Aqueous Assembly of Oxide and Fluoride Nanoparticles into 3D Microassemblies.

We demonstrate rapid [∼mm3/(h·L)] organic ligand-free self-assembly of three-dimensional, >50 μm single-domain microassemblies containing up to 107 individual aligned nanoparticles through a scalable aqueous process. Organization and alignment of aqueous solution-dispersed nanoparticles are induced by decreasing their pH-dependent surface charge without organic ligands, which could be temperature-sensitive or infrared light absorbing. This process is exhibited by transforming both dispersed iron oxide hydroxide nanorods and lithium yttrium fluoride nanoparticles into high packing density microassemblies. The approach is generalizable to nanomaterials with pH-dependent surface charge (e.g., oxides, fluorides, and sulfides) for applications requiring long-range alignment of nanostructures as well as high packing density.

[1]  T. Randall Lee,et al.  Stability: A key issue for self-assembled monolayers on gold as thin-film coatings and nanoparticle protectants , 2011 .

[2]  Paul A. Heiney,et al.  Millimeter‐Scale Assembly of CdSe Nanorods into Smectic Superstructures by Solvent Drying Kinetics , 2008 .

[3]  Jianbin Luo,et al.  Mechanical properties of nanoparticles: basics and applications , 2014 .

[4]  M. Pileni,et al.  Nanosized Particles Made in Colloidal Assemblies , 1997 .

[5]  M. Raza,et al.  Interaction and UV-Stability of Various Organic Capping Agents on the Surface of Anatase Nanoparticles , 2014, Materials.

[6]  J. M. Kikkawa,et al.  A generalized ligand-exchange strategy enabling sequential surface functionalization of colloidal nanocrystals. , 2011, Journal of the American Chemical Society.

[7]  Christopher J. Tassone,et al.  High-temperature crystallization of nanocrystals into three-dimensional superlattices , 2017, Nature.

[8]  Tie Wang,et al.  Interparticle Forces Underlying Nanoparticle Self-Assemblies. , 2015, Small.

[9]  B. Grzybowski Charged nanoparticles crystallizing and controlling crystallization: from coatings to nanoparticle surfactants to chemical amplifiers , 2014 .

[10]  C. Mirkin,et al.  Optical Properties of One-, Two-, and Three-Dimensional Arrays of Plasmonic Nanostructures , 2016 .

[11]  Aram Amassian,et al.  Colloidal-quantum-dot photovoltaics using atomic-ligand passivation. , 2011, Nature materials.

[12]  A Paul Alivisatos,et al.  Device-scale perpendicular alignment of colloidal nanorods. , 2010, Nano letters.

[13]  W. Shaw,et al.  The Decomposition of Urea in Aqueous Media , 1955 .

[14]  Yong Wang,et al.  Lanthanide-doped LiYF4 nanoparticles: Synthesis and multicolor upconversion tuning , 2010 .

[15]  Tanapon Phenrat,et al.  Nanoparticle aggregation: challenges to understanding transport and reactivity in the environment. , 2010, Journal of environmental quality.

[16]  C. Mirkin,et al.  Conformal, Macroscopic Crystalline Nanoparticle Sheets Assembled with DNA , 2015, Advanced materials.

[17]  Jun Chen,et al.  Morphologically controlled synthesis of colloidal upconversion nanophosphors and their shape-directed self-assembly , 2010, Proceedings of the National Academy of Sciences.

[18]  E. Coronado,et al.  The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric Environment , 2003 .

[19]  Alexander D. Q. Li,et al.  Cylindrical superparticles from semiconductor nanorods. , 2009, Journal of the American Chemical Society.

[20]  L. Manna,et al.  Self‐Assembled Multilayers of Vertically Aligned Semiconductor Nanorods on Device‐Scale Areas , 2011, Advanced materials.

[21]  George A. Parks,et al.  The Isoelectric Points of Solid Oxides, Solid Hydroxides, and Aqueous Hydroxo Complex Systems , 1965 .

[22]  S. J. van der Molen,et al.  Ordered nanoparticle arrays interconnected by molecular linkers: electronic and optoelectronic properties. , 2015, Chemical Society reviews.

[23]  Lan-sun Zheng,et al.  pH-induced simultaneous synthesis and self-assembly of 3D layered beta-FeOOH nanorods. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[24]  Bartosz A Grzybowski,et al.  Controlling the growth of "ionic" nanoparticle supracrystals. , 2007, Nano letters.

[25]  K. Ryan,et al.  Assembly of CuIn(1-x)Ga(x)S2 nanorods into highly ordered 2D and 3D superstructures. , 2012, ACS nano.

[26]  M. Kosmulski Surface Charging and Points of Zero Charge , 2020 .

[27]  Yao Lin,et al.  Nucleation-controlled polymerization of nanoparticles into supramolecular structures. , 2013, Journal of the American Chemical Society.

[28]  Diandra L. Leslie-Pelecky,et al.  Magnetic Properties of Nanostructured Materials , 1996 .

[29]  L. Manna,et al.  Assembly of colloidal semiconductor nanorods in solution by depletion attraction. , 2010, Nano letters.

[30]  Paras N. Prasad,et al.  Multiple exciton generation and electrical extraction from a PbSe quantum dot photoconductor , 2008 .

[31]  Ming Xiao,et al.  Bioinspired bright noniridescent photonic melanin supraballs , 2017, Science Advances.

[32]  Jiaqing Wang,et al.  Novel Metal Nanomaterials and Their Catalytic Applications , 2015, Molecules.