Role of Interface Chemistry in Opening New Radiative Pathways in InP/CdSe Giant Quantum Dots with Blinking-Suppressed Two-Color Emission

Dennis, Allison M.; Buck, Matthew R.; Wang, Feng; Hartmann, Nicolai F.; Majumder, Somak; Casson, Joanna L.; Watt, John Daniel; Doorn, Stephen K.; Htoon, Han; Sykora, Milan; Hollingsworth, Jennifer Ann

doi:10.1002/adfm.201809111

Role of Interface Chemistry in Opening New Radiative Pathways in InP/CdSe Giant Quantum Dots with Blinking-Suppressed Two-Color Emission

Journal Article · Mon Jun 24 00:00:00 EDT 2019 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.201809111· OSTI ID:1569573

Dennis, Allison M. ^[1]; Buck, Matthew R. ^[2]; Wang, Feng ^[3]; Hartmann, Nicolai F. ^[3]; Majumder, Somak ^[4]; Casson, Joanna L. ^[3]; ^[3]; ^[3]; ^[3]; Sykora, Milan ^[5]; ^[3]

Boston Univ., Boston, MA (United States)
United States Naval Academy, Annapolis, MD (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Center for Integrated NanotechnologiesMaterials Physics and Applications DivisionLos Alamos National Laboratory Los Alamos NM 87545 USA
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Comenius Univ., Bratislava (Slovakia)

InP/CdSe core/thick–shell “giant” quantum dots (gQDs) that exhibit blinking–suppressed two–color excitonic emission have been synthesized and optically characterized. These type II heterostructures exhibit photoluminescence from both a charge–separated, near–infrared type II excitonic state, and a shell–localized visible–color excitonic state. Infrared emission is intrinsic to the type II QD, while visible emission can either be eliminated or enhanced through chemical modification of the InP surface prior to CdSe shell growth. Single–QD photoluminescence measurements confirm that the dual color emission is from individual nanocrystals. Here, the probability of observing dual emission from individual QDs and the extent of blinking suppression increases with shell thickness. Visible emission can be stabilized by the addition of a second shell of CdS, where the resulting InP/CdSe/CdS core/shell/shell nanocrystals afford the strongest blinking suppression, determined by analysis of the Mandel Q parameter. Transient absorption spectroscopy verifies that dual emission arises when hole relaxation from the shell to the core is impeded, possibly as a result of enhanced interfacial hole trapping at F^– or O^2– defect sites. Electron–hole recombination in the shell then competes with slower type II recombination, providing a different mechanism for breaking Kasha's rule and allowing two colors of light to be emitted from one nanostructure.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Building Technologies Office (EE-5B); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1569573

