Oxygen- and fluorine-doped cesium and rubidium lead perovskite compounds for hard radiation detection

Patent metadata

Field	Value
Publication number	US-12313796-B2
Application number	US-202117919825-A
Country	US
Kind code	B2
Filing date	May 5, 2021
Priority date	May 5, 2020
Publication date	May 27, 2025
Grant date	May 27, 2025

Abstract

Inorganic perovskites doped with oxygen atoms or fluorine atoms, methods for making the doped perovskites, and hard radiation detectors incorporating the doped perovskites as photoactive layers are provided. The doped perovskites utilize lead oxide, lead fluoride, or compounds that thermally decompose into lead oxide or lead fluoride as dopant atom sources. During the crystallization of a perovskite in the presence of the dopant atom sources, oxygen or fluoride atoms from the dopant source are incorporated into the perovskite crystal lattice.

First claim

What is claimed is:

1. A doped perovskite comprising:
a perovskite single-crystal having a chemical formula CsAX 3 , a chemical formula RbAX 3 , or a chemical formula Cs 1-x Rb x PbX 3 , where 0<x<1, wherein A represents Pb or a combination of Pb and one or more of Sn, Si, and Ge, and X represents one or more halogen atoms; and
oxygen atom dopants or fluorine atom dopants in a crystal lattice of the perovskite single-crystal.

2. The doped perovskite of claim 1 , comprising the oxygen atom dopants.

3. The doped perovskite of claim 2 , wherein the perovskite single-crystal has a chemical formula CsPbBr 3 , and the crystal lattice of the perovskite single-crystal is doped with the oxygen atom dopants.

4. The doped perovskite of claim 3 , wherein the oxygen-doped CsPbBr 3 has a concentration of the oxygen atom dopants in a range from 1 ppm to 10000 ppm.

5. The doped perovskite of claim 1 , wherein the doped perovskite has a concentration of the oxygen atom dopants or a concentration of the fluorine atom dopants in a range from 1 ppm to 10000 ppm.

6. The doped perovskite of claim 1 , comprising the fluorine atom dopants.

7. A device for a detection of incident radiation comprising:
a photoactive layer comprising:
a perovskite single-crystal having a chemical formula CsAX 3 , a chemical formula RbAX 3 , or a chemical formula Cs 1-x RbxPbX 3 , where 0<x<1, wherein A represents Pb or a combination of Pb and one or more of Sn, Si, and Ge, and X represents one or more halogen atoms; and
oxygen atom dopants or fluorine atom dopants in a crystal lattice of the perovskite single-crystal;
a first electrode in electrical communication with the photoactive layer;
a second electrode in electrical communication with the photoactive layer,
wherein the first electrode and the second electrode are configured to apply an electric field across the photoactive layer; and
a signal detector configured to measure a photocurrent generated in the photoactive layer when the photoactive layer is exposed to incident X-rays, gamma-rays, and/or alpha-particles.

8. The device of claim 7 , wherein the crystal lattice of the perovskite single-crystal is doped with the oxygen atom dopants.

9. The device of claim 8 , wherein the perovskite single-crystal has the chemical formula CsPbBr 3 .

10. The device of claim 7 , wherein a concentration of the oxygen atom dopants or a concentration of the fluorine atom dopants in the crystal lattice of the perovskite single-crystal is in a range from 1 ppm to 10000 ppm.

11. The device of claim 7 , wherein the photoactive layer comprises only a single perovskite phase.

12. The device of claim 7 , wherein the crystal lattice of the perovskite single-crystal is doped with the fluorine atom dopants.

13. A method for detecting incident radiation using a device comprising:
a photoactive layer comprising:
a perovskite single-crystal having a chemical formula CsAX 3 , a chemical formula RbAX 3 , or a chemical formula Cs 1-x Rb x PbX 3 , where 0<x<1, wherein A represents Pb or a combination of Pb and one or more of Sn, Si, and Ge, and X represents one or more halogen atoms; and
oxygen atom dopants or fluorine atom dopants in a crystal lattice of the perovskite single-crystal;
a first electrode in electrical communication with the photoactive layer;
a second electrode in electrical communication with the photoactive layer, wherein
the first electrode and the second electrode are configured to apply an electric field across the photoactive layer; and
a signal detector configured to measure a photocurrent generated in the photoactive layer when the photoactive layer is exposed to incident X-rays, gamma-rays, and/or alpha-particles, the method comprising:
exposing the photoactive layer of the device to incident radiation comprising X-rays, gamma rays, and/or alpha particles, whereby the photoactive layer absorbs the incident radiation and a photocurrent is generated in the photoactive layer; and
measuring at least one of an energy and an intensity of the absorbed incident radiation by detecting the photocurrent.

14. A method of making an oxygen-doped perovskite or a fluorine-doped perovskite having a chemical formula CsAX 3 , a chemical formula RbAX 3 , or a chemical formula Cs 1-x Rb x PbX 3 , where 0<x<1, where A represents Pb or a combination of Pb and one or more of Sn, Si, and Ge, X represents one or more halogen atoms, the method comprising:
forming a mixture of a perovskite having the chemical formula CsAX 3 , the chemical formula RbAX 3 , or the chemical formula Cs 1-x Rb x PbX 3 , where 0<x<1, where A represents Pb, Sn, Si, Ge, or a combination of two or more thereof, and X represents one or more halogen atoms, and a dopant source compound comprising:
PbO;
a lead and oxygen-containing compound that decomposes into PbO when the lead and oxygen-containing compound is heated;
PbF 2 ; or
a lead and fluorine-containing compound that decomposes into PbF 2 when the lead and fluorine-containing compound is heated;

melting the perovskite and the dopant source compound to form a melt; and
crystalizing the oxygen-doped perovskite or the fluorine-doped perovskite from the melt.

15. The method of claim 14 , wherein the oxygen-doped perovskite or the fluorine-doped perovskite has a concentration of oxygen atom dopants or a concentration of fluoride atom dopants in a range from 1 ppm to 10000 ppm.

16. The method of claim 15 , wherein the perovskite is an oxygen-doped perovskite and the dopant source compound comprises PbO.

17. The method of claim 14 , wherein a concentration of the dopant source compound in the mixture of the perovskite and the dopant source compound is in a range from 0.01 mol. % to 1 mol. %.

18. The method of claim 14 , wherein the perovskite is CsPbBr 3 .

19. The method of claim 14 , wherein the perovskite is the oxygen-doped perovskite, and the dopant source compound comprises PbO 2 , Pb 3 O 4 , Pb(OH) 2 , PbCO 3 , Pb 2 (OH) 2 CO 3 , or a combination of two or more thereof.

20. The method of claim 14 , wherein the perovskite is the fluorine-doped perovskite and the dopant source compound comprises PbF 2 .

Assignees

• Univ Northwestern
• Uchicago Argonne Llc

Inventors

• Lin Wenwen
• Chung Duck Young
• Kanatzidis Mercouri G

Classifications

• G01T1/2023

  Selection of materials · CPC title

• C30B29/12 Primary

  Halides · CPC title

• C30B11/02

  without using solvents (C30B11/06 takes precedence) · CPC title

• C09K11/665

  with alkali or alkaline earth metals · CPC title

• C01P2006/40

  Electric properties · CPC title