Quantum Dot-Containing Composition for Growth Enhancement in Photosynthetic Organisms

Abstract

Quantum dot (QD) LEDs useful for plant, algael and photosynthetic bacterial growth applications. The QD LEDs utilizes a solid state LED (typically emitting blue or UV light) as the primary light source and one or more QD elements as a secondary light source that down-converts the primary light. The emission profile of the QD LED can be tuned to correspond to the absorbance spectrum of one or more photosynthetic pigments of the organism.

Claims

1. A photobioreactor, the photobioreactor comprising: a transparent container; a culture medium placed in the transparent container; a plurality of water-soluble microbeads in the culture medium, each water-soluble microbead having a population of quantum dots incorporated therein; and a light emitting device.

2. The photobioreactor of claim 1, wherein the light emitting device comprises a primary light-emitting element that emits light at a first wavelength; and the quantum dots are positioned to absorb a portion of light emitted by the primary light emitting element and to emit light at a second wavelength.

3. The photobioreactor of claim 1, wherein the culture medium is used as medium that promotes the growth of photosynthetic bacteria or algae.

4. The photobioreactor of claim 3, wherein the quantum dot are positioned to absorb a portion of light emitted by the light emitting device and to emit light corresponding to a wavelength within a peak in an absorption spectrum of a photosynthetic pigment of the photosynthetic bacteria or algae.

5. The photobioreactor of claim 4, wherein the photosynthetic pigment is chlorophyll.

6. The photobioreactor of claim 1, wherein the culture medium comprises agar.

7. The photobioreactor of claim 1, wherein the water-soluble microbeads are made from a material selected from polymers, sol-gels, silica gel, and glass.

8. The photobioreactor of claim 7, wherein the water-soluble microbeads comprise a coating disposed upon the surface of the water-soluble microbeads, the coating comprising a material that is different than the material of the water-soluble beads.

9. The photobioreactor of claim 8, wherein the coating comprises a material selected from polymers, silica-based materials, metal nitrides, metal oxides, and any combination thereof.

10. The photobioreactor of claim 1, wherein the first wavelength is in the UV or blue region of the electromagnetic spectrum.

11. The photobioreactor of claim 1, wherein the quantum dots do not contain cadmium.

12. The photobioreactor of claim 11, wherein the population of quantum dots comprises quantum dots having indium phosphide cores and shells of zinc sulphide or zinc selenide.

13. The photobioreactor of claim 1, wherein the water-soluble microbeads are disposed on a substrate, the substrate being immersed in the culture medium.

14. The photobioreactor of claim 13, wherein the substrate has finger-like projections.

15. The photobioreactor of claim 1, wherein the quantum dots are CdSe/CdS/CdZnS/ZnS core-multishell quantum dots.

16. A composition, the composition comprising: a culture medium; and a plurality of water-soluble microbeads mixed in the culture medium; each water-soluble microbead having a population of quantum dots incorporated therein;

17. The composition of claim 16, wherein the culture medium comprises agar.

18. The composition of claim 16, wherein the water-soluble microbeads are made from a material selected from polymers, sol-gels, silica gel, and glass.

19. The composition of claim 16, wherein the water-soluble microbeads comprise a coating disposed upon the surface of the water-soluble microbeads, the coating comprising a material that is different than the material of the water-soluble microbeads.

20. The composition of claim 19, wherein the coating comprises a material selected from polymers, silica-based materials, metal nitrides, metal oxides, and any combination thereof.

21. The composition of claim 16, wherein the quantum dots do not contain cadmium.

22. The composition of claim 21, wherein the population of quantum dots comprises quantum dots having indium phosphide cores and shells of zinc sulphide or zinc selenide.

23. The composition of claim 16, wherein the water-soluble microbeads are disposed on a substrate, the substrate being immersed in the culture medium.

24. The composition of claim 23, wherein the substrate has finger-like projections.

25. The composition of claim 16, wherein the quantum dots are CdSe/CdS/CdZnS/ZnS core-multishell quantum dots.

26. The composition of claim 16, further comprising photosynthetic bacteria or algae mixed in the culture medium.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

[0057] FIG. 1 shows the molecular structure of chlorophyll a.

[0058] FIG. 2 is a UV-vis absorption spectra of chlorophyll a in methanol (A), chlorophyll b in diethyl ether (B) and β-carotene in hexane (C). All data were taken from the photochemCAD database [H. Du et al., Photochem. & Photobiol., 1998, 68, 141]. N.B. the absorption spectra are solvent dependent.

[0059] FIG. 3 is a schematic diagram of a QD LED, wherein red and blue QDs are embedded in beads and illuminated with a UV LED primary light source.

[0060] FIG. 4 is a schematic diagram of a QD LED, wherein red and blue QDs are embedded in separate beads and illuminated by a primary UV light source.

[0061] FIG. 5 is a diagram illustrated the structure of a QD LED chip. The QDs in resin are loaded into the LED case, which is illuminated from below by a UV or blue solid state LED.

[0062] FIG. 6 is a schematic diagram showing a remote phosphor architecture. In the illustrated example, a blue solid state LED illuminates a red QD phosphor from below, which emits both blue and red light.

[0063] FIG. 7 illustrates preparation of a QD phosphor sheet: (A) QD ink is drop cast on the region between the spacers of the PET substrate (B). QD ink is distributed uniformly between the spacers by using a glass slide.

[0064] FIG. 8 is a diagram showing an arrangement for illumination of a QD phosphor by a solid state LED (in the illustrated example emitting UV light) positioned to the side of the phosphor sheet. In the example, UV light from the LED passes through the QD phosphor, while down-converted blue and red light from the QD phosphor is emitted towards the plant below.

