Surface-passivated silicon quantum dot phosphors
View Patent ↗Phosphors formed using silicon nanoparticles are provided. The phosphors exhibit bright fluorescence and high quantum yield, making them ideal for lighting applications. Methods for making the silicon phosphors are also provided, along with lighting devices that incorporate the silicon phosphors.
1. A silicon phosphor comprising:
a core comprising a silicon particle;
a plurality of silicon nanoparticles attached to the core;
an oxygen-free surface passivation layer substantially encapsulating each of the plurality of silicon nanoparticles; and
a passivating layer comprising a plurality of passivating ligands bound to the oxygen-free surface passivation layer.
2. The silicon phosphor of claim 1 , wherein the core has a diameter of between about 10 nm and about 10 μm.
3. The silicon phosphor of claim 1 , wherein the core is capable of scattering UV, visible, and infrared light.
4. The silicon phosphor of claim 1 , wherein each nanoparticle in the plurality of silicon nanoparticles has a diameter between 1 nm and 5 nm.
5. The silicon phosphor of claim 1 , wherein the plurality of passivating ligands are selected from the group consisting of alkyls, alkenyls, alkynyls, aromatics, aromatic heterocycles, conjugated aromatics, polyenes, cyanides, hydroxys, alkoxys, carboxylates, phenoxys, siloxys, cyanates, thioalkyls, thioaryls, thiocyanates, silylthios, substituted silyl groups, amino groups, mono-substituted amines, di-substituted amines, imino groups, silylaminos, alkoxy silanes, alkyl alkoxysilanes, and amino alkoxysilanes.
6. The silicon phosphor of claim 1 , wherein the plurality of passivating ligands includes trimethoxypropylsilanes.
7. The silicon phosphor of claim 1 , wherein the plurality of passivating ligands includes (3-aminopropyl)trimethoxysilanes.
8. A method of making silicon phosphors comprising:
(a) electrochemically etching silicon to provide a plurality of core silicon particles each having a plurality of silicon nanoparticles attached thereto;
(b) isotropically etching the plurality of silicon nanoparticles to provide a plurality of etched silicon nanoparticles;
(c) capping the plurality of etched silicon nanoparticles with an oxygen-free surface passivation layer; and
(d) passivating the oxygen-free surface passivation layer with surface ligands.
9. The method of claim 8 , wherein the silicon is electrochemically etched in a solution of HF and methanol.
10. The method of claim 8 , wherein the silicon is a p-type silicon wafer.
11. The method of claim 10 , wherein the plurality of silicon nanoparticles are obtained from the wafer surface by mechanically pulverizing the electrochemically etched silicon.
12. The method of claim 8 , wherein the plurality of silicon nanoparticles are isotropically etched in an aqueous solution comprised of HNO 3 and HF.
13. The method of claim 8 , wherein the plurality of etched silicon nanoparticles are capped with the oxygen-free surface passivation layer by a hydrosilylation reaction with an alkene or an alkyne.
14. The method of claim 8 , wherein the surface ligands are selected from alkyls, alkenyls, alkynyls, aromatics, aromatic heterocycles, conjugated aromatics, polyenes, cyanides, hydroxys, alkoxys, carboxylates, phenoxys, siloxys, cyanates, thioalkyls, thioaryls, thiocyanates, silylthios, substituted silyl groups, amino groups, mono-substituted amines, di-substituted amines, imino groups, silylaminos, alkoxy silanes, alkyl alkoxysilanes and amino alkoxysilanes.
15. The method of claim 8 , wherein the plurality of surface ligands includes trimethoxypropylsilane.
16. The method of claim 8 , wherein the plurality of surface ligands includes (3-aminopropyl)trimethoxysilane.
17. The method of claim 8 further comprising the step of separating the silicon phosphors into nano-scale silicon phosphors and micron-scale silicon phosphors.
18. The method of claim 17 , wherein separating comprises centrifuging a solution of the silicon phosphors such that the micron-scale silicon phosphors sediment and the nano-scale silicon phosphors remain in a supernatant, wherein the method further comprises collecting the supernatant comprising the nano-scale silicon phosphors.
19. A lighting device comprising a silicon phosphor of claim 1 .
20. The lighting device of claim 19 , wherein the silicon phosphor is applied directly to a blue or UV emitting light source.
21. The lighting device of claim 19 , wherein the silicon phosphor is incorporated in a substantially optically translucent matrix placed adjacent to a blue or UV emitting light source.
22. The lighting device of claim 19 , wherein the silicon phosphor is embedded within a bulb which encapsulates a blue or UV emitting light source.
23. The lighting device of claim 19 , wherein the lighting device is selected from the group consisting of a light-emitting diode and a fluorescent lamp.
24. The lighting device of claim 19 , wherein the silicon phosphor has an emission peak of 590 nm or greater.
25. The lighting device of claim 19 , wherein the silicon phosphor is a blue or green emitter.