Alternating multi-source vapor transport deposition

Abstract

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.   
     
     
         2 . A method of making a perovskite film, comprising the steps of:
 (a) 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;   (b) flowing a second carrier gas from a second inlet through the second source tube and exposing a substrate to the sublimated organic halide and the second carrier gas at the second pressure from about 1×10 −4  Torr to about 1×10 2  Torr, thereby forming an organic halide-coated substrate;   (c) 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; and   (d) flowing a first carrier gas from a first inlet through the first source tube and exposing the organic halide-coated 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 the perovskite film.   
     
     
         3 . A method of making a perovskite film, comprising the steps of:
 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;   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   flowing a first carrier gas from a first inlet through the first source tube and flowing a second carrier gas from a second inlet through the second source tube exposing a substrate to the sublimated metal halide and the first carrier gas and the sublimated organic halide and the second carrier gas at a second pressure from about 1×10 −4  Torr to about 1×10 2  Torr, thereby forming the perovskite film.   
     
     
         4 . 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. 
     
     
         5 . The method of  claim 1 , wherein the metal halide is PbI 2 . 
     
     
         6 . 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. 
     
     
         7 . The method of  claim 1 , wherein the organic halide is methylammonium iodide. 
     
     
         8 . The method of  claim 1 , wherein the first carrier gas is N 2  or Ar. 
     
     
         9 . The method of  claim 1 , wherein the second carrier gas is N 2  or Ar. 
     
     
         10 . The method of  claim 1 , wherein the substrate is reversibly fastened to a temperature-controlled stage. 
     
     
         11 . The method of  claim 10 , wherein the temperature of the temperature-controlled stage is from about 60° C. to about 150° C. 
     
     
         12 . The method of  claim 1 , wherein the first pressure is about 10 Torr. 
     
     
         13 . The method of  claim 1 , wherein the second pressure is about 10 Torr. 
     
     
         14 . 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. 
     
     
         15 . (canceled) 
     
     
         16 . (canceled) 
     
     
         17 . The method of  claim 1 , wherein the metal halide coating is from about 50 nm to about 700 nm. 
     
     
         18 . 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 
     
     
         19 . (canceled) 
     
     
         20 . (canceled) 
     
     
         21 . The method of  claim 1 , further comprising repeating steps (b) and (d) up to 50 times. 
     
     
         22 . The method of  claim 1 , wherein the first source tube and the second source tube are oriented horizontally. 
     
     
         23 . The method of  claim 1 , wherein the surface of the substrate is oriented vertically. 
     
     
         24 . (canceled) 
     
     
         25 . A source tube comprising a carrier gas inlet, a metal halide or an organic halide disposed between a first filter and a second filter, and a gas outlet, wherein the first filter and the second filter are substantially permeable to the carrier gas comprising sublimated metal halide or sublimated organic halide. 
     
     
         26 . (canceled)