[0065] FIG. 9 is an illustration showing a petri-dish filled with agar (as a culture for growing photosynthetic bacteria) embedded with IR-emitting QD beads. The petri-dish is illuminated by UV or blue solid state LEDs.

[0066] FIG. 10 is a plot showing the emission spectrum of a remote phosphor QD LED comprising a blue solid state LED (22 mW) as the primary light source and a red quantum dot (InP/ZnS) silicone resin (emitting at 648 nm with FWHM of 59 nm) at a concentration of 20 ODs per 10 mmol of solution as a secondary light source (A), alongside the absorption spectra of chlorophyll a (B), chlorophyll b (C), and the combined chlorophyll a and b spectra (D). The plot shows that the emission maxima and relative peak intensities of the QD-phosphor LED are well matched to the absorption spectra of chlorophyll a and b.

[0067] FIG. 11 is a plot showing the emission spectrum of a remote phosphor QD LED comprising a blue solid state LED as the primary light source and a red quantum dot (CdSe/CdS/CdZnS/ZnS) silicone resin (emitting at 625 nm with FWHM of 35 nm) as a secondary light source (A), alongside the absorption spectrum of chlorophyll b (B). The plot shows that the emission spectrum of the QD-phosphor LED is well matched to the absorption spectrum of chlorophyll b.

[0068] FIG. 12 is a diagram showing an arched (or caged) lighting arrangement that allows blue and red QD LEDs to illuminate a plant from many directions, to promote uniform plant growth.

[0069] FIG. 13 is an illustration of a photobioreactor for growing algae. A red QD phosphor sheet shaped with finger-like projections is immersed in the photobioreactor, which is illuminated from above (and/or below) with blue solid state LEDs, emitting blue and red light throughout the reactor.

DETAILED DESCRIPTION OF THE INVENTION

[0070] Disclosed is a method of fabricating LEDs optimised for promoting growth of photosynthetic organisms, using a blue or UV solid state LED, with tuned emission using red (and/or other colours, as required, of) quantum dots, to emit light of the correct wavelengths and relative intensities to enhance photosynthesis. QD LEDs may be produced to emit from the blue to the UV region of the electromagnetic spectrum to match the absorption characteristics of chlorophylls and other pigments present in photosynthetic organisms to promote and support their growth.

[0071] Plant factory lighting described in the prior art utilises incandescent, fluorescent or solid state LED lighting, while patented photobioreactors focus little attention on the lighting source. The solid state LEDs described in the prior art are relatively expensive to produce. QD LEDs provide a less expensive alternative, since a very small amount of semiconductor material is required to produce bright, stable emission. The lifetime of QD LEDs is in the region of 25,000-50,000 hours, which is far superior to incandescent bulbs (500 hour typical lifetime) and compact fluorescent lamps (3000 hour typical lifetime). Further, QD LEDs have high energy efficiency, typically 30-70 lumens per Watt, compared to 10-18 lm/W for incandescent bulbs and 35-60 lm/W for fluorescent lamps. Thus, though the initial installation cost of QD LED lighting in plant factories or photobioreactors may be higher than that using incandescent or fluorescent bulbs, the superior longevity and efficiency of QD LEDs make them a favourable long-term investment.

[0072] Stable, intense emission at 660 nm, which corresponds to the red absorption maximum of chlorophyll a, is difficult to achieve with solid state LEDs, for which the emission is determined by the band gap of the semiconducting material. Solid state materials emitting at 660 nm are typically limited to AlGaInP-based semiconductors. Using QD LEDs, emission at 660 nm is far more easily achieved, since the emission wavelength may be tuned by changing the nanoparticle size. Thus, red emission may be obtained using a variety of materials, including CdSe/ZnS and InP/ZnS core-shell nanoparticles.

[0073] Because of the facile wavelength tuneability of QDs, QD LEDs may be easily modified to suit a variety of different photosynthetic organisms, including plant species, algae and photosynthetic bacteria. Simple modifications to the synthesis of the QDs may be employed to alter the PL emission, without having to change the inherent semiconducting material or the reagents used for the synthesis. Wavelength tuneability is far more easily achieved using QD LEDs than solid state LEDs. Thus, bespoke QD LED systems may more easily be produced by selecting the desired combination of QD materials from a given range, to be incorporated into the QD LED device.

[0074] Narrow emission FWHM (less than 40 nm) is most easily achieved using cadmium-based QDs, however core-shell CFQD material with FWHM less than 60 nm may be synthesised. Further, it is possible to tune the FWHM of QD material to match the absorption spectra of various photosynthetic pigments. For instance, the absorption spectrum of chlorophyll b shows narrower peak widths than that of chlorophyll a; using QDs it is possible to fabricate LEDs that emit not just at the absorption maxima of chlorophyll a and b, but also with similar FWHM and relative intensities. IR-emitting QDs, such as CdTe, PbS and PbSe could be used to produce QD LEDs emitting in the IR with emission characteristics to coincide with the absorption spectra of bacteriochlorophylls.

[0075] One of the drawbacks of the lighting systems described in the prior art is the amount of energy emitted as heat. High power solid state LEDs also give off a relatively large amount of heat in comparison to QD LEDs. Thus, for plant factory settings where temperature control is important to plant development, QD LEDs with their low heat emission are ideal. Using QD LED lighting, systems to cool the lighting device, as described in the prior art, are not required. This reduces the complexity of the lighting apparatus, keeping the cost low.

[0076] Emission of multiple wavelengths of light from a single geometric location is preferable to emission of each wavelength from a discrete location, since it eliminates colour hot spots and colour specific shadows that may lead to non-uniformity in growth. An advantage of the systems described herein is that multiple wavelengths of light may be emitted from a single direction using a single solid state LED source. Using QDs to tune the emission eliminates the need for multiple solid state LEDs that may be costly. Further, the present invention requires less circuitry than lighting arrangements using multiple solid state LEDs, which require separate circuitry for each colour LED. Not only does this reduce the cost associated with the circuitry, it is also particularly advantageous for portable devices, which could be used, for example, for stimulating grass growth for reseeding sports pitches, or for domestic grow lights.