Alternate ID(s):: OSTI ID: 1529019

Report Number(s):: LA-UR--18-28614

Journal Information:: Advanced Functional Materials, Journal Name: Advanced Functional Materials Journal Issue: 37 Vol. 29; ISSN 1616-301X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Etching of Colloidal InP Nanocrystals with Fluorides: Photochemical Nature of the Process Resulting in High Photoluminescence Efficiency. Talapin, Dmitri V.; Gaponik, Nikolai; Borchert, Holger ChemInform, Vol. 34, Issue 9 https://doi.org/10.1002/chin.200309013	journal	March 2003
The effects of staggered bandgap in the InP/CdSe and CdSe/InP core/shell quantum dots Kim, Sunghoon; Park, Jaehyun; Kim, Sungwoo Journal of Colloid and Interface Science, Vol. 346, Issue 2 https://doi.org/10.1016/j.jcis.2010.03.030	journal	June 2010
Effect of Trace Water on the Growth of Indium Phosphide Quantum Dots Xie, Lisi; Harris, Daniel K.; Bawendi, Moungi G. Chemistry of Materials, Vol. 27, Issue 14 https://doi.org/10.1021/acs.chemmater.5b01626	journal	July 2015
Mechanistic Insight and Optimization of InP Nanocrystals Synthesized with Aminophosphines Buffard, Aude; Dreyfuss, Sébastien; Nadal, Brice Chemistry of Materials, Vol. 28, Issue 16 https://doi.org/10.1021/acs.chemmater.6b02456	journal	August 2016
Synthesis of Oxide-Free InP Quantum Dots: Surface Control and H ₂ -Assisted Growth Baquero, Edwin A.; Virieux, Héloïse; Swain, Robert A. Chemistry of Materials, Vol. 29, Issue 22 https://doi.org/10.1021/acs.chemmater.7b04069	journal	November 2017
Probing Surface Defects of InP Quantum Dots Using Phosphorus Kα and Kβ X-ray Emission Spectroscopy Stein, Jennifer L.; Holden, William M.; Venkatesh, Amrit Chemistry of Materials, Vol. 30, Issue 18 https://doi.org/10.1021/acs.chemmater.8b02590	journal	August 2018
Interfacial Oxidation and Photoluminescence of InP-Based Core/Shell Quantum Dots Tessier, Mickael D.; Baquero, Edwin A.; Dupont, Dorian Chemistry of Materials, Vol. 30, Issue 19 https://doi.org/10.1021/acs.chemmater.8b03117	journal	September 2018
Trap Passivation in Indium-Based Quantum Dots through Surface Fluorination: Mechanism and Applications Kim, Tae-Gon; Zherebetskyy, Danylo; Bekenstein, Yehonadav ACS Nano, Vol. 12, Issue 11 https://doi.org/10.1021/acsnano.8b06692	journal	October 2018
Dual-Emitting Nanoscale Temperature Sensors McLaurin, Emily J.; Bradshaw, Liam R.; Gamelin, Daniel R. Chemistry of Materials, Vol. 25, Issue 8 https://doi.org/10.1021/cm304034s	journal	March 2013
Heterostructuring Nanocrystal Quantum Dots Toward Intentional Suppression of Blinking and Auger Recombination Hollingsworth, Jennifer A. Chemistry of Materials, Vol. 25, Issue 8 https://doi.org/10.1021/cm304161d	journal	March 2013
Dual Emissive Cu:InP/ZnS/InP/ZnS Nanocrystals: Single-Source “Greener” Emitters with Flexibly Tunable Emission from Visible to Near-Infrared and Their Application in White Light-Emitting Diodes Zhang, Zhuolei; Liu, Dong; Li, Dongze Chemistry of Materials, Vol. 27, Issue 4 https://doi.org/10.1021/cm5047269	journal	February 2015
Type-II Quantum Dots: CdTe/CdSe(Core/Shell) and CdSe/ZnTe(Core/Shell) Heterostructures Kim, Sungjee; Fisher, Brent; Eisler, Hans-Jürgen Journal of the American Chemical Society, Vol. 125, Issue 38, p. 11466-11467 https://doi.org/10.1021/ja0361749	journal	September 2003
Effect of the Thiol−Thiolate Equilibrium on the Photophysical Properties of Aqueous CdSe/ZnS Nanocrystal Quantum Dots Jeong, Sohee; Achermann, Marc; Nanda, Jagjit Journal of the American Chemical Society, Vol. 127, Issue 29 https://doi.org/10.1021/ja042591p	journal	July 2005
Coupled and Decoupled Dual Quantum Systems in One Semiconductor Nanocrystal Battaglia, David; Blackman, Bridgette; Peng, Xiaogang Journal of the American Chemical Society, Vol. 127, Issue 31 https://doi.org/10.1021/ja0437297	journal	August 2005
Type-II Core/Shell CdS/ZnSe Nanocrystals: Synthesis, Electronic Structures, and Spectroscopic Properties Ivanov, Sergei A.; Piryatinski, Andrei; Nanda, Jagjit Journal of the American Chemical Society, Vol. 129, Issue 38 https://doi.org/10.1021/ja068351m	journal	September 2007
Surface Chemistry of InP Quantum Dots: A Comprehensive Study Cros-Gagneux, Arnaud; Delpech, Fabien; Nayral, Céline Journal of the American Chemical Society, Vol. 132, Issue 51 https://doi.org/10.1021/ja104673y	journal	December 2010
New Insights into the Complexities of Shell Growth and the Strong Influence of Particle Volume in Nonblinking “Giant” Core/Shell Nanocrystal Quantum Dots Ghosh, Yagnaseni; Mangum, Benjamin D.; Casson, Joanna L. Journal of the American Chemical Society, Vol. 134, Issue 23 https://doi.org/10.1021/ja212032q	journal	May 2012
InP/ZnS Nanocrystals: Coupling NMR and XPS for Fine Surface and Interface Description Virieux, Héloïse; Le Troedec, Marianne; Cros-Gagneux, Arnaud Journal of the American Chemical Society, Vol. 134, Issue 48 https://doi.org/10.1021/ja307124m	journal	November 2012
“Giant” Multishell CdSe Nanocrystal Quantum Dots with Suppressed Blinking Chen, Yongfen; Vela, Javier; Htoon, Han Journal of the American Chemical Society, Vol. 130, Issue 15 https://doi.org/10.1021/ja711379k	journal	April 2008
Ligand-Controlled Polytypism of Thick-Shell CdSe/CdS Nanocrystals Mahler, Benoît; Lequeux, Nicolas; Dubertret, Benoît Journal of the American Chemical Society, Vol. 132, Issue 3 https://doi.org/10.1021/ja9034973	journal	January 2010
Giant PbSe/CdSe/CdSe Quantum Dots: Crystal-Structure-Defined Ultrastable Near-Infrared Photoluminescence from Single Nanocrystals Hanson, Christina J.; Hartmann, Nicolai F.; Singh, Ajay Journal of the American Chemical Society, Vol. 139, Issue 32 https://doi.org/10.1021/jacs.7b03705	journal	August 2017
Etching of Colloidal InP Nanocrystals with Fluorides: Photochemical Nature of the Process Resulting in High Photoluminescence Efficiency Talapin, Dmitri V.; Gaponik, Nikolai; Borchert, Holger The Journal of Physical Chemistry B, Vol. 106, Issue 49 https://doi.org/10.1021/jp026380n	journal	December 2002
Light Harvesting and Carrier Transport in Core/Barrier/Shell Semiconductor Nanocrystals Dias, Eva A.; Sewall, Samuel L.; Kambhampati, Patanjali The Journal of Physical Chemistry C, Vol. 111, Issue 2 https://doi.org/10.1021/jp0658389	journal	January 2007
Radiative and Nonradiative Lifetime Engineering of Quantum Dots in Multiple Solvents by Surface Atom Stoichiometry and Ligands Omogo, Benard; Aldana, Jose F.; Heyes, Colin D. The Journal of Physical Chemistry C, Vol. 117, Issue 5 https://doi.org/10.1021/jp309368q	journal	January 2013
Single Dot Spectroscopy of Two-Color Quantum Dot/Quantum Shell Nanostructures Dias, Eva A.; Grimes, Amy F.; English, Douglas S. The Journal of Physical Chemistry C, Vol. 112, Issue 37 https://doi.org/10.1021/jp806621q	journal	July 2008
Re-examination of the Size-Dependent Absorption Properties of CdSe Quantum Dots Jasieniak, Jacek; Smith, Lisa; van Embden, Joel The Journal of Physical Chemistry C, Vol. 113, Issue 45 https://doi.org/10.1021/jp906827m	journal	October 2009
Optical Nonlinearities and Ultrafast Carrier Dynamics in Semiconductor Nanocrystals Klimov, Victor I. The Journal of Physical Chemistry B, Vol. 104, Issue 26 https://doi.org/10.1021/jp9944132	journal	July 2000
Charge Separation and Recombination in CdTe/CdSe Core/Shell Nanocrystals as a Function of Shell Coverage: Probing the Onset of the Quasi Type-II Regime Chuang, Chi-Hung; Lo, Shun S.; Scholes, Gregory D. The Journal of Physical Chemistry Letters, Vol. 1, Issue 17 https://doi.org/10.1021/jz1008399	journal	August 2010
Growth and Optical Properties of Strained GaAs−Ga _x In ₁ _- _x P Core−Shell Nanowires Sköld, Niklas; Karlsson, Lisa S.; Larsson, Magnus W. Nano Letters, Vol. 5, Issue 10 https://doi.org/10.1021/nl051304s	journal	October 2005
Tunable Dual Emission in Doped Semiconductor Nanocrystals Vlaskin, Vladimir A.; Janssen, Nils; van Rijssel, Jos Nano Letters, Vol. 10, Issue 9, p. 3670-3674 https://doi.org/10.1021/nl102135k	journal	September 2010
Multiexcitonic Dual Emission in CdSe/CdS Tetrapods and Nanorods Lutich, Andrey A.; Mauser, Christian; Da Como, Enrico Nano Letters, Vol. 10, Issue 11 https://doi.org/10.1021/nl1028057	journal	November 2010
Two-Color Antibunching from Band-Gap Engineered Colloidal Semiconductor Nanocrystals Deutsch, Zvicka; Schwartz, Osip; Tenne, Ron Nano Letters, Vol. 12, Issue 6 https://doi.org/10.1021/nl300638t	journal	May 2012
Giant Nanocrystal Quantum Dots: Stable Down-Conversion Phosphors that Exploit a Large Stokes Shift and Efficient Shell-to-Core Energy Relaxation Kundu, Janardan; Ghosh, Yagnaseni; Dennis, Allison M. Nano Letters, Vol. 12, Issue 6 https://doi.org/10.1021/nl3008659	journal	May 2012
Suppressed Blinking and Auger Recombination in Near-Infrared Type-II InP/CdS Nanocrystal Quantum Dots Dennis, Allison M.; Mangum, Benjamin D.; Piryatinski, Andrei Nano Letters, Vol. 12, Issue 11 https://doi.org/10.1021/nl302453x	journal	October 2012
Dynamic Hole Blockade Yields Two-Color Quantum and Classical Light from Dot-in-Bulk Nanocrystals Galland, Christophe; Brovelli, Sergio; Bae, Wan Ki Nano Letters, Vol. 13, Issue 1 https://doi.org/10.1021/nl3045316	journal	December 2012
Direct Measure of Strain and Electronic Structure in GaAs/GaP Core−Shell Nanowires Montazeri, Mohammad; Fickenscher, Melodie; Smith, Leigh M. Nano Letters, Vol. 10, Issue 3 https://doi.org/10.1021/nl903547r	journal	March 2010
An Accessible Approach to Preparing Water-Soluble Mn²⁺-Doped (CdSSe)ZnS (Core)Shell Nanocrystals for Ratiometric Temperature Sensing Hsia, Chih-Hao; Wuttig, Anna; Yang, Haw ACS Nano, Vol. 5, Issue 12, p. 9511-9522 https://doi.org/10.1021/nn2025622	journal	November 2011
Simultaneous Type-I/Type-II Emission from CdSe/CdS/ZnSe Nano-Heterostructures Soni, Udit; Pal, Anuushka; Singh, Sajan ACS Nano, Vol. 8, Issue 1 https://doi.org/10.1021/nn404537s	journal	December 2013
Dual Wavelength Electroluminescence from CdSe/CdS Tetrapods Wong, Jen It; Mishra, Nimai; Xing, Guichuan ACS Nano, Vol. 8, Issue 3 https://doi.org/10.1021/nn500030t	journal	March 2014
Design and Synthesis of Heterostructured Quantum Dots with Dual Emission in the Visible and Infrared Lin, Qianglu; Makarov, Nikolay S.; Koh, Weon-kyu ACS Nano, Vol. 9, Issue 1 https://doi.org/10.1021/nn505793y	journal	December 2014
Using shape to turn off blinking for two-colour multiexciton emission in CdSe/CdS tetrapods Mishra, Nimai; Orfield, Noah J.; Wang, Feng Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15083	journal	May 2017
Towards non-blinking colloidal quantum dots Mahler, Benoit; Spinicelli, Piernicola; Buil, Stéphanie Nature Materials, Vol. 7, Issue 8 https://doi.org/10.1038/nmat2222	journal	June 2008
One-step synthesis of alloyed dual-emitting semiconductor nanocrystals McLaurin, Emily J.; Fataftah, Majed S.; Gamelin, Daniel R. Chem. Commun., Vol. 49, Issue 1 https://doi.org/10.1039/C2CC36862E	journal	January 2013
Shell thickness effects on quantum dot brightness and energy transfer Chern, Margaret; Nguyen, Thuy T.; Mahler, Andrew H. Nanoscale, Vol. 9, Issue 42 https://doi.org/10.1039/C7NR04296E	journal	January 2017
Growth and optical properties of type-II InP/GaAs self-organized quantum dots Wang, Benzhong; Chua, Soo-Jin Applied Physics Letters, Vol. 78, Issue 5 https://doi.org/10.1063/1.1342204	journal	January 2001
The effect of nanocrystal surface structure on the luminescence properties: Photoemission study of HF-etched InP nanocrystals Adam, S.; Talapin, D. V.; Borchert, H. The Journal of Chemical Physics, Vol. 123, Issue 8 https://doi.org/10.1063/1.2004901	journal	August 2005
Structural and optical properties of type II GaSb/GaAs self-assembled quantum dots grown by molecular beam epitaxy Suzuki, K.; Hogg, R. A.; Arakawa, Y. Journal of Applied Physics, Vol. 85, Issue 12 https://doi.org/10.1063/1.370622	journal	June 1999
Multiexcitons in type-II colloidal semiconductor quantum dots Oron, Dan; Kazes, Miri; Banin, Uri Physical Review B, Vol. 75, Issue 3 https://doi.org/10.1103/PhysRevB.75.035330	journal	January 2007
Near-Unity Quantum Yields of Biexciton Emission from CdSe / CdS Nanocrystals Measured Using Single-Particle Spectroscopy Park, Y. -S.; Malko, A. V.; Vela, J. Physical Review Letters, Vol. 106, Issue 18 https://doi.org/10.1103/PhysRevLett.106.187401	journal	May 2011
Bandgap Engineering of Indium Phosphide-Based Core/Shell Heterostructures Through Shell Composition and Thickness Toufanian, Reyhaneh; Piryatinski, Andrei; Mahler, Andrew H. Frontiers in Chemistry, Vol. 6 https://doi.org/10.3389/fchem.2018.00567	journal	November 2018