Two-dimensional perovskite phosphor and method of formation

Patent metadata

Field	Value
Publication number	US-10087366-B2
Application number	US-201415031561-A
Country	US
Kind code	B2
Filing date	Oct 23, 2014
Priority date	Oct 23, 2013
Publication date	Oct 2, 2018
Grant date	Oct 2, 2018

Abstract

Intrinsic broadband white-light emitting phosphors and a solution-state method for producing them are disclosed. Emitters in accordance with the present invention include layered perovskite-based phosphors that comprise metals and halides and have an emission spectrum that spans the entire visible-light spectrum.

First claim

What is claimed is:

1. A phosphor having an emission spectrum that includes a visible-light spectrum, the phosphor comprising:
alternating inorganic and organic layers, arranged in a two-dimensional perovskite-based crystal structure, wherein
each inorganic layer of the inorganic layers comprise a metal-halide sheet comprising a metal and at least one halide,
each organic layer of the organic layers comprises organic molecules, wherein the crystal structure of the two-dimensional perovskite crystal is directed by the organic molecules, selected from the group consisting of EDBE, N-MEDA and N-MPDA, and
the emission spectrum of the phosphor comprises a continuous visible light spectrum in a range of 400 to 700 nm and a shape of the emission spectrum and a peak wavelength are dependent on a choice of at least one halide in the metal-halide sheet.

2. The phosphor of claim 1 , wherein the metal comprises metal that is selected from the group consisting of lead, bismuth, tin, and germanium.

3. The phosphor of claim 1 , wherein the a least one halide comprising a first halide and a second halide, wherein the first metal, the first halide, and second halide are arranged in the two-dimensional perovskite-based crystal structure, and wherein the shape of the emission spectrum is based on the ratio of the first halide and the second halide.

4. The phosphor of claim 3 , wherein the at least one halide, the first halide or second halide comprises a halide that is selected from the group consisting of fluorine, chlorine, bromine, and iodine.

5. The phosphor of claim 1 , wherein the metal-halide sheets are corrugated.

6. The phosphor of claim 1 , wherein the emission spectrum is based on a bulk effect within the perovskite-based crystal structure.

7. The phosphor of claim 1 , wherein the perovskite-based crystal structure comprises (110) inorganic sheets.

8. The phosphor of claim 1 , wherein the organic molecule comprises hydrogen bonding with at least one halide.

9. A phosphor having an emission spectrum that includes a visible-light spectrum, the phosphor comprising:
alternating inorganic and organic layers, arranged in a two-dimensional perovskite-based crystal structure, wherein
each inorganic layer of the inorganic layers comprises a metal-halide sheet comprising a metal and at least two halides: a first halide and a second halide,
each organic layer of the organic layers comprises organic molecules, selected from the group consisting of EDBE, N-MEDA, N-MPDA and alkyl ammonium, wherein the crystal structure of the two-dimensional perovskite crystal is directed by the organic molecules, and
the shape of the emission spectrum is based on the ratio of the first halide and the second halide.

10. A method comprising:
mixing a first liquid and a second liquid to form a first solution, the first liquid comprising organic molecules, selected from the group consisting of EDBE, N-MEDA and N-MPDA, dissolved in a first hydrohalic acid and the second liquid comprising an inorganic compound dissolved in the first hydrohalic acid, wherein the inorganic compound includes a metal and a first halide, and wherein the first hydrohalic acid comprises the first halide; and
precipitating a first phosphor from the first solution, wherein the first phosphor having an emission spectrum that includes a visible-light spectrum and arranged in a two-dimensional perovskite-based crystal structure with alternating inorganic and organic layers, wherein each inorganic layer comprises a metal-halide sheet comprising the metal and the first halide, each organic layer comprises the organic molecules, wherein the crystal structure of the two-dimensional perovskite crystal is directed by the organic molecules;
wherein the emission spectrum of the first phosphor comprises a continuous visible light spectrum in a range of 400 to 700 nm and a shape of the emission spectrum and a peak wavelength are dependent on a choice of the first halide in the metal-halide sheet.

11. The method of claim 10 , wherein enabling the precipitation of the first phosphor comprises one of:
a) heating the first solution such that it is a saturated solution at a first temperature that is greater than a room temperature, and cooling the first solution to a second temperature that is at or below the room temperature, and
b) diffusing an organic solvent into the first solution.

12. The method of claim 10 , wherein the organic molecule comprises hydrogen bonding with at least two halide.

13. The method of claim 10 , wherein the first liquid is maintained at or below a room temperature before mixing with the second liquid to form the first solution.

14. The method of claim 10 further comprising:
dissolving the first phosphor in a second solution including the first hydrohalic acid and a second hydrohalic acid that comprises a second halide;
adding a third liquid to the second solution to form a third solution, the third liquid containing the organic molecules, wherein the third liquid is added while at a temperature below room temperature; and
precipitating a second phosphor from the third solution, wherein the second phosphor precipitating a having a further emission spectrum that includes a modified visible-light spectrum and arranged in a further two-dimensional perovskite-based crystal structure with alternating further inorganic and organic layers, wherein each further inorganic layer of the further inorganic layers comprises a further metal-halide sheet comprising the metal, the first halide and the second halide, each further organic layer of the further organic layers comprises the organic molecules, wherein the crystal structure of the further two-dimensional perovskite crystal is directed by the organic molecules,
wherein a shape of the further emission spectrum of the second phosphor is based on the ratio of the first halide and the second halide.

15. The method of claim 14 , further comprising:
providing the first hydrohalic acid such that the first or second halide is selected from the group consisting of fluorine, chlorine, bromine, and iodine; and providing the first inorganic compound such that the first metal is selected from the group consisting of lead, bismuth, tin, and germanium.

16. The method of claim 14 , wherein the organic molecule, the first metal and the first and second halides collectively define a layered hybrid perovskite crystal structure in the second phosphor.

Assignees

• Univ Leland Stanford Junior

Inventors

• Dohner Emma Rose
• Karunadasa Hemamala Indivari

Classifications

• C09K11/08

  containing inorganic luminescent materials · CPC title

• C09K11/66

  containing germanium, tin or lead · CPC title

• C09K11/664 Primary

  Halogenides (C09K11/661 takes precedence) · CPC title

• Y02B20/181

  Cross-Sectional Technologies · mapped topic

• C09K2211/188

  of other metals not provided for in one of the previous groups · CPC title