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Title: Self-Assembly of Quantum Dot–Gold Heterodimer Nanocrystals with Orientational Order

Abstract

The self-assembly of nanocrystals into ordered superlattices is a powerful strategy for the production of functional nanomaterials. The assembly of well-ordered target structures, however, requires control over the building blocks’ size and shape as well as their interactions. While nanocrystals with homogeneous composition are now routinely synthesized with high precision and assembled into various ordered structures, high-quality multicomponent nanocrystals and their ordered assemblies are rarely reported. In this paper, we demonstrate the synthesis of quantum dot–gold (QD-Au) heterodimers. These heterodimers possess a uniform shape and narrow size distribution and are capped with oleylamine and dodecyltrimethylammonium bromide (DTAB). Assembly of the heterodimers results in a superlattice with long-range orientational alignment of dimers. Using synchrotron-based X-ray measurements, we characterize the complex superstructure formed from the dimers. Molecular dynamics simulations of a coarse-grained model suggest that anisotropic interactions between the quantum dot and gold components of the dimer drive superlattice formation. The high degree of orientational order demonstrated in this work is a potential route to nanomaterials with useful optoelectronic properties.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [2];  [1];  [3]; ORCiD logo [3];  [4]; ORCiD logo [2]; ORCiD logo [1]
  1. Brown Univ., Providence, RI (United States). Dept. of Chemistry
  2. Univ. of Utah, Salt Lake City, UT (United States). Dept. of Chemistry
  3. Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemistry
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1475146
Report Number(s):
BNL-209103-2018-JAAM
Journal ID: ISSN 1530-6984
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 18; Journal Issue: 8; Journal ID: ISSN 1530-6984
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Self-assembly; colloidal nanocrystals; heterodimer; anisotropic interparticle interactions; molecular dynamics simulation

Citation Formats

Zhu, Hua, Fan, Zhaochuan, Yuan, Yucheng, Wilson, Mitchell A., Hills-Kimball, Katie, Wei, Zichao, He, Jie, Li, Ruipeng, Grünwald, Michael, and Chen, Ou. Self-Assembly of Quantum Dot–Gold Heterodimer Nanocrystals with Orientational Order. United States: N. p., 2018. Web. doi:10.1021/acs.nanolett.8b01860.
Zhu, Hua, Fan, Zhaochuan, Yuan, Yucheng, Wilson, Mitchell A., Hills-Kimball, Katie, Wei, Zichao, He, Jie, Li, Ruipeng, Grünwald, Michael, & Chen, Ou. Self-Assembly of Quantum Dot–Gold Heterodimer Nanocrystals with Orientational Order. United States. https://doi.org/10.1021/acs.nanolett.8b01860
Zhu, Hua, Fan, Zhaochuan, Yuan, Yucheng, Wilson, Mitchell A., Hills-Kimball, Katie, Wei, Zichao, He, Jie, Li, Ruipeng, Grünwald, Michael, and Chen, Ou. Tue . "Self-Assembly of Quantum Dot–Gold Heterodimer Nanocrystals with Orientational Order". United States. https://doi.org/10.1021/acs.nanolett.8b01860. https://www.osti.gov/servlets/purl/1475146.
@article{osti_1475146,
title = {Self-Assembly of Quantum Dot–Gold Heterodimer Nanocrystals with Orientational Order},
author = {Zhu, Hua and Fan, Zhaochuan and Yuan, Yucheng and Wilson, Mitchell A. and Hills-Kimball, Katie and Wei, Zichao and He, Jie and Li, Ruipeng and Grünwald, Michael and Chen, Ou},
abstractNote = {The self-assembly of nanocrystals into ordered superlattices is a powerful strategy for the production of functional nanomaterials. The assembly of well-ordered target structures, however, requires control over the building blocks’ size and shape as well as their interactions. While nanocrystals with homogeneous composition are now routinely synthesized with high precision and assembled into various ordered structures, high-quality multicomponent nanocrystals and their ordered assemblies are rarely reported. In this paper, we demonstrate the synthesis of quantum dot–gold (QD-Au) heterodimers. These heterodimers possess a uniform shape and narrow size distribution and are capped with oleylamine and dodecyltrimethylammonium bromide (DTAB). Assembly of the heterodimers results in a superlattice with long-range orientational alignment of dimers. Using synchrotron-based X-ray measurements, we characterize the complex superstructure formed from the dimers. Molecular dynamics simulations of a coarse-grained model suggest that anisotropic interactions between the quantum dot and gold components of the dimer drive superlattice formation. The high degree of orientational order demonstrated in this work is a potential route to nanomaterials with useful optoelectronic properties.},
doi = {10.1021/acs.nanolett.8b01860},
journal = {Nano Letters},
number = 8,
volume = 18,
place = {United States},
year = {2018},
month = {7}
}

