A DISPERSION COMPRISING EU2+ DOPED INORGANIC LUMINESCENT NANOPARTICLES FOR GREENHOUSE APPLICATIONS AND SHEET STRUCTURES AND COATINGS FOR GREENHOUSES COMPRISING SUCH NANOPARTICLES

Abstract

A luminescent layer is described comprising an Eu.sup.2+ doped inorganic luminescent material comprising or consisting essentially of the elements Al and/or Si and the elements O and/or N, the doped inorganic luminescent material converting radiation of the UV region between 200 nm and 400 nm of the solar spectrum into the photosynthetically active radiation (PAR) region (400 nm-700 nm) of the solar spectrum, wherein the Si concentration in the inorganic luminescent material is selected between 0 and 45 at. %, the Al concentration between 0 and 50 at. %, the O concentration between 0 and 70 at. %, the N concentration between 0 and 60 at. % and the Eu2+ between 0.01 and 30 at. %.

Claims

1. A dispersion of luminescent nanoparticles for coating a greenhouse glazing structure, said dispersion comprising: an organic or aqueous medium; and luminescent nanoparticles, wherein the nanoparticles comprise Eu.sup.2+ doped SiAlON and the Eu.sup.2+ doped SiAlON has a Si concentration between 0 at. % and 33 at. %, an Al concentration between 0 at. % and 40 at. %, an O concentration between 50 at. % and 66 at. %, an N concentration between 0 at. % and 10 at. % and an Eu.sup.2+ concentration between 0.0001 at. % and 5 at. %.

2. The dispersion according to claim 1, wherein the Si concentration is between 15 at. % and 33 at. %, the Al concentration is between 0.001 at. % and 12 at. %, the O concentration is between 50 at. % and 66 at. %, the N concentration is between 0.1 at. % and 5 at. % and the Eu.sup.2+ concentration is between 0.0001 at. % and 3 at. %.

3. The dispersion according to claim 1, wherein the nanoparticles have an average particle size between 1 nm and 1000 nm.

4. The dispersion according to claim 1, wherein the dispersion comprises between 1 wt. % and 80 wt. % of the nanoparticles.

5. The dispersion according to claim 1, wherein the dispersion comprises the organic medium and the organic medium comprises an organic solvent and between 0.5 wt. % and 10 wt. % of polymer additives.

6. The dispersion according to claim 1, wherein the dispersion comprises the aqueous medium and aqueous medium comprises an alkali aqueous solution and between 1 wt. % and 10 wt. % of water-borne polymer additives.

7. The dispersion according to claim 1, wherein a surface of the nanoparticles is modified based on one or more types of ligands of the nanoparticles and the modification includes sonication of the nanoparticles.

8. The dispersion according to claim 1, wherein a surface of the nanoparticles is modified by formation of chemical bonds for coupling the nanoparticles to one or more long organic side chains having a carbon chain length of between 8 and 18 carbon atoms.

9. The dispersion according to claim 1, wherein the dispersion further comprises inorganic porous nanoparticles.

10. A transparent plastic sheet for a greenhouse, said plastic sheet comprising: a transparent polymeric material; and Eu.sup.2+ doped inorganic luminescent nanoparticles dispersed in the polymeric material, wherein the nanoparticles comprise Eu.sup.2+ doped SiAlON, and the Eu.sup.2+ doped SiAlON has a Si concentration between 0 at. % and 33 at. %, an Al concentration between 0 at. % and 40 at. %, an O concentration between 50 at. % and 66 at. %, an N concentration between 0 at. % and 10 at. % and an Eu.sup.2+ concentration between 0.0001 at. % and 5 at. %.

11. The transparent plastic sheet according to claim 10, wherein a thickness of the sheet is between 1 micrometer and 1000 micrometers.

12. A luminescent glazing structure for a greenhouse comprising: a glazing structure; a coating provided over at least part of a surface of the glazing structure, the coating comprising a transparent polymeric material and Eu.sup.2+ doped inorganic luminescent nanoparticles dispersed in the polymeric material, wherein the nanoparticles comprise Eu.sup.2+ doped SiAlON, and the Eu.sup.2+ doped SiAlON has a Si concentration between 0 at. % and 33 at. %, and Al concentration between 0 at. % and 40 at. %, an O concentration between 50 at. % and 66 at. %, an N concentration between 0 at. % and 10 at. % and an Eu.sup.2+ concentration between 0.0001 at. % and 5 at. %.

13. The luminescent glazing structure according to claim 12, wherein a thickness of the coating is between 10 micrometers and 200 micrometers.

14. A greenhouse comprising the luminescent glazing structure according to claim 12.

15. The dispersion as claimed in claim 1, said dispersion consisting essentially of: an organic or aqueous medium; and luminescent nanoparticles, wherein the nanoparticles comprise Eu.sup.2+ doped SiAlON and the Eu.sup.2+ doped SiAlON has a Si concentration between 0 at. % and 33 at. %, an Al concentration between 0 at. % and 40 at. %, an O concentration between 50 at. % and 66 at. %, an N concentration between 0 at. % and 10 at. % and an Eu.sup.2+ concentration between 0.0001 at. % and 5 at. %.

16. The dispersion as claimed in claim 2, wherein the Si concentration is between 30 at. % and 33 at. %, the Al concentration is between 0.01 at. % and 2 at. %, the O concentration is between 50 at. % and 66 at. %, the N concentration is between 0.1 at. % and 1 at. % and the Eu.sup.2+ concentration is between 0.0005 at. % and 1 at. %.

17. The dispersion according to claim 3, wherein the nanoparticles have an average particle size between 20 nm and 600 nm.

18. The dispersion according to claim 4, wherein the dispersion comprises between 15 wt. % and 35 wt. % of the nanoparticles.

19. The transparent plastic sheet according to claim 10, wherein the Si concentration is between 30 at. % and 33 at. %, the Al concentration is between 0.01 at. % and 2 at. %, the O concentration is between 50 at. % and 66 at. %, the N concentration is between 0.1 at. % and 1 at. % and the Eu.sup.2+ concentration is between 0.0005 and 1 at. %.

20. The luminescent glazing structure according to claim 12, wherein the Si concentration is between 30 at. % and 33 at. %, the Al concentration is between 0.01 at. % and 2 at. %, the O concentration is between 50 at. % and 66 at. %, the N concentration is between 0.1 at. % and 1 at. % and the Eu.sup.2+ concentration is between 0.0005 and 1 at. %.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0056] FIG. 1A and 1B depict a photograph and an IQE graph of a luminescent nanoparticle coating according to an embodiment of the invention;

[0057] FIG. 2 depict excitation and emission spectra luminescent nanoparticle coating according to an embodiment of the invention;

[0058] FIG. 3 depicts the transmission of a luminescent coated sample according to an embodiment of the invention illuminated by solar radiation;

[0059] FIG. 4 depicts a luminescent nanoparticle coating according to an embodiment of the invention.

[0060] FIG. 5 depicts a transparent sheet structure comprising a luminescent nanoparticle coating according to various embodiments of the invention.

[0061] FIG. 6 depicts a transparent sheet structure comprising luminescent nanoparticle coating according to various embodiments of the invention.

[0062] FIG. 7 depicts a transparent sheet structure comprising luminescent particle-based anti-reflection coating according to an embodiment of the invention.

DETAILED DESCRIPTION

[0063] In this disclosure, divalent Europium (Eu.sup.2+) doped SiAlON luminescent nanoparticle materials are described that have superior and improved properties for greenhouse and crop growth applications. The improved properties include improved luminescent, optical and/or material properties when compared to luminescent materials for greenhouse applications known from the prior art.

