Light-emitting devices having closely-spaced broad-spectrum and narrow-spectrum luminescent materials and related methods
View Patent ↗A semiconductor light emitting device includes an LED and an associated recipient luminophoric medium that includes respective first through fourth luminescent materials that down-convert respective first through fourth portions of the radiation emitted by the LED to radiation having respective first through fourth peak wavelengths. The first peak wavelength is in the green color range and the second through fourth peak wavelengths are in the red color range. The second and third luminescent materials each emit light having a full-width half maximum bandwidth of at least 70 nanometers, while the fourth luminescent material emits light having a full-width half maximum bandwidth of less than 60 nanometers. Embodiments that only include three luminescent materials are also disclosed.
1. A method of manufacturing a semiconductor light emitting device, comprising:
synthesizing a narrow-spectrum phosphor by:
dissolving MO 2 powder in a first hydrofluoric acid (HF) solution to provide an MO 2 +HF solution, where M is one or more of Si, Ge, Sn, Ti, Zr or Hf;
adding A 2 MnF 6 to the MO 2 +HF solution to provide a A 2 MnF 6 +MO 2 +HF solution, where A is an Alkali metal;
dissolving AHF 2 in a second hydrofluoric acid solution to provide an AHF 2 +HF solution;
adding the AHF 2 +HF solution to the A 2 MnF 6 +MO 2 +HF solution;
extracting solid precipitates of A 2 MF 6 :Mn 4+ from the combination of the AHF 2 +HF and the A 2 MnF 6 +MO 2 +HF solutions;
providing a light emitting diode (“LED”); and
providing a recipient luminophoric medium that is configured to down-convert at least some of the light emitted by the LED, the recipient luminophoric medium including:
a first luminescent material that down-converts a first portion of the radiation emitted by the LED to radiation having a first peak wavelength in the green color range;
a second luminescent material that down-converts a second portion of the radiation emitted by the LED to radiation having a second peak wavelength in the red color range, the second luminescent material having a full-width half maximum bandwidth of at least 70 nanometers;
a third luminescent material that down-converts a third portion of the radiation emitted by the LED to radiation having a third peak wavelength in the red color range; and
a fourth luminescent material that includes the narrow-spectrum phosphor A 2 MF 6 :Mn 4+ precipitates, the fourth luminescent material configured to down-convert a fourth portion of the radiation emitted by the LED to radiation having a fourth peak wavelength in the red color range.
2. The method of claim 1 , wherein M is silicon (Si) and A is potassium (K).
3. The method of claim 1 , wherein the AHF 2 +HF solution is added to the A 2 MnF 6 +MO 2 +HF solution at a temperature between 40° C. and 90° C.
4. The method of claim 1 , wherein the fourth peak wavelength is greater than the second peak wavelength and less than the third peak wavelength.
5. The method of claim 1 , wherein the second peak wavelength is within 30 nanometers of the third peak wavelength.
6. The method of claim 1 , wherein an emission spectrum of the semiconductor light emitting device includes a first peak at the fourth peak wavelength that is at least 50% greater than any point in the emission spectrum in the yellow or green color ranges.
7. The method of claim 1 , further comprising:
adding the solid precipitates of A 2 MF 6 :Mn 4+ to a saturated A + +M 4+ +HF solution;
adding an AF+HF solution to the A + +M 4+ +HF solution that includes the solid precipitates of A 2 MF 6 :Mn 4+ ; and
extracting solid precipitates of A 2 MF 6 :Mn 4+ having an A 2 MF 6 coating thereon from the combined AF+HF solution and A + +M 4+ +HF solution that includes the solid precipitates of A 2 MF 6 :Mn 4+ .
8. A method of manufacturing a semiconductor light emitting device, comprising:
synthesizing a narrow-spectrum phosphor by:
dissolving MO 2 powder in a first hydrofluoric acid (HF) solution to provide an MO 2 +HF solution, where M is one or more of Si, Ge, Sn, Ti, Zr or Hf;
adding A 2 MnF 6 to the MO 2 +HF solution to provide an A 2 MnF 6 solution, where A is an alkali metal;
adding a compound comprising fluorine and the alkali metal to a second hydrofluoric acid solution to provide an alkali metal/HF solution;
adding the A 2 MnF 6 solution to the alkali metal/HF solution; and
extracting a solid precipitate of A 2 MF 6 :Mn 4+ from the combination of the alkali metal/HF solution and the A 2 MnF 6 solution;
providing a light emitting diode (“LED”); and
providing a recipient luminophoric medium that is configured to down-convert at least some of the light emitted by the LED, the recipient luminophoric medium including:
a first luminescent material that down-converts a first portion of the radiation emitted by the LED to radiation having a first peak wavelength in the green color range;
a second luminescent material that down-converts a second portion of the radiation emitted by the LED to radiation having a second peak wavelength in the red color range, the second luminescent material having a full-width half maximum bandwidth of at least 70 nanometers; and
a third luminescent material that includes the narrow-spectrum phosphor A 2 MF 6 :Mn 4+ precipitates, the third luminescent material configured to down-convert a third portion of the radiation emitted by the LED to radiation having a third peak wavelength in the red color range.
9. The method of claim 8 , wherein an emission spectrum of the semiconductor light emitting device includes a first peak at the third peak wavelength that is at least 50% greater than any point in the emission spectrum in the yellow or green color ranges.
10. The method of claim 8 , wherein the A 2 MnF 6 solution is added to the alkali metal/HF solution at a temperature between 40° C. and 90° C.
11. The method of claim 8 , further comprising:
adding the solid precipitates of A 2 MF 6 :Mn 4+ to a saturated A + +M 4+ +HF solution;
adding an AF+HF solution to the A + +M 4+ +HF solution that includes the solid precipitates of A 2 MF 6 :Mn 4+ ; and
extracting solid precipitates of A 2 MF 6 :Mn 4+ having an A 2 MF 6 coating thereon from the combined AF+HF solution and A + +M 4+ +HF solution that includes the solid precipitates of A 2 MF 6 :Mn 4+ .
12. The method of claim 8 , wherein adding the A 2 MnF 6 solution to the alkali metal/HF solution comprises adding the A 2 MnF 6 solution to the alkali metal/HF solution in a dropwise fashion.
13. The method of claim 8 , wherein adding the A 2 MnF 6 solution to the alkali metal/HF solution comprises adding the alkali metal/HF solution to the A 2 MnF 6 solution in a dropwise fashion.
14. The method of claim 8 , wherein M is silicon (Si) and A is potassium (K).
15. A method of manufacturing a semiconductor light emitting device, comprising:
synthesizing a narrow-spectrum phosphor by:
dissolving SiO 2 powder in a first hydrofluoric acid (HF) solution to provide a SiO 2 +HF solution;
adding K 2 MnF 6 to the SiO 2 +HF solution to provide a K 2 MnF 6 solution;
adding a compound comprising fluorine and potassium (K) to a second hydrofluoric acid solution to provide a potassium/HF solution;
adding the K 2 MnF 6 solution to the potassium/HF solution; and
extracting a solid precipitate of K 2 SiF 6 :Mn 4+ from the combination of the potassium/HF solution and the K 2 MnF 6 solution;
providing a light emitting diode (“LED”); and
providing a recipient luminophoric medium that is configured to down-convert at least some of the light emitted by the LED, the recipient luminophoric medium including:
a first luminescent material that down-converts a first portion of the radiation emitted by the LED to radiation having a first peak wavelength in the green color range;
a second luminescent material that down-converts a second portion of the radiation emitted by the LED to radiation having a second peak wavelength in the red color range, the second luminescent material having a full-width half maximum bandwidth of at least 70 nanometers; and
a third luminescent material that includes the narrow-spectrum phosphor K 2 SiF 6 :Mn 4+ precipitates, the third luminescent material configured to down-convert a fourth portion of the radiation emitted by the LED to radiation having a third peak wavelength in the red color range.
16. The method of claim 15 , wherein an emission spectrum of the semiconductor light emitting device includes a first peak at the third peak wavelength that is at least 50% greater than any point in the emission spectrum in the yellow or green color ranges.
17. The method of claim 15 , wherein the K 2 MnF 6 solution is added to the potassium/HF solution at a temperature between 40° C. and 90° C.
18. The method of claim 15 , further comprising:
adding the solid precipitates of K 2 SiF 6 :Mn 4+ to a saturated K + +Si 4+ +HF solution;
adding a KF+HF solution to the K + +Si 4+ +HF solution that includes the solid precipitates of K 2 SiF 6 :Mn 4+ ; and
extracting solid precipitates of K 2 SiF 6 :Mn 4+ having a K 2 SiF 6 coating thereon from the combined KF+HF solution and K + +Si 4+ +HF solution that includes the solid precipitates of K 2 SiF 6 :Mn 4+ .
19. The method of claim 15 , wherein adding the K 2 MnF 6 solution to the potassium/HF solution comprises adding the K 2 MnF 6 solution to the potassium/HF solution in a dropwise fashion.
20. The method of claim 15 , wherein adding the K 2 MnF 6 solution to the potassium/HF solution comprises adding the potassium/HF solution to the K 2 MnF 6 solution in a dropwise fashion.