Quantum Dots Stabilized With A Metal Thiol Polymer

Abstract

A composition of matter comprises a plurality of quantum dots and a metal thiol polymer that acts to stabilize the quantum dots. In certain embodiments, the metal thiol polymer is a zinc thiol polymer. The zinc thiol polymer may be a zinc alkanethiolate. The zinc alkanethiolate may be zinc dodecanethiolate (Zn-DDT). A composition comprising a plurality of quantum dots and a metal thiol polymer may be formulated with one or more additional polymers as a quantum dot-containing bead or as a quantum dot-containing composite materiale.g., a multilayer film.

Claims

1. A method for preparing quantum dot beads comprising: preparing a first solution comprising a monomer, a cross-linker, and a polymerization photoinitiator; dispersing quantum dots in the first solution to produce a second solution; mixing the second solution with zinc thiol polymer to produce a third solution; adding the third solution to an aqueous solution of polyvinyl alcohol and a surfactant under continuous stirring to form a fourth solution; and exposing the fourth solution to ultraviolet light to form quantum dot beads.

2. The method of claim 1, wherein the zinc thiol polymer is a zinc alkanethiolate.

3. The method of claim 2, wherein the zinc alkanethiolate is zinc dodecanethiolate (Zn-DDT).

4. Quantum dot beads prepared according to the method of claim 1.

5. A method for preparing zinc dodecanethiolate (Zn-DDT) polymer comprising: adding a zinc salt to a synthetic heat transfer fluid to form a first solution; annealing the first solution under an inert atmosphere; adding dodecanethiol to the first solution in an amount relative to the amount of the anhydrous zinc salt used to provide a second solution; annealing the second solution; cooling the second solution; and adding a non-solvent to precipitate Zn-DDT polymer.

6. The method of claim 5, further comprising: dissolving the precipitated Zn-DDT in a non-polar solvent to produce a third solution and insoluble material; and drying the insoluble material.

7. The method of claim 5, further comprising: drying the precipitated Zn-DDT polymer to produce a powder consisting essentially of Zn-DDT polymer.

8. The method of claim 5, wherein adding dodecanethiol to the first solution in an amount relative to the amount of anhydrous zinc salt used to provide a second solution comprises adding dodecanethiol in an amount such that the second solution has a Zn-to-S ratio of about 1:0.9.

9. The method of claim 5, wherein the zinc salt is zinc acetate.

10. The method of claim 5, wherein the zinc salt is zinc dimethacrylate.

11. A method for preparing quantum dot beads comprising: preparing a first solution comprising a monomer, a cross-linker, and a polymerization photoinitiator; dispersing quantum dots in the first solution to produce a second solution; mixing the second solution with a Zn-DDT polymer produced according to the method of claim 5 to produce a third solution; adding the third solution to an aqueous solution of polyvinyl alcohol and a surfactant under continuous stirring to form a fourth solution; and exposing the fourth solution to ultraviolet light to form quantum dot beads.

12. A composite material comprising: quantum dots embedded in a resin comprising a Zn-DDT polymer produced according to the method of claim 5, wherein the quantum dots embedded in the resin comprising the Zn-DDT polymer are in the form of a ground composite powder.

13. A composition of matter comprising: a plurality of quantum dots; and a Zn-DDT polymer produced according to the method of claim 5.

14. The composition recited in claim 13, further comprising a resin material different from the Zn-DDT polymer.

15. The composition recited in claim 13 formulated as a dry powder.

16. The composition recited in claim 13 formulated as a solution.

Description

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

[0032] FIG. 1 is a contemplated structure of one particular zinc thiol polymer.

[0033] FIG. 2 is a schematic diagram of the synthesis of small QD beads with Zn-DDT by a suspension/emulsion polymerization according to the invention.

[0034] FIG. 3A shows the backlight unit (BLU) spectrum and FIG. 3B shows the resulting color gamut simulation for a particular film according to the invention.

DETAILED DESCRIPTION OF THE INVENTION

[0035] As discussed above, quantum dots with a thin or incomplete inorganic shell or quantum dots with sufficiently high purity (those lacking a sufficiently large excess of stabilizing ligands) exhibit an unacceptable loss of luminescence intensity over time when photo-excited. This has been a significant obstacle to their incorporation into commercial applications such as use as a color conversion material in display and lighting applications.