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Figures / Tables:

Figure 1 Figure 1: (a) Typical TEM image of the heterodimer NCs. (Inset) Model of a heterodimer NC. (b) UV−vis absorption spectra before (black) and after (red) Au growth. (c) HR-TEM image clearly showing the dimer feature and the measured d spacings of the ZB-QD(220) and Au(111) planes. The scale bar ismore » 3nm.« less

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Works referenced in this record:

Self-Assembly of Colloidal Nanocrystals: From Intricate Structures to Functional Materials
journal, August 2016


Binary nanocrystal superlattice membranes self-assembled at the liquid–air interface
journal, July 2010

  • Dong, Angang; Chen, Jun; Vora, Patrick M.
  • Nature, Vol. 466, Issue 7305
  • DOI: 10.1038/nature09188

Synergism in binary nanocrystal superlattices leads to enhanced p-type conductivity in self-assembled PbTe/Ag2Te thin films
journal, January 2007

  • Urban, Jeffrey J.; Talapin, Dmitri V.; Shevchenko, Elena V.
  • Nature Materials, Vol. 6, Issue 2, p. 115-121
  • DOI: 10.1038/nmat1826

Mechanical Properties of Face-Centered Cubic Supercrystals of Nanocrystals
journal, July 2010

  • Tam, Enrico; Podsiadlo, Paul; Shevchenko, Elena
  • Nano Letters, Vol. 10, Issue 7
  • DOI: 10.1021/nl1001313

Structural, Optical, and Electrical Properties of Self-Assembled Films of PbSe Nanocrystals Treated with 1,2-Ethanedithiol
journal, January 2008

  • Luther, Joseph M.; Law, Matt; Song, Qing
  • ACS Nano, Vol. 2, Issue 2
  • DOI: 10.1021/nn7003348

Optical Properties of CdSe Superlattices
journal, July 2005

  • Zaitseva, Natalia; Dai, Zu Rong; Leon, Francisco R.
  • Journal of the American Chemical Society, Vol. 127, Issue 29
  • DOI: 10.1021/ja051069f

Multi-component superstructures self-assembled from nanocrystal building blocks
journal, January 2016


Synthesis and Characterization of Monodisperse Nanocrystals and Close-Packed Nanocrystal Assemblies
journal, August 2000


Clathrate colloidal crystals
journal, March 2017


High-temperature crystallization of nanocrystals into three-dimensional superlattices
journal, July 2017

  • Wu, Liheng; Willis, Joshua J.; McKay, Ian Salmon
  • Nature, Vol. 548, Issue 7666
  • DOI: 10.1038/nature23308

Nanoscale Forces and Their Uses in Self-Assembly
journal, July 2009

  • Bishop, Kyle J. M.; Wilmer, Christopher E.; Soh, Siowling
  • Small, Vol. 5, Issue 14
  • DOI: 10.1002/smll.200900358

DNA-programmable nanoparticle crystallization
journal, January 2008

  • Park, Sung Yong; Lytton-Jean, Abigail K. R.; Lee, Byeongdu
  • Nature, Vol. 451, Issue 7178, p. 553-556
  • DOI: 10.1038/nature06508

A general strategy for the DNA-mediated self-assembly of functional nanoparticles into heterogeneous systems
journal, October 2013

  • Zhang, Yugang; Lu, Fang; Yager, Kevin G.
  • Nature Nanotechnology, Vol. 8, Issue 11
  • DOI: 10.1038/nnano.2013.209

Properties and emerging applications of self-assembled structures made from inorganic nanoparticles
journal, December 2009

  • Nie, Zhihong; Petukhova, Alla; Kumacheva, Eugenia
  • Nature Nanotechnology, Vol. 5, Issue 1
  • DOI: 10.1038/nnano.2009.453

