionally substituted, the alkenylene being optionally substituted, optionally Substituted arlydene, heteroarylidene, ketone and the ester being optionally substituted；Or R1And R2It can link together and form ring；
D1And D2The alkoxy that be each independently selected from hydrogen, is optionally substituted, the aryloxy group being optionally substituted, optionally by Substituted acyloxy, the alkyl being optionally substituted, the aryl being optionally substituted, the heteroaryl being optionally substituted, optionally Amino, acylamino-, cyclic amido and the ring-type acylimino that ground is substituted, condition is D1And D2Both are not all hydrogen, and And D1And D2For be optionally substituted heteroaryl when, be not the thienyl being optionally substituted；
When substitution, substituent is the group of more than 1 selected from following radicals independently of one another, and the group is：C1-C6Alkane Base, C1-C6Alkenyl, C1-C6Alkynyl, C3-C7Cycloalkyl, the cycloalkyl together with connection, C1-C6Miscellaneous alkyl, C3-C10Heterocyclylalkyl, virtue Base, aralkyl, heteroaryl, halo, cyano group, hydroxyl, the ring-type acylimino optionally substituted, amino, acylimino, acylamino-, C1-C6Alkoxy, aryloxy group, acyloxy, sulfydryl, halo (C1-C6) alkyl, C1-C6Alkylthio group, arylthio, single- and di- (C1- C6) alkyl amino, quaternary ammonium salt, amino (C1-C6) alkoxy, hydroxyl (C1-C6) alkyl amino, amino (C1-C6) alkylthio group, cyano group Amino, nitro, carbamoyl, epoxide, carbonyl, carboxyl, glycolyl, glycyl, diazanyl, amidino groups, sulfamic, sulphonyl Base, sulfinyl, thiocarbonyl, thiocarboxyl group, sulfonamide, ester, C- acid amides, N- acid amides, N- carbamates, O- carbamic acids Ester, urea and combinations thereof, in above-mentioned substituent, C3-C7Cycloalkyl is optionally with halogen, alkyl, alkoxy, carboxyl, halogen Substituted alkyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution；C3-C10Heterocyclylalkyl be optionally with halogen, alkyl, alkoxy, Carboxyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution；Aryl is optionally with halogen, alkyl, optionally uses C1-C6Alkyl takes Aryl, aralkyl, alkoxy, aryloxy group, carboxyl, amino, acylimino, acylamino-, the ring-type imide optionally substituted in generation Base, cyclic amido, CN ,-NH-C (=O)-alkyl ,-CF3、–OCF3Substitution；Aralkyl is optionally with halogen, alkyl, alkane Epoxide, aryl, carboxyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution；Heteroaryl be optionally with halogen, alkyl, alkoxy, Aryl, heteroaryl, aralkyl, carboxyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution.
2. for the encapsulating structure of device for converting solar energy, including：
Luminescent wavelength conversion material, it includes at least one chromophore and optically transparent polymer substrate；And
Wherein described luminescent wavelength conversion material is arranged to encapsulate the device for converting solar energy and suppresses moisture and Oxygen permeation To the device for converting solar energy,
At least one of wherein described chromophore is also represented by formula (II-a) or (II-b)：
Wherein
I is 0~100；
LiIndependently selected from the alkylidene optionally substituted, the alkenylene optionally substituted, the alkynylene optionally substituted, optionally substitute Arlydene, the heteroarylidene optionally substituted；
Ar is the aryl being optionally substituted or the heteroaryl being optionally substituted；
R4It isOr the ring-type acylimino being optionally substituted；
R1It is each independently selected from H, alkyl, alkenyl, aryl, heteroaryl, aralkyl and alkaryl；
R3Selected from the alkyl being optionally substituted, the alkenyl being optionally substituted, the aryl being optionally substituted and optionally by Substituted heteroaryl；Or R1And R3It can link together and form ring；
