Bandgap Engineering of Indium Phosphide-Based Core/Shell Heterostructures Through Shell Composition and Thickness
Abstract
The large bulk bandgap (1.35 eV) and Bohr radius (~10 nm) of InP semiconductor nanocrystals provides bandgap tunability over a wide spectral range, providing superior color tuning compared to that of CdSe quantum dots. In this paper, the dependence of the bandgap, photoluminescence emission, and exciton radiative lifetime of core/shell quantum dot heterostructures has been investigated using colloidal InP core nanocrystals with multiple diameters (1.5, 2.5, and 3.7 nm). The shell thickness and composition dependence of the bandgap for type-I and type-II heterostructures was observed by coating the InP core with ZnS, ZnSe, CdS, or CdSe through one to ten iterations of a successive ion layer adsorption and reaction (SILAR)-based shell deposition. The empirical results are compared to bandgap energy predictions made with effective mass modeling. Photoluminescence emission colors have been successfully tuned throughout the visible and into the near infrared (NIR) wavelength ranges for type-I and type-II heterostructures, respectively. Based on sizing data from transmission electron microscopy (TEM), it is observed that at the same particle diameter, average radiative lifetimes can differ as much as 20-fold across different shell compositions due to the relative positions of valence and conduction bands. In this direct comparison of InP/ZnS, InP/ZnSe, InP/CdS, andmore »
- Authors:
- Boston Univ., MA (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1482841
- Alternate Identifier(s):
- OSTI ID: 1484664
- Report Number(s):
- LA-UR-18-28366
Journal ID: ISSN 2296-2646
- Grant/Contract Number:
- 89233218CNA000001
- Resource Type:
- Published Article
- Journal Name:
- Frontiers in Chemistry
- Additional Journal Information:
- Journal Volume: 6; Journal ID: ISSN 2296-2646
- Publisher:
- Frontiers Research Foundation
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Material Science
Citation Formats
Toufanian, Reyhaneh, Piryatinski, Andrei, Mahler, Andrew H., Iyer, Radhika, Hollingsworth, Jennifer A., and Dennis, Allison M. Bandgap Engineering of Indium Phosphide-Based Core/Shell Heterostructures Through Shell Composition and Thickness. United States: N. p., 2018.
Web. doi:10.3389/fchem.2018.00567.
Toufanian, Reyhaneh, Piryatinski, Andrei, Mahler, Andrew H., Iyer, Radhika, Hollingsworth, Jennifer A., & Dennis, Allison M. Bandgap Engineering of Indium Phosphide-Based Core/Shell Heterostructures Through Shell Composition and Thickness. United States. doi:10.3389/fchem.2018.00567.
Toufanian, Reyhaneh, Piryatinski, Andrei, Mahler, Andrew H., Iyer, Radhika, Hollingsworth, Jennifer A., and Dennis, Allison M. Tue .
"Bandgap Engineering of Indium Phosphide-Based Core/Shell Heterostructures Through Shell Composition and Thickness". United States. doi:10.3389/fchem.2018.00567.
@article{osti_1482841,
title = {Bandgap Engineering of Indium Phosphide-Based Core/Shell Heterostructures Through Shell Composition and Thickness},
author = {Toufanian, Reyhaneh and Piryatinski, Andrei and Mahler, Andrew H. and Iyer, Radhika and Hollingsworth, Jennifer A. and Dennis, Allison M.},
abstractNote = {The large bulk bandgap (1.35 eV) and Bohr radius (~10 nm) of InP semiconductor nanocrystals provides bandgap tunability over a wide spectral range, providing superior color tuning compared to that of CdSe quantum dots. In this paper, the dependence of the bandgap, photoluminescence emission, and exciton radiative lifetime of core/shell quantum dot heterostructures has been investigated using colloidal InP core nanocrystals with multiple diameters (1.5, 2.5, and 3.7 nm). The shell thickness and composition dependence of the bandgap for type-I and type-II heterostructures was observed by coating the InP core with ZnS, ZnSe, CdS, or CdSe through one to ten iterations of a successive ion layer adsorption and reaction (SILAR)-based shell deposition. The empirical results are compared to bandgap energy predictions made with effective