[0064] It has been surprisingly found that certain SiAlON:Eu.sup.2+ compositions exhibit UV absorbing PAR emitting Eu.sup.2+ doped SiAlON material wherein the absorption and emission spectra exhibit no or almost no overlap. In particular, it has been found that luminescent Eu.sup.2+ doped SiAlON materials absorb a substantial part of the UV band of the solar spectrum and convert radiation in this band to radiation of a longer wavelength, in particular radiation in the photosynthetically active radiation (PAR) region. The SiAlON host material exhibits superior properties in terms of mechanical strength, chemical inertness and thermal resistance and is for that reason used in protection and anti-reflection coatings in the glass industry. The Eu.sup.2+ doped SiAlON material forms a very stable conversion material which has optical properties at are compatible with glazing structures for greenhouses. The nanoparticle materials, their advantages and their uses in luminescent coatings for greenhouses and luminescent sheet structures for greenhouses are described hereunder in more detail with reference to the figures.

[0065] FIG. 1A depicts a photograph of a structured glass pane coated with a nano-particle SiAlON:Eu.sup.2+ coating which is illuminated by UV light. The photograph was taken under illumination by broad band UV light causing the nano-particle SiAlON:Eu.sup.2+ coating to emit radiation in the PAR region, i.e. between 400 and 700 nm. A dispersion of Eu.sup.2+ doped SiAlON nano-particles was made by dispersing 3.5 wt. % nanoparticles in uncured acrylic polymer matrix at a pH 11. Prior to the coating step, the glass pane was cleaned with 36% wt. hydrochloric acid, ethanol, DI water with sonication. The coating was thermally treated at 150° C. with 30 minutes. FIG. 1B depicts an internal quantum efficiently (IQE) graph of the nanoparticle coating showing very high quantum efficiencies. A BaSO4 was used as a reference by assuming it reflects uniformly in the UV-VIS light. This reference is then used how much light (incl sample holder) was being absorbed. Then the absorptance and the IQE can be determined, wherein the IQE is measured based on the so-called “DeMello method.

[0066] FIG. 2 depicts the excitation and emission spectra of the particle-based coating as shown in FIG. 1A. As shown in the figure the spectra exhibit no or almost no overlap not overlap and show excellent UV abortion centered at 320 nm and PAR emission centered at 450 nm. The nanoparticles were synthesized using exemplary synthesis steps of a sol-gel technique as described below. The composition of the particles was

[0067] Si.sub.1.92Al.sub.0.08O.sub.1.08N.sub.1.92 including a doping concentration of 1 mol % Eu.sup.2+. In this embodiment, the nanoparticles may have an average particle size (average diameter) between 100 and 300 nm. The size distribution of the nanoparticles may be determined based on scanning electron microscopy (SEM) picture or a dynamic light scatting (DLS) measurement which is well known in the art.

[0068] The SiAlON:Eu.sup.2+ nanoparticle coatings described with reference to the embodiments of this application exhibit excellent conversion characteristics. FIG. 3 represents a graph of the transmission of a coated SiAlO:Eu.sup.2+ sample showing >100% transmission in the PAR region, in this example in the range between (approx.) 440 and 520 nm, and a strong reduction in the transmission for wavelength smaller than 400 nm.

[0069] The SiAlON:Eu.sup.2+ luminescent particles may be synthesized based on a wet-chemical process such as a sol-gel synthesis method using different precursors for the elements Si, Al, O, N, and Eu. Different post-deposition treatments, e.g. thermal annealing, can be applied to material for the desired optical, chemical, and mechanical performances.

[0070] The SiAlON:Eu.sup.2+ particles may be synthesized using a sol-gel method including compounds such Tetraethylorthosilicate (TEOS) with formula Si(OC.sub.2H.sub.5).sub.4, Al(NO.sub.3).sub.3 and Europium salts. Optionally, ethanol and/or citric acid may be added to assist the formation of nanoparticles. Nitridation can be promoted by a nitrogen-filled sintering environment. Polymeric coating and/or lamination can be made by dispersing the nanoparticles in a matrix material. Choices and optimization of such matrix polymer can be made based on their applications and conditions. Epoxy resins, polymethylmethacrylate) (PMMA), and polysiloxane) are some common materials that can incorporate these nanoparticles.