R2Selected from the alkylidene being optionally substituted, the alkenylene being optionally substituted, the arlydene being optionally substituted and appoint The substituted heteroarylidene of selection of land；
D1And D2The alkoxy that be each independently selected from hydrogen, is optionally substituted, the aryloxy group being optionally substituted, optionally by Substituted acyloxy, the alkyl being optionally substituted, the aryl being optionally substituted, the heteroaryl being optionally substituted, optionally Amino, acylamino-, cyclic amido and the ring-type acylimino that ground is substituted, condition is D1And D2Both are not all hydrogen；
When substitution, substituent is the group of more than 1 selected from following radicals independently of one another, and the group is：C1-C6Alkane Base, C1-C6Alkenyl, C1-C6Alkynyl, C3-C7Cycloalkyl, the cycloalkyl together with connection, C1-C6Miscellaneous alkyl, C3-C10Heterocyclylalkyl, virtue Base, aralkyl, heteroaryl, halo, cyano group, hydroxyl, the ring-type acylimino optionally substituted, amino, acylimino, acylamino-, C1-C6Alkoxy, aryloxy group, acyloxy, sulfydryl, halo (C1-C6) alkyl, C1-C6Alkylthio group, arylthio, single- and di- (C1- C6) alkyl amino, quaternary ammonium salt, amino (C1-C6) alkoxy, hydroxyl (C1-C6) alkyl amino, amino (C1-C6) alkylthio group, cyano group Amino, nitro, carbamoyl, epoxide, carbonyl, carboxyl, glycolyl, glycyl, diazanyl, amidino groups, sulfamic, sulphonyl Base, sulfinyl, thiocarbonyl, thiocarboxyl group, sulfonamide, ester, C- acid amides, N- acid amides, N- carbamates, O- carbamic acids Ester, urea and combinations thereof, in above-mentioned substituent, C3-C7Cycloalkyl is optionally with halogen, alkyl, alkoxy, carboxyl, halogen Substituted alkyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution；C3-C10Heterocyclylalkyl be optionally with halogen, alkyl, alkoxy, Carboxyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution；Aryl is optionally with halogen, alkyl, optionally uses C1-C6Alkyl takes Aryl, aralkyl, alkoxy, aryloxy group, carboxyl, amino, acylimino, acylamino-, the ring-type imide optionally substituted in generation Base, cyclic amido, CN ,-NH-C (=O)-alkyl ,-CF3、–OCF3Substitution；Aralkyl is optionally with halogen, alkyl, alkane Epoxide, aryl, carboxyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution；Heteroaryl be optionally with halogen, alkyl, alkoxy, Aryl, heteroaryl, aralkyl, carboxyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution.
3. encapsulating structure as claimed in claim 1, wherein at least one chromophore is also by formula (III-a) or (III-b) Represent：
Wherein
I is 0~100；
LiIndependently selected from the alkylidene optionally substituted, the alkenylene optionally substituted, the alkynylene optionally substituted, optionally substitute Arlydene, the heteroarylidene optionally substituted；
A0It is each independently selected from the alkyl being optionally substituted, the alkenyl being optionally substituted, the miscellaneous alkane being optionally substituted Base, the acylamino- being optionally substituted, the alkoxy being optionally substituted, the carbonyl being optionally substituted and optionally taken The carboxyl in generation；
Each R5Independently selected from the alkoxy being optionally substituted, the alkyl being optionally substituted, the fragrant oxygen being optionally substituted Base, the acyloxy being optionally substituted and amino；
A2Selected from the alkylidene being optionally substituted, the alkenylene being optionally substituted, the arlydene being optionally substituted, optionally Heteroarylidene that ground is substituted, ketone, ester and