[0077] The QD LED devices described herein may be produced in a variety of shapes and sizes, from small LED chips to QD phosphor sheets that may be fabricated in any shape or size and could be printed on flexible substrates. This enables their use in a range of applications.

[0078] The QDs used herein are optimally made from core-shell semiconductor nanoparticles. For example, the core material may be made from:

[0079] II-VI compounds including a first element from group 12 (II) of the periodic table and a second element from group 16 (VI) of the periodic table, as well as ternary and quaternary materials including, but not restricted to: CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe.

[0080] II-V compounds incorporating a first element from group 12 of the periodic table and a second element from group 15 of the periodic table, and also including ternary and quaternary materials and doped materials. Nanoparticle material includes, but is not restricted to: Zn.sub.3P.sub.2, Zn.sub.3As.sub.2, Cd.sub.3P.sub.2, Cd.sub.3As.sub.2, Cd.sub.3N.sub.2, Zn.sub.3N.sub.2.

[0081] III-V compounds including a first element from group 13 (III) of the periodic table and a second element from group 15 (V) of the periodic table, as well as ternary and quaternary materials. Examples of nanoparticle core materials include, but are not restricted to: BP, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, BN, GaNP, GaNAs, InNP, InNAs, GAlnPAs, GaAlPAs, GaAlPSb, GaInNSb, InAlNSb, InAlPAs, InAlPSb.

[0082] III-VI compounds including a first element from group 13 of the periodic table and a second element from group 16 of the periodic table and also including ternary and quaternary materials. Nanoparticle material includes, but is not restricted to: Al.sub.2S.sub.3, Al.sub.2Se.sub.3, Al.sub.2Te.sub.3, Ga.sub.2S.sub.3, Ga.sub.2Se.sub.3, In.sub.2S.sub.3, In.sub.2Se.sub.3, Ga.sub.2Te.sub.3, In.sub.2Te.sub.3.

[0083] IV compounds including elements from group 14 (IV): Si, Ge, SiC, SiGe.

[0084] IV-VI compounds including a first element from group 14 (IV) of the periodic table and a second element from group 16 (VI) of the periodic table, as well as ternary and quaternary materials including, but not restricted to: PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbSe, SnPbTe, SnPbSeTe, SnPbSTe.

[0085] The shell layer(s) grown on the nanoparticle core may include any one or more of the following materials:

[0086] IIA-VIB (2-16) material, incorporating a first element from group 2 of the periodic table and a second element from group 16 of the periodic table, and also including ternary and quaternary materials and doped materials. Nanoparticle material includes, but is not restricted to: MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe.

[0087] IIB-VIB (12-16) material incorporating a first element from group 12 of the periodic table and a second element from group 16 of the periodic table, and also including ternary and quaternary materials and doped materials. Nanoparticle material includes, but is not restricted to: ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe.

[0088] II-V material incorporating a first element from group 12 of the periodic table and a second element from group 15 of the periodic table, and also including ternary and quaternary materials and doped materials. Nanoparticle material includes, but is not restricted to: Zn.sub.3P.sub.2, Zn.sub.3As.sub.2, Cd.sub.3P.sub.2, Cd.sub.3As.sub.2, Cd.sub.3N.sub.2, Zn.sub.3N.sub.2.

[0089] III-V material incorporating a first element from group 13 of the periodic table and a second element from group 15 of the periodic table, and also including ternary and quaternary materials and doped materials. Nanoparticle material includes, but is not restricted to: BP, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, AlN, BN.

[0090] III-IV material incorporating a first element from group 13 of the periodic table and a second element from group 14 of the periodic table, and also including ternary and quaternary materials and doped materials. Nanoparticle material includes, but is not restricted to: B.sub.4C, Al.sub.4C.sub.3, Ga.sub.4C.

[0091] III-VI material incorporating a first element from group 13 of the periodic table and a second element from group 16 of the periodic table, and also including ternary and quaternary materials. Nanoparticle material includes, but is not restricted to: Al.sub.2S.sub.3, Al.sub.2Se.sub.3, Al.sub.2Te.sub.3, Ga.sub.2S.sub.3, Ga.sub.2Se.sub.3, In.sub.2S.sub.3, In.sub.2Se.sub.3, Ga.sub.2Te.sub.3, In.sub.2Te.sub.3.

[0092] IV-VI material incorporating a first element from group 14 of the periodic table and a second element from group 16 of the periodic table, and also including ternary and quaternary materials and doped materials. Nanoparticle material includes, but is not restricted to: PbS, PbSe, PbTe, Sb.sub.2Te.sub.3, SnS, SnSe, SnTe.

[0093] Nanoparticle material incorporating a first element from any group in the d-block of the periodic table, and a second element from group 16 of the periodic table, and also including ternary and quaternary materials and doped materials. Nanoparticle material includes, but is not restricted to: NiS, CrS, CuInS.sub.2, CuInSe.sub.2, CuGaS.sub.2, CuGaSe.sub.2.

[0094] The coordination around the atoms on the surface of any core, core-shell or core-multishell, doped or graded nanoparticle is incomplete and the non-fully coordinated atoms have dangling bonds which make them highly reactive and may lead to particle agglomeration. This problem is overcome by passivating (capping) the “bare” surface atoms with protecting organic groups.

