A Charge-Orbital Balance Picture of Doping in Colloidal Quantum Dot Solids

Oleksandr Voznyy; David Zhitomirsky; Philipp Stadler; Zhijun Ning; Sjoerd Hoogland; Edward H. Sargent

doi:10.1021/nn303364d

A Charge-Orbital Balance Picture of Doping in Colloidal Quantum Dot Solids

Oleksandr Voznyy, David Zhitomirsky, Philipp Stadler, Zhijun Ning, Sjoerd Hoogland, Edward H. Sargent

Research output: Contribution to journal › Article › peer-review

223 Scopus citations

Abstract

We present a framework-validated using both modeling and experiment-to predict doping in CQD films. In the ionic semiconductors widely deployed in CQD films, the framework reduces to a simple accounting of the contributions of the oxidation state of each constituent, including both inorganic species and organic ligands. We use density functional theory simulations to confirm that the type of doping can be reliably predicted based on the overall stoichiometry of the CQDs, largely independent of microscopic geometrical bonding configurations. Studies employing field-effect transistors constructed from CQDs that have undergone various chemical treatments, coupled with Rutherford backscattering and X-ray photoelectron spectroscopy to provide compositional analysis, allow us to test and confirm the proposed model in an experimental framework. We investigate both p- and n-type electronic doping spanning a wide range of carrier concentrations from 10 16 cm -3 to over 10 18 cm -3, and demonstrate reversible switching between p- and n-type doping by changing the CQD stoichiometry. We show that the summation of the contributions from all cations and anions within the film can be used to predict accurately the majority carrier type. The findings enable predictable control over majority carrier concentration via tuning of the overall stoichiometry. © 2012 American Chemical Society.

Original language	English (US)
Pages (from-to)	8448-8455
Number of pages	8
Journal	ACS Nano
Volume	6
Issue number	9
DOIs	https://doi.org/10.1021/nn303364d
State	Published - Sep 7 2012
Externally published	Yes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): KUS-11-009-21
Acknowledgements: This publication is based in part on work supported by Award KUS-11-009-21, made by King Abdullah University of Science and Technology (KAUST), by the Ontario Research Fund Research Excellence Program, and by the Natural Sciences and Engineering Research Council (NSERC) of Canada. David Zhitomirsky would like to acknowledge his NSERC CGS D scholarship. We thank Angstrom Engineering, Inc. and Innovative Technology, Inc. for useful discussions regarding material deposition methods and control of the glovebox environment, respectively. We thank Lyudmila Goncharova for help in RBS measurements and Mark Greiner for help in XPS measurements. We thank Larissa Levina for PbS COD synthesis and Melissa Furukawa for FET measurements. Computations were performed on the GPC supercomputer at the SciNet49 HPC Consortium. SciNet is funded by the Canada Foundation for Innovation under the auspices of Compute Canada, the Government of Ontario, Ontario Research Fund-Research Excellence, and the University of Toronto.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.

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title = "A Charge-Orbital Balance Picture of Doping in Colloidal Quantum Dot Solids",

abstract = "We present a framework-validated using both modeling and experiment-to predict doping in CQD films. In the ionic semiconductors widely deployed in CQD films, the framework reduces to a simple accounting of the contributions of the oxidation state of each constituent, including both inorganic species and organic ligands. We use density functional theory simulations to confirm that the type of doping can be reliably predicted based on the overall stoichiometry of the CQDs, largely independent of microscopic geometrical bonding configurations. Studies employing field-effect transistors constructed from CQDs that have undergone various chemical treatments, coupled with Rutherford backscattering and X-ray photoelectron spectroscopy to provide compositional analysis, allow us to test and confirm the proposed model in an experimental framework. We investigate both p- and n-type electronic doping spanning a wide range of carrier concentrations from 10 16 cm -3 to over 10 18 cm -3, and demonstrate reversible switching between p- and n-type doping by changing the CQD stoichiometry. We show that the summation of the contributions from all cations and anions within the film can be used to predict accurately the majority carrier type. The findings enable predictable control over majority carrier concentration via tuning of the overall stoichiometry. {\textcopyright} 2012 American Chemical Society.",