mass modeling. Photoluminescence emission colors have been successfully tuned throughout the visible and into the near infrared (NIR) wavelength ranges for type-I and type-II heterostructures, respectively. Based on sizing data from transmission electron microscopy (TEM), it is observed that at the same particle diameter, average radiative lifetimes can differ as much as 20-fold across different shell compositions due to the relative positions of valence and conduction bands. In this direct comparison of InP/ZnS, InP/ZnSe, InP/CdS, and InP/CdSe core/shell heterostructures, we clearly delineate the impact of core size, shell composition, and shell thickness on the resulting optical properties. Specifically, Zn-based shells yield type-I structures that are color tuned through core size, while the Cd-based shells yield type-II particles that emit in the NIR regardless of the starting core size if several layers of CdS(e) have been successfully deposited. Particles with thicker CdS(e) shells exhibit longer photoluminescence lifetimes, while little shell-thickness dependence is observed for the Zn-based shells. Taken together, these InP-based heterostructures demonstrate the extent to which we are able to precisely tailor the material properties of core/shell particles using core/shell dimensions and composition as variables.},
doi = {10.3389/fchem.2018.00567},
journal = {Frontiers in Chemistry},
number = ,
volume = 6,
place = {United States},
year = {2018},
month = {11}
}
DOI: 10.3389/fchem.2018.00567
Web of Science
Figures / Tables:

Works referenced in this record:
Elucidation of Two Giants: Challenges to Thick-Shell Synthesis in CdSe/ZnSe and ZnSe/CdS Core/Shell Quantum Dots
journal, March 2015
- Acharya, Krishna P.; Nguyen, Hue M.; Paulite, Melissa
- Journal of the American Chemical Society, Vol. 137, Issue 11
The effect of nanocrystal surface structure on the luminescence properties: Photoemission study of HF-etched InP nanocrystals
journal, August 2005
- Adam, S.; Talapin, D. V.; Borchert, H.
- The Journal of Chemical Physics, Vol. 123, Issue 8
Semiconductor Clusters, Nanocrystals, and Quantum Dots
journal, February 1996
- Alivisatos, A. P.
- Science, Vol. 271, Issue 5251, p. 933-937
Effect of Thermal Fluctuations on the Radiative Rate in Core/Shell Quantum Dots
journal, February 2017
- Balan, Arunima D.; Eshet, Hagai; Olshansky, Jacob H.
- Nano Letters, Vol. 17, Issue 3
Colloidal Two-Dimensional Systems: CdSe Quantum Shells and Wells
journal, October 2003
- Battaglia, David; Li, Jack J.; Wang, Yunjun
- Angewandte Chemie International Edition, Vol. 42, Issue 41, p. 5035-5039
Formation of High Quality InP and InAs Nanocrystals in a Noncoordinating Solvent
journal, September 2002
- Battaglia, David; Peng, Xiaogang
- Nano Letters, Vol. 2, Issue 9
Exciton Fine Structure and Lattice Dynamics in InP/ZnSe Core/Shell Quantum Dots
journal, July 2018
- Brodu, Annalisa; Ballottin, Mariana V.; Buhot, Jonathan
- ACS Photonics, Vol. 5, Issue 8
Quantum dots as fluorescent probes: Synthesis, surface chemistry, energy transfer mechanisms, and applications
journal, April 2018
- H. R., Chandan; Schiffman, Jessica D.; Balakrishna, R. Geetha
- Sensors and Actuators B: Chemical, Vol. 258
Nearly Blinking-Free, High-Purity Single-Photon Emission by Colloidal InP/ZnSe Quantum Dots
journal, September 2017
- Chandrasekaran, Vigneshwaran; Tessier, Mickaël D.; Dupont, Dorian
- Nano Letters, Vol. 17, Issue 10
Compact high-quality CdSe–CdS core–shell nanocrystals with narrow emission linewidths and suppressed blinking
journal, February 2013
- Chen, Ou; Zhao, Jing; Chauhan, Vikash P.
- Nature Materials, Vol. 12, Issue 5
Improved performance and stability in quantum dot solar cells through band alignment engineering
journal, May 2014
- Chuang, Chia-Hao M.; Brown, Patrick R.; Bulović, Vladimir
- Nature Materials, Vol. 13, Issue 8, p. 796-801
(CdSe)ZnS Core−Shell Quantum Dots: Synthesis and Characterization of a Size Series of Highly Luminescent Nanocrystallites
journal, November 1997
- Dabbousi, B. O.; Rodriguez-Viejo, J.; Mikulec, F. V.