[0036] It has been discovered that the addition of a zinc thiol polymer to quantum dot-containing beads or a composite materials unexpectedly increases the QY of the quantum dot beads or composite in comparison to quantum dots or composites synthesized without a metal thiol polymer. Moreover, quantum dot composites made with the inclusion of a metal thiol polymer are more thermally stable.

[0037] A zinc thiol polymer is relatively easy to make and incorporate into quantum dots. One particular method of the prior art is described by Su Chen, Chunhui Hu, Li Chen and Nanping Xu, in Chem. Commun., 2007, 1919-1921.

[0038] Very little or no loss in the solution quantum dot quantum yield (QY) was observed when a zinc thiol polymer was included in the preparation of quantum dot beads and composites. Incorporation of the polymer additive into the QD-containing resin helps to stabilize the photo-luminescence (PL) QYi.e., there was less loss of PL QY in beads and composites having a metal thiol polymer incorporated therein.

[0039] The present invention involves the enhancement of quantum dot stability to environmental factors and processing conditions by inclusion into quantum dot-(metal-thiol polymer) beads and composite materials and the subsequent use of stabilized quantum dots in efficient and stable color down-conversion applications.

[0040] The stability enhancement of Zn-dodecanethiol polymer on quantum dots suggested that, if that polymer were used as a host material for the quantum dots in the inner phase of a two-phase resin system, a beneficial improvement in stability and performance could be realized.

[0041] A quantum dot-(metal-thiol polymer) composite material was developed and combined with various outer phase type resins and the performance and lifetimes of the quantum dots in films evaluated. The use of the metal-thiol polymer as the host material proved beneficial for maintaining external quantum efficiency (EQE) of the film, as well as edge ingress stability under light stress and dark ingress stability under thermal stress.

[0042] The present invention also has application in the use of metal-thiol coordination polymers as hosts for quantum dots to improve the maintenance of the quantum yield (QY) of the quantum dots during processing into an application format, in an exemplary case (but not limited to) a film made from an aggressive polar polymer which would ordinarily be expected to degrade quantum dot performance.

[0043] Zn-DDT polymer may be synthesized by a variety of techniques and different alkane chain lengths of the ligands may be used. However, each synthesis path produces material that has varying properties. The synthesis pathway that produces the most useful material known as of the filing date hereof is as described below. Ratios of each precursor may be varied to produce polymer with different properties:

[0044] Anhydrous zinc acetate was degassed at 100 C. in THERMINOL 66 [SOLUTIA INC., 575 MARYVILLE CENTRE DRIVE, ST. LOUIS, MISSOURI 63141], a synthetic heat transfer fluid comprising a modified terphenyl, for 1 hr. The solution was placed under an inert N2 atmosphere and raised to a temperature of 230 C. and annealed for 1 hr. After one hour, dodecanethiol was added in an amount relative to the amount of anhydrous zinc acetate used (Zn-to-S ratio of 1:0.9). The solution was left to anneal for one hour and was then cooled to 70 C. The solution was precipitated at 70 C. with a volume of acetone equal to the amount of THERMINOL 66 used.

[0045] The Zn-DDT polymer precipitated out as a thick, waxy dilatant. This material showed shear thickening properties reminiscent of corn starch in water. The produced material was washed with acetone and then dissolved into toluene at 90 C. for 30 minutes. The toluene solution produced was colorless and did not precipitate upon cooling to room temperature. Not all of the material was soluble in toluene. The insoluble material was then dried using a vacuum and subsequently ground into a fine powder.

[0046] For the material that was soluble in toluene, the toluene solution was precipitated with two volume equivalents of acetone. The precipitated material was then centrifuged and sonicated in acetone in order to remove toluene. Toluene seemed to have an affinity to this material. The precipitate was then dissolved into cyclohexane and re-precipitated with acetone. This final precipitate was then dried under vacuum and ground using a pestle and mortar. The drying and crushing process was repeated three times, producing a free-flowing, white solid.

[0047] Both the insoluble and soluble part were analyzed and tested in beads. In general, the insoluble fraction contains crystalline material and dispenses well in conventional bead resins (e.g., LMA/TMPTM). The soluble Zn-DDT fraction may be useful in other applications which are not detailed here.