Anisotropic Self-Assembly of Hairy Inorganic Nanoparticles
journal, December 2016


Optical Properties of Self-Assembled 2D and 3D Superlattices of Silver Nanoparticles
journal, March 1998

  • Taleb, A.; Petit, C.; Pileni, M. P.
  • The Journal of Physical Chemistry B, Vol. 102, Issue 12
  • DOI: 10.1021/jp972807s

Cobalt Nanosized Particles Organized in a 2D Superlattice:  Synthesis, Characterization, and Magnetic Properties
journal, March 1999

  • Petit, C.; Pileni, M. P.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 11
  • DOI: 10.1021/jp982755m

Long-range orientation and atomic attachment of nanocrystals in 2D honeycomb superlattices
journal, May 2014


Tubular Monolayer Superlattices of Hollow Mn 3 O 4 Nanocrystals and Their Oxygen Reduction Activity
journal, August 2017

  • Li, Tongtao; Xue, Bin; Wang, Biwei
  • Journal of the American Chemical Society, Vol. 139, Issue 35
  • DOI: 10.1021/jacs.7b06587

Topotactic Interconversion of Nanoparticle Superlattices
journal, August 2013


Orientationally Ordered Silicon Nanocrystal Cuboctahedra in Superlattices
journal, November 2016


Visible Light-Induced Charge Retention and Photocatalysis with Hybrid CdSe−Au Nanodumbbells
journal, February 2008

  • Costi, Ronny; Saunders, Aaron E.; Elmalem, Einat
  • Nano Letters, Vol. 8, Issue 2
  • DOI: 10.1021/nl0730514

Disordered, quasicrystalline and crystalline phases of densely packed tetrahedra
journal, December 2009

  • Haji-Akbari, Amir; Engel, Michael; Keys, Aaron S.
  • Nature, Vol. 462, Issue 7274
  • DOI: 10.1038/nature08641

Shape-dependent ordering of gold nanocrystals into large-scale superlattices
journal, January 2017

  • Gong, Jianxiao; Newman, Richmond S.; Engel, Michael
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14038

A general approach to DNA-programmable atom equivalents
journal, May 2013

  • Zhang, Chuan; Macfarlane, Robert J.; Young, Kaylie L.
  • Nature Materials, Vol. 12, Issue 8
  • DOI: 10.1038/nmat3647

Self-Assembled Colloidal Superparticles from Nanorods
journal, October 2012


Self-Assembling Nanocomposite Tectons
journal, December 2016

  • Zhang, Jianyuan; Santos, Peter J.; Gabrys, Paul A.
  • Journal of the American Chemical Society, Vol. 138, Issue 50
  • DOI: 10.1021/jacs.6b11052

Polymerization-Like Co-Assembly of Silver Nanoplates and Patchy Spheres
journal, July 2017


Polymorphic Assembly from Beveled Gold Triangular Nanoprisms
journal, April 2017


Self-Assembly of Tetrahedral CdSe Nanocrystals: Effective “Patchiness” via Anisotropic Steric Interaction
journal, April 2014

  • Boles, Michael A.; Talapin, Dmitri V.
  • Journal of the American Chemical Society, Vol. 136, Issue 16
  • DOI: 10.1021/ja501596z

Framework for nanocomposites
journal, November 2004


Janus Particles: Synthesis, Self-Assembly, Physical Properties, and Applications
journal, March 2013

  • Walther, Andreas; Müller, Axel H. E.
  • Chemical Reviews, Vol. 113, Issue 7, p. 5194-5261
  • DOI: 10.1021/cr300089t

Design and synthesis of Janus micro- and nanoparticles
journal, January 2005

  • Perro, Adeline; Reculusa, Stéphane; Ravaine, Serge
  • Journal of Materials Chemistry, Vol. 15, Issue 35-36
  • DOI: 10.1039/b505099e

Fabrication, properties and applications of Janus particles
journal, January 2012

  • Hu, Jing; Zhou, Shuxue; Sun, Yangyi
  • Chemical Society Reviews, Vol. 41, Issue 11
  • DOI: 10.1039/c2cs35032g

Heterodimers: Plasmonic Properties of Mismatched Nanoparticle Pairs
journal, January 2010

  • Brown, Lisa V.; Sobhani, Heidar; Lassiter, J. Britt
  • ACS Nano, Vol. 4, Issue 2
  • DOI: 10.1021/nn9017312

Recent Progress in Syntheses and Applications of Dumbbell-like Nanoparticles
journal, August 2009


A General Approach to Binary and Ternary Hybrid Nanocrystals
journal, April 2006

  • Shi, Weili; Zeng, Hao; Sahoo, Yudhisthira
  • Nano Letters, Vol. 6, Issue 4
  • DOI: 10.1021/nl0600833

Dumbbell-like Au−Fe 3 O 4 Nanoparticles for Target-Specific Platin Delivery
journal, April 2009

  • Xu, Chenjie; Wang, Baodui; Sun, Shouheng
  • Journal of the American Chemical Society, Vol. 131, Issue 12
  • DOI: 10.1021/ja900790v

Interfaced heterogeneous nanodimers
journal, July 2015


Highly Asymmetric, Interfaced Dimers Made of Au Nanoparticles and Bimetallic Nanoshells: Synthesis and Photo-Enhanced Catalysis
journal, January 2014

  • Hu, Yongxing; Liu, Yuzi; Li, Zheng
  • Advanced Functional Materials, Vol. 24, Issue 19
  • DOI: 10.1002/adfm.201303557

Synthesis, properties and perspectives of hybrid nanocrystal structures
journal, January 2006

  • Cozzoli, Pantaleo Davide; Pellegrino, Teresa; Manna, Liberato
  • Chemical Society Reviews, Vol. 35, Issue 11, p. 1195-1208
  • DOI: 10.1039/b517790c

Heterodimers of Nanoparticles:  Formation at a Liquid−Liquid Interface and Particle-Specific Surface Modification by Functional Molecules
journal, January 2005

  • Gu, Hongwei; Yang, Zhimou; Gao, Jinhao
  • Journal of the American Chemical Society, Vol. 127, Issue 1
  • DOI: 10.1021/ja045220h

Precise hierarchical self-assembly of multicompartment micelles
journal, January 2012

  • Gröschel, André H.; Schacher, Felix H.; Schmalz, Holger
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms1707

Anisotropic particles with patchy, multicompartment and Janus architectures: preparation and application
journal, January 2011

  • Du, Jianzhong; O'Reilly, Rachel K.
  • Chemical Society Reviews, Vol. 40, Issue 5
  • DOI: 10.1039/c0cs00216j

Hierarchical Assembly of Complex Block Copolymer Nanoparticles into Multicompartment Superstructures through Tunable Interparticle Associations
journal, November 2012

  • Zhu, Jiahua; Zhang, Shiyi; Zhang, Fuwu
  • Advanced Functional Materials, Vol. 23, Issue 14
  • DOI: 10.1002/adfm.201202323

Linking synchronization to self-assembly using magnetic Janus colloids
journal, November 2012

  • Yan, Jing; Bloom, Moses; Bae, Sung Chul
  • Nature, Vol. 491, Issue 7425, p. 578-581
  • DOI: 10.1038/nature11619

Janus Particle Synthesis and Assembly
journal, January 2010


Janus and Ternary Particles Generated by Microfluidic Synthesis:  Design, Synthesis, and Self-Assembly
journal, July 2006

  • Nie, Zhihong; Li, Wei; Seo, Minseok
  • Journal of the American Chemical Society, Vol. 128, Issue 29
  • DOI: 10.1021/ja060882n

Synthesis, properties and applications of Janus nanoparticles
journal, June 2011


Janus Nanoparticles: Preparation, Characterization, and Applications
journal, December 2013


Macromol. Rapid Commun. 2/2010
journal, January 2010

  • Pawar, Amar B.; Kretzschmar, Ilona
  • Macromolecular Rapid Communications, Vol. 31, Issue 2
  • DOI: 10.1002/marc.201090000

Preparation and Self-Assembly of Dendronized Janus Fe 3 O 4 –Pt and Fe 3 O 4 –Au Heterodimers
journal, August 2017


Pressure-Enabled Synthesis of Hetero-Dimers and Hetero-Rods through Intraparticle Coalescence and Interparticle Fusion of Quantum-Dot-Au Satellite Nanocrystals
journal, June 2017

  • Zhu, Hua; Nagaoka, Yasutaka; Hills-Kimball, Katie
  • Journal of the American Chemical Society, Vol. 139, Issue 25
  • DOI: 10.1021/jacs.7b04018

Decoding the Superlattice and Interface Structure of Truncate PbS Nanocrystal-Assembled Supercrystal and Associated Interaction Forces
journal, August 2014

  • Li, Ruipeng; Bian, Kaifu; Hanrath, Tobias
  • Journal of the American Chemical Society, Vol. 136, Issue 34
  • DOI: 10.1021/ja5057032

Solvent-Mediated Self-Assembly of Nanocube Superlattices
journal, January 2014

  • Quan, Zewei; Xu, Hongwu; Wang, Chenyu
  • Journal of the American Chemical Society, Vol. 136, Issue 4
  • DOI: 10.1021/ja408250q

Vacancy-Buckling Model for the (2×2) GaAs(111) Surface
journal, May 1984


Magneto-fluorescent core-shell supernanoparticles
journal, October 2014

  • Chen, Ou; Riedemann, Lars; Etoc, Fred
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms6093

Kinetics of the self-assembly of nanocrystal superlattices measured by real-time in situ X-ray scattering
journal, March 2016

  • Weidman, Mark C.; Smilgies, Detlef-M.; Tisdale, William A.
  • Nature Materials, Vol. 15, Issue 7
  • DOI: 10.1038/nmat4600

Synthesis and Self-Assembly of Cetyltrimethylammonium Bromide-Capped Gold Nanoparticles
journal, October 2003

  • Cheng, Wenlong; Dong, Shaojun; Wang, Erkang
  • Langmuir, Vol. 19, Issue 22
  • DOI: 10.1021/la034818k

Utilizing Self-Exchange To Address the Binding of Carboxylic Acid Ligands to CdSe Quantum Dots
journal, July 2010

  • Fritzinger, Bernd; Capek, Richard K.; Lambert, Karel
  • Journal of the American Chemical Society, Vol. 132, Issue 29
  • DOI: 10.1021/ja104351q

Molecular Simulations of Interacting Nanocrystals
journal, September 2008

  • Schapotschnikow, Philipp; Pool, René; Vlugt, Thijs J. H.
  • Nano Letters, Vol. 8, Issue 9
  • DOI: 10.1021/nl8017862

Explicit all-atom modeling of realistically sized ligand-capped nanocrystals
journal, March 2012

  • Kaushik, Ananth P.; Clancy, Paulette
  • The Journal of Chemical Physics, Vol. 136, Issue 11
  • DOI: 10.1063/1.3689973

Capping Ligand Vortices as “Atomic Orbitals” in Nanocrystal Self-Assembly
journal, September 2017


Orientational Ordering of Passivating Ligands on CdS Nanorods in Solution Generates Strong Rod–Rod Interactions
journal, December 2013

  • Widmer-Cooper, Asaph; Geissler, Phillip
  • Nano Letters, Vol. 14, Issue 1
  • DOI: 10.1021/nl403067p

Packing of Soft Asymmetric Dumbbells
journal, June 2011

  • Šarić, Anđela; Bozorgui, Behnaz; Cacciuto, Angelo
  • The Journal of Physical Chemistry B, Vol. 115, Issue 22
  • DOI: 10.1021/jp107545w

Works referencing / citing this record:

Superstructures of Multielement Colloidal Molecules: Efficient Pathways to Construct Reconfigurable Photonic and Phononic Crystals
journal, February 2019

  • Aryana, Kiumars; Stahley, James B.; Parvez, Nishan
  • Advanced Theory and Simulations, Vol. 2, Issue 5
  • DOI: 10.1002/adts.201800198

2D Freestanding Janus Gold Nanocrystal Superlattices
journal, May 2019

  • Shi, Qianqian; Gómez, Daniel E.; Dong, Dashen
  • Advanced Materials, Vol. 31, Issue 28
  • DOI: 10.1002/adma.201900989

2D Freestanding Janus Gold Nanocrystal Superlattices
journal, July 2019

  • Shi, Qianqian; Gómez, Daniel E.; Dong, Dashen
  • Advanced Materials, Vol. 31, Issue 37
  • DOI: 10.1002/adma.201904636

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