- The Journal of Physical Chemistry B, Vol. 101, Issue 46, p. 9463-9475
Synthesis of Luminescent Thin-Film CdSe/ZnSe Quantum Dot Composites Using CdSe Quantum Dots Passivated with an Overlayer of ZnSe
journal, January 1996
- Danek, Michal; Jensen, Klavs F.; Murray, Chris B.
- Chemistry of Materials, Vol. 8, Issue 1
Suppressed Blinking and Auger Recombination in Near-Infrared Type-II InP/CdS Nanocrystal Quantum Dots
journal, October 2012
- Dennis, Allison M.; Mangum, Benjamin D.; Piryatinski, Andrei
- Nano Letters, Vol. 12, Issue 11
Quantum Dot–Fluorescent Protein FRET Probes for Sensing Intracellular pH
journal, March 2012
- Dennis, Allison M.; Rhee, Won Jong; Sotto, David
- ACS Nano, Vol. 6, Issue 4
The Electronic Structure of Semiconductor Nanocrystals
journal, August 2000
- Efros, Al. L.; Rosen, M.
- Annual Review of Materials Science, Vol. 30, Issue 1
Mysteries of TOPSe Revealed: Insights into Quantum Dot Nucleation
journal, August 2010
- Evans, Christopher M.; Evans, Meagan E.; Krauss, Todd D.
- Journal of the American Chemical Society, Vol. 132, Issue 32, p. 10973-10975
InP quantum dots: Electronic structure, surface effects, and the redshifted emission
journal, July 1997
- Fu, Huaxiang; Zunger, Alex
- Physical Review B, Vol. 56, Issue 3
Synthesis of Size-Selected, Surface-Passivated InP Nanocrystals
journal, January 1996
- Guzelian, A. A.; Katari, J. E. B.; Kadavanich, A. V.
- The Journal of Physical Chemistry, Vol. 100, Issue 17
Near-infrared fluorophores for biomedical imaging
journal, January 2017
- Hong, Guosong; Antaris, Alexander L.; Dai, Hongjie
- Nature Biomedical Engineering, Vol. 1, Issue 1
Highly Emissive Multiexcitons in Steady-State Photoluminescence of Individual “Giant” CdSe/CdS Core/Shell Nanocrystals
journal, July 2010
- Htoon, H.; Malko, A. V.; Bussian, D.
- Nano Letters, Vol. 10, Issue 7
InP/ZnSe/ZnS: A Novel Multishell System for InP Quantum Dots for Improved Luminescence Efficiency and Its application in a Light-Emitting Device
journal, June 2012
- Ippen, Christian; Greco, Tonino; Wedel, Armin
- Journal of Information Display, Vol. 13, Issue 2
On the use of time-resolved photoluminescence as a probe of nanocrystal photoexcitation dynamics
journal, January 2010
- Jones, Marcus; Scholes, Gregory D.
- Journal of Materials Chemistry, Vol. 20, Issue 18
A Reduction Pathway in the Synthesis of PbSe Nanocrystal Quantum Dots
journal, August 2009
- Joo, Jin; Pietryga, Jeffrey M.; McGuire, John A.
- Journal of the American Chemical Society, Vol. 131, Issue 30
Building devices from colloidal quantum dots
journal, August 2016
- Kagan, C. R.; Lifshitz, E.; Sargent, E. H.
- Science, Vol. 353, Issue 6302
Quantum Confinement Theory of Auger-Assisted Biexciton Recombination Dynamics in Type-I and Quasi Type-II Quantum Dots
journal, July 2018
- Kaledin, Alexey L.; Kong, Degui; Wu, Kaifeng
- The Journal of Physical Chemistry C, Vol. 122, Issue 32
Shell-Thickness-Dependent Biexciton Lifetime in Type I and Quasi-Type II CdSe@CdS Core/Shell Quantum Dots
journal, December 2017
- Kong, Degui; Jia, Yanyan; Ren, Yueping
- The Journal of Physical Chemistry C, Vol. 122, Issue 25
Ultrastable, highly luminescent quantum dot composites based on advanced surface manipulation strategy for flexible lighting-emitting
journal, June 2018
- Kong, Lingqing; Zhang, Lin; Meng, Zhaohui
- Nanotechnology, Vol. 29, Issue 31
Charge-extraction strategies for colloidal quantum dot photovoltaics
journal, February 2014
- Lan, Xinzheng; Masala, Silvia; Sargent, Edward H.