Wherein Ar is the aryl being optionally substituted or the heteroaryl being optionally substituted；R1Selected from H, alkyl, alkenyl, aryl, miscellaneous Aryl, aralkyl and alkaryl；And R2Selected from the alkylidene being optionally substituted, the alkenylene being optionally substituted, appoint The substituted arlydene of selection of land, the heteroarylidene, ketone and the ester that are optionally substituted；Or R1And R2It can link together and shape Cyclization.
4. for the encapsulating structure of device for converting solar energy, including：
Luminescent wavelength conversion material, it includes at least one chromophore and optically transparent polymer substrate；And
Wherein described luminescent wavelength conversion material is arranged to encapsulate the device for converting solar energy and suppresses moisture and Oxygen permeation To the device for converting solar energy,
At least one of wherein described chromophore is represented by formula (IV)：
Wherein,
I is 0~100；
LiIndependently selected from the alkylidene optionally substituted, the alkenylene optionally substituted, the alkynylene optionally substituted, optionally substitute Arlydene, the heteroarylidene optionally substituted；
Z be selected from-O-,-S-,-Se-,-Te-,-NR6–、–CR6=CR6- and-CR6=N-, wherein R6It is hydrogen, is optionally substituted C1-C6Alkyl or the C being optionally substituted1-C10Aryl；And
D1And D2Independently selected from the alkoxy being optionally substituted, the aryloxy group being optionally substituted, the acyl being optionally substituted Epoxide, the alkyl being optionally substituted, the aryl being optionally substituted, the heteroaryl being optionally substituted, it is optionally substituted Amino, acylamino-, cyclic amido and ring-type acylimino；
J is 0,1 or 2, and k is 0,1 or 2；
Y1And Y2Independently selected from the aryl being optionally substituted, the alkyl being optionally substituted, the cycloalkanes being optionally substituted Base, the alkoxy being optionally substituted and the amino being optionally substituted；
When substitution, substituent is the group of more than 1 selected from following radicals independently of one another, and the group is：C1-C6Alkane Base, C1-C6Alkenyl, C1-C6Alkynyl, C3-C7Cycloalkyl, the cycloalkyl together with connection, C1-C6Miscellaneous alkyl, C3-C10Heterocyclylalkyl, virtue Base, aralkyl, heteroaryl, halo, cyano group, hydroxyl, the ring-type acylimino optionally substituted, amino, acylimino, acylamino-, C1-C6Alkoxy, aryloxy group, acyloxy, sulfydryl, halo (C1-C6) alkyl, C1-C6Alkylthio group, arylthio, single- and di- (C1- C6) alkyl amino, quaternary ammonium salt, amino (C1-C6) alkoxy, hydroxyl (C1-C6) alkyl amino, amino (C1-C6) alkylthio group, cyano group Amino, nitro, carbamoyl, epoxide, carbonyl, carboxyl, glycolyl, glycyl, diazanyl, amidino groups, sulfamic, sulphonyl Base, sulfinyl, thiocarbonyl, thiocarboxyl group, sulfonamide, ester, C- acid amides, N- acid amides, N- carbamates, O- carbamic acids Ester, urea and combinations thereof, in above-mentioned substituent, C3-C7Cycloalkyl is optionally with halogen, alkyl, alkoxy, carboxyl, halogen Substituted alkyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution；C3-C10Heterocyclylalkyl be optionally with halogen, alkyl, alkoxy, Carboxyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution；Aryl is optionally with halogen, alkyl, optionally uses C1-C6Alkyl takes Aryl, aralkyl, alkoxy, aryloxy group, carboxyl, amino, acylimino, acylamino-, the ring-type imide optionally substituted in generation Base, cyclic amido, CN ,-NH-C (=O)-alkyl ,-CF3、–OCF3Substitution；Aralkyl is optionally with halogen, alkyl, alkane Epoxide, aryl, carboxyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution；Heteroaryl be optionally with halogen, alkyl, alkoxy, Aryl, heteroaryl, aralkyl, carboxyl, CN ,-SO2- alkyl ,-CF3、–OCF3Substitution.
