Ankit Agrawal

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:In2O3). Ce:In2O3 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(2)V(-1) s(-1) 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:In2O3 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.

Direct observation of narrow mid-infrared plasmon linewidths of single metal oxide nanocrystals

Infrared-responsive doped metal oxide nanocrystals are an emerging class of plasmonic materials whose localized surface plasmon resonances (LSPR) can be resonant with molecular vibrations. This presents a distinctive opportunity to manipulate light–matter interactions to redirect chemical or spectroscopic outcomes through the strong local electric fields they generate. Here we report a technique for measuring single nanocrystal absorption spectra of doped metal oxide nanocrystals, revealing significant spectral inhomogeneity in their mid-infrared LSPRs. Our analysis suggests dopant incorporation is heterogeneous beyond expectation based on a statistical distribution of dopants. The broad ensemble linewidths typically observed in these materials result primarily from sample heterogeneity and not from strong electronic damping associated with lossy plasmonic materials. In fact, single nanocrystal spectra reveal linewidths as narrow as 600 cm−1 in aluminium-doped zinc oxide, a value less than half the ensemble linewidth and markedly less than homogeneous linewidths of gold nanospheres.

The Interplay of Shape and Crystalline Anisotropies in Plasmonic Semiconductor Nanocrystals

Doped semiconductor nanocrystals are an emerging class of materials hosting localized surface plasmon resonance (LSPR) over a wide optical range. Studies so far have focused on tuning LSPR frequency by controlling