[0095] The outermost layer (capping agent) of organic material or sheath material helps to inhibit particle-particle aggregation, further protecting the nanoparticles from their surrounding electronic and chemical environments. In many cases, the capping agent is the solvent in which the nanoparticle preparation is undertaken, and consists of a Lewis base compound, or a Lewis base compound diluted in an inert solvent such as a hydrocarbon. There is a lone pair of electrons on the Lewis base capping agent that is capable of a donor-type coordination to the surface of the nanoparticle and include mono- or multi-dentate ligands such as phosphines (trioctylphosphine, triphenylphosphine, t-butylphosphine, etc.), phosphine oxides (trioctylphosphine oxide, triphenylphosphine oxide, etc.), alkyl phosphonic acids, alkyl-amines (octadecylamine, hexadecylamine, octylamine, etc.), aryl-amines, pyridines, long chain fatty acids (myristic acid, oleic acid, undecylenic acid, etc.) and thiophenes but is, as one skilled in the art will know, not restricted to these materials.

[0096] The outermost layer (capping agent) of a QD may also include a coordinated ligand with additional functional groups that may be used as chemical linkage to other inorganic, organic or biological material, whereby the functional group is pointing away from the QD surface and is available to bond/react/interact with other available molecules, such as amines, alcohols, carboxylic acids, esters, acid chlorides, anhydrides, ethers, alkyl halides, amides, alkenes, alkanes, alkynes, allenes, amino acids, azide groups, etc. but is, as one skilled in the art will know, not limited to these functionalised molecules. The outermost layer (capping agent) of a QD may also include of a coordinated ligand with a functional group that is polymerisable and may be used to form a polymer layer around the particle.

[0097] The outermost layer (capping agent) may also include organic units that are directly bonded to the outermost inorganic layer such as via an S—S bond between the inorganic surface (ZnS) and a thiol capping molecule. These may also possess additional functional group(s), not bonded to the surface of the particle, which may be used to form a polymer around the particle, or for further reaction/interaction/chemical linkage.

[0098] The LEDs described herein may be fabricated with “bare” QDs embedded directly into the LED encapsulant, or more preferably, they may be incorporated into microbeads prior to their embedment into the LED encapsulant; the QD microbeads exhibit superior robustness and longer lifetimes than bare QDs, and are more stable to the mechanical and thermal processing protocols of LED fabrication. The terms “beads” and “microbeads” are used interchangeably herein. Polymer beads are discussed herein, but the beads may also be of different materials, such as sol-gels, silica, or glass, as described in co-owned patent application Ser. No. 12/622,012, filed Nov. 19, 2009, (Pub. No.: 2010/0123155) the contents of which are incorporated herein by reference.

[0099] By incorporating the QD material into polymer microbeads, the nanoparticles become more resistant to air, moisture and photo-oxidation, opening up the possibility for processing in air that would vastly reduce the manufacturing cost. The bead size may be tuned from 20 nm to 0.5 mm, enabling control over the ink viscosity without changing the inherent optical properties of the QDs. The viscosity dictates how the QD bead ink flows through a mesh, dries, and adheres to a substrate, so thinners are not required to alter the viscosity, reducing the cost of the ink formulation. By incorporating the QDs into microbeads, the detrimental effect of particle agglomeration on the optical performance of bare encapsulated QDs is eliminated. QD beads provide an effective means of colour mixing.

[0100] FIG. 3 illustrates an LED device 300 made using a mixture of red and blue QDs 301 mixed together in beads 302. FIG. 4 illustrates an alternative embodiment of an LED device 400 wherein red QDs 401 are contained in bead 402 and blue QDs 403 are contained in bead 404.

[0101] One such method for incorporating QDs into microbeads involves growing the polymer bead around the QDs. A second method incorporates QDs into pre-existing microbeads.

[0102] With regard to the first option, by way of example, hexadecylamine-capped CdSe-based semiconductor nanoparticles may be treated with at least one, more preferably two or more polymerisable ligands (optionally one ligand in excess) resulting in the displacement of at least some of the hexadecylamine capping layer with the polymerisable ligand(s). The displacement of the capping layer with the polymerisable ligand(s) may be accomplished by selecting a polymerisable ligand or ligands with structures similar to that of trioctylphosphine oxide (TOPO), which is a ligand with a known and very high affinity for CdSe-based nanoparticles. It will be appreciated that this basic methodology may be applied to other nanoparticle/ligand pairs to achieve a similar effect. That is, for any particular type of nanoparticle (material and/or size), it is possible to select one or more appropriate polymerisable surface binding ligands by choosing polymerisable ligands comprising a structural motif which is analogous in some way (e.g. has a similar physical and/or chemical structure) to the structure of a known surface binding ligand. Once the nanoparticles have been surface-modified in this way, they may then be added to a monomer component of a number of microscale polymerisation reactions to form a variety of QD-containing resins and beads. Another option is the polymerisation of one or more polymerisable monomers from which the optically transparent medium is to be formed in the presence of at least a portion of the semiconductor nanoparticles to be incorporated into the optically transparent medium. The resulting materials incorporate the QDs covalently and appear highly coloured even after prolonged periods of Soxhlet extraction.

[0103] Examples of polymerisation methods that may be used to construct QD-containing beads include, but are not restricted to, suspension, dispersion, emulsion, living, anionic, cationic, RAFT, ATRP, bulk, ring-closing metathesis and ring-opening metathesis. Initiation of the polymerisation reaction may be induced by any suitable method that causes the monomers to react with one another, such as by the use of free radicals, light, ultrasound, cations, anions, or heat. A preferred method is suspension polymerisation, involving thermal curing of one or more polymerisable monomers from which the optically transparent medium is to be formed. Said polymerisable monomers preferably comprise methyl (meth)acrylate, ethylene glycol dimethacrylate and vinyl acetate. This combination of monomers has been shown to exhibit excellent compatibility with existing commercially available LED encapsulants and has been used to fabricate a light emitting device exhibiting significantly improved performance compared to a device prepared using essentially prior art methodology. Other preferred polymerisable monomers are epoxy or polyepoxide monomers, which may be polymerised using any appropriate mechanism, such as curing with ultraviolet irradiation.

