Sequential infiltration synthesis of group 13 oxide electronic materials

Patent metadata

Field	Value
Publication number	US-2021017649-A1
Application number	US-201916515718-A
Country	US
Kind code	A1
Filing date	Jul 18, 2019
Priority date	Jul 18, 2019
Publication date	Jan 21, 2021
Grant date	—

Abstract

The sequential infiltration synthesis (SIS) of group 13 indium and gallium oxides (In2O3 and Ga2O3) into polymethyl methacrylate (PMMA) thin films is demonstrated. Examples highlight the an SIS process using trimethylindium (TMIn) and trimethylgallium (TMGa), respectively, with water. In situ Fourier transform infrared (FTIR) spectroscopy reveals that these metal alkyl precursors reversibly associate with the carbonyl groups of PMMA in analogy to trimethylaluminum (TMAl), however with significantly lower affinity. SIS with TMIn and water enables the growth of In2O3 at 80° C., well below the onset temperature of atomic layer deposition (ALD) using these precursors.

First claim

What is claimed is:

1 . A method depositing a group 13 oxide comprising:
providing a base material in a reactor; and depositing an oxide of indium or gallium using sequential infiltration synthesis (SIS) process including at least one cycle of:
pulsing a first metal precursor comprising indium or gallium into the reactor for a first metal precursor pulse time;
exposing the base material to the first metal precursor for a first metal precursor exposure time and at a first partial pressure, the first metal precursor infiltrating at least a portion of the base material and binding therein with the base material;
purging the reactor of the first metal precursor;
pulsing a co-reactant precursor into the reactor for a first co-reactant pulse time;
exposing the base material to the co-reactant precursor for a co-reactant precursor exposure time and at a second partial pressure, the co-reactant precursor infiltrating at least a portion of the base material and binding therein to form the oxide; and
purging the reactor of the co-reactant precursor.

2 . The method of claim 1 , wherein the first metal precursor pulse time is greater than 0 seconds to 30 seconds.

3 . The method of claim 1 , wherein the first metal precursor exposure time is greater than 0 seconds to 500 seconds.

4 . The method of claim 1 , wherein purging the reactor proceeds for a first metal precursor purge time of greater than 0 seconds to 30 seconds and comprises reducing the pressure within the reactor to substantially a vacuum.

5 . The method of claim 4 , wherein the first metal precursor purge time of 2 to 5 seconds.

6 . The method of claim 1 , wherein the co-reactant precursor pulse time is greater than 0 seconds to 120 seconds.

7 . The method of claim 1 , wherein the co-reactant precursor exposure time is greater than 0 seconds to 500 seconds.

8 . The method of claim 1 , wherein purging the reactor of the co-reactant precursor proceeds for greater than 0 seconds to 500 seconds and comprises reducing the pressure within the reactor to substantially a vacuum.

9 . The method of claim 1 , wherein the first metal precursor is selected from the group consisting of trimethylindium and trimethylgallium.

10 . The method of claim 1 , wherein the co-reactant precursor is selected from the group consisting of water, ozone, and hydrogen peroxide.

11 . The method of claim 1 , wherein the first metal precursor comprises gallium and the oxide is gallium oxide.

12 . The method of claim 1 , further comprising depositing an dopant using sequential infiltration synthesis (SIS) process.

13 . The method of claim 1 , wherein the base material comprises PMMA, PVP, or PAA.

14 . The method of claim 1 wherein the first partial pressure is at least 50 Torr.

15 . The method of claim 1 , wherein the SIS proceeds at a temperature of 70-90° C.

16 . A method depositing a group 13 oxide comprising:
providing a base material in a reactor; and depositing an oxide of indium or gallium using sequential infiltration synthesis (SIS) process including at least one cycle of:
pulsing a first metal precursor comprising indium or gallium into the reactor for a first metal precursor pulse time;
exposing the base material to the first metal precursor to form a first metal adduct between the first metal precursor and the base material within the base material;
purging the reactor of the first metal precursor for a first metal precursor purge time that is less than the lifespan of the first metal adduct;
pulsing a co-reactant precursor into the reactor for a first co-reactant pulse time;
exposing the base material to the co-reactant precursor for a co-reactant precursor exposure time and at a second partial pressure, the co-reactant precursor infiltrating at least a portion of the base material and reacting with the first metal adduct within the base material to form the oxide; and
purging the reactor of the co-reactant precursor.

17 . The method of claim 16 , wherein the at least once cycle comprises at least 10 cycles.

18 . The method of claim 16 , wherein the SIS is at a reaction temperature of 70-90° C.

19 . The method of claim 16 , wherein 70% of the first metal aducts are reacted with the co-reactant.

20 . A composition of matter comprising:
a polymer; and an oxide of indium or gallium deposited therein.

Assignees

• Uchicago Argonne Llc

Inventors

• Martinson Alex B
• Darling Seth B
• Waldman Ruben

Classifications

• C08F293/00

  Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule (on to polymers modified by introduction of unsaturated end groups C08F290/02) · CPC title

• C08F126/10

  N-Vinyl-pyrrolidone · CPC title

• C08F120/14

  Methyl esters {, e.g. methyl (meth)acrylate} · CPC title

• C08F120/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C23C16/407 Primary

  of zinc, germanium, cadmium, indium, tin, thallium or bismuth · CPC title