author = "Oleksandr Voznyy and David Zhitomirsky and Philipp Stadler and Zhijun Ning and Sjoerd Hoogland and Sargent, {Edward H.}",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-11-009-21 Acknowledgements: This publication is based in part on work supported by Award KUS-11-009-21, made by King Abdullah University of Science and Technology (KAUST), by the Ontario Research Fund Research Excellence Program, and by the Natural Sciences and Engineering Research Council (NSERC) of Canada. David Zhitomirsky would like to acknowledge his NSERC CGS D scholarship. We thank Angstrom Engineering, Inc. and Innovative Technology, Inc. for useful discussions regarding material deposition methods and control of the glovebox environment, respectively. We thank Lyudmila Goncharova for help in RBS measurements and Mark Greiner for help in XPS measurements. We thank Larissa Levina for PbS COD synthesis and Melissa Furukawa for FET measurements. Computations were performed on the GPC supercomputer at the SciNet49 HPC Consortium. SciNet is funded by the Canada Foundation for Innovation under the auspices of Compute Canada, the Government of Ontario, Ontario Research Fund-Research Excellence, and the University of Toronto. This publication acknowledges KAUST support, but has no KAUST affiliated authors.",

year = "2012",

month = sep,

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doi = "10.1021/nn303364d",

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AU - Stadler, Philipp

AU - Ning, Zhijun

AU - Hoogland, Sjoerd

AU - Sargent, Edward H.

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-11-009-21 Acknowledgements: This publication is based in part on work supported by Award KUS-11-009-21, made by King Abdullah University of Science and Technology (KAUST), by the Ontario Research Fund Research Excellence Program, and by the Natural Sciences and Engineering Research Council (NSERC) of Canada. David Zhitomirsky would like to acknowledge his NSERC CGS D scholarship. We thank Angstrom Engineering, Inc. and Innovative Technology, Inc. for useful discussions regarding material deposition methods and control of the glovebox environment, respectively. We thank Lyudmila Goncharova for help in RBS measurements and Mark Greiner for help in XPS measurements. We thank Larissa Levina for PbS COD synthesis and Melissa Furukawa for FET measurements. Computations were performed on the GPC supercomputer at the SciNet49 HPC Consortium. SciNet is funded by the Canada Foundation for Innovation under the auspices of Compute Canada, the Government of Ontario, Ontario Research Fund-Research Excellence, and the University of Toronto. This publication acknowledges KAUST support, but has no KAUST affiliated authors.

PY - 2012/9/7

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N2 - We present a framework-validated using both modeling and experiment-to predict doping in CQD films. In the ionic semiconductors widely deployed in CQD films, the framework reduces to a simple accounting of the contributions of the oxidation state of each constituent, including both inorganic species and organic ligands. We use density functional theory simulations to confirm that the type of doping can be reliably predicted based on the overall stoichiometry of the CQDs, largely independent of microscopic geometrical bonding configurations. Studies employing field-effect transistors constructed from CQDs that have undergone various chemical treatments, coupled with Rutherford backscattering and X-ray photoelectron spectroscopy to provide compositional analysis, allow us to test and confirm the proposed model in an experimental framework. We investigate both p- and n-type electronic doping spanning a wide range of carrier concentrations from 10 16 cm -3 to over 10 18 cm -3, and demonstrate reversible switching between p- and n-type doping by changing the CQD stoichiometry. We show that the summation of the contributions from all cations and anions within the film can be used to predict accurately the majority carrier type. The findings enable predictable control over majority carrier concentration via tuning of the overall stoichiometry. © 2012 American Chemical Society.

AB - We present a framework-validated using both modeling and experiment-to predict doping in CQD films. In the ionic semiconductors widely deployed in CQD films, the framework reduces to a simple accounting of the contributions of the oxidation state of each constituent, including both inorganic species and organic ligands. We use density functional theory simulations to confirm that the type of doping can be reliably predicted based on the overall stoichiometry of the CQDs, largely independent of microscopic geometrical bonding configurations. Studies employing field-effect transistors constructed from CQDs that have undergone various chemical treatments, coupled with Rutherford backscattering and X-ray photoelectron spectroscopy to provide compositional analysis, allow us to test and confirm the proposed model in an experimental framework. We investigate both p- and n-type electronic doping spanning a wide range of carrier concentrations from 10 16 cm -3 to over 10 18 cm -3, and demonstrate reversible switching between p- and n-type doping by changing the CQD stoichiometry. We show that the summation of the contributions from all cations and anions within the film can be used to predict accurately the majority carrier type. The findings enable predictable control over majority carrier concentration via tuning of the overall stoichiometry. © 2012 American Chemical Society.

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JO - ACS Nano

JF - ACS Nano

IS - 9

ER -

A Charge-Orbital Balance Picture of Doping in Colloidal Quantum Dot Solids

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