Copper-doped double perovskites and uses thereof

Patent metadata

Field	Value
Publication number	US-11479477-B2
Application number	US-202016909072-A
Country	US
Kind code	B2
Filing date	Jun 23, 2020
Priority date	Jun 26, 2019
Publication date	Oct 25, 2022
Grant date	Oct 25, 2022

Abstract

The present application relates to copper-doped double perovskites, for example, copper-doped double perovskites of the formula (I) and to uses thereof, for example as low-bandgap materials such as a semiconducting material in a device. The present application also relates to methods of tuning the bandgap of a Cs 2 SbAgZ 6 double perovskite (for example, wherein Z is Cl) comprising doping the double perovskite with copper.

Cs 2 Sb 1-a Ag 1-b Cu 2x Z 6   (I)

First claim

The invention claimed is:

1. An inorganic copper-doped double perovskite of the formula (I):
Cs 2 Sb 1-a Ag 1-b Cu 2x Z 6   (I)

wherein
Z is Cl or Br;
a+b=2x; and
x is in the range of from about 0.005 to about 0.25.

2. The inorganic copper-doped double perovskite of claim 1 , wherein Z is Cl.

3. The inorganic copper-doped double perovskite of claim 1 , wherein x is in the range of from about 0.005 to about 0.015.

4. The inorganic copper-doped double perovskite of claim 1 , wherein x is about 0.10.

5. The inorganic copper-doped double perovskite of claim 1 , having an optical indirect bandgap of less than 2.65 eV, as determined using a UV-Vis NIR spectrophotometer with each measurement being acquired between the wavelengths of 2500 nm and 200 nm.

6. The inorganic copper-doped double perovskite of claim 1 , having an optical indirect bandgap of from about 1 eV to about 1.4 eV, as determined using a UV-Vis NIR spectrophotometer with each measurement being acquired between the wavelengths of 2500 nm and 200 nm.

7. The inorganic copper-doped double perovskite of claim 5 , having no substantial change in the optical indirect bandgap, or having no substantial change in 133 Cs magic-angle spinning nuclear magnetic resonance spectrum, powder x-ray diffraction pattern and/or absorption spectrum, after being subjected to a relative humidity of about 55% at a temperature of about 295K for a period of about 365 days.

8. The inorganic copper-doped double perovskite of claim 5 , having no substantial change in the optical indirect bandgap, or having no substantial change in 133 Cs magic-angle spinning nuclear magnetic resonance spectrum, powder x-ray diffraction pattern and/or absorption spectrum, after being subjected to a temperature of about 110° C. for a period of about 6 days.

9. A device comprising a semiconducting material, wherein the semiconducting material comprises, consists essentially of or consists of an inorganic copper-doped double perovskite as defined in claim 1 .

10. The device of claim 9 , wherein the device is a photovoltaic device, a thermoelectric device, a magneto-electric device or a magneto-optic device.

11. The device of claim 10 , wherein the photovoltaic device is a solar cell or a semiconductor and the thermoelectric device is a sensor or a heat transfer device.

12. The device of claim 9 , wherein the device is a photovoltaic device.

13. The device of claim 9 , wherein the device comprises:
a layer comprising an n-type material;
a layer comprising a p-type material; and
wherein the semiconducting material is between the layer comprising the n-type material and the layer comprising the p-type material.

14. The device of claim 13 , wherein the device is a solar cell, and the device further comprises a cathode that is coupled to the layer comprising the p-type material and an anode that is coupled to the layer comprising the n-type material.

15. A method of tuning the bandgap of a Cs 2 SbAgZ 6 double perovskite, wherein Z is CI or Br, the method comprising doping the double perovskite with copper to obtain an inorganic copper-doped double perovskite of the formula (I):
Cs 2 Sb 1-a Ag 1-b Cu 2x Z 6   (I)

wherein
Z is Cl or Br;
a+b=2x; and
x is in the range of from about 0.005 to about 0.25.

16. The method of claim 15 , wherein Z is Cl.

17. The method of claim 16 , wherein the inorganic copper-doped double perovskite is prepared by a method comprising:
(i) dissolving Sb 2 O 3 and AgCl in an aqueous solution comprising HCl; and
(ii) adding CsCl and CuCl 2 .2H 2 O to the solution obtained in step (i).

18. The method of claim 17 , wherein prior to addition of the solution obtained in step (i), the CuCl 2 .2H 2 O is dissolved in an aqueous solution comprising HCl.

19. The method of claim 17 , wherein the Sb 2 O 3 and AgCl are dissolved in the aqueous solution comprising HCl, while heating.

20. The method of any one of claim 17 , wherein the mixture obtained in step (ii) is heated for a time of about 0.5 to about 1.5 hours then allowed to stand at ambient temperature for a time of about 1 hour to about 4 hours.

Assignees

• Univ Alberta

Inventors

• Michaelis Vladimir
• Karmakar Abhoy

Classifications

• Y02E10/542

  Dye sensitized solar cells · CPC title

• C01P2006/40

  Electric properties · CPC title

• C01P2002/84

  by UV- or VIS- data · CPC title

• H01G9/0036

  Formation of the solid electrolyte layer · CPC title

• C01P2002/88

  by thermal analysis data, e.g. TGA, DTA, DSC · CPC title