[0071] In an embodiment, a sol-gel synthesis method may be used to produce a SiAlON:Eu.sup.2+ nanopowder material may include the steps of: [0072] stoichiometrically weighting TEOS and Al, N, O and Eu precursors: 7.7447 g Si(OC.sub.2H.sub.5).sub.4, 0.3299 g Al(NO.sub.3).sub.3, 0.0681 g Eu.sub.2O.sub.3; [0073] dissolving the europium oxide Eu.sub.2O.sub.3 in minimal amount of diluted nitric acid; [0074] dissolving the aluminum nitrate (Al(NO.sub.3).sub.3) in ethanol and placing it on a heating plate; [0075] dissolving TEOS (Si(OC.sub.2H.sub.5).sub.4) in ethanol and placing it on a heating plate; [0076] mixing the TEOS solution with Al(NO.sub.3).sub.3 solution and Eu.sub.2O.sub.3 solution to form a mixture of a colloidal solution (sol); [0077] evaporating the mixture on the heating plate to form ˜20 ml of sol; [0078] aging the sol for 72 hours at 60° C. in the dryer to form a gel structure; [0079] calcinating the gel at 500° C. in air to remove any residual organic content; [0080] sintering at 1100° C. under a reducing atmosphere; [0081] grinding the product in an agate mortar to form particles, for example nano-sized particles or micron-sized particles.

[0082] In another embodiment, a sol-gel synthesis method for producing SiAlO(N):Eu2+ particles may include the steps of: [0083] Stoichiometrically weigh TEOS and Al, N, O and Eu precursors: 7.7447 g Si(OC.sub.2H.sub.5).sub.4; (TEOS), 0.3299 g Al(NO.sub.3).sub.3.9H.sub.2O, and 0.1274 g Eu(C.sub.2H.sub.3O.sub.2).sub.3 (Eu(Ace)); [0084] Dissolve Eu(Ace) in DI water to form a first colloidal solution (sol 1); [0085] Dissolve Al(NO.sub.3).sub.3.9H.sub.2O in 6 g of ethanol to form a second colloidal solution (sol 2); pre-heat the solution at 60° C. for 15 min; [0086] Dissolve TEOS in 3.4253 g of ethanol to form a third colloidal solution (sol 3) (EtOH:TEOS≈2:1 molar ratio); pre-heat the mixture at 60° C. for 15 min; [0087] Mix sol 1 and sol 2 to form a fourth colloidal solution (sol 4); [0088] Dropwise add sol 3 to sol 4; [0089] Evaporate the mixture on a heating plate to form ˜20 ml of sol; [0090] Age the sol for 24 hours at 60° C. in an oven to form a gel structure; [0091] Grind the product using a mortar and pestle to form a white SiAlO(N):Eu2+ powder; [0092] Calcinate at 500° C. for 5 hours in air to remove any residual organic content with a heating rate of 3° C./min; naturally cool the product; [0093] Grind the product after calcination; [0094] Sinter at 1100° C. for 3 hours under a reducing atmosphere (7%H.sub.2/93%N.sub.2) with a heating rate of 3° C./min; naturally cool the product; [0095] Grind the product to form the nanophosphor.

[0096] The process described above allows 2 grams nanoparticles, wherein the composition of the nanoparticles Si.sub.1.92Al.sub.0.08O.sub.3.96:1mol % Eu, with a Si/Al ratio of 24, and Eu doping concentration of 1% resulting in a composition Si: 32.0 at. %, Al: 1 at. %, O2 66 at. % and Eu: 1 at. %. Based on the above syntheses methods, SiAlON:Eu.sup.2different nanoparticle materials may be produced. The SiAlON:Eu.sup.2+ nanoparticle materials may be realized with the Si concentration being selected between 0 and 33 at. %, the Al concentration between 0 and 40 at. %, the O concentration between 50 and 66 at. %, the N concentration between 0 and 10 at. % and the Eu.sup.2+ between 0.0001 and 5 at. %.

[0097] In an embodiment, nanoparticles of the SiAlON:Eu.sup.2+ material may be synthesized wherein the average particle size may be selected between 1 and 500 nm in diameter. In another embodiment, the average particle size may be selected between 2 and 400 nm in diameter. In a further embodiment, the average particle size may be selected between 5 and 100 nm in diameter. The nano-sized particles may provide advantageous optical properties to a nanoparticle coating, for example it may eliminate or at least minimize the light scattering that could reduce the efficiency of such luminescent coating.

