Controlled crystallization to grow large grain organometal halide perovskite thin film

Patent metadata

Field	Value
Publication number	US-9570240-B1
Application number	US-201615228112-A
Country	US
Kind code	B1
Filing date	Aug 4, 2016
Priority date	Aug 4, 2016
Publication date	Feb 14, 2017
Grant date	Feb 14, 2017

Abstract

A method of forming perovskite thin films with micron-sized perovskite grains is provided. A layer of PbX 2 in a solution containing a metal ion additive is applied to a structure. The structure with the PbX 2 layer is annealed a first time. The PbX 2 is exposed to CH 3 NH 3 X in a solvent. The structure with the exposed PbX 2 layer is annealed a second time resulting in a CH 3 NH 3 PbX 3 layer. X is selected from a group consisting of Cl, Br, I, CN, and SCN.

First claim

What is claimed is:

1. A method of forming perovskite thin films with micron-sized perovskite grains, the method comprising:
applying a layer of PbX 2 in a solution containing a metal ion additive to a structure;
annealing the structure with the PbX 2 layer a first time;
exposing the PbX 2 to CH 3 NH 3 X in a solvent; and
annealing the structure with the exposed PbX 2 layer a second time resulting in a CH 3 NH 3 PbX 3 layer,
wherein X is selected from a group consisting of Cl, Br, I, CN, and SCN.

2. The method of claim 1 , wherein the metal ion additive is selected from a group consisting of: Li+, K+, Na+, Rb+, Cs+, Ag+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Zn2+, Cd2+, Hg2+, Fe2+/Fe3+, Ru2+/Ru3+, Os4+, Mn2+, Pt2+, Pd2+, Sb3+, Ga3+, In3+, Al3+, Bi3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Sn4+, Ti4+, Ge4+, Zr4+, V4+, Nb5+, Ta5+, Zr4+, Hf4+, Sc3+, Y2+/Y3+, Tc4+/Tc7+, Cr3+/Cr2+/Cr6+, Mo4+/Mo6+, W4+/W6+, Co2+/Co3+, Rh3+, Ir3+/Ir2+/Ir4+, Ni2+, Cu1+/Cu2+, Au1+/Au3+, and combinations thereof.

3. The method of claim 2 , wherein an oxidation state of the metal ion additive ranges from 0 to 6.

4. The method of claim 2 , wherein the metal ion additive is Na+.

5. The method of claim 1 , wherein a concentration of the metal ion additive is between about 1 mol % and about 6 mol %.

6. The method of claim 5 , wherein the concentration of the metal ion additive is about 2 mol %.

7. The method of claim 1 , wherein the solvent is anhydrous 2-propanol.

8. The method of claim 1 , wherein the first annealing is at 80° C. for 10 minutes.

9. The method of claim 1 , wherein the second annealing is at 100° C. for 80 minutes.

10. A method for making a layered perovskite structure, the method comprising:
applying a PEDOT:PSS coating to an ITO glass substrate;
drying the PEDOT:PSS coated surface;
applying a layer of PbX 2 in a solution containing a metal ion additive to the PEDOT:PSS coating;
annealing the PEDOT:PSS coated ITO glass substrate with the PbX 2 layer a first time;
exposing the PbX 2 to CH 3 NH 3 X in a solvent; and
annealing the PEDOT:PSS coated ITO glass substrate with the exposed PbX 2 layer a second time resulting in a CH 3 NH 3 PbX 3 layer,
wherein X is selected from a group consisting of Cl, Br, I, CN, and SCN.

11. The method of claim 10 , wherein the metal ion additive is selected from a group consisting of: Li+, K+, Na+, Rb+, Cs+, Ag+, Be2+, Mg2+, Ca2+, Sr2+, Ba2+, Zn2+, Cd2+, Hg2+, Fe2+/Fe3+, Ru2+/Ru3+, Os4+, Mn2+, Pt2+, Pd2+, Sb3+, Ga3+, In3+, Al3+, Bi3+, La3+, Ce3+, Pr3+, Nd3+, Pm3+, Sm3+, Eu3+, Gd3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Sn4+, Ti4+, Ge4+, Zr4+, V4+, Nb5+, Ta5+, Zr4+, Hf4+, Sc3+, Y2+/Y3+, Tc4+/Tc7+, Cr3+/Cr2+/Cr6+, Mo4+/Mo6+, W4+/W6+, Co2+/Co3+, Rh3+, Ir3+/Ir2+/Ir4+, Ni2+, Cu1+/Cu2+, Au1+/Au3+, and combinations thereof.

12. The method of claim 11 , where an oxidation state of the metal ion additive ranges 0 to 6.

13. The method of claim 10 , wherein a concentration of the metal ion additive is between about 1 mol % and about 6 mol %.

14. The method of claim 10 , wherein the PEDOT:PSS is spin-coated onto the ITO glass substrate.

15. The method of claim 14 , wherein the PEDOT:PSS is spin-coated onto the ITO glass substrate at 300 rpm for 60 seconds and dried at 140° C. for 20 minutes in an ambient atmosphere.

16. The method claim 10 , wherein the layer of PbX 2 is spun on the top of the PEDOT:PSS coating in a solvent.

17. The method of claim 16 , wherein the solvent is dimethyl formamide (DMF).

18. The method claim 10 , wherein the CH 3 NH 3 X is dripped onto the PbX 2 layer while spinning at 6000 rpm for 35 seconds.

19. The method of claim 10 , wherein the solvent is anhydrous 2-propanol.

20. The method of claim 10 , wherein the first annealing is at 80° C. for 10 minutes.

21. The method of claim 10 , wherein the second annealing is at 100° C. for 80 minutes.

22. The method of claim 10 , wherein the second annealing is performed with a drop of DMF on the CH 3 NH 3 X and PbX 2 layers.

23. The method of claim 10 , further comprising:
depositing a layer of PC 71 BM atop the resulting CH 3 NH 3 Pb 3 layer; and
performing thermal evaporation of C 60 and Al onto the PC 71 BM layer.

Assignees

• Us Air Force
• The United States of America represented by the Secretary of the Air Force

Inventors

• Durstock Michael F
• Bag Santanu

Classifications

• H10K85/50

  Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3 · CPC title

• H10K30/50

  Photovoltaic [PV] devices · CPC title

• H10K30/20

  comprising organic-organic junctions, e.g. donor-acceptor junctions · CPC title

• H10K71/12

  using liquid deposition, e.g. spin coating · CPC title

• C30B28/04 Primary

  from liquids · CPC title