[0048] An alternative synthetic pathway, using the precursor zinc dimethacrylate was developed to change the functionality of the Zn(DDT) polymer:

[0049] Anhydrous zinc dimethacrylate was degassed at 100 C. in THERM INOL 66 for 1 hr. The solution was then placed under an inert atmosphere (N.sub.2) and the temperature was raised to 230 C. and annealed for 1 hr. After 1 hour, dodecanethiol was added relative to the amount of anhydrous zinc dimethacrylate used (Zn-to-S ratio of 1:0.9). The solution was left to anneal for 1 hr. and was then cooled to 70 C.

[0050] The solution was precipitated at 70 C. with a volume of acetone equal to the amount of THERM INOL 66 used. This produced a very fine precipitate which was completely insoluble in any solvent previously mentioned. The precipitate was further washed with acetone to purify the end product. The washed solid was then dried under vacuum for 24 hrs. to produce a very fine, free-flowing, off-white powder.

[0051] It is contemplated that other alkanethiols including functionalized alkanethiols may have application in the present invention. For example, the DDT may have a reactive functional group on the end of the alkane chain opposite the thiol group (or, in the case of branched alkanes, at a position remote from the thiol group) which reactive functional group allows cross linking or bonding into the polymer host itself.

[0052] The application of the present invention is illustrated below in two exemplarsQD beads, and QD-containing composite materials:

Quantum Dot Beads

[0053] The synthetic procedure of making QD beads by suspension polymerization is illustrated schematically in FIG. 2.

Example 1: Preparation of Low Cross-Linked Small, Bright Red Beads Using Zn-DDT Polymer

[0054] Preparation of PVOH Solution: Aqueous polyvinyl alcohol (PVOH) solution was prepared by dissolving PVOH in deionized water and stirring overnight. Prior to bead synthesis, the PVOH solution was filtered to remove any undissolved PVOH or dust particles. 1% TWEEN 80 surfactant [CRODA AMERICAS LLC, 1209 ORANGE STREET, WILMINGTON DELAWARE 19801] was added to the 4% aqueous PVOH solution.

[0055] Preparation of Zn-DDT Resin Solution: To prepare the resin, red InPZnS-based alloyed quantum dots (13 mg/3 mL of resin) [PLmax=627 nm, FWHM=56 nm, QY (dilute, toluene)=80%] dissolved in toluene were transferred to an amber glass vial containing a stirrer bar, under an inert atmosphere. The toluene was removed under reduced pressure and continuous stirring. Once all visible traces of solvent were removed, the residue was heated to 40 C., for 45 minutes, under vacuum to remove any residual solvent. A stock solution was prepared by adding degassed lauryl methacrylate (LMA, 5.2 mL) and trimethyloyl propane methacrylate cross-linker (TMPTM, 0.8 mL) to the photoinitiator mixture IRGACURE 819 initiator (40 mg, 0.74 wt. %) and IRGACURE 651 (40 mg, 0.74%) [BASF SE COMPANY, CARL-BOSCH-STR. 38 LUDWIGSHAFEN GERMANY 67056]. The mixture was stirred in the dark to ensure complete dissolution. The required amount of the stock solution was then added to the dry QD residue, under an inert atmosphere and dark conditions, to form a resin solution. The resin solution was stirred overnight to ensure complete dispersion of the QDs. The next day, the required amount of Zn-DDT powder was degassed for 1 hr. then the QD resin solution was added into it and stirred overnight.

[0056] Preparation of QD Beads with Zn-DDT: In a 20 mL glass vial, PVOH/Tween80 solution (4/1 wt. %, 10 mL) was degassed for a few hours under a vacuum/nitrogen cycle. For each experiment, 1 g resin solution was injected into an aqueous solution of PVOH/Tween80, under continuous stirring at 800 rpm, under N.sub.2. The solution was allowed to equilibrate for 15 minutes, then cured for 10 minutes under a UV LED kit to form QD beads. The QD beads were subsequently washed with water and acetonitrile, then dried under vacuum. Characterization data is presented in Table 1, along with the QY after heating in vacuum for over 48 hrs.