- Nature Materials, Vol. 13, Issue 3
First principle study of core/shell structure quantum dots
journal, May 2004
- Li, Jingbo; Wang, Lin-Wang
- Applied Physics Letters, Vol. 84, Issue 18
Large-Scale Synthesis of Nearly Monodisperse CdSe/CdS Core/Shell Nanocrystals Using Air-Stable Reagents via Successive Ion Layer Adsorption and Reaction
journal, October 2003
- Li, J. Jack; Wang, Y. Andrew; Guo, Wenzhuo
- Journal of the American Chemical Society, Vol. 125, Issue 41, p. 12567-12575
One-pot Synthesis of Highly Luminescent InP/ZnS Nanocrystals without Precursor Injection
journal, September 2008
- Li, Liang; Reiss, Peter
- Journal of the American Chemical Society, Vol. 130, Issue 35
Highly Efficient Cadmium-Free Quantum Dot Light-Emitting Diodes Enabled by the Direct Formation of Excitons within InP@ZnSeS Quantum Dots
journal, September 2013
- Lim, Jaehoon; Park, Myeongjin; Bae, Wan Ki
- ACS Nano, Vol. 7, Issue 10
Biocompatible Semiconductor Quantum Dots as Cancer Imaging Agents
journal, February 2018
- McHugh, Kevin J.; Jing, Lihong; Behrens, Adam M.
- Advanced Materials, Vol. 30, Issue 18
Synthesis and Characterization of InP Quantum Dots
journal, May 1994
- Micic, Olga I.; Curtis, Calvin J.; Jones, Kim M.
- The Journal of Physical Chemistry, Vol. 98, Issue 19
Highly efficient band‐edge emission from InP quantum dots
journal, May 1996
- Mićić, Olga I.; Sprague, Julian; Lu, Zhenghao
- Applied Physics Letters, Vol. 68, Issue 22
Phosphine synthetic route features and postsynthetic treatment of InP quantum dots
journal, January 2014
- Mordvinova, Natalia; Vinokurov, Alexander; Dorofeev, Sergey
- Journal of Alloys and Compounds, Vol. 582
Highly luminescent core–shell InP/ZnX (X = S, Se) quantum dots prepared via a phosphine synthetic route
journal, January 2017
- Mordvinova, Natalia; Vinokurov, Alexander; Kuznetsova, Tatiana
- Dalton Transactions, Vol. 46, Issue 4
Synthesis and characterization of nearly monodisperse CdE (E = sulfur, selenium, tellurium) semiconductor nanocrystallites
journal, September 1993
- Murray, C. B.; Norris, D. J.; Bawendi, M. G.
- Journal of the American Chemical Society, Vol. 115, Issue 19, p. 8706-8715
One-pot/three-step synthesis of zinc-blende CdSe/CdS core/shell nanocrystals with thick shells
journal, October 2016
- Niu, Yuan; Pu, Chaodan; Lai, Runchen
- Nano Research, Vol. 10, Issue 4
Radiative and Nonradiative Lifetime Engineering of Quantum Dots in Multiple Solvents by Surface Atom Stoichiometry and Ligands
journal, January 2013
- Omogo, Benard; Aldana, Jose F.; Heyes, Colin D.
- The Journal of Physical Chemistry C, Vol. 117, Issue 5
Formation of High-Quality CdTe, CdSe, and CdS Nanocrystals Using CdO as Precursor
journal, January 2001
- Peng, Z. Adam; Peng, Xiaogang
- Journal of the American Chemical Society, Vol. 123, Issue 1, p. 183-184
Effect of Quantum and Dielectric Confinement on the Exciton−Exciton Interaction Energy in Type II Core/Shell Semiconductor Nanocrystals
journal, January 2007
- Piryatinski, Andrei; Ivanov, Sergei A.; Tretiak, Sergei
- Nano Letters, Vol. 7, Issue 1
Chemical Structure, Ensemble and Single-Particle Spectroscopy of Thick-Shell InP–ZnSe Quantum Dots
journal, January 2018
- Reid, Kemar R.; McBride, James R.; Freymeyer, Nathaniel J.
- Nano Letters, Vol. 18, Issue 2
Core/Shell Semiconductor Nanocrystals
journal, January 2009
- Reiss, Peter; Protière, Myriam; Li, Liang
- Small, Vol. 5, Issue 2
Multiple Exciton Generation and Dynamics in InP/CdS Colloidal Quantum Dots
journal, January 2017
- Smith, Charles T.; Leontiadou, Marina A.; Clark, Pip C. J.
