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Title: Oxygen-free atomic layer deposition of indium sulfide

Abstract

A method for synthesizing an In(III) N,N'-diisopropylacetamidinate precursor including cooling a mixture comprised of diisopropylcarbodiimide and diethyl ether to approximately -30.degree. C., adding methyllithium drop-wise into the mixture, allowing the mixture to warm to room temperature, adding indium(III) chloride as a solid to the mixture to produce a white solid, dissolving the white solid in pentane to form a clear and colorless solution, filtering the mixture over a celite plug, and evaporating the solution under reduced pressure to obtain a solid In(III) N,N'-diisopropylacetamidinate precursor. This precursor has been further used to develop a novel atomic layer deposition technique for indium sulfide by dosing a reactor with the precursor, purging with nitrogen, dosing with dilute hydrogen sulfide, purging again with nitrogen, and repeating these steps to increase growth.

Inventors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1260247
Patent Number(s):
9,382,618
Application Number:
14/335,745
Assignee:
UChicago Argnonne, LLC (Chicago, IL) ANL
DOE Contract Number:
AC02-06CH11357
Resource Type:
Patent
Resource Relation:
Patent File Date: 2014 Jul 18
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Martinson, Alex B., Hock, Adam S., McCarthy, Robert, and Weimer, Matthew S.. Oxygen-free atomic layer deposition of indium sulfide. United States: N. p., 2016. Web.
Martinson, Alex B., Hock, Adam S., McCarthy, Robert, & Weimer, Matthew S.. Oxygen-free atomic layer deposition of indium sulfide. United States.
Martinson, Alex B., Hock, Adam S., McCarthy, Robert, and Weimer, Matthew S.. 2016. "Oxygen-free atomic layer deposition of indium sulfide". United States. doi:. https://www.osti.gov/servlets/purl/1260247.
@article{osti_1260247,
title = {Oxygen-free atomic layer deposition of indium sulfide},
author = {Martinson, Alex B. and Hock, Adam S. and McCarthy, Robert and Weimer, Matthew S.},
abstractNote = {A method for synthesizing an In(III) N,N'-diisopropylacetamidinate precursor including cooling a mixture comprised of diisopropylcarbodiimide and diethyl ether to approximately -30.degree. C., adding methyllithium drop-wise into the mixture, allowing the mixture to warm to room temperature, adding indium(III) chloride as a solid to the mixture to produce a white solid, dissolving the white solid in pentane to form a clear and colorless solution, filtering the mixture over a celite plug, and evaporating the solution under reduced pressure to obtain a solid In(III) N,N'-diisopropylacetamidinate precursor. This precursor has been further used to develop a novel atomic layer deposition technique for indium sulfide by dosing a reactor with the precursor, purging with nitrogen, dosing with dilute hydrogen sulfide, purging again with nitrogen, and repeating these steps to increase growth.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2016,
month = 7
}

Patent:

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  • Atomic layer deposition (ALD) of indium sulfide (In2S3) films was achieved using a newly synthesized indium precursor and hydrogen sulfide. We obtain dense and adherent thin films free from halide and oxygen impurities. Self-limiting half-reactions are demonstrated at temperatures up to 200°C, where oriented crystalline thin films are obtained without further annealing. Low temperature growth of 0.89 Å/cycle is observed at 150°C while higher growth temperatures gradually reduce the per-cycle growth rate. Rutherford backscattering spectroscopy (RBS) together with depth-profiling Auger electron spectroscopy (AES) reveal a S/In ratio of 1.5 with no detectable carbon, nitrogen, halogen, or oxygen impurities. The resistivitymore » of thin films prior to air exposure decreases with increasing deposition temperature, reaching <1 ohm-cm for films deposited at 225°C. Hall measurements reveal n-type conductivity due to free electron concentrations up to 1018 cm-3 and mobilities of order 1 cm2/(V*s). The digital synthesis of In2S3 via ALD at temperatures up to 225°C may allow high quality thin films to be leveraged in optoelectronic devices including photovoltaic absorbers, buffer layers, and intermediate band materials.« less
  • A method for preparing a metal sulfide thin film using ALD and structures incorporating the metal sulfide thin film. The method includes providing an ALD reactor, a substrate, a first precursor comprising a metal and a second precursor comprising a sulfur compound. The first and the second precursors are reacted in the ALD precursor to form a metal sulfide thin film on the substrate. In a particular embodiment, the metal compound comprises Bis(N,N'-di-sec-butylacetamidinato)dicopper(I) and the sulfur compound comprises hydrogen sulfide (H.sub.2S) to prepare a Cu.sub.2S film. The resulting metal sulfide thin film may be used in among other devices, photovoltaicmore » devices, including interdigitated photovoltaic devices that may use relatively abundant materials for electrical energy production.« less
  • This paper explores the atomic layer deposition (ALD) of indium oxide (In{sub 2}O{sub 3}) films using cyclopentadienyl indium (InCp) and combinations of both molecular oxygen and water as the co-reactants. When either O{sub 2} or H{sub 2}O were used individually as the oxygen source the In{sub 2}O{sub 3} growth was negligible over the temperature range 100-250 C. However, when oxygen and water were used in combination either as a simultaneous exposure or supplied sequentially, In{sub 2}O{sub 3} films were deposited at growth rates of 1.0-1.6 {angstrom}/cycle over the full range of deposition temperatures. In situ quadrupole mass spectrometry and quartzmore » crystal microbalance measurements revealed that water serves the function of releasing ligands from the surface while oxygen performs the role of oxidizing the indium. Since both processes are necessary for sustained growth, both O{sub 2} and H{sub 2}O are required for the In{sub 2}O{sub 3} ALD. The electrical resistivity, mobility, and carrier concentration of the In{sub 2}O{sub 3} films varied dramatically with both the deposition temperature and co-reactant sequence and correlated to a crystallization occurring at {approx}140 C observed by X-ray diffraction and scanning electron microscopy. Using this new process we successfully deposited ALD In{sub 2}O{sub 3} films over large area substrates (12 in. x 18 in.) with very high uniformity in thickness and resistivity.« less
  • This paper explores the atomic layer deposition (ALD) of indium oxide (In 2O 3) films using cyclopentadienyl indium (InCp) and combinations of both molecular oxygen and water as the co-reactants. When either O 2 or H 2O were used individually as the oxygen source the In 2O 3 growth was negligible over the temperature range 100-250 °C. However, when oxygen and water were used in combination either as a simultaneous exposure or supplied sequentially, In 2O 3 films were deposited at growth rates of 1.0-1.6 Å/cycle over the full range of deposition temperatures. In situ quadrupole mass spectrometry and quartzmore » crystal microbalance measurements revealed that water serves the function of releasing ligands from the surface while oxygen performs the role of oxidizing the indium. Since both processes are necessary for sustained growth, both O 2 and H 2O are required for the In 2O 3 ALD. The electrical resistivity, mobility, and carrier concentration of the In 2O 3 films varied dramatically with both the deposition temperature and co-reactant sequence and correlated to a crystallization occurring at ~140 °C observed by X-ray diffraction and scanning electron microscopy. Using this new process we successfully deposited ALD In 2O 3 films over large area substrates (12 in. × 18 in.) with very high uniformity in thickness and resistivity.« less