WO2012052947A1 - Wavelength converter - Google Patents
Wavelength converter Download PDFInfo
- Publication number
- WO2012052947A1 WO2012052947A1 PCT/IB2011/054673 IB2011054673W WO2012052947A1 WO 2012052947 A1 WO2012052947 A1 WO 2012052947A1 IB 2011054673 W IB2011054673 W IB 2011054673W WO 2012052947 A1 WO2012052947 A1 WO 2012052947A1
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- WIPO (PCT)
- Prior art keywords
- converter according
- silicate
- metal
- ecs
- silicates
- Prior art date
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- 229910052914 metal silicate Inorganic materials 0.000 claims abstract description 48
- 238000001228 spectrum Methods 0.000 claims abstract description 28
- 230000005855 radiation Effects 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 14
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 11
- 102100023513 Flotillin-2 Human genes 0.000 claims description 8
- 101000828609 Homo sapiens Flotillin-2 Proteins 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- -1 lanthanide cations Chemical class 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 239000004411 aluminium Chemical group 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000001131 transforming effect Effects 0.000 abstract description 2
- 150000004760 silicates Chemical class 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 9
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KENDGHJJHKCUNB-UHFFFAOYSA-N triethoxy-[4-(4-triethoxysilylphenyl)phenyl]silane Chemical group C1=CC([Si](OCC)(OCC)OCC)=CC=C1C1=CC=C([Si](OCC)(OCC)OCC)C=C1 KENDGHJJHKCUNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- JIOGKDWMNMIDEY-UHFFFAOYSA-N triethoxy-(2-triethoxysilylphenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1[Si](OCC)(OCC)OCC JIOGKDWMNMIDEY-UHFFFAOYSA-N 0.000 description 2
- YYJNCOSWWOMZHX-UHFFFAOYSA-N triethoxy-(4-triethoxysilylphenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=C([Si](OCC)(OCC)OCC)C=C1 YYJNCOSWWOMZHX-UHFFFAOYSA-N 0.000 description 2
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- RPPBZEBXAAZZJH-UHFFFAOYSA-N cadmium telluride Chemical compound [Te]=[Cd] RPPBZEBXAAZZJH-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
Definitions
- US 4,584,428, for example describes devices which contain inorganic materials such as Zn selenides Zn (ZnSe)
- the spectrum converter can contain one or more of said hybrid organic -inorganic silicates or metal- silicates .
- a preferred aspect of the present invention relates to a converter containing hybrid silicates or metal- silicates containing structural units having formula (a), wherein R is an organic aromatic group:
- the materials of the present invention by absorbing light and emitting it at higher wavelengths by the formation of excimers, are photoactive and can therefore be used in wavelength converters, particularly in solar converters .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Surface Acoustic Wave Elements And Circuit Networks Thereof (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to a spectrum converter, capable of absorbing at least part of an incident radiation and re-emitting it to a longer wavelength, wherein said converter contains particular hybrid organic-inorganic silicates or metal-silicates. Said converter is particularly useful for transforming light with a higher energy of the solar spectrum into light with a lower energy for use in solar devices: its use coupled with a photovoltaic cell optimizes the portion of solar spectrum which can be used by the cell for conversion to electric current, and also avoids that light with an excessively high energy causes damaging the cell itself.
Description
WAVELENGTH CONVERTER
The present invention is included in the field of luminescent compositions which can be used for preparing spectrum converters capable of improving the performances of devices for the exploitation of solar energy, hereinafter called "solar devices", such as for example photovoltaic cells and photo-electrolytic cells .
The invention relates to a spectrum converter, capable of absorbing at least part of an incident radiation and re-emitting it to a longer wavelength, wherein said converter contains particular hybrid organic-inorganic silicates or metal-silicates. Said converter is particularly useful for transforming light with a higher energy of the solar spectrum into light with a lower energy for use in solar cells: its use coupled with a photovoltaic cell or photo-electrolytic cell increases the portion of solar spectrum which can be used by the cell for conversion to electric current, and also prevents light with an excessively high energy from damaging the cell itself.
In the state of the art, one of the main limits in exploiting solar radiation energy lies in the capacity of solar devices of optimally and exclusively absorbing radiations having wavelengths which fall within a narrow spectral range. Against a spectral range of solar radiation which extends from wavelengths of about 300 nm to wavelengths of about 2,500 nm, the various types of solar cells each have their own optimal zone
of absorbtion, and in some cases, as has been verified for polymeric solar cells, for example, they can be damaged by radiations having a wavelength lower than about 400 nm, due to induced photodegradation phenomena which become significant below this limit. In order to overcome these drawbacks, devices have been developed which, when interposed between the light radiation source, the sun, and the solar device, selectively absorb incident radiations having wavelengths outside the effective spectrum of the device, re-emitting the energy absorbed in the form of photons having a wavelength comprised within the effective spectrum. These devices are called "spectrum converters" or "luminescent concentrators" .
The spectrum converters known in the state of the art typically consist of a support made of a material transparent to the radiations of interest comprising photoluminescent compounds composed of organic molecules or metallic complexes and having emission frequencies which fall within the effective frequency absorption range of the solar device.
US 4,584,428, for example describes devices which contain inorganic materials such as Zn selenides Zn (ZnSe) , EP 1,865,562 describes devices containing fluorescent powders of oxides with the following composition (Y,Gd)3 Al5-X (Mg, Si) x012 (x=0 -3 ) .
US 7,518,160 describes a wavelength converter containing a fluorescent substance dispersed in a transparent matrix which contains semiconductor
particles comprising a compound having the formula ZnaA.
The technical problems relating to Spectrum Converter devices are linked to the light emission efficiency (quantic yield) and the wavelength reached in the emission.
WO 2008/017513 describes new hybrid organic- inorganic silicates and metal-silicates characterized by an X-ray diffractogram having reflections exclusively at angular values higher than 4.0° of 2Θ, preferably exclusively at angular values higher than
4.7° of 2θ, and by an ordinate structure containing structural units having formula (a) , wherein R is an organic group:
-0
\ /
-O-Si-R-Si-0- (a)
/ \
O- and optionally containing one or more elements T selected from the elements belonging to groups IIIB, IVB, VB, and transition metals, with a Si/ (Si+T) molar ratio in said structure higher than 0.3 and lower than or equal to 1, wherein Si is the silicon contained in the structural unit having formula (a) . These materials can be applied, for example, as molecular sieves, adsorbers, in the field of catalysis.
These materials, called ECS (Eni Carbon Silicates) , have the feature, revealed by structural and spectroscopic studies (G. Bellussi, A. Carati, E. Di Paola, R. Millini, W.O. Parker Jr., C. Rizzo, S.
Zanardi, Microporous and Mesoporous Materials 113 (2008) 252-260) of having incorporated alkoxydisilane integrally within the crystalline structure. In this way, the latter thus consists of silicate or metal- silicate layers, in particular aluminium silicates, covalently bound to the organic component which is orderly arranged inside the crystalline structure. With respect to more conventional silica structures, functionalized by means of grafting or co-condensation procedures, the organic groups in the ECS materials are a direct part of the 3D framework: variations in the structure of the organic group can be used for specifically selecting the physico-chemical properties of these materials.
We have now found that hybrid organic-inorganic materials belonging to the ECS family, wherein R is an aromatic group, can be used within the range of wavelength converters, and can consequently be applied in the field of photovoltaic systems and in that of light systems based on the use of LED (light emitting diodes) .
Light absorption is due to the aromatic nature of the organic species, but the aromatic compounds do not generally produce luminescence unless they are under high dilution conditions, due to the intermolecular interaction which cause quenching of the fluorescence and, in general, greatly reduce its intensity.
We have now found that the structural organization which substituents of the aromatic type can take in ECS
materials, prevents the quenching phenomenon and favours the formation of excimers, i.e. excited dimers . The formation of excimers generally takes place between aromatic rings which must be arranged parallelly at distances in the order of about 3-4 A. In the case of pyrene, for example, this distance is 3.37 A, and its excimers are characterized by light emission (fluorescence) at longer wavelengths and, in some cases, more intense than the single monomer species.
An object of the present invention therefore relates to a wavelength converter, capable of absorbing at least part of an incident radiation and re-emitting it to- a longer wavelength, comprising a hybrid organic- inorganic silicates or metal-silicate, ECS type, characterized by an X-ray diffractogram having reflections exclusively at angular values higher than
4.0° of 2θ, preferably exclusively at angular values higher than 4.7° of 2Θ, and characterized by an orderly structure containing structural units having formula (a) , wherein R is an organic aromatic group:
-0 O-
\ /
-O-Si-R-Si-0- (a)
/ \
-0 o- and possibly containing one or more elements T selected from the elements belonging to groups IIIB, IVB, VB, and transition metals, with a Si/ (Si+T) molar ratio in said structure higher than 0.3 and lower than or equal to 1, wherein Si is the silicon contained in the
structural unit having formula (a) .
The spectrum converter can contain one or more of said hybrid organic -inorganic silicates or metal- silicates .
The converter of the present invention preferably contains a transparent matrix: a particular object of the present invention therefore relates to a converter containing one or more of the hybrid silicates or metal -silicates described above and a transparent matrix, wherein the term transparent matrix means any transparent material used in the form of a carrier, ligand or material in which the hybrid silicate or metal-silicate is dispersed or englobed. The material used for the matrix is transparent, as such, to the radiations of interest, and in particular is transparent to radiations having a frequency within the effective spectrum of the solar device. Materials suitable for the purpose consequently do not absorb radiations having a wavelength longer than 250 nm.
A further object of the present invention relates to the use of said hybrid organic -inorganic silicates and metal-silicates as luminescent material in a spectrum converter.
An object of the present invention also relates to the solar device comprising the spectrum converter containing the hybrid organic -inorganic silicates and metal-silicates described above.
The converter according to the present invention improves the conversion efficiency of solar radiations:
the hybrid silicates and metal-silicates used in the present invention are capable of intercepting a portion of the radiations of the solar spectrum (radiation absorbed) and re-emitting it to a longer wavelength (radiation emitted) , and preferably the radiations emitted have a wavelength which falls within the wavelength range of the effective spectrum of a solar device. In particular, these compounds absorb radiations having a wavelength within the range of 200- 400 nm and re-emit them by photoluminescence within the range of 300-650 nm.
In the converters of the present invention, the hybrid organic-inorganic silicates and metal-silicates can also be used in a mixture with other photoluminescent compounds. In particular, they can be mixed with compounds capable of absorbing the radiation emitted by hybrid silicates and metal-silicates and re- emitting it to a wavelength range higher than 650 nm, i.e. within a spectrum which can be well used by solar devices of the inorganic type, for example based on crystalline Si, amorphous Si, Cadmium Tellurium, CIGS (copper indium gallium diselenide) .
According to another aspect of the present invention, the hybrid organic- inorganic silicates and metal-silicates in the converters can be used in a mixture with other photoluminescent compounds, where the role of the hybrid silicates and metal-silicates is to protect the solar cell: in the case of polymer solar cells, for example, which can be damaged by radiations
having a wavelength lower than approximately 300 nm, due to induced photodegradation phenomena which become significant below this limit, the presence in the converter of hybrid silicates or metal-silicates in accordance with the invention exerts a protective role by absorbing harmful radiations and re-emitting them to a wavelength which does not fall within the range which damages the cell.
A preferred aspect of the present invention relates to a converter containing hybrid silicates and metal- silicates characterized by an X-ray diffractogram having reflections exclusively at angular values higher than 4.0° of 2θ, preferably and exclusively at angular values higher than 4.7° of 2Θ, and characterized by an ordinate structure containing structural units having formula (a), wherein R is an organic aromatic group:
-0 O-
\ /
-O-Si-R-Si-0- (a)
/ \
-0 0- and possibly containing one or more elements T selected from the elements belonging to groups IIIB, IVB, VB, and transition metals, with a Si/ (Si+T) molar ratio in said structure higher than 0.3 and lower than or equal to 1, wherein Si is the silicon contained in the structural unit having formula (a) , said units (a) being connected with each other and with the element T, when present, by means of oxygen atoms.
Hybrid silicates and metal-silicates are
particularly preferred, wherein the Si/ (Si+T) ratio is greater than or equal to 0.5 and lower than or equal to 1.
Hybrid silicates and metal-silicates are even more particularly preferred, wherein the Si/ (Si+T) ratio is greater then or equal to 0.5 and lower than 1.
When the Si/ (Si+T) ratio is equal to 1, the structure does not contain elements belonging to groups III B, IV B, V B, and transition metals.
The elements T are tri- or tetravalent, are in tetrahedral coordination and are inserted in the structure by means of four oxygen bridges, forming T04 units. In particular, said T04 units in the structure can be bound, by means of these oxygen bridges, not only with the structural units of type (a) , but also with each other.
T is preferably an element selected from Si, Al, Fe, Ti, B, P, Ge, Ga or is a mixture thereof. Even more preferably, T is silicon, aluminium, iron or mixtures thereof.
When T is a trivalent element in tetrahedral coordination, the structure of the hybrid metal- silicates of the present invention also contains Me cations which neutralize its corresponding negative charge. The cations can for example be cations of alkaline metals, alkaline-earth metals, lanthanide cations or mixtures thereof . Me cations deriving from the reagents used in the synthesis can also be contained in the silicates and metal-silicates wherein
T is a tetravalent element.
A preferred aspect of the present invention relates to a converter containing hybrid silicates or metal- silicates containing structural units having formula (a), wherein R is an organic aromatic group:
-0 O-
\ /
-O-Si-R-Si-0- (a)
/ \
-0 o- characterized by the following formula (b) :
SiOi. 5 . x T02 . y/n Me . z C (b) wherein Si is the silicon contained in the structural unit (a)
T is at least one element selected from elements belonging to groups IIIB, IVB, VB and transition metals ;
Me is at least one cation having a valence n
C is carbon
x ranges from 0 to 2.3, and preferably from 0 to 1
y ranges from 0 to 2.3, and preferably from 0 to 1
n is the valence of the cation Me
z ranges from 0.5 to 10.
The organic aromatic group R contained in the structural unit (a) is preferably a group containing one or more benzene rings .
Even more preferably, R can contain a benzene ring, a biphenyl group, two or more condensed benzene rings, possibly substituted. The substituents can be alkyls, alkenyls or groups containing heteroatoms. R is
preferably selected from the following groups:
-C6H4-; -CH2-(C6H4)-CH2-, -C2H4-(C6H4)-C2H4-, - (C6H4 ) - (C6H4 ) -
, -CH2-(C6H4)-(C6H4) -CH2-, -C2H4- (C6H4) - (C6H4) -C2H4- .
According to a preferred aspect, when the aromatic group R contains only one benzene ring, the substituents of said ring containing silicon atoms are in position 1,4. According to another preferred aspect, when the aromatic group R contains a biphenyl group, the substituents of said biphenyl containing silicon atoms are in position 4,4'.
According to a preferred aspect, the organic- inorganic silicates and metal-silicates, containing structural units (a) wherein R is an organic aromatic group, which are used in the present invention, are of the type ECS-1, ECS-2, ECS-3, ECS-5, ECS-6.
The silicates and metal-silicates called ECS-1 which can be used in the present invention, have a crystalline structure and are characterized by an X-ray powder diffraction pattern, containing the main reflections indicated in Table 1:
Table 1.
N° 2Θ (°) Intensity
[ (I/Io) -100]
1 6. 7 60
2 7. 2 100
3 12 .5 24
4 13 .3 67
5 19 .2 82
6 20 .1 36
7 21 .5 25
8 25 .1 84
9 26 .2 35
10 26 .9 29
11 29 .0 33
12 32 .0 21
13 33 .3 55
14 34 .0 18
15 35 .9 11
In the unit (a) of the silicates and metal- silicates called ECS-1, R is preferably -C6H4- and the silicon atoms are in position 1,4.
The crystalline silicates and metal-silicates according to the invention of the type ECS- 2, are characterized by an X-ray powder diffraction pattern, containing the main reflections indicated in Table 2:
Table 2.
N° 2Θ(°) Intensity
1 9.0 100
2 12.6 71
3 13.9 2
4 14.9 5
5 18.0 18
6 19.2 12
7 21.3 6
8 23.3 44
9 23.8 7
10 24.3 7
11 25.5 6
12 25.7 13
13 26.6 18
14 30.0 7
15 34.0 5
16 39.4 5
In the unit (a) of the silicates and metal- silicates called ECS-2, R is preferably -C6H4- and the silicon atoms are in position 1,4.
The silicates and metal-silicates of the type ECS-3 which can be used in the present invention, are crystalline and are characterized by an X-ray powder diffraction pattern, containing the main reflections indicated in Table 3 :
Table 3 .
N° 2Θ ( ° ) Intensity
5 1 5.6 10
2 9.3 100
3 13.3 14
4 14.2 9
5 16.3 14
10
6 18.5 9
7 18.8 14
8 19.8 16
9 20.5 27
15 10 22.5 5
11 23.4 10
12 26.5 9
13 27.3 23
20 14 27.7 9
15 29.0 20
16 29.8 9
17 30.5 10
18 31 .4 12
25
19 32.1 6
20 36.4 10
In the unit (a) of the silicates and metal -
silicates called ECS-3, R is preferably -C6H4- and the silicon atoms are in position 1,4.
With respect to the silicates and metal-silicates of the type ECS-5 which can be used in the present invention, these are crystalline and are characterized by an X-ray powder diffraction pattern, containing the main reflections indicated in Table 4:
Table 4.
N° 2Θ0 Intensity
1 4.9 100
2 7.4 12
3 9.8 7
4 12.3 17
5 12.5 19
6 13.2 3
7 14.8 23
8 17.3 35
9 18.0 31
10 19.4 32
1 1 19.8 20
12 20.8 9
13 21 .5 8
14 22.4 9
15 22.9 6
16 23.7 3
17 24.6 7
18 24.8 10
19 26.5 8
20 27.6 25
21 28.0 5
22 28.7 7
23 29.4 7
24 29.9 8
25 30.2 10
26 31.5 15
27 32.1 3
28 32.8 8
In the unit (a) of the silicates and metal- silicates called ECS-5, R is preferably 1,1'biphenyl and the silicon atoms are in position 4,4'.
The silicates and metal-silicates of the type ECS-6 which can be used in the present invention are crystalline and are characterized by an X-ray powder diffraction pattern, containing the main reflections indicated in Table 5 :
Table 5
N° 2Θ Intensity N° 2Θ Intensi
(°) [ (I/Io) -100] (°) [(I/Io) ·
1 5.1 100 12 25.9 2
2 6.2 19 13 26.4 5
3 12.2 12 14 27.4 24
4 14.3 7 15 28.2 14
5 15.5 36 16 31 .3 17
6 17.1 1 1 17 31 .9 12
7 17.5 20 18 32.2 4
8 19.3 22 19 34.8 3
9 20.5 1 20 38.3 4
10 21 .3 2 21 39.6 2
11 23.3 20 22 49.1 6
In the unit (a) of the silicates and metal- silicates called ECS-6, R is preferably -C6H4- and the silicon atoms are in position 1,4.
Structures of the type ECS-1, ECS- 2, ECS- 3, ECS- 5, ECS-6, wherein Si/ (Si+T) is greater than or equal to 0.5 or lower than or equal to 0.9 are preferred, more particularly those wherein the element T is silicon or aluminium.
The X-ray powder diffractograms of the materials ECS-1, ECS-2, ECS- 3, ECS-5 and ECS-6 provided above, were all registered by means of a vertical goniometer equipped with an electronic pulse counting system and using CuKa radiation (λ = 1.54178 A) .
The preparation of the silicates and metal-
silicates used in the present invention, and in particular of the materials ECS-1, ECS-2, ECS-3, ECS-5 and ECS-6, is described in WO2008/017513. The disilanes used in the preparation of the hybrid silicates and metal-silicates of the present invention have the following formula (c) :
X3Si-R-SiX3 (c)
wherein R is the desired organic aromatic group and X is a substituent which can be hydrolyzed. The synthesis is effected by adding the disilane to an aqueous mixture containing at least one hydroxide of at least one metal Me selected from alkaline and/or alkaline earth metals, and possibly containing a source of metal T; the mixture is kept under hydrothermal conditions, at autogenous pressure, until a solid is formed, which is recovered and dried. The disilane (c) used for the preparation of ECS-1, ECS-2, ECS-3, and ECS-6, is preferably 1,4 bis (triethoxysilyl) benzene . The disilane (c) used for the preparation of ECS-5 is preferably 4 , 4 ' bis- (triethoxysilyl) 1 , 1 ' biphenyl .
The transparent matrix which can be used in the present invention, can, for example, be a polymeric material or vitreous material. Said matrix is characterized by a high transparency and a high duration with respect to heat and light. Polymeric materials which can be conveniently used are, for example, epoxy resins, silicon resins, polyalkylene terephthalates , polycarbonates, polystyrene, polypropylene. Examples of vitreous materials are for
example silica, titania, zirconia. When the matrix is of the polymeric type, the silicates and metal- silicates can be dispersed in the matrix, for example, by means of dispersion in the molten state or solubilization of the polymer and silicate or metal- silicate in a solvent and evaporation of the solvent with the formation of a polymer film and silicate, according to the technique called "casting"; in the case of carriers of vitreous material, the silicates or metal-silicates can be deposited in the form of a thin film.
An object of the present invention also relates to solar devices comprising the wavelengths converter of the present invention containing the hybrid organic- inorganic silicates and metal-silicates described above .
The solar devices are obtained by assembling the wavelength converter with the cell, wherein said cell is, for example, a photovoltaic cell or a photoelectrolytic cell. The spectrum converters of the present invention, for example, can be produced in the form of prisms or polymer sheets to be coupled with the solar devices. Alternatively, according to another construction technique, they can be produced by forming a thin film extended on the surface of a transparent sheet or prism which is coupled with the solar device.
A further object of the present invention relates to the light or lighting systems containing the wavelengths converter of the present invention,
containing the hybrid organic-inorganic silicates and metal-silicates described above, obtained by assembling, preferably on a substrate, a light source, in particular a led (light emitting diode) , and the wavelength converter: the use of the converter allows an improvement in the light efficiency and colour yield of the system.
The following embodiment examples are provided for purely illustrative purposes of the present invention and should not be considered as limiting the protection scope defined by the enclosed claims.
EXAMPLE 1
Preparation of ECS-2
The material is prepared as described in Example 3 of WO2008/017513 : 0.59 g of NaOH are dissolved in 11.8 g of demineralized water. 2.44 g of NaAl02 (54% by weight of A1203) are added to the limpid solution thus obtained, under vigorous stirring, until the formation of a limpid or slightly gelatinous solution. Finally, 12.0 g of 1,4 bis (triethoxy-silyl) benzene are added to the reaction environment. The mixture thus obtained has the following composition, expressed as molar ratios: Si/ (Si+T) = 0.70 , wherein T=A1
Na+/Si = 0.68
OH"/Si = 0.25
H20/Si = 11
wherein Si is silicon deriving from bis (triethoxy- silyl) benzene .
The sample is charged into an inox steel autoclave
subjected to an oscillating movement in an oven heated to 100°C, for 28 days.
At the end of the treatment, the autoclave is cooled, the suspension contained therein is filtered, the solid is washed with demineralized water and dried at 60 °C for about two hours.
Upon chemical analysis, the washed and dried sample has the following molar composition:
1.00 Si . 0.44 Al . 0.53 Na . 2.53 C The diffraction pattern provided in Table 2 shows that the sample ECS-2 is crystalline and prevalently consists of the new phase ECS-2 and a smaller quantity of a known zeolite, sodalite.
After pretreatment at 60°C under vacuum for 16 hours, the sample has a surface area equal to 25 m2/g. EXAMPLE 2
Synthesis of ECS-5
The material is prepared as described in Example 6 of WO2008/017513 : 0.56 g of NaOH are dissolved in 5.56 g of demineralized water. 1.15 g of NaAl02 (54% by weight of A1203) are added to the limpid solution thus obtained, under vigorous stirring, until the formation of a limpid or slightly gelatinous solution. Finally, 6.72 g of 4,4' bis (triethoxy-silyl) 1 , 1 ' biphenyl , whose chemical formula is indicated hereunder:
(CH3CH20) 3Si-C6H4-C6H4-Si (OCH2CH3) 3
are added to the reaction environment.
The mixture thus obtained has the following composition, expressed as molar ratios:
Si/ (Si+T) = 0.70 , wherein T=A1
Na+/Si = 0.93
H20/Si02 = 11
wherein Si is silicon deriving from 4,4' bis (triethoxy- silyl) 1,1' biphenyl .
The sample is charged into an inox steel autoclave subjected to an oscillating movement in an oven heated to 100°C, for 14 days.
At the end of the treatment, the autoclave is cooled, the suspension contained therein is filtered, the solid is washed with demineralized water and dried at 60 °C for about two hours.
The diffractogram provided in Table 4 shows that the sample ECS-5 is crystalline.
After pretreatment at 60°C under vacuum for 16 hours, the sample has a surface area equal to 210 m2/g and a pore volume of 0.56 ml/g.
EXAMPLE 3 - Fluorescence test
The fluorescence spectra of samples ECS-2 and ECS-5 are registered on the powders as such exciting the samples within the range of 270-280 nm and registering the emission spectrum within the range of 300-500 nm.
The spectra were registered at room temperature with a continuous-wave spectrofluorimeter (Perkin Elmer LS
50B) ; the powders are charged into the specific sample- holders with quartz windows .
Figure 1 shows the fluorescence spectrum of sample
ECS-2 (dotted line) compared with the spectrum of
disilane Bis (triethoxy-silyl) benzene (dashed line) obtained in a diluted solution in cyclohexane. The wavelength expressed in nm is indicated in the abscissa, the fluorescence intensity expressed in arbitrary units is indicated in the ordinate .
The disilane in solution shows an emission band centered at 300 nm. In the sample ECS-2, the component with a wavelength lower than 300 nm, representing the species isolated, is only a shoulder whereas the most intense emission is at much longer wavelengths, equal to 338 nm, with a shift of about 38 nm. The spectrum of the sample ECS-2 shows a lower signal/noise ratio with respect to the disilane spectrum as, in order to register its extremely intense fluorescence, the application of a neutral filter was necessary, which reduced its intensity by a factor 0.02.
Figure 2 shows the fluorescence spectrum of the sample ECS-5 (dotted line) compared with the spectrum of the relative disilane 4 , 4 ' bis (triethoxy- silyl) 1 , 1 ' biphenyl (dashed line) obtained in a diluted solution in cyclohexane. The wavelength expressed in nm is indicated in the abscissa, the fluorescence intensity expressed in arbitrary units is indicated in the ordinate .
The disilane shows an emission band centered at
310-320 nm. In the sample ECS-5, the emission is maximum at 330 nm, with a red shift of 10-20 nm with respect to the monomer species in solution. Furthermore, a long asymmetrical tail towards longer
wavelengths can be observed, indicating the presence of other species, in which the units active in fluorescence interact more strongly. The spectrum of the sample ECS-5 shows a lower signal/noise ratio with respect to the disilane spectrum as, in order to register its extremely intense fluorescence, the application of a neutral filter was necessary, which reduced its intensity by a factor 0.02.
It has therefore been demonstrated that the materials of the present invention, by absorbing light and emitting it at higher wavelengths by the formation of excimers, are photoactive and can therefore be used in wavelength converters, particularly in solar converters .
Claims
1. A wavelength converter comprising a silicate or metal-silicate of the hybrid organic-inorganic type, characterized by an X-ray diffractogram having reflections exclusively at angular values higher than
4.0° of 2θ, and characterized by an ordinate structure containing structural units having formula (a) , wherein
R is an organic aromatic group:
-0 0- \ /
-O-Si-R-Si-0- (a)
/ \
-0 0- and possibly containing one or more elements T selected from the elements belonging to groups IIIB, IVB, VB, and transition metals, with a Si/ (Si+T) molar ratio in said structure higher than 0.3 and lower than or equal to 1, wherein Si is the silicon contained in the structural unit having formula (a) .
2. The wavelength converter according to claim 1, containing a transparent matrix.
3. The wavelength converter according to claim 1 or 2 , comprising a silicate or metal-silicate of the hybrid organic- inorganic type, characterized by an X-ray diffractogram having reflections exclusively at angular values higher than 4.7° of 2θ.
4. The wavelength converter according to claim 2, wherein the transparent matrix does not absorb radiations having a wavelength higher than 250 nra.
5. The converter according to claim 1, capable of absorbing radiations having a wavelength within the range of 200-400 nm and re-emitting photoluminescent radiation within the range of 300-650 nm.
6. The converter according to claim 1, wherein the structural units (a) contained in the structure of the silicate or metal-silicate are connected to each other and with the element T, when present, by means of oxygen atoms .
7. The converter according to claim 1, wherein the element T contained in the structure of the silicate or metal-silicate is selected from Si, Al, Fe, Ti, B, P, Ge, Ga or is a mixture thereof.
8. The converter according to claim 7, wherein T is silicon, aluminium, iron or mixtures thereof.
9. The converter according to claim 1, wherein the silicate or metal-silicate contains metal cations.
10. The converter according to claim 9, wherein the metal cation is selected from cations of alkaline metals, alkaline-earth metals, lanthanide cations or mixtures thereof .
11. The converter according to claim 1 or 6 , wherein the silicate or metal-silicate is characterized by the following formula (b) :
SiOi.5 . x T02 . y/n Me . z C (b) wherein Si is the silicon contained in the structural unit (a)
T is at least one element selected from the elements belonging to groups IIIB, IVB, VB and transition metals;
Me is at least one cation having a valence n
C is carbon
x ranges from 0 to 2.3, and preferably from 0 to 1 y ranges from 0 to 2.3, and preferably from 0 to 1 n is the valence of the cation Me
z ranges from 0.5 to 10.
12. The converter according to claim 1, wherein the organic aromatic group R contained in the structural unit (a) is a group containing one or more benzene rings .
13. The converter according to claim 12, wherein R contains a benzene ring, a biphenyl group, two or more condensed benzene rings, possibly substituted with alkyls, alkenyls or groups containing heteroatoms.
14. The converter according to claim 13, wherein R is selected from the groups: -C6H4- , -CH2- (C6H4) -CH2- , -C2H4- (C6H4) -C2H4- , — (C6H4) - (ΟβΗ4) - , -CH2- (C6H4) - (C6H4) -
Ct-2- , -C2H.4— (06¾)— (C6H4) -C2H4- .
15. The converter according to one or more of the previous claims, wherein, when the aromatic group R of the structural unit (a) contains only one benzene ring, the substituents of said ring containing the silicon atoms are in position 1,4 and when the aromatic group R of the structural unit (a) contains a biphenyl group, the substituents of said biphenyl containing the silicon atoms are in position 4,4'.
16. The converter according to one or more of the previous claims containing a silicate or metal-silicate selected from ECS-1, ECS-2, ECS-3, ECS-5, ECS-6 or mixtures thereof.
17. The converter according to claim 2, wherein the transparent matrix is a polymeric material or vitreous material .
18. The converter according to claim 17, wherein the polymeric material is selected from epoxy resins, silicon resins, polyalkylene terephthalates , polycarbonates, polystyrene, polypropylene.
19. The converter according to claim 17, wherein the vitreous materials are selected from silica, titania, zirconia .
20. A solar device comprising a converter according to any of the claims from 1 to 19.
21. A light system comprising a converter according to any of the claims from 1 to 19, a light source and possibly a substrate.
22. Use as a photoluminescent material, in a spectrum converter, of a silicate or metal-silicate of the hybrid organic-inorganic type, characterized by an X- ray diffractogram having reflections exclusively at angular values higher than 4.0° of 2θ, and characterized by an ordinate structure containing structural units having formula (a) , wherein R is an organic aromatic group:
-O 0-
\ /
-O-Si-R-Si-0- (a)
/ \
■0 0- possibly containing one or more elements T selected from the elements belonging to groups IIIB, IVB, VB and transition metals, with a Si/ (Si+T) molar ratio in said structure higher than 0.3 and lower than or equal to 1, wherein Si is a silicon contained in the structural unit having formula (a) .
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| ITMI2010A001926A IT1402397B1 (en) | 2010-10-21 | 2010-10-21 | WAVE LENGTH CONVERTER. |
| ITMI2010A001926 | 2010-10-21 |
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| ITMI20122250A1 (en) * | 2012-12-28 | 2014-06-29 | Eni Spa | "LUMINESCENT SOLAR CONCENTRATOR" |
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| WO2007067257A2 (en) * | 2005-12-02 | 2007-06-14 | Vanderbilt University | Broad-emission nanocrystals and methods of making and using same |
| WO2008017513A2 (en) * | 2006-08-07 | 2008-02-14 | Eni S.P.A. | Organic-inorganic hybrid silicates and metal-silicates having an ordered structure |
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| WO2007067257A2 (en) * | 2005-12-02 | 2007-06-14 | Vanderbilt University | Broad-emission nanocrystals and methods of making and using same |
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|---|---|---|---|---|
| ITMI20122250A1 (en) * | 2012-12-28 | 2014-06-29 | Eni Spa | "LUMINESCENT SOLAR CONCENTRATOR" |
| WO2014102742A1 (en) * | 2012-12-28 | 2014-07-03 | Eni S.P.A. | Luminescent solar concentrator |
| US9853172B2 (en) | 2012-12-28 | 2017-12-26 | Eni S.P.A. | Luminescent solar concentrator |
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