Non-hydrolytic metal oxide films for perovskite halide overcoating and stabilization

Patent metadata

Field	Value
Publication number	US-2017040560-A1
Application number	US-201514819248-A
Country	US
Kind code	A1
Filing date	Aug 5, 2015
Priority date	Aug 5, 2015
Publication date	Feb 9, 2017
Grant date	—

Abstract

A method of protecting a perovskite halide film from moisture and temperature includes positioning the perovskite halide film in a chamber. The chamber is maintained at a temperature of less than 200 degrees Celsius. An organo-metal compound is inserted into the chamber. A non-hydrolytic oxygen source is subsequently inserted into the chamber. The inserting of the organo-metal compound and subsequent inserting of the non-hydrolytic oxygen source into the chamber is repeated for a predetermined number of cycles. The non-hydrolytic oxygen source and the organo-metal compound interact in the chamber to deposit a non-hydrolytic metal oxide film on perovskite halide film. The non-hydrolytic metal oxide film protects the perovskite halide film from relative humidity of greater than 35% and a temperature of greater than 150 degrees Celsius, respectively.

First claim

What is claimed is:

1 . A method of protecting a perovskite halide film from moisture and temperature, comprising:
positioning the perovskite halide film in a chamber; maintaining the chamber at a temperature of less than 200 degrees Celsius; inserting an organo-metal compound into the chamber; subsequently inserting a non-hydrolytic oxygen source into the chamber; and repeating the inserting of the organo-metal compound and subsequent inserting of the non-hydrolytic oxygen source into the chamber for a predetermined number of cycles, wherein, the non-hydrolytic oxygen source and the organo-metal compound interact in the chamber to deposit a non-hydrolytic metal oxide film on the perovskite halide film, the non-hydrolytic metal oxide film protecting the perovskite halide film from relative humidity of greater than 35% and a temperature of greater than 150 degrees Celsius.

2 . The method of claim 1 , further comprising:
inserting an organo-metal compound into the chamber; subsequently inserting a hydrolytic oxygen source into the chamber; and repeating the inserting of the organo-metal compound and subsequent inserting of the hydrolytic oxygen source into the chamber for a second predetermined number of cycles, wherein, the organo-metal compound and hydrolytic oxygen source interact in the chamber to deposit a hydrolytic metal oxide film on the non-hydrolytic metal oxide film.

3 . The method of claim 1 , wherein the non-hydrolytic oxygen source includes a carboxylic acid.

4 . The method of claim 3 , wherein the carboxylic acid includes at least one of acetic acid and formic acid.

5 . The method of claim 1 , wherein the organo-metal compound includes at least one of aluminum isopropoxide, aluminum triisopropoxide, titanium isopropoxide, titanium tetraisopropoxide, trimethylaluminum, dimethylaluminum isopropoxide, titanium phenyltriisopropoxide, titanocene dichloride, methyltitanium trichloride, aluminum trichloride, titanium tetrachloride or methyltriisopropoxytitanium.

6 . The method of claim 5 , wherein the non-hydrolytic metal oxide film includes at least one of aluminum oxide, titanium dioxide, zirconium oxide, hafnium oxide or silicon oxide.

7 . The method of claim 2 , wherein the hydrolytic oxygen source includes at least one of water or ozone.

8 . The method of claim 1 , wherein the perovskite halide film includes a compound of formula I:
ABX 3   (I)
wherein,
A is organic or inorganic cation,
B is a metal cation, and
X is a halide.

9 . The method of claim 8 , wherein the perovskite halide film includes a compound of formula II:
ABY 3-x Z x   (II)
wherein,
A is methylammonium or formamidinium,
B is Pb or Sn,
Y is I, Cl or Br,
Z is I, Cl or Br, and
x is 0, 1, 2 or 3.

10 . A method of fabricating a photovoltaic cell, comprising:
depositing a perovskite halide film on a substrate; positioning the substrate in a chamber; maintaining the chamber at a temperature of less than 200 degrees Celsius; inserting a titanium isopropoxide gas into the chamber; subsequently inserting a non-hydrolytic oxygen source into the chamber; and repeating the inserting of titanium isopropoxide gas and subsequent inserting of the non-hydrolytic oxygen source into the chamber for a predetermined number of cycles, wherein, the non-hydrolytic oxygen source and the titanium isopropoxide gas interact in the chamber to deposit a non-hydrolytic titanium dioxide film on the perovskite halide film, the non-hydrolytic titanium dioxide film protecting the perovskite halide film from relative humidity of greater than 35% and a temperature of greater than 150 degrees Celsius, the non-hydrolytic titanium dioxide film transporting charges created in the perovskite halide film to an electrode in contact with the non-hydrolytic titanium dioxide film.

11 . The method of claim 10 , wherein the substrate includes a conductive substrate or an electronically conducting film positioned on the substrate.

12 . The method of claim 11 , wherein the method further comprises:
prior to depositing the perovskite halide film on the substrate, positioning the substrate in the chamber; inserting the titanium isopropoxide gas into the chamber; subsequently inserting the non-hydrolytic oxygen source into the chamber; and repeating the inserting of the titanium isopropoxide gas and subsequent inserting of the non-hydrolytic oxygen source into the chamber for a predetermined number of cycles, wherein, the non-hydrolytic oxygen source and the titanium isopropoxide interact on the substrate to deposit a base non-hydrolytic titanium dioxide film on the substrate, the perovskite halide film coated on the base non-hydrolytic titanium dioxide film.

13 . The method of claim 10 , wherein the non-hydrolytic oxygen source includes a carboxylic acid.

14 . The method of claim 10 , further comprising:
inserting an organo-metal compound into the chamber; subsequently inserting a hydrolytic oxygen source into the chamber; and repeating the inserting of the organo-metal compound and subsequent inserting of the hydrolytic oxygen source into the chamber for a predetermined number of cycles, wherein, the hydrolytic oxygen source and the organo-metal compound interact in the chamber to deposit a hydrolytic metal oxide film on the non-hydrolytic titanium dioxide film.

15 . The method of claim 14 , wherein the organo-metal compound includes at least one of a aluminum isopropoxide, aluminum triisopropoxide, titanium isopropoxide, titanium tetraisopropoxide, trimethyl aluminum, dimethylaluminum isopropoxide, titanium phenyltriisopropoxide, titanocene dichloride, methyltitanium trichloride, aluminum chloride, titanium chloride or methyltriisopropoxytitanium.

16 . The method of claim 14 , wherein the hydrolytic oxygen source includes at least one of water or ozone.

17 . The method of claim 10 , wherein the perovskite halide film includes a compound of formula I:
ABX 3   (I)
wherein,
A is organic or inorganic cation,
B is a metal cation, and
X is a halide.

18 . A photovoltaic device comprising:
a substrate; a conductive film positioned on the substrate; a semiconducting film positioned on the conductive film; a perovskite halide film positioned on the semiconducting film; and a non-hydrolytic metal oxide film positioned on the perovskite halide film, the non-hydrolytic metal oxide film protecting the perovskite halide film from relative humidity of greater than 35% and a temperature of greater than 150 degrees Celsius.

19 . The photovoltaic device of claim 18 , wherein the semi-conducting film includes a non-hydrolytic titanium dioxide film.

20 . The photovoltaic device of claim 18 , wherein the non-hydrolytic metal oxide film includes at least one of a non-hydrolytic aluminum oxide film or a non-hydrolytic titanium dioxide film.

21 . The photovoltaic device of claim 18 , wherein the photovoltaic device further comprises:
a hydrolytic metal oxide film deposited on the non-hydrolytic metal oxide film.

Assignees

• Uchicago Argonne Llc

Inventors

• Martinson Alex B
• Kim In Soo

Classifications

• H01L2251/303

  Electricity · mapped topic

• H01L51/4253

  Electricity · mapped topic

• H01L31/032

  Electricity · mapped topic

• H01L51/448 Primary

  Electricity · mapped topic

• H01L31/02167

  Electricity · mapped topic