- The Journal of Physical Chemistry C, Vol. 121, Issue 4
Etching of Colloidal InP Nanocrystals with Fluorides: Photochemical Nature of the Process Resulting in High Photoluminescence Efficiency
journal, December 2002
- Talapin, Dmitri V.; Gaponik, Nikolai; Borchert, Holger
- The Journal of Physical Chemistry B, Vol. 106, Issue 49
Chemistry of InP Nanocrystal Syntheses
journal, April 2016
- Tamang, Sudarsan; Lincheneau, Christophe; Hermans, Yannick
- Chemistry of Materials, Vol. 28, Issue 8
Generating Free Charges by Carrier Multiplication in Quantum Dots for Highly Efficient Photovoltaics
journal, January 2015
- ten Cate, Sybren; Sandeep, C. S. Suchand; Liu, Yao
- Accounts of Chemical Research, Vol. 48, Issue 2
Economic and Size-Tunable Synthesis of InP/ZnE (E = S, Se) Colloidal Quantum Dots.
journal, June 2015
- Tessier, Mickael D.; Dupont, Dorian; De Nolf, Kim
- Chemistry of Materials, Vol. 27, Issue 13
Effect of shell thickness and composition on blinking suppression and the blinking mechanism in ‘giant’ CdSe/CdS nanocrystal quantum dots
journal, July 2010
- Vela, Javier; Htoon, Han; Chen, Yongfen
- Journal of Biophotonics, Vol. 3, Issue 10-11
Quasi-Type II Carrier Distribution in CdSe/CdS Core/Shell Quantum Dots with Type I Band Alignment
journal, May 2018
- Wang, Li; Nonaka, Kouhei; Okuhata, Tomoki
- The Journal of Physical Chemistry C, Vol. 122, Issue 22
Calculated natural band offsets of all II–VI and III–V semiconductors: Chemical trends and the role of cation d orbitals
journal, April 1998
- Wei, Su-Huai; Zunger, Alex
- Applied Physics Letters, Vol. 72, Issue 16
Colloidal InP Nanocrystals as Efficient Emitters Covering Blue to Near-Infrared
journal, December 2007
- Xie, Renguo; Battaglia, David; Peng, Xiaogang
- Journal of the American Chemical Society, Vol. 129, Issue 50
Nucleation Kinetics vs Chemical Kinetics in the Initial Formation of Semiconductor Nanocrystals
journal, October 2009
- Xie, Renguo; Li, Zheng; Peng, Xiaogang
- Journal of the American Chemical Society, Vol. 131, Issue 42
Synthesis of Cu-Doped InP Nanocrystals (d-dots) with ZnSe Diffusion Barrier as Efficient and Color-Tunable NIR Emitters
journal, August 2009
- Xie, Renguo; Peng, Xiaogang
- Journal of the American Chemical Society, Vol. 131, Issue 30
Rapid synthesis of highly luminescent InP and InP/ZnS nanocrystals
journal, January 2008
- Xu, Shu; Ziegler, Jan; Nann, Thomas
- Journal of Materials Chemistry, Vol. 18, Issue 23
Highly-photoluminescent ZnSe nanocrystals via a non-injection-based approach with precursor reactivity elevated by a secondary phosphine
journal, January 2011
- Yu, Kui; Hrdina, Amy; Zhang, Xinguo
- Chemical Communications, Vol. 47, Issue 31
A Two-Step Synthetic Strategy toward Monodisperse Colloidal CdSe and CdSe/CdS Core/Shell Nanocrystals
journal, May 2016
- Zhou, Jianhai; Pu, Chaodan; Jiao, Tianyu
- Journal of the American Chemical Society, Vol. 138, Issue 20
Ideal CdSe/CdS Core/Shell Nanocrystals Enabled by Entropic Ligands and Their Core Size-, Shell Thickness-, and Ligand-Dependent Photoluminescence Properties
journal, November 2017
- Zhou, Jianhai; Zhu, Meiyi; Meng, Renyang
- Journal of the American Chemical Society, Vol. 139, Issue 46
Works referencing / citing this record:
Influence of the Core/Shell Structure of Indium Phosphide Based Quantum Dots on Their Photostability and Cytotoxicity
journal, June 2019
- Wegner, Karl David; Dussert, Fanny; Truffier-Boutry, Delphine
- Frontiers in Chemistry, Vol. 7
Figures / Tables found in this record: