Gas Barrier Coating For Semiconductor Nanoparticles

Abstract

A thin silazane coating cured with short-wavelength UV radiation is highly transparent, exhibits good oxygen-barrier properties, and does minimal damage to quantum dots in a quantum dot-containing film.

Claims

1. A fluorescent film comprising: a quantum dot-containing layer having a first side and an opposing second side; a silazane coating on at least one of the first side and the second side of the quantum dot-containing layer.

2. The fluorescent film recited in claim 1 further comprising a silazane coating on both the first side and the second side of the quantum dot-containing layer.

3. The fluorescent film recited in claim 1 wherein the silazane coating is on the first side of the quantum dot-containing layer and further comprising a barrier film on the second side of the quantum dot-containing layer.

4. The fluorescent film recited in claim 1 wherein the quantum dot-containing layer produces green light when illuminated by a source of blue light.

5. The fluorescent film recited in claim 1 wherein the quantum dot-containing layer comprises quantum dots embedded in a polymer resin.

6. A fluorescent bead comprising: a quantum dot-containing body; a silazane coating on the quantum dot-containing body.

7. A fluorescent cap for a light emitting diode (LED) comprising: a quantum dot-containing body having a top surface, an opposing bottom surface, and at least one side surface; a silazane coating on at least one of the top surface, the bottom surface, and the at least one side surface of the quantum dot-containing body.

8. The fluorescent cap for an LED recited in claim 7 wherein the silazane coating is on each of the top surface, the bottom surface, and the at least one side surface of the quantum dot-containing body.

9. The fluorescent cap for an LED recited in claim 7 wherein the quantum dot-containing body is configured such that the bottom surface is illuminated by the LED and the top surface emits fluorescent light produced by the quantum dots when the cap is installed on a package containing the LED.

10. The fluorescent cap for an LED recited in claim 7 wherein the quantum dot-containing body comprises quantum dots embedded in a polymer resin.

11. A method for applying a silazane coating to a thin film comprising quantum dots, the method comprising: applying a silazane precursor to at least one side of the thin film comprising quantum dots; curing the silazane precursor by exposing the thin film having a silazane precursor applied thereto to ultraviolet (UV) radiation.

12. The method recited in claim 11 wherein the UV radiation is short-wavelength UV radiation.

13. The method recited in claim 12 wherein the UV radiation has a wavelength of about 172 nm.

14. The method recited in claim 11 wherein the thin film having a silazane precursor applied thereto is exposed to the UV radiation at an intensity of about 7 J/cm.sup.2.

15. The method recited in claim 11 wherein the silazane precursor is perhydrosilazane

16. The method recited in claim 11 further comprising heating the thin film having applied silazane precursors to a temperature and for a time sufficient to substantially remove a solvent in which the silazane precursors are dissolved.

17. The method recited in claim 16 wherein the heating to remove the solvent is performed at about 80 C. for about 3 minutes.

18. A method for applying a silazane coating to polymer beads comprising quantum dots, the method comprising: fluidizing the polymer beads comprising quantum dots; applying a silazane precursor to the fluidized polymer beads comprising quantum dots; curing the silazane precursor by exposing the polymer beads having a silazane precursor applied thereto to ultraviolet (UV) radiation.

19. The method recited in claim 18 wherein fluidizing the polymer beads comprises fluidizing the polymer beads using an inert gas.

20. The method recited in claim 18 wherein fluidizing the polymer beads comprises fluidizing the polymer beads using a non-solvent for the silazane precursors.

Description

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

[0013] FIG. 1 is a schematic representation of the preparation of a silazane coating for quantum dot-containing films according to an embodiment of the invention.

[0014] FIG. 2 is a cross-sectional view of the QD-containing films for which test results are presented in FIG. 3.

[0015] FIG. 3 contains graphs showing the change versus time (relative to initial values) in green QD emission peak intensity, LED intensity, and external quantum efficiency (EQE) for various quantum dot-containing films.

[0016] FIG. 4A shows the general chemical structure of a substituted silazane.

[0017] FIG. 4B is the chemical structure of one particular representative polycyclic silazane.

[0018] FIG. 4C is the chemical structure of another silazane. In certain trials reported hereinbelow, R.sup.8, R.sup.9, and R.sup.19H in the particular silazane used.

DETAILED DESCRIPTION OF THE INVENTION

[0019] 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 PL.sub.max, 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 FIG. 1. Spin coating was used for this particular study but dip coating or spraying may also be used to control the thickness of the silazane coating (see FIG. 1). Slot die coating is also feasible and may be preferable for industrial-scale production. The coated films were then baked (80 C., 3 min.) to remove solvent before being irradiated (under nitrogen) with short-wavelength UV radiation (172-nm Xenon excimer lamp; >100 mV/cm.sup.2; 2-6-mm radiation gap) at different doses. The thickness of the silazane coating may be controlled by varying the silazane concentration and the speed of rotation or dipping if spin or dip coating is used, respectively. Two-phase resin systems may provide enhanced protection for the quantum dots from damage by the UV curing radiation.

[0020] Referring now to FIG. 3, stability test results for various QD-containing films are presented in graphical format. Graph A is for QD two-phase system films encapsulated between two commercial barrier films (I-Component Co. Ltd.) as a control. Graph B is for QD films with a commercial barrier film (I-Component Co. Ltd.) on one side only. Graph C is for a QD film with a commercial barrier film (I-Component Co. Ltd.) on one side and a 200-nm silazane coating cured with high-dose [7 J/cm.sup.2] UV radiation on the other side. Graph D is for a QD film with a commercial barrier film (I-Component Co. Ltd.) film on one side and 200-nm silazane coating cured at low dose [4 J/cm.sup.2] on the other side. Graph E is for a QD film with a commercial barrier film (I-Component Co. Ltd.) on one side and a 100-nm silazane coating cured with high-dose [7 J/cm.sup.2] UV radiation on the other side. Graph F is for a QD film with a commercial barrier film (I-Component Co. Ltd.) on one side and a 100-nm silazane coating cured with low-dose [4 J/cm.sup.2] UV radiation on the other side.

[0021] 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.

TABLE-US-00001 TABLE 1 Quantum yield and quantum efficiency of the QD-containing films shown in FIG. 2. Sample QY EQE Abs code Barrier (%) (%) (%) A (control) Commercial barrier film 61 45 47 B No silazane coating 40 32 50 C 200-nm silazane coating; low dose 45 33 49 [4 J/cm.sup.2] D 200-nm silazane coating; high dose 46 33 50 [7 J/cm.sup.2] E 100-nm silazane coating; low dose 53 37 49 [4 J/cm.sup.2] F 100-nm silazane coating; high dose 52 37 50 [7 J/cm.sup.2]

[0022] 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/cm.sup.2 at 60 C. and at 90% relative humidity. QD emission peak intensity was monitored versus time (FIG. 3). Without a gas barrier, the green-emitting QDs in sample B degraded completely within a few hours while the control films and silazane-coated films behaved similarly to one anotheri.e. green-emitting quantum dots remained stable after 500 hours. The green-emitting quantum dots were more stable in thicker silazane-coated films than those in films with a thinner silazane coating. The stability of QD films with a silazane coating suggests that the oxygen-barrier property of a silazane coating is equal to or even better than that of the commercial barrier film. It is noted that the dosage of the curing UV radiation does not affect QY and/or EQE, and the stability of the silazane-coated films confirms the advantages of short-UV curing for the thin barrier coating (which minimizes damage to the quantum dots due to its low penetration depth).

[0023] 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.

[0024] 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.