[0104] QD-containing microbeads may be produced by dispersing a population of QDs within a polymer matrix, curing the polymer and then grinding the resulting cured material. This is particularly suitable for use with polymers that become relatively hard and brittle after curing, such as many common epoxy or polyepoxide polymers (e.g. Optocast™ 3553 from Electronic Materials, Inc., USA).

[0105] QD-containing beads may be generated simply by adding QDs to the mixture of reagents used to construct the beads. In some instances, nascent QDs will be used as isolated from the reaction employed for their synthesis, and are thus generally coated with an inert outer organic ligand layer. In an alternative procedure, a ligand exchange process may be carried out prior to the bead-forming reaction. Here, one or more chemically reactive ligands (for example a ligand for the QDs that also contains a polymerizable moiety) are added in excess to a solution of nascent QDs coated in an inert outer organic layer. After an appropriate incubation time the QDs are isolated, for example by precipitation and subsequent centrifugation, washed and then incorporated into the mixture of reagents used in the bead forming reaction/process.

[0106] Both QD incorporation strategies will result in statistically random incorporation of the QDs into the beads and thus the polymerisation reaction will result in beads containing statistically similar amounts of the QDs. It will be obvious to one skilled in the art that bead size may be controlled by the choice of polymerisation reaction used to construct the beads, and additionally once a polymerisation method has been selected bead size may also be controlled by selecting appropriate reaction conditions, e.g. by stirring the reaction mixture more quickly in a suspension polymerisation reaction to generate smaller beads. Moreover, the shape of the beads may be readily controlled by choice of procedure in conjunction with whether or not the reaction is carried out in a mould. The composition of the beads may be altered by changing the composition of the monomer mixture from which the beads are constructed. Similarly, the beads may also be cross-linked with varying amounts of one or more cross-linking agents (e.g. divinyl benzene). If beads are constructed with a high degree of cross-linking, e.g. greater than 5 mol % cross-linker, it may be desirable to incorporate a porogen (e.g. toluene or cyclohexane) during the bead-forming reaction. The use of a porogen in such a way leaves permanent pores within the matrix constituting each bead. These pores may be sufficiently large to allow the ingress of QDs into the bead.

[0107] QDs may also be incorporated in beads using reverse emulsion-based techniques. The QDs may be mixed with precursor(s) to the optically transparent coating material and then introduced into a stable reverse emulsion containing, for example, an organic solvent and a suitable salt. Following agitation the precursors form microbeads encompassing the QDs, which may then be collected using any appropriate method, such as centrifugation. If desired, one or more additional surface layers or shells of the same or a different optically transparent material may be added prior to isolation of the QD-containing beads by addition of further quantities of the requisite shell layer precursor material(s).

[0108] In respect of the second option for incorporating QDs into beads, the QDs may be immobilised in polymer beads through physical entrapment. For example, a solution of QDs in a suitable solvent (e.g. an organic solvent) may be incubated with a sample of polymer beads. Removal of the solvent using any appropriate method results in the QDs becoming immobilised within the matrix of the polymer beads. The QDs remain immobilised in the beads unless the sample is resuspended in a solvent (e.g. organic solvent) in which the QDs are freely soluble. Optionally, at this stage the outside of the beads may be sealed. Alternatively, at least a portion of the QDs may be physically attached to prefabricated polymer beads. Said attachment may be achieved by immobilisation of the portion of the semiconductor nanoparticles within the polymer matrix of the prefabricated polymeric beads or by chemical, covalent, ionic, or physical connection between the portion of semiconductor nanoparticles and the prefabricated polymeric beads. Examples of prefabricated polymeric beads comprise polystyrene, polydivinyl benzene and a polythiol.

[0109] QDs may be irreversibly incorporated into prefabricated beads in a number of ways, e.g. chemical, covalent, ionic, physical (e.g. by entrapment) or any other form of interaction. If prefabricated beads are to be used for the incorporation of QDs, the solvent-accessible surfaces of the bead may be chemically inert (e.g. polystyrene) or alternatively they may be chemically reactive/functionalised (e.g. Merrifield's Resin). The chemical functionality may be introduced during the construction of the bead, for example by the incorporation of a chemically functionalised monomer, or, alternatively, chemical functionality may be introduced in a post bead construction treatment, for example by conducting a chloromethylation reaction. Additionally, chemical functionality may be introduced by a post-bead construction polymeric graft or other similar process whereby chemically reactive polymer(s) are attached to the outer layers/accessible surfaces of the bead. More than one such post-construction derivation process may be carried out to introduce chemical functionality onto/into the bead.

[0110] As with QD incorporation into beads during the bead forming reaction, i.e. the first option described above, the pre-fabricated beads may be of any shape, size and composition, may have any degree of cross-linker and may contain permanent pores if constructed in the presence of a porogen. QDs may be imbibed into the beads by incubating a solution of QDs in an organic solvent and adding this solvent to the beads. The solvent must be capable of wetting the beads and, in the case of lightly cross-linked beads, preferably 0-10% cross-linked and most preferably 0-2% cross-linked, the solvent should cause the polymer matrix to swell in addition to solvating the QDs. Once the QD-containing solvent has been incubated with the beads, it is removed, for example by heating the mixture and causing the solvent to evaporate, and the QDs become embedded in the polymer matrix constituting the bead or alternatively by the addition of a second solvent in which the QDs are not readily soluble but which mixes with the first solvent causing the QDs to precipitate within the polymer matrix constituting the beads. Immobilisation may be reversible if the bead is not chemically reactive, or else if the bead is chemically reactive the QDs may be held permanently within the polymer matrix by chemical, covalent, ionic, or any other form of interaction.

[0111] Optically transparent media that are sol-gels and glasses, intended to incorporate QDs, may be formed in an analogous fashion to the method used to incorporate QDs into beads during the bead-forming process as described above. For example, a single type of QD (e.g. one colour) may be added to the reaction mixture used to produce the sol-gel or glass. Alternatively, two or more types of QD (e.g. two or more colours) may be added to the reaction mixture used to produce the sol-gel or glass. The sol-gels and glasses produced by these procedures may have any shape, morphology or 3-dimensional structure. For example, the particles may be spherical, disc-like, rod-like, ovoid, cubic, rectangular, or any of many other possible configurations.

[0112] By incorporating QDs into beads in the presence of materials that act as stability-enhancing additives, and optionally providing the beads with a protective surface coating, migration of deleterious species, such as moisture, oxygen and/or free radicals, is eliminated or at least reduced, with the result of enhancing the physical, chemical and/or photo-stability of the semiconductor nanoparticles.

[0113] An additive may be combined with “bare” semiconductor nanoparticles and precursors at the initial stages of the production process of the beads. Alternatively, or additionally, an additive may be added after the semiconductor nanoparticles have been entrapped within the beads.

[0114] The additives that may be added singly or in any desirable combination during the bead formation process may be grouped according to their intended function, as follows:

[0115] Mechanical sealing: fumed silica (e.g. Cab-O-Sil™), ZnO, TiO2, ZrO, Mg stearate, Zn stearate, all used as a filler to provide mechanical sealing and/or reduce porosity.

[0116] Capping agents: tetradecyl phosphonic acid (TDPA), oleic acid, stearic acid, polyunsaturated fatty acids, sorbic acid, Zn methacrylate, Mg stearate, Zn stearate, isopropyl myristate. Some of these have multiple functionalities and may act as capping agents, free radical scavengers and/or reducing agents.

[0117] Reducing agents: ascorbic acid palmitate, alpha tocopherol (vitamin E), octane thiol, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), gallate esters (propyl, lauryl, octyl, etc.), a metabisulfite (e.g. the sodium or potassium salt).

[0118] Free radical scavengers: benzophenones.

[0119] Hydride reactive agents: 1,4-butanediol, 2-hydroxyethyl methacrylate, allyl methacrylate, 1,6-heptadiene-4-ol, 1,7-octadiene, and 1,4-butadiene.

[0120] The selection of the additive(s) for a particular application will depend upon the nature of the semiconductor nanoparticle material (e.g. how sensitive the nanoparticle material is to physical, chemical and/or photo-induced degradation), the nature of the primary matrix material (e.g. how porous it is to potentially deleterious species, such as free-radicals, oxygen, moisture, etc.), the intended function of the final material or device which will contain the primary particles (e.g. the operating conditions of the material or device), and the process conditions required to fabricate the said final material or device. With this in mind, one or more appropriate additives may be selected from the above five lists to suit any desirable semiconductor nanoparticle application.

[0121] Once the QDs are incorporated into the beads, the formed QD-beads may be further coated with a suitable material to provide each bead with a protective barrier to prevent the passage or diffusion of potentially deleterious species, e.g. oxygen, moisture or free radicals from the external environment, through the bead material to the semiconductor nanoparticles. As a result, the semiconductor nanoparticles are less sensitive to their surrounding environment and the various processing conditions typically required to utilise the nanoparticles in applications such as the fabrication of LEDs.

[0122] The coating is preferably a barrier to the passage of oxygen or any type of oxidising agent through the bead material. The coating may be a barrier to the passage of free radical species and/or is preferably a moisture barrier so that moisture in the environment surrounding the beads cannot contact the semiconductor nanoparticles incorporated within the beads.

[0123] The coating may provide a layer of material on a surface of the bead of any desirable thickness, provided it affords the required level of protection. The surface layer coating may be around 1 to 10 nm thick, up to around 400 to 500 nm thick, or more. Preferred layer thicknesses are in the range 1 nm to 200 nm, more preferably around 5 nm to 100 nm.

[0124] The coating may comprise an inorganic material, such as a dielectric (insulator), a metal oxide, a metal nitride or a silica-based material (e.g. a glass).

[0125] The metal oxide may be a single metal oxide (i.e. oxide ions combined with a single type of metal ion, e.g. Al.sub.2O.sub.3), or may be a mixed metal oxide (i.e. oxide ions combined with two or more types of metal ion, e.g. SrTiO.sub.3). The metal ion(s) of the (mixed) metal oxide may be selected from any suitable group of the periodic table, such as group 2, 13, 14 or 15, or may be a transition metal, d-block metal, or lanthanide metal.

[0126] Preferred metal oxides are selected from the group consisting of Al.sub.2O.sub.3, B.sub.2O.sub.3, Co.sub.2O.sub.3, Cr.sub.2O.sub.3, CuO, Fe.sub.2O.sub.3, Ga.sub.2O.sub.3, HfO.sub.2, In.sub.2O.sub.3, MgO, Nb.sub.2O.sub.5, NiO, SiO.sub.2, SnO.sub.2, Ta.sub.2O.sub.5, TiO.sub.2, ZrO.sub.2, Sc.sub.2O.sub.3, Y.sub.2O.sub.3, GeO.sub.2, La.sub.2O.sub.3, CeO.sub.2, PrO.sub.x (x=appropriate integer), Nd.sub.2O.sub.3, Sm.sub.2O.sub.3, EuO.sub.y (y=appropriate integer), Gd.sub.2O.sub.3, Dy.sub.2O.sub.3, Ho.sub.2O.sub.3, Er.sub.2O.sub.3, Tm.sub.2O.sub.3, Yb.sub.2O.sub.3, Lu.sub.2O.sub.3, SrTiO.sub.3, BaTiO.sub.3, PbTiO.sub.3, PbZrO.sub.3, Bi.sub.mTi.sub.nO (m, n=appropriate integer), Bi.sub.aSi.sub.bO (a, b=appropriate integer), SrTa.sub.2O.sub.6, SrBi.sub.2Ta.sub.2O.sub.9, YScO.sub.3, LaAlO.sub.3, NdAlO.sub.3, GdScO.sub.3, LaScO.sub.3, LaLuO.sub.3, Er.sub.3Ga.sub.5O.sub.13.

[0127] Preferred metal nitrides may be selected from the group consisting of BN, AlN, GaN, InN, Zr.sub.3N.sub.4, Cu.sub.2N, Hf.sub.3N.sub.4, SiNc (c=appropriate integer), TiN, Ta.sub.3N.sub.5, Ti—Si—N, Ti—Al—N, TaN, NbN, MoN, WNd (d=appropriate integer), WNeCf (e, f=appropriate integer).

[0128] The inorganic coating may comprise silica in any appropriate crystalline form.

[0129] The coating may incorporate an inorganic material in combination with an organic or polymeric material, e.g. an inorganic/polymer hybrid, such as a silica-acrylate hybrid material.

[0130] The coating may comprise a polymeric material which may be a saturated or unsaturated hydrocarbon polymer, or may incorporate one or more heteroatoms (e.g. O, S, N, halo) or heteroatom-containing functional groups (e.g. carbonyl, cyano, ether, epoxide, amide, etc.).

[0131] Examples of preferred polymeric coating materials include acrylate polymers (e.g. polymethyl(meth)acrylate, polybutylmethacrylate, polyoctylmethacrylate, alkylcyanoacryaltes, polyethyleneglycol dimethacrylate, polyvinylacetate, etc.), epoxides (e.g. EPOTEK 301 A and B Thermal curing epoxy, EPOTEK OG112-4 single-pot UV curing epoxy, or EX0135 A and B Thermal curing epoxy), polyamides, polyimides, polyesters, polycarbonates, polythioethers, polyacrylonitryls, polydienes, polystyrene polybutadiene copolymers (Kratons), pyrelenes, poly-para-xylylene (parylenes), polyetheretherketone (PEEK), polyvinylidene fluoride (PVDF), polydivinyl benzene, polyethylene, polypropylene, polyethylene terephthalate (PET), polyisobutylene (butyl rubber), polyisoprene, and cellulose derivatives (methyl cellulose, ethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropylmethylcellulose phthalate, nitrocellulose), and combinations thereof.

Device Architectures

[0132] The QD LED device architectures described herein serve only as examples, but the invention is not restricted to these. Any suitable device architecture incorporating QDs to emit at wavelengths to promote plant growth and development may be employed.

[0133] QD LED devices may be fabricated using the structure of the QD LED chip shown in FIG. 5. Device 500 includes an LED assembly 501 mounted in a housing 502. The LED assembly includes a solid-state LED material 503, which is generally a UV or blue-emitting LED material, such as YAG. LED material 503 is contained within an LED package 504 and protected by an LED encapsulant material 505. An example of an LED encapsulant material 505 is silicone, although any encapsulant material can be used. QD-containing resin 506 is disposed on top encapsulant material 505. Exemplary resins, as described above, include polymer resins containing QDs dispersed therein. The QDs can be embedded in beads or can be “naked.” In other embodiments, the QD-containing resin 506 may be disposed directly on LED material 503. In other words, the LED encapsulant material and the QD-resin may be a single layer, rather than two layers as illustrated in FIG. 5. The QD-containing resin 506 is protected by a thin transparent material 507, such as glass, which can be sealed in place by adhesive 508, such as epoxy.

[0134] The embodiment illustrated in FIG. 5 can be made as follows: In a nitrogen-filled glove box, the LED chip is first covered with a blank silicone resin to protect the chip from any damage from the acrylate resin in which the QDs are embedded. The silicone resin is cured on a hotplate. The LED cup is then filled with the QD-embedded acrylate resin, which is cured under UV light. The LED is then encapsulated using a thin layer of gas barrier, attached using a UV curing epoxy resin (e.g. Optocast™), and cured under UV light. A UV or blue solid state LED is fitted to the bottom of the LED chip to illuminate the QDs.

[0135] As an example of embodiments wherein QDs are contained in beads, silicone resin can be mixed with a small amount of a Pt catalyst. Then the QD beads are added to the silicone mixture and the mixture is transferred to LED packages. The packages are cured under a nitrogen atmosphere, then encapsulated under a thin layer of gas barrier, attached using a UV curing epoxy resin, as described above. The LEDs are cured under UV light.

[0136] FIG. 6 illustrates a QD LED device having a remote phosphor architecture, i.e., an architecture in which the QD material is outside the LED package. As illustrated in FIG. 6, a polymer film containing red QDs 601 is disposed on a substrate to provide a QD phosphor sheet 602, which is situated remote from LED package 603. As above, QDs 601 may be in beads or may be “naked.” QDs 601 absorb blue light 604 produced by the LED in package 603 (in the case that package 603 contains a blue LED). Light emanating from the phosphor sheet 602 is a mixture of red light 605 emitted by the QDs 601 and blue light 606 transmitted through phosphor sheet 602.

[0137] FIG. 7 illustrates an embodiment of how the remote QD phosphor sheet used in the architecture illustrated in FIG. 6 is prepared. QD ink is prepared by mixing a known quantity of QD solution with appropriate solvents and polymerisable materials. A PET sheet (or other suitable substrate) 701 of predetermined dimensions is cleaned with an air gun to remove dust particles and fitted with two Teflon spacers 702, ensuring that a constant gap is left between the spacers. Under a nitrogen atmosphere, the ink is drop 703 casted on the region between the spacers of the substrate and the ink is distributed uniformly between the spacers. The substrate is placed on a preheated hotplate to remove any solvent, then allowed to dry. The encapsulated QD phosphor is illuminate from behind using a series of UV or blue solid state LEDs. These excite the QDs in the phosphor layer, which emit at a specific wavelength that is selected to optimise photosynthetic growth, while some UV or blue light from the SS LEDs is still transmitted through the glass. The emission of the QD phosphor and the UV or blue LEDs may be tuned to match the absorption spectra of chlorophyll and the accessory pigments in specific organisms, thus optimising photosynthesis.

[0138] FIG. 8 illustrates an embodiment wherein a solid state LED 801 is located at the side of the QD phosphor sheet 802. The remote QD phosphor sheet 802 is prepared as described above (see FIG. 7). In the embodiment illustrated in FIG. 8, QD phosphor sheet 802 includes red-emitting 803 and blue-emitting 804 QDs. The encapsulated QD phosphor sheet 802 is illuminated from the side by a solid state UV or blue-emitting LED 801. The down-converted red 805 and blue 806 emission of the QDs is emitted perpendicular to the incident LED emission.

[0139] FIG. 9 illustrates an embodiment wherein water-soluble QD microbeads 901 are mixed into an agar preparation 902, which is used as a growth culture for photosynthetic bacteria 903. The QD-agar preparation is placed in a transparent container and illuminated externally using UV or blue LED light (904). The QDs in the agar down-convert the emission from the LED, while some of the primary LED light is still transmitted through the culture medium.

[0140] FIG. 10 shows the overlap of emission from a QD LED chip with the absorbance wavelengths of chlorophyll a and chlorophyll b. A QD LED chip having a blue solid state LED as the primary light source and adapted with a red-emitting QD/silicone resin was fabricated according to the following procedure: Silicone resin was mixed with a small amount of a Pt catalyst, then red InP/ZnS QD beads (20 ODs per 10 mmol solution in toluene) were added and the mixture was transferred to an LED case. The LED was cured under a nitrogen atmosphere. The QD LED was illuminated by a 22 mW blue solid state LED. Blue emission was seen around 455 nm from the solid state LED. The red QD material emitted with PL.sub.max=648 nm and FWHM=59 nm. The relative intensity of the blue (LED) to red (QD phosphor) light was 1:0.45.

[0141] A QD LED chip comprising a blue solid state LED as the primary light source and a red quantum dot silicone resin was fabricated according to the following procedure: Red InP/ZnS QD beads were diluted to 10 ODs/10 mmol in toluene. Silicone resin was mixed with a small amount of a Pt catalyst, then the QD beads were added and the mixture is transferred to an LED case. The LED was cured under a nitrogen atmosphere. The QD LED was illuminated by a 22 mW blue solid state LED. Blue emission was seen around 455 nm from the solid state LED. The red QD material emitted with PLmax=646 nm and FWHM=60 nm. The relative intensity of the blue (LED) to red (QD phosphor) light was 1:0.27.

[0142] A QD LED chip comprising a blue solid state LED as the primary light source and a red quantum dot silicone resin, with an emission spectrum that is well matched to the absorption spectrum of chlorophyll b, was fabricated using CdSe/CdS/CdZnS/ZnS core-multishell QDs illuminated by a blue solid state LED backlight emitting at 446 nm. The QD PLmax of 625 nm is well-matched to the red absorption maximum of chlorophyll b, with a narrow FWHM of 35 nm, as shown in FIG. 11. The relative blue and red peak intensities may be matched to those of the absorption spectrum of chlorophyll b by altering the QD concentration.

Lighting Arrangements

[0143] Because QD LED chips can vary from very small LED cups to large printed QD LED phosphor sheets encased in glass, many different lighting arrangements are possible. The QD LED chips described herein are suitable for both small, light, portable devices and large permanent fixtures. For example, an LED backlight combined with a QD phosphor sheet, as illustrated in FIG. 6, can be used to make a portable device that can be used to promote grass growth for reseeding areas of turf. The device emits both blue and red light. Using a portable, retractable lighting fixture, the light may be focussed on small areas to accelerate grass growth and may be quickly and easily transported.

[0144] FIG. 12 illustrates an arched or caged framework fitted QD LEDs 1201, as shown in FIG. 3 or 4, in which red and blue QDs are illuminated by a UV solid state LED. One or more plants 1202 may be placed inside the framework, which provides illumination from many directions to not only promote photosynthesis, but also uniform growth. The framework may be constructed from any suitable material, though a reflective material may be advantageous.

[0145] FIG. 13 illustrates a lighting arrangement wherein a red QD phosphor is printed on a substrate 1302 with finger-like projections that is immersed in a photobioreactor 1303. The QD phosphor is illuminated, either from above and/or below, with blue solid state LEDs. Secondary emission from the QD phosphor is projected into the photobioreactor. Alternatively (or in additionally), the photobioreactor itself can be fabricated using a transparent material printed with red QD ink. When the photobioreactor is illuminated from outside the photobioreactor by blue (or UV) solid state LEDs, both blue (from the LED) and red (from the QD phosphor) light is emitted into the photobioreactor.

[0146] Although particular embodiments of the invention have been shown and described, they are not intended to limit what this patent covers. One skilled in the art will understand that that various changes and modifications may be made without departing from the scope of the present invention as literally and equivalently covered by the following claims.