Patent Application
20180072857
Not Applicable
The present invention generally relates to semiconductor nanoparticles—also known as “quantum dots” (QDs). More particularly, it relates to coatings applied to QD-containing films, beads, and the like to protect the QDs from deleterious environmental factors, especially oxygen and moisture.
Quantum dots benefit from gas barrier encapsulation when used in display and lighting applications. In one particular preferred method, QDs are first dispersed in highly compatible materials such as organic amphiphilic macromolecules or polymers to form an inner phase that prevents agglomeration of the quantum dots thereby maintaining the optical performance of the quantum dots. The inner phase is subsequently encapsulated in an outer phase resin having lower oxygen permeability.
U.S. Pat. No. 9,708,532 discloses multi-phase polymer films of quantum dots. The QDs are absorbed in a host matrix, which is dispersed within an outer polymer phase. The host matrix is hydrophobic and is compatible with the surface of the QDs. The host matrix may also include a scaffolding material that prevents the QDs from agglomerating. The outer polymer is typically more hydrophilic and prevents oxygen from contacting the QDs. U.S. Pat. No. 9,680,068 also discloses multi-phase polymer films containing quantum dots. The films have domains of primarily hydrophobic polymer and domains of primarily hydrophilic polymer. QDs, being generally more stable within a hydrophobic matrix, are dispersed primarily within the hydrophobic domains of the films. The hydrophilic domains tend to be effective at excluding oxygen.
Such organic two-phase resins show better oxygen barrier properties but are insufficient to stabilize the quantum dots under irradiation at high temperatures and high humidity such as may be encountered in back light units (BLUs) inasmuch as oxygen can still migrate through the encapsulant to the surface of the quantum dots which can lead to photo-oxidation and a resulting drop in quantum yield. Current practice is to sandwich the quantum dot-containing resin between two barrier films. Polymer beads embedded with QDs are more challenging to stabilize inasmuch as they require a conformal layer of a thin inorganic coating (e.g., Al2O3). Coating beads or the like using atomic layer deposition (ALD) processes is very time-consuming and difficult to scale up. Moreover, significantly decreased quantum yields (QYs) have been observed after ALD coating.
Silazane-based coatings are an alternative to both barrier films and an inorganic coating on beads. A silazane is a hydride of silicon and nitrogen having a straight or branched chain of silicon and nitrogen atoms joined by covalent bonds. Organic derivatives of such compounds are also called silazanes. They are analogous to siloxanes, with —NH— replacing —O—. Their individual names are dependent on the number of silicon atoms in the chemical structure. For example, hexamethyldisilazane (or bis(trimethylsilyl)amine; [(CH3)3Si]2NH) contains two silicon atoms bonded to the nitrogen atom.
Thermal curing of silazane coatings has been tested by Applicant. However, thermal curing was found to cause significant damage to the QDs. The thermally cured silazane coating was not sufficient to stabilize the quantum dots in films or beads. Accordingly, a UV-curable silazane rather than a thermally cured silazane was tested in order to minimize damage to the quantum dots.
It has been discovered that a thin silazane coating cured with short-wavelength UV radiation is highly transparent, exhibits good oxygen-barrier properties, and causes minimal damage to quantum dots. The process is not as time-consuming as ALD and may be used for the large-scale production of QD-containing films and polymer or inorganic beads containing quantum dots.
It has been discovered that the silazane coating works particularly well when the quantum dots are embedded in a two-phase resin system. It is contemplated that the use of a two-phase resin system may enhance the stability of the quantum dots particularly when the silazane is undergoing UV curing.
In a test, 10-cm×10-cm peelable films with an approximately 100-μm white resin layer comprising green-fluorescing CFQD® quantum dots [Nanoco Technologies Ltd., Manchester UK] laminated between 125-μm barrier films were prepared. Unmodified films were used as control samples. Test samples were prepared by peeling off one of the barrier films, coating the surface so exposed with a UV-curable silazane coating [poly(perhydrosilazane); CAS number: 90387-00-1 ENCS number: (2)-3642] on the films, and then exposing the silazane precursor to UV radiation. Optical and lifetime reliability of the silazane-coated films were then evaluated. This method can be extended to coating polymer beads containing embedded quantum dots.
Silazane-coated, QD-containing films are particularly advantageous in ultra-thin devices (e.g., mobile phones) inasmuch as a relatively thin layer of silazane is required relative to the barrier coatings of the prior art.
In one particular exemplary embodiment of the invention, 100-micron thick, QD films were prepared using a two-phase resin system. A resin layer containing green-emitting quantum dots having a 521-nm PLmax, a 43-nm FWHM, and an 80% QY was laminated between two 125-micron barrier films (I-Component Co. Ltd., S. Korea). The films showed either excellent adhesion to the barrier film or one-side peelable depending on which side of the barrier film the QD-containing resin was in contact with. The bare side of the peelable QD films was then coated with silazane precursors as shown in
Referring now to
Table 1 presents certain optical data of the control film (sample A, QD film encapsulated between two commercial barrier films) and for films having a commercial barrier film on one side and either no barrier or a silazane coating on the other side. The control film shows high QY of 61% and EQE of 45% while QY and EQE of the QD film having no barrier on one side (sample B) are only 40% and 32%, respectively suggesting the commercial barrier film protected the quantum dots from (photo-) oxidation. The QYs of silazane coated films, however, are slightly lower than the control indicating that the coating process had some negative impact on quantum dots. The films with thinner silazane coatings (sample E and F) show higher QY and EQE than films having thicker silazane coatings suggesting that an optimum silazane coating thickness for QD films may exist.
Lifetimes of the above QD films on a light test were performed by illuminating these films with 450-nm blue light having an intensity of 106 mW/cm2 at 60° C. and at 90% relative humidity. QD emission peak intensity was monitored versus time (
It is also possible to coat QD-containing polymer beads or other three-dimensional objects (such as LED caps and the like) with a silazane. Quantum dot-containing beads may be coated with a silazane precursor in, for example, a fluidized bed using either an inert gas or a non-solvent for the silazane precursors before the curing process takes place.
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. One 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.
This application claims the benefit of U.S. Provisional Patent Application No. 62/393,325 filed on Sep. 12, 2016, the contents of which are hereby incorporated by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| 62393325 | Sep 2016 | US |