[0098] The SiAlON:Eu.sup.2+ nanoparticles may be (mono)dispersed in a transparent polymeric binder medium to form a nanoparticle dispersion. A nanoparticle dispersion may be realized by dispersing nanoparticles in a carrying medium (which may be referred to in short as a binder or medium), applying the nanoparticle dispersion as a coating onto a transparent substrate, such as a glazing structure or a polymer sheet, and drying the nanoparticle coating to form a polymer nanoparticle coating on the substrate. The coating may be formed using known coating techniques such as spray coating. To form a nanoparticle dispersion, the surface of the nanoparticles may be modified using a surface modification process.

[0099] In an embodiment, the surface of nanoparticles may be modified by sonication (i.e. applying ultrasound wave energy with frequencies >20 KHz to the particles) in different types of ligands. Examples of such ligands may include stearic acid, oleic acid, octanoic acid, oleylamine, octylamine, octanthiol and trioctylphosphine. Alternatively, in an embodiment, the surface of nanoparticles may be modified by chemical bonds formation such as silanization, esterification, or similar processes. Such chemical bond formation processes may be used to attached long organic side chain(s), with a carbon chain length between 8 and 18, to the surface of the nanoparticles. The surface modifications of the nanoparticles based on a ligand and/or chemical bond formation may allow nanoparticles to easily disperse in the carrying mediums so that nucleation of the particles can be prevented.

[0100] Based on the above-mentioned particle treatments, a nanoparticle dispersion may be formed. The weight percentage wt % of the nanoparticles in the nanoparticle dispersion may be selected between 1% and 80 wt %, preferably between 5 and 50 wt %, more preferably between 15 wt % and 35 wt %.

[0101] In an embodiment, the (modified) nanoparticles may be dispersed in organic solvents between 1% to 80%, more preferably 5% to 50%, more preferably 15% to 35%. In some embodiments, the (modified) nanoparticles may be dispersed in organic solvents between 25±10%. Organic solvents may include hexane, ethanol, heptane, toluene, chloroform, dichloromethane between. The solvent may further include between 0.5% and 10% polymer dispersants. Examples of such polymeric dispersants may include PP, PE, PVP, PMA-derivatives, PS, PU, etc.

[0102] In another embodiment, the (modified) nanoparticles may be dispersed in an aqueous solvent, such as alkali aqueous solution, including an ammonium solution and a sodium hydroxide solution. The aqueous solvent may further include 1% to 10% waterborne polymeric dispersants, including polyacrylates, polyurethanes, copolymers etc. (PP, PE, PVP, PMA-derivatives, PS, PU, etc.).

[0103] In an embodiment, the polymeric dispersants and binders are acrylic acid-, urathane-, acylate-, epoxy-. based polymeric dispersants or binders respectively.

[0104] In further embodiments, a dispersion may be formed on the basis of polymeric binders as described in WO2018/169404, which is hereby incorporated by reference into this application.

[0105] The polymeric dispersants may act as dispersants to disperse the nanoparticles and will cross-link during drying to form a polymeric nanoparticle coating. Polymeric dispersants enhanced the long-term stabilization of the nanoparticles in a medium by combining steric hindrance of solubilizing side chains and electrostatic repulsion of charges on anchoring groups. Additionally, the polymeric dispersant allows a controlled polymerization process to provide a high-quality nanoparticle coating layer.

[0106] In an embodiment, a refractive index-matched organic binder (such as PET, PE, PVB, PVA, PC, PP, PVP, Epoxy resin, Silicone, PS, PMA-derivatives, etc.) may be used to form a nanoparticle dispersion.

[0107] A (mono)dispersed nanoparticle coating may be formed by applying a nanoparticle dispersion onto a transparent (clear of diffused) substrate, e.g. a glass pane or a transparent polymer sheet, using a wet-coating technique such as spray coating, roll-to-roll coating, dip coating, doctor blade coating, brush coating, etc. This way, high-quality substantially scatter-free or low-scattering SiAlON:Eu.sup.2+ luminescent nanoparticle coatings may be realized in an efficient and cheap way. Based on the above-mentioned wet-coating techniques, nanoparticle coatings with a thickness between 10 and 200 micrometer, preferably between 20 and 180 micrometer, more preferably between 50 and 150 micron can be realized.

