5 research outputs found
Resolving the Growth of 3D Colloidal Nanoparticle Superlattices by Real-Time Small-Angle X‑ray Scattering
The kinetics and intricate interactions governing the
growth of
3D single nanoparticle (NP) superlattices (SLs, SNSLs) and binary
NP SLs (BNSLs) in solution are understood by combining controlled
solvent evaporation and <i>in situ</i>, real-time small-angle
X-ray scattering (SAXS). For the iron oxide (magnetite) NP SLs studied
here, the larger the NP, the farther apart are the NPs when the SNSLs
begin to precipitate and the closer they are after ordering. This
is explained by a model of NP assembly using van der Waals interactions
between magnetite cores in hydrocarbons with a ∼21 zJ Hamaker
constant. When forming BNSLs of two different sized NPs, the NPs that
are in excess of that needed to achieve the final BNSL stoichiometry
are expelled during the BNSL formation, and these expelled NPs can
form SNSLs. The long-range ordering of these SNSLs and the BNSLs can
occur faster than the NP expulsion
Resolving the Growth of 3D Colloidal Nanoparticle Superlattices by Real-Time Small-Angle X‑ray Scattering
The kinetics and intricate interactions governing the
growth of
3D single nanoparticle (NP) superlattices (SLs, SNSLs) and binary
NP SLs (BNSLs) in solution are understood by combining controlled
solvent evaporation and <i>in situ</i>, real-time small-angle
X-ray scattering (SAXS). For the iron oxide (magnetite) NP SLs studied
here, the larger the NP, the farther apart are the NPs when the SNSLs
begin to precipitate and the closer they are after ordering. This
is explained by a model of NP assembly using van der Waals interactions
between magnetite cores in hydrocarbons with a ∼21 zJ Hamaker
constant. When forming BNSLs of two different sized NPs, the NPs that
are in excess of that needed to achieve the final BNSL stoichiometry
are expelled during the BNSL formation, and these expelled NPs can
form SNSLs. The long-range ordering of these SNSLs and the BNSLs can
occur faster than the NP expulsion
Resolving the Growth of 3D Colloidal Nanoparticle Superlattices by Real-Time Small-Angle X‑ray Scattering
The kinetics and intricate interactions governing the
growth of
3D single nanoparticle (NP) superlattices (SLs, SNSLs) and binary
NP SLs (BNSLs) in solution are understood by combining controlled
solvent evaporation and <i>in situ</i>, real-time small-angle
X-ray scattering (SAXS). For the iron oxide (magnetite) NP SLs studied
here, the larger the NP, the farther apart are the NPs when the SNSLs
begin to precipitate and the closer they are after ordering. This
is explained by a model of NP assembly using van der Waals interactions
between magnetite cores in hydrocarbons with a ∼21 zJ Hamaker
constant. When forming BNSLs of two different sized NPs, the NPs that
are in excess of that needed to achieve the final BNSL stoichiometry
are expelled during the BNSL formation, and these expelled NPs can
form SNSLs. The long-range ordering of these SNSLs and the BNSLs can
occur faster than the NP expulsion
Electrochemically Induced Transformations of Vanadium Dioxide Nanocrystals
Vanadium dioxide (VO<sub>2</sub>)
undergoes significant optical, electronic, and structural changes
as it transforms between the low-temperature monoclinic and high-temperature
rutile phases. Recently, alternative stimuli have been utilized to
trigger insulator-to-metal transformations in VO<sub>2</sub>, including
electrochemical gating. Here, we prepare and electrochemically reduce
mesoporous films of VO<sub>2</sub> nanocrystals, prepared from colloidally
synthesized V<sub>2</sub>O<sub>3</sub> nanocrystals that have been
oxidatively annealed, in a three-electrode electrochemical cell. We
observe a reversible transition between infrared transparent insulating
phases and a darkened metallic phase by in situ visible–near-infrared
spectroelectrochemistry and correlate these observations with structural
and electronic changes monitored by X-ray absorption spectroscopy,
X-ray diffraction, Raman spectroscopy, and conductivity measurements.
An unexpected reversible transition from conductive, reduced monoclinic
VO<sub>2</sub> to an infrared-transparent insulating phase upon progressive
electrochemical reduction is observed. This insulator–metal–insulator
transition has not been reported in previous studies of electrochemically
gated epitaxial VO<sub>2</sub> films and is attributed to improved
oxygen vacancy formation kinetics and diffusion due to the mesoporous
nanocrystal film structure
Defect Engineering in Plasmonic Metal Oxide Nanocrystals
Defects may tend to make crystals
interesting but they do not always improve performance. In doped metal
oxide nanocrystals with localized surface plasmon resonance (LSPR),
aliovalent dopants and oxygen vacancies act as centers for ionized
impurity scattering of electrons. Such electronic damping leads to
lossy, broadband LSPR with low quality factors, limiting applications
that require near-field concentration of light. However, the appropriate
dopant can mitigate ionized impurity scattering. Herein, we report
the synthesis and characterization of a novel doped metal oxide nanocrystal
material, cerium-doped indium oxide (Ce:In<sub>2</sub>O<sub>3</sub>). Ce:In<sub>2</sub>O<sub>3</sub> nanocrystals display tunable mid-infrared
LSPR with exceptionally narrow line widths and the highest quality
factors observed for nanocrystals in this spectral region. Drude model
fits to the spectra indicate that a drastic reduction in ionized impurity
scattering is responsible for the enhanced quality factors, and high
electronic mobilities reaching 33 cm<sup>2</sup>V<sup>–1</sup> s<sup>–1</sup> are measured optically, well above the optical
mobility for tin-doped indium oxide (ITO) nanocrystals. We investigate
the microscopic mechanisms underlying this enhanced mobility with
density functional theory calculations, which suggest that scattering
is reduced because cerium orbitals do not hybridize with the In orbitals
that dominate the bottom of the conduction band. Ce doping may also
reduce the equilibrium oxygen vacancy concentration, further enhancing
mobility. From the absorption spectra of single Ce:In<sub>2</sub>O<sub>3</sub> nanocrystals, we determine the dielectric function and by
simulation predict strong near-field enhancement of mid-IR light,
especially around the vertices of our synthesized nanocubes