TABLE-US-00001 TABLE 1 Low cross linked beads, 1/0.154 LMA/TMPTM, as typically used in bead films. Sample Zn-DDT QY % after ID Concentration % QY % PL FWHM heating at 80 C. B361 0 48 639 58 27 B362 2.5 60 640 55 n/a B363 5 62 639 53 45 B364 7.5 67 637 54 n/a B365 10 69 634 53 58 B380 12.5 74 636 54 n/a B381 15 73 637 54 58

[0057] The data in Table 1 illustrates that the QY of the beads increased with increasing the Zn-DDT concentration. Additionally, the FWHM was reduced and the amount of red shift of the dots in the beads was reduced. The data in Table 1 also illustrates that beads made with more than about 10% of Zn-DDT polymer retain a significantly higher proportion of the initial QY on heating.

[0058] As shown in FIG. 3, the incorporation of Zn-DDT polymer into beads occurs as beads with higher Zn-DDT loading (sample IDs B364-365) settled on the bottom of the vial. Whereas beads with no or less Zn-DDT float (sample IDs B361 and B362). Interestingly, it has been found that beads with 5% Zn-DDT will make a stable colloidal latex solution.

Example 2: Preparation of Higher Cross-Linked Bright Red Beads Using Zn-DDT Polymer

[0059] A similar procedure to Example 1 was followed, except using TWEEN 80 surfactant (3 wt. %) [CRODA AMERICAS LLC, 1209 ORANGE STREET, WILMINGTON DELAWARE 19801], a 1:0.5 ratio of LMA:TMPTM and 1 wt. % of IRGACURE 819 for the resin solution preparation. 3 mL of the Zn-DDT QD resin solution was injected into a deoxygenated PVOH solution in a 250 mL tornedo reaction vessel. The equilibrium time was 5 minutes and the curing time 10 minutes at 800 RPM. The characterization data is shown in Table Y.

TABLE-US-00002 TABLE 2 Details of higher cross-linked beads before and after ALD coating with Al.sub.2O.sub.3. Zn-DDT Initial QY concentration QY after ALD After:before Bead ID (%) (%) (%) ratio B199 41 0 15 0.37 B200 55 10 44 0.80 B201 62 20 56 0.90

[0060] The data in Table 2 demonstrates that the QY of higher cross-linked beads has increased by increasing the Zn-DDT concentration. Table 2 also illustrates that the QY of the beads with 20% Zn-DDT retained about 90% of the initial QY after ALD coating with Al.sub.2O.sub.3. For the beads with no Zn-DDT only 37% of the initial QY was retained after ALD coating.

QD-Containing Composite Materials

[0061] Preparation of a quantum dot-(metal-thiol polymer) composite material may be achieved by mixing the two components, quantum dots and metal-thiol polymer, as toluene solutions followed by removal of the toluene by vacuum distillation. Additionally, a scattering agent (to aid blue light absorption and light extraction) may be added. An example of the preparation of a composite using Zn-dodecanethiol polymer is given in Example 3. In this case, the metal-thiol polymer used was Zn-dodecanethiol polymer which was prepared following a literature method (S. Chen, C. Hu, L. Chen and N. Xu, Chem. Commun., 2007, 1919). Post preparation, the photo-luminescent (PL) optical properties of the ground powders were investigated by fluorescence spectroscopy using a Hamamatsu spectrometer equipped with an integrating sphere accessory. The PL peak wavelength, full width at half maximum (FWHM) of the emission peak and the photo-luminescent quantum yield (PLQY) were determined using an excitation wavelength of 450 nm. Example data is presented in Table 3.

[0062] The PLQY performance of the ground composite powders compares favorably to other solid forms such as polymerized beads for, example, where PLQY measurements are usually lower than 70% due to damage induced by the action of the free radical polymerization and the aggressive outer-phase material needed during the bead synthesis.

TABLE-US-00003 TABLE 3 Example photo-luminescent PL, FWHM and PLQY data for quantum dot-(metal-thiol polymer) composite material samples. QD Composite Material Dilute Toluene QD Specs QD Loading PLQY Measurements Sample PL FWHM PLQY (mg/g polymer) PL FWHM PLQY % Abs 1101+ (<35 m) 528 45 77 35 535 45 74 20% 1129 (>35 m) 522 45 80 35 529 44 71 21% 1116 (>35 m) 524 44 79 35 533 43 68 22% 1116 (<35 m) 524 44 79 35 528 45 72 25% 1101+ (>35 m) 528 45 77 35 536 44 74 20% 1129 (<35 m) 522 45 80 35 527 47 74 17% 1130 (<35 m) 634 53 83 8 642 57 85 19% 258A (<35 m) 631 51 78 8 635 55 68 19% 1130 (>35 m) 634 53 83 14 642 57 78 18% 1182 (<35 m) 525 43 78 35 530 44 63 11% 1183 (<35 m) 628 52 81 14 631 53 78 11%

[0063] To test the utility of these powders, a number of LEDs were prepared using small, low-power LEDs in a standard SMD 3528 package. The method of preparation for these is detailed in Example 4. After preparation, the external quantum efficiency (EQE) of the composites in the LEDs was determined by comparison with blank LEDs (i.e., LEDs without QDs) prepared using the same Optocast 3553 UV-cure epoxy resin without any composite material present and operating at a forward current of 20 mA. Given the very high absorbances of the composites in the LED, the EQEs are quite good and much better than could be achieved with dots dispersed directly into Optocast UV and/or heat-cured epoxy alone wherein they undergo significant quenching due to the negative interaction with the polar epoxy.

TABLE-US-00004 TABLE 4 Example photo-luminescent PL, FWHM and PLQY data for quantum dot-(metal-thiol polymer) composite material samples incorporated into low-power, SMD 3528, LEDs. Dilute Toluene QD Specs QD Loading Cured Optocast LEDs Sample ID PL FWHM PLQY (mg/g polymer) PL FWHM EQE % Abs 1101+ (<35 m) 528 45 77 35 544 42 43 84% 1129 (>35 m) 522 45 80 35 541 40 55 81% 1116 (>35 m) 524 44 79 35 540 42 59 70% 1116 (<35 m) 524 44 79 35 536 42 54 64% 1101+ (>35 m) 528 45 77 35 542 42 50 75% 1129 (<35 m) 522 45 80 35 538 41 48 79% 1130 (<35 m) 634 53 83 8 646 56 41 72% 258A (<35 m) 631 51 78 8 641 54 32 78% 1130 (>35 m) 634 53 83 14 644 56 57 60% 1182 (<35 m) 525 43 78 35 538 40 57 73% 1183 (<35 m) 628 52 81 14 635 54 65 47%

[0064] To further test the utility of the prepared composite powders, they were dispersed into various polar resins and luminescent films were prepared by sandwiching the resin between two pieces of barrier film and curing the resin by UV light exposure. An example of the preparation of the resin mixture and subsequent film preparation is presented in Example 5. Following preparation, the films were cut into pieces approximately 1418 mm for EQE and lifetime stress test measurements. A number of polar resins were investigated and the composite materials yielded films with relatively high EQEs in nearly all cases. Details of resins and amounts of composite materials along with film EQEs are presented in Table 5. Across a range of samples and resins, the lowest EQE achieved was 41% with most resins yielding films with EQEs of 49%.

TABLE-US-00005 TABLE 5 Composite-resin formulation details and resulting film EQEs. Mass Mass Green Red Mass Film QDs, QDs, Mass Resin, Code mg mg BaSO.sub.4 Resin mg EQE 403B 100 60 65 Epotek OG142 740 48% 404 100 60 65 Epotek OG142 500 48% 407A 100 60 65 Custom acrylate 1 500 49% 407B 100 60 65 Custom acrylate 1 500 49% 411A 110 41 65 Custom acrylate 1 500 49% 411B 110 41 65 Custom acrylate 2 500 41% 412D 110 52 65 Custom acrylate 2/ 500 47% Custom acrylate 1 (75/25 mix) 416A 110 52 65 Custom acrylate 3 600 45% 416B 110 52 65 Custom acrylate 4 600 50% 416C 110 52 65 Optocast 3553 600 46% 418A 172 98 73 Custom acrylate 3 1600 52% 425A 520 300 0 Custom acrylate 5 2400 47% 425B 541 315 0 Custom acrylate 5 2400 48% 425C 568 340 0 Custom acrylate 5 2400 49%

[0065] Some of the resins used were commercially available. However, some were prepared as custom formulations. The different resin formulations can generally be described as: [0066] custom acrylate 1: Epoxy acrylate resin with bi-functional monomer [0067] custom acrylate 2: Low glass transition temperature (T.sub.g) acrylate resin [0068] custom acrylate 3: Epoxy acrylate resin with bi-functional monomer [0069] custom acrylate 4: High T.sub.g acrylate resin [0070] custom acrylate 5: Epoxy acrylate resin with bi-functional monomer

[0071] Further illustration of the impact of the quantum dot-(metal-thiol polymer) composite material on performance maintenance can be seen in Table where it is clear that the EQEs of films using a solid QD-(metal-thiol polymer) composite is much improved compared to those using a QD in a liquid monomer inner phase. In particular, custom acrylate 2, which produces a low T.sub.g acrylate, is clearly damaging to the liquid monomer inner-phase performance producing a low EQE of 13% compared to around 40% when a more benign resin (like custom acrylate 1) is used. This is most likely due to the metal-thiol polymers ability to form super hydrophobic structures [S. Chen, C. Hu, L. Chen and N. Xu, Chem. Commun., 2007, 1919] which is very good at protecting the quantum dots from deleterious components in the outer phase resin.

TABLE-US-00006 TABLE 6 Comparison of film EQEs when dots are incorporated in metal thiol polymer composites or in a liquid monomer inner phase in the resin prior to curing. Inner Phase Outer Phase Film EQE liquid LMA/TMPTM Custom acrylate 2 13% QD-(metal-thiol polymer) composite solid Custom acrylate 2 41% liquid LMA/TMPTM Custom acrylate 1 38% QD-(metal-thiol polymer) composite solid Custom acrylate 1 49%

[0072] Further evidence of how the metal-thiol polymer helps to protect the quantum dots is provided by heat-treating the samples. Table 7 shows PLQY measurements of samples before and after heat treatment and indicates that the composites maintain PLQY performance very well compared to other types of solids with embedded quantum dots, in this case, acrylate beads.

TABLE-US-00007 TABLE 7 Comparison of QY maintenance after heat treatment of acrylate beads and Zn-thiol polymer composite solids. Initial PLQY after After:before Bead PLQY heat treatment ratio B199 acrylate polymer beads 41% 15% 0.37 QD-Zn/DDT polymer composite 79% 73% 0.92

[0073] To test the usability of the composites in liquid crystal display (LCD) BLUs as a color conversion material, the QD-(metal-thiol polymer) composite materials were dispersed into different resins and sandwich-type films were made wherein a QD-containing layer is sandwiched between two pieces of barrier film. Following fabrication, the films were tested on a blue BLU for performance in terms of luminance and white point and using liquid crystal module (LCM) transmission spectra for the red, green and blue pixels possible color gamut performance simulated. An example spectrum of a QD-(metal-thiol polymer) composite film and subsequent color gamut are reproduced in FIG. 3A and FIG. 3B, respectively. In the case of this sample film (425B), the luminance on a 550-nit BLU was 2280 nits and utilized a diffuser/BEF/DBEF optical film stack. The color gamut simulation was done using transmission spectra determined from a commercially available television receiver and, when applied to the BLU data, gave a large color gamut with overlap of 96% of the Digital Cinema Initiatives P3 (DCI-P3) standard. The BLU white point (x,y) was 0.267, 0.238 which gave a desired white point of 0.290, 0.296 after transmission spectra were applied.

[0074] Further to BLU performance data, the films were also cut into smaller pieces (approximately 19 mm14 mm) and subjected to a number of different lifetime stress tests designed to test the maintenance of performance of the film under accelerated use conditions. In the real-world application the film would ordinarily be exposed to approximately 3-10 mW/cm.sup.2 of blue light irradiance within the BLU. As such, the films were stress tested with irradiances and humidities of 2.4 mW/cm.sup.2 at room temperature (real time test) and 106 mW/cm.sup.2 at 60 C./90% relative humidity (accelerated test). Additionally, they were subjected to a dark test at 60 C./90% relative humidity (RH).

[0075] In all tests, the films maintained good performance, evidencing no degradation in performance in the real-time test over the course of 2500 hrs. of testing. At 60 C./90% RH conditions, the films also showed relatively good maintenance of performance, maintaining over 80% relative performance when exposed to 106 mW/cm.sup.2 blue light stress and over 90% for green-emitting quantum dots and over 70% for red-emitting quantum dots when stressed in the dark. Importantly, in the dark test, there was no visual sign of edge ingress which has proven to be a problem in other systems.

Example 3. Preparation of Quantum Dot-(Metal-Thiol Polymer) Composite Material

[0076] Two milliliters of a toluene solution of green-emitting quantum dots (heavy metal-free semiconductor nanoparticles) at a concentration of 35 mg/mL were added to 14 mL of glacial acetic acid. The resulting precipitate was isolated by centrifugation and the supernatant discarded. The solid collected was rinsed with acetonitrile and then dissolved in n-hexane and centrifuged. Any remaining undissolved solids were discarded and the hexane solution was transferred to a separating funnel. Acetonitrile (15 mL) was added and the funnel shaken. After phase separation, the polar layer was discarded. This extraction process was repeated twice more to yield a coating on the separating funnel glass and two colorless liquid phases, which were discarded. The coating was rinsed once more with acetonitrile. If the washings were acidic, the coating was rinsed again until the rinse solvent tested pH neutral. Finally, the coating was dissolved in toluene (3 mL).

[0077] Separately, 1 g of Zn-dodecanethiol polymer was dissolved in toluene (10 mL) and mixed with 1 mL of the above prepared quantum dot solution. Barium sulfate powder (70 mg) was added and the mixture sonicated. The resulting suspension was evaporated to dryness in vacuo to yield a yellow solid that was placed under nitrogen. Traces of solvent were then removed using a freeze drying technique. The sample was cooled with liquid nitrogen, placed under reduced pressure for a several minutes, brought slowly back to room temperature (where it was left under reduced pressure for several minutes), then backfilled with a nitrogen atmosphere. The cycle was repeated at least 5 times until a free flowing solid was obtained. The sample was then transferred to an inert-atmosphere glove box where it was ground in an agate pestle and mortar and sieved through a 35-micron sieve to yield a free-flowing, highly luminescent powder.

Example 4. Preparation of Test LEDs

[0078] Ground and sieved QD-(Zn-dodecanethiol polymer)-BaSO.sub.4 composite material (9 mg) was weighed into a clean glass vial. UV curing epoxy Optocast 3553 (120 L) was added and the suspension thoroughly mixed. A small volume (3 L) of the suspension was deposited into the empty well of a 3528 LED package and the resin cured by exposure to UV light (360 nm, 170 mW/cm.sup.2, 64 seconds).

Example 5. Preparation of Luminescent Composite Films

[0079] Sample 1116 (172 mg), sample 1130 (98 mg) and BaSO4 were weighed into a clean amber vial in an inert-atmosphere glove box. An epoxy-acrylate-based resin (800 mg) was added and the mixture mixed well with a clean metal spatula until an even-colored viscous mixture was obtained. The vial was then capped and removed from the glove box and, under yellow light, dispensed onto the barrier side of a PET-based barrier film with an oxygen transmission rate (OTR) of approximately 10.sup.2 g/m.sup.2/day. Another piece of barrier film was placed on the top of the resin with the barrier side towards the resin and the sandwich pulled through a mangle to spread the resin and define the film thickness. Following this step, the film was placed in a UV curing oven for 30 seconds where a dose of approximately 800 mJ was delivered and the film fully cured.

Advantages

[0080] The use of metal-thiol coordination polymers as hosts for quantum dots in composite materials has a number of advantages. First, there is a strong interaction between the polymer and the quantum dots such that the quantum dots are very stable when interacting with the polymer and the polymer shields the quantum dots from deleterious outside agents such as initiators and polar outer phase components. Second, the composite can be prepared as a solid so that subsequent color rendering of films is relatively straightforward and only involves the weighing of different powders followed by mixing with the outer phase resin. Third, different colored solid composites will not mix when mixed into the outer phase resin, keeping color rendering simple. Finally, because there is no curing step and the quantum dots are simply embedded in the host matrix there are no losses of performance resulting from damage to the quantum dots by curing.

[0081] The foregoing presents particular embodiments of a system embodying the principles of the invention. Those skilled in the art will be able to devise alternatives and variations which, even if not explicitly disclosed herein, embody those principles and are thus within the scope of the invention. Although particular embodiments of the present invention have been shown and described, they are not intended to limit what this patent covers. Those skilled in the art will understand 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.