[0108] In an embodiment, the SiAlON:Eu.sup.2+ luminescent material may be synthesized as micron-sized particles. The micron-sized particles may be (mono)dispersed in a binder material and applied as a coating on a transparent substrate in a similar way as described above with reference to the nano-sized particles. In an embodiment, the micron-sized particles may have an average particle size selected between 0.5 μm and 15 μm in diameter. The particles may promote diffusion of the solar irradiation and the luminescent emission which is beneficial for plant growth. The diffusion of light can uniformly distribute incoming light that has advantages such as improved crop yield, higher leaf count, lower crop temperature and shorter crop time. This way, the luminescent micron-sized SiAlON:Eu.sup.2+ particles may act both as a light conversion layer and a light diffusion layer.

[0109] The luminescent particle-based materials described with reference to the embodiments in this application may be used in glazing structures and transparent sheet structures for greenhouses and buildings for indoor farming. Exemplary advantageous optical structures are described hereunder with reference to FIG. 4-7.

[0110] FIG. 4 depicts a glazing structure comprising a luminescent particle-based coating according to an embodiment of the invention. As shown in the figure, the optical structure may include a transparent glass pane or transparent polymer sheet 402 having a first surface 404 and second surface 406, wherein the first surface may be configured to receive external solar light 410 and the second surface may be configured to couple light 414 out of the glazing structure into the greenhouse. The glazing structure or the polymer sheet may be part of or used in a greenhouse. In case of a glazing structure, the length of the glazing may be selected between 300 and 100 cm, preferably 250 and 140 cm, more preferably 220 and 160 cm and the width of the glazing may be selected between 200 and 40, preferably 180 and 50, more preferably between 160 and 60 cm. Typical dimensions (length×width) may include: 2.140×1.122, 1.650×1.22, 1.650×997 and 1.650×730 mm. Further, a glazing may have a thickness between 6 and 3 mm, preferably 5.5 and 3.5 mm, more preferably 5.0 and 3.5 mm.

[0111] The SiAlON:Eu.sup.2 nanoparticle coating may be applied by spray-coating a nanoparticle dispersion as described above on the first surface of the substrate, e.g. a glazing. A further coating 412 without nanoparticles may be applied using a wet-coating process over the luminescent nanoparticle coating for protection. Typically, the composition of the protective coating may be identical or similar to the polymeric binder material of the nanoparticle coating.

[0112] In an embodiment, the surface of the glazing may be subjected to a surface treatment to introduce a light scattering top surface. The surface scattering interface may be introduced to maximize light coupling out of the second (bottom) surface of the glazing. The surface treatment may include an etching step resulting in a textured surface.

[0113] The etching process may be a wet etching process or a dry etching process. The wet etching process works by dissolving parts of the surface by immersing it in a chemical solution. In an embodiment, a mask may be used to selectively etch the material. A dry etching process may be based on sputtering or dissolution of the material at. This may be achieved by a reactive ion etching step or ion beams. The resulting surface characteristics (and therefore scattering properties) can be tuned by adjusting various etching parameters (e.g. plasma feed gas, reactive gas types and flows, gas pressure, etch time etc.) and measuring the scattering properties of the textured surface. The textured surface may have a regular (period) pattern or it may have a random pattern.

[0114] The texture patterns may have features (diameters and heights) in the nanometer to micrometer range. Texture features fabricated on the basis of a mask-based etching process may include cones, pyramids, microlenses in nanometer range (approx. 10 nm up to 1000 nm) or features in the micrometer range, e.g. 1 micrometer up to 500 micrometer. Alternatively, texture features fabricated on the basis of a mask-les etching process, may result in substantially random texture features with dimensions in the nanometer range or micrometer range.

[0115] A measure for the surface roughness of the surface interface is the standard deviation of the Gaussian scattering distribution of light scattered at the surface interface.