5. the encapsulating structure as described in any claim in Claims 1-4, wherein the encapsulating structure includes two kinds or more Kind chromophore.
6. the encapsulating structure as described in any claim in Claims 1-4, wherein the optically transparent polymer substrate Include one or more polymer.
7. encapsulating structure as claimed in claim 6, wherein the polymer is selected from polyethylene terephthalate, poly- methyl Methyl acrylate, polyvinyl butyral resin, ethylene vinyl acetate, ethylene tetrafluoroethylene, polyimides, amorphous poly- carbonic acid Ester, polystyrene, siloxane sol-gel, polyurethane, polyacrylate and combinations thereof.
8. the encapsulating structure as described in any claim in Claims 1-4, wherein the refractive index of the polymer substrate is 1.4 to 1.7.
9. the encapsulating structure as described in any claim in Claims 1-4, wherein the chromophore with 0.01wt% extremely 3wt% amount is present in the polymer substrate.
10. the encapsulating structure as described in any claim in Claims 1-4, wherein the luminescent wavelength conversion material Composition also includes one or more plasticizer.
11. the encapsulating structure as described in any claim in Claims 1-4, wherein the luminescent wavelength conversion material is also Include UV stabilizer, antioxidant and/or absorbent.
12. the encapsulating structure as described in any claim in Claims 1-4, it also includes one or more glass plates, anti- Penetrate backboard, edge seal band, frame material, polymer packaging material or the adhesion layer that extra layer is adhered to the system.
13. the encapsulating structure as described in any claim in Claims 1-4, it is extra also including the absorbent containing UV Polymeric layer.
14. the encapsulating structure for device for converting solar energy as described in any claim in Claims 1-4, it includes：
Environmental protection cover, it is arranged to suppress moisture and Oxygen permeation to the luminescent wavelength conversion material and the solar energy turn In changing device；And
Wherein described luminescent wavelength conversion material and the environmental protection cover are arranged to encapsulate the device for converting solar energy, from And light has to pass through the luminescent wavelength conversion material and the environmental protection cover before the device for converting solar energy is reached.
15. encapsulating structure as claimed in claim 14, wherein the environmental protection cover includes glassy layer or plastic layer.
16. encapsulating structure as claimed in claim 14, it also includes the band around the device for converting solar energy.
17. improving the method for the performance of device for converting solar energy, it is included using in Claims 1-4 described in any claim Encapsulating structure encapsulate the device for converting solar energy.
18. method as claimed in claim 17, wherein the device for converting solar energy include it is at least one selected from III-V or II-VI PN junctions device, copper-indium-gallium-selenium (CIGS) film apparatus, organic sensitizer device, organic thin film device, cadmium sulfide/ Cadmium telluride (CdS/CdTe) film apparatus, amorphous si solar cells, microcrystalline silicon solar cell and crystal silicon solar The device of battery.
CN201510744883.1A 2011-12-06 2012-09-28 As the material for transformation of wave length for improving day light collecting efficiency encapsulated used in solar modules system Active CN105419782B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US201161567548P 2011-12-06 2011-12-06
US61/567,548 2011-12-06
US201261662848P 2012-06-21 2012-06-21
US61/662,848 2012-06-21
CN201280001372.5A CN103339221B (en) 2011-12-06 2012-09-28 As the encapsulation used of solar modules system raising day light collecting efficiency material for transformation of wave length

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201280001372.5A Division CN103339221B (en) 2011-12-06 2012-09-28 As the encapsulation used of solar modules system raising day light collecting efficiency material for transformation of wave length

Publications (2)

Publication Number Publication Date
CN105419782A CN105419782A (en) 2016-03-23
CN105419782B true CN105419782B (en) 2017-12-05

Family

ID=48773416

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201510744901.6A Active CN105219377B (en) 2011-12-06 2012-09-28 It is used as the material for transformation of wave length for improving day light collecting efficiency encapsulated used in solar modules system
CN201510744883.1A Active CN105419782B (en) 2011-12-06 2012-09-28 As the material for transformation of wave length for improving day light collecting efficiency encapsulated used in solar modules system

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201510744901.6A Active CN105219377B (en) 2011-12-06 2012-09-28 It is used as the material for transformation of wave length for improving day light collecting efficiency encapsulated used in solar modules system

Country Status (2)

Country Link
JP (1) JP2013120926A (en)
CN (2) CN105219377B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6328891B2 (en) * 2013-07-30 2018-05-23 京セラ株式会社 Solar cell and solar cell module
EP3113233A4 (en) 2014-02-26 2017-03-08 Panasonic Intellectual Property Management Co., Ltd. Solar cell module
JP6531953B2 (en) * 2014-02-26 2019-06-19 パナソニックＩｐマネジメント株式会社 Solar cell module
EP3157066A4 (en) * 2014-06-13 2017-06-21 Panasonic Intellectual Property Management Co., Ltd. Solar cell module
JP6384162B2 (en) * 2014-07-11 2018-09-05 大日本印刷株式会社 Solar cell module
EP4043206A1 (en) * 2021-02-15 2022-08-17 Kuraray Europe GmbH Drying processes for composite films comprising polyvinyl acetal and polyvinyl ethylene acetal resins
CN114823944B (en) * 2022-04-25 2023-04-07 长沙精英军纳米科技有限公司 Solar alternating current battery capable of improving 4 times of absorption, storage and release of solar energy
CN117510421B (en) * 2024-01-08 2024-04-05 河北美星化工有限公司 Fluorine-containing benzotriazolyl fluorescent compound for optical transfer film and synthesis method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003104976A (en) * 2001-07-24 2003-04-09 Mitsubishi Chemicals Corp Benzothiadiazole derivative, liquid crystal composition, wavelength-converting element, electroluminescent element, electric charge transportation material and photoelectric transfer element
WO2005054212A2 (en) * 2003-12-05 2005-06-16 Ciba Specialty Chemicals Holding Inc. Electroluminescent device
CN101263608A (en) * 2005-09-12 2008-09-10 巴斯夫欧洲公司 Fluorescent solar conversion cells based on fluorescent terylene dyes
CN101908572A (en) * 2009-06-08 2010-12-08 日东电工株式会社 The controlling optical property of wavelength conversion sheet, the manufacture method of wavelength conversion sheet, cadmium telluride are that solar cell is a solar cell with wavelength conversion sheet and cadmium telluride
JP2011238639A (en) * 2010-05-06 2011-11-24 Toppan Printing Co Ltd Sealing material sheet for solar cell module and solar cell module

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003104976A (en) * 2001-07-24 2003-04-09 Mitsubishi Chemicals Corp Benzothiadiazole derivative, liquid crystal composition, wavelength-converting element, electroluminescent element, electric charge transportation material and photoelectric transfer element
WO2005054212A2 (en) * 2003-12-05 2005-06-16 Ciba Specialty Chemicals Holding Inc. Electroluminescent device
CN101263608A (en) * 2005-09-12 2008-09-10 巴斯夫欧洲公司 Fluorescent solar conversion cells based on fluorescent terylene dyes
CN101908572A (en) * 2009-06-08 2010-12-08 日东电工株式会社 The controlling optical property of wavelength conversion sheet, the manufacture method of wavelength conversion sheet, cadmium telluride are that solar cell is a solar cell with wavelength conversion sheet and cadmium telluride
JP2011238639A (en) * 2010-05-06 2011-11-24 Toppan Printing Co Ltd Sealing material sheet for solar cell module and solar cell module

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A New Dithienylbenzotriazole-Based Poly(2,7-carbazole) for Efficient Photovoltaics;Bo Peng et al.;《Macromol. Chem. Phys.》;20100816;第211卷;2026–2033 *
Thiophene-2-aryl-2H-benzotriazole-thiophene Oligomers with Adjustable Electronic Properties;Felix M.Pasker等;《ORGANIC LETTERS》;20110413;第13卷;2338-2341 *

Also Published As

Publication number Publication date
CN105219377B (en) 2017-11-03
CN105419782A (en) 2016-03-23
JP2013120926A (en) 2013-06-17
CN105219377A (en) 2016-01-06

Similar Documents

Publication Publication Date Title
CN103339221B (en) As the encapsulation used of solar modules system raising day light collecting efficiency material for transformation of wave length
CN105419782B (en) As the material for transformation of wave length for improving day light collecting efficiency encapsulated used in solar modules system
CN105073947B (en) Wavelength conversion films with multiple photostable organic chromophores
CN104428907B (en) Wavelength conversion layer on glass plate to enhance solar harvesting efficiency
JP6300347B2 (en) A highly fluorescent and photostable chromophore for enhanced sunlight collection efficiency
CN103415589B (en) There is the Wavelength conversion film of the pressure sensitive adhesive layer improving day light collecting efficiency
WO2014197393A1 (en) Photostable wavelength conversion composition
WO2015023574A1 (en) Luminescent solar concentrator utilizing organic photostable chromophore compounds
JP2014185286A (en) Chromophore having benzotriazole structure and wavelength conversion light-emitting medium using the same
JP2013084872A (en) Wavelength conversion film having pressure sensitive adhesive layer for increasing photovoltaic light collection efficiency

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20200713

Address after: Yamaguchi Japan

Patentee after: CHOSHU INDUSTRY Co.,Ltd.

Address before: Da Banfu

Patentee before: NITTO DENKO Corp.