Alternating multi-source vapor transport deposition
Disclosed are vapor transport deposition systems and methods for alternating sequential vapor transport deposition of multi-component perovskite thin-films. The systems include multiple vaporizing sources that are mechanically or digitally controlled for high throughput deposition. Alternating sequential deposition provides faster sequential deposition, and allows for reduced material degradation due to different vapor temperatures.
1. A method of making a perovskite film, comprising the steps of:
(a) heating a metal halide in a first source tube at a first temperature from about 350° C. to about 480° C. at a first pressure from about 1×10 −4 Torr to about 1×10 2 Torr, thereby producing a sublimated metal halide;
(b) flowing a first carrier gas from a first inlet through the first source tube and exposing a substrate to the sublimated metal halide and the first carrier gas at a second pressure from about 1×10 4 Torr to about 1×10 2 Torr, thereby forming a metal halide-coated substrate;
(c) heating an organic halide in a second source tube at a second temperature from about 100° C. to about 250° C. at a third pressure from about 1×10 −4 Torr to about 1×10 2 Torr, thereby producing a sublimated organic halide; and
(d) flowing a second carrier gas from a second inlet through the second source tube and exposing the metal halide-coated substrate to the sublimated organic halide and a second carrier gas at the second pressure from about 1×10 −4 Torr to about 1×10 2 Torr, thereby forming the perovskite film,
wherein the metal halide is disposed between a first filter disc and a second filter disc in the first source tube; the organic halide is disposed between a first filter disc and a second filter disc in the second source tube; and each first filter disc and each second filter disc comprises silicon carbide (SiC),
steps (b) and (d) are alternatingly repeated at least 3 times, and the perovskite film comprises an alternating sequence of deposited layer pairs.
2. The method of claim 1 , wherein the metal halide is PbI 2 , PbBr 2 , PbCl 2 , SnI 2 , SnBr 2 , SnCl 2 , CsI, CsBr, or CsCl.
3. The method of claim 1 , wherein the metal halide is PbI 2 .
4. The method of claim 1 , wherein the organic halide is methylammonium iodide (MAI), methylammonium bromide, methylammonium chloride, formamidinium iodide (FAI), formamidinium bromide, or formamidinium chloride.
5. The method of claim 1 , wherein the organic halide is methylammonium iodide.
6. The method of claim 1 , wherein the first carrier gas is N 2 or Ar.
7. The method of claim 1 , wherein the second carrier gas is N 2 or Ar.
8. The method of claim 1 , wherein the substrate is reversibly fastened to a temperature-controlled stage.
9. The method of claim 8 , wherein the temperature of the temperature-controlled stage is from about 60° C. to about 150° C.
10. The method of claim 1 , wherein the first pressure is about 10 Torr.
11. The method of claim 1 , wherein the second pressure is about 10 Torr.
12. The method of claim 1 , wherein the substrate is exposed to the sublimated metal halide and the first carrier gas for a first period of time.
13. The method of claim 12 , wherein the first period of time is from about 1 millisecond to about 5 minutes.
14. The method of claim 12 , wherein the first period of time is about 3 minutes.
15. The method of claim 14 , wherein the metal halide coating is from about 50 nm to about 700 nm.
16. The method of claim 1 , wherein the metal halide-coated substrate is exposed to the sublimated organic halide and the second carrier gas for a second period of time.
17. The method of claim 16 , wherein the second period of time is from about 1 millisecond to about 3 min.
18. The method of claim 16 , wherein the second period of time is about 90 seconds.
19. The method of claim 1 , wherein the first source tube and the second source tube are oriented horizontally.
20. The method of claim 1 , wherein the surface of the substrate is oriented vertically.
21. The method of claim 1 , wherein steps (b) and (d) are repeated up to 12 times.
22. The method of claim 1 , wherein steps (b) and (d) are repeated up to 50 times.
23. The method of claim 1 , wherein the metal halide-coated substrate has a growth rate of at least 1.3 nm/s.
24. The method of claim 1 , wherein the perovskite film has a perovskite crystal grain size of about 150-200 nm.