[0116] Such measurements are well known in the art, e.g. Kurita et al, Optical surface roughness measurement from scattered light approximated by two-dimensional Gaussian function, Transactions on Engineering Sciences vol. 2, 1993. This article may hereby incorporated by reference in this disclosure.

[0117] In another embodiment, possible backscattering effects by the nanoparticles may be reduced using SiO2 porous nanoparticles. In an embodiment, the porous nanoparticles may be added to the luminescent nanoparticles. In an embodiment, 0.1-5 wt % porous nanoparticles may be added to the luminescent nanoparticles. In further embodiments, 0.5 to 2.0 wt % may be added to the luminescent nanoparticles. In another embodiment, the typically, the porous nanoparticles may have the same or a similar size or size distribution as the luminescent nanoparticles. The porous nanoparticles will provide the coating antireflective properties. The SiO2 porous nanoparticles will reduce the refractive index of the coating layer relative to the substrate thereby substantially reducing back-scattering and increasing coupling light via the second surface out of the substrate. A luminescent layer may be deposited (e.g. coated or sputtered) directly onto the surface of the substrate. Alternatively, before depositing a luminescent layer onto the substrate one or more layers, e.g. adhesion layers, buffer layers and/or passivation layers may be deposited over the substrate.

[0118] In a further embodiment, instead of a coating over a substrate, the nano-sized and micron-sized SiAlON:Eu.sup.2+ particles can be dispersed in a transparent polymer (such as PE, ETFE, PVC, PMMA, polycarbonate, etc.) that is shaped as a transparent plastic film or sheet which can be used in a greenhouse. Typically, the thickness of such sheet may be between 1 and 1000 micrometer, preferably 10 and 500 mm, more preferably 40 and 120 micrometer. Further, between 1 and 80 wt %, preferably 5 and 50 wt %, more preferably 15 and 35 wt %, of luminescent nanoparticles may be dispersed in the film.

[0119] In the embodiment of FIG. 5, the optical structure may comprise a substantially scattering free or low-scattering SiAlON:Eu.sup.2+ nanoparticle coating 508 and high-scattering transparent substrate 502 (also referred to as a diffused transparent substrate). Such layer may include SiAlON:Eu.sup.2+ nanoparticles in an inorganic or organic matrix material. In an embodiment, the matrix material may be an amorphous dielectric material such as SiAlON, Si.sub.3N.sub.4, Al.sub.2O.sub.3, Ti.sub.2O.sub.3, etc. In another embodiment, the matrix material may be a transparent organic dielectric material such as PMMA, polyacrylic acid, polycarbonate, polyethylene, fiberglass. Such nanoparticle coating may be realized based on suitable particle synthesis methods and coating techniques as described in this application.

[0120] The substrate 502 may include a diffused transparent substrate. For example, in an embodiment, the substrate may be a diffused glass substrate. The diffusive glass material may be optimized for light transmission (in particular light transmission in the PAR region), while scattering the light in random directions when the light leaves the substrate. In an embodiment, the diffused glass substrate may comprise scattering structures for scattering the light in a diffusive way. Instead of a glass substrate, a (diffused) transparent polymer-based substrate may be used, wherein the substrate is provided with light scattering structures so that diffusive light leaves optical structure on the second surface.

[0121] The optical structure depicted in FIG. 5 will receive radiation of the solar spectrum ranging from UV to IR radiation. UV light will be transformed by the divalent Eu dopants 512 in the SiAlON nanoparticles into radiation of the PAR. The PAR light generated by the Eu.sup.2+ doping sites 514 and the PAR light from the solar light 518 will exit the optical structure as diffused light, which is advantageous for plant growth.

[0122] In the embodiment of FIG. 6, the optical structure may comprise a high-scattering luminescent thin-film layer 608 and low-scattering transparent substrate 602. In an embodiment, the luminescent thin-film layer may be a thin-film polycrystalline SiAlON:Eu.sup.2+ provided over a low-scattering transparent substrate, e.g. a glass substrate or a transparent polymer based substrate. In another embodiment, instead of a thin-film polycrystalline SiAlON:Eu.sup.2+ as high-scattering micro-particle based coating layer may be used. Such layer may include SiAlON:Eu.sup.2+ micron-sized particles in an inorganic or organic matrix material. In an embodiment, the matrix material may be an amorphous dielectric material such as SiAlON, Si.sub.3N.sub.4, Al.sub.2O.sub.3, Ti.sub.2O.sub.3, etc. In another embodiment, the matrix material may be a transparent organic dielectric material such as PMMA, polyacrylic acid, polycarbonate, polyethylene, fiberglass. Such micron-particle coating may be realized based on suitable particle synthesis methods and coating techniques as described in this application.

[0123] The optical structure depicted in FIG. 6 will receive radiation of the solar spectrum ranging from UV to IR radiation, wherein UV light will be transformed by the divalent Eu dopants 612 in the SiAlON layer into radiation of the PAR. As the SiAlON layer is a high-scattering layer, the PAR light emitted by the Eu.sup.2+ doped material will be scattered into the low-scattering transparent substrate. Further, the doped SiAlON layer will act as a scattering layer for the visible part, including the PAR region. Hence, this part of the solar light will be scattered into the diffused substrate. The PAR light generated by the Eu.sup.2+ doping sites 614 and the PAR light from the solar light 618 will exit the optical structure as diffused light, which is advantageous for plant growth.

[0124] It is submitted that the invention is not limited to the optical structures as described with reference to FIG. 4-6. For example, in a further embodiment, the optical structure may include a high-scattering luminescent thin-film layer as well as a high-scattering transparent substrate. Hence, both the luminescent layer and the substrate are configured to generate diffusive light that leaves the optical structure. In such embodiment, the optical structure may be optimized for transmitting and generating highly diffused light in the PAR region when the optical structure is exposed to solar radiation.

[0125] Further, in an embodiment, instead of providing one or more luminescent layers over the first surface (or in addition to providing one or more luminescent layers over a the first surface), a low-scattering or low-scattering luminescent layer may be provided over the second surface of the transparent substrate, which—deepening on the application—may either be a high-scattering (diffused) substrate or a low-scattering substrate.

[0126] FIG. 7A and 7B depict an optical structure according to yet another embodiment. In this embodiment, luminescent nanoparticles 708 having average dimensions between 100 and 300 nm are parsley distributed over a first (top) surface 704 of a transparent substrate 702. Here, sparsely distributed means that the average distance between particles is between 200 and 700 nm. The luminescent particles may be luminescent SiAlON:Eu.sup.2+ based nano-particles having a relatively high refractive index. For example, in an embodiment, the particle material may include AlN doped with a few at. % of Si.sup.4+, O.sup.2+ and Eu.sup.2+ ions, in particular 5% of lower, so that the refractive index of the luminescent material is approximately 2.14 to form a luminescent anti-reflection coating according to an embodiment of the invention.

[0127] It is known from US2013/0194669 that a layer of high-refractive index nanoparticles which are sparsely distributed over a surface of a low-refractive index material, e.g. glass substrate, may function as a broadband antireflection coating. Here, the nanoparticles may be arranged in an ordered array or alternatively the nanoparticles may be randomly distributed over the surface of the transparent substrate. The antireflective properties of such nanoparticle layer may be attributed to the formation of plasmonic modes when solar light 710 interacts with nanoparticles having dimensions in the range 200 and 700 nm. These plasmonic modes will cause the light to be effectively scattered into the substrate as shown in the figure. The luminescent nanoparticle AR layer will both convert UV light of the solar spectrum in to PAR light and acts as an efficient broadband antireflection layer for the rest of the solar spectrum, in particular the visible part of the solar spectrum.

[0128] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising,” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

[0129] The corresponding structures, materials, acts, and equivalents of all means or step plus function elements in the claims below are intended to include any structure, material, or act for performing the function in combination with other claimed elements as specifically claimed. The description of the present invention has been presented for purposes of illustration and description but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope of the appending claims and spirit of the invention. The embodiment was chosen and described in order to best explain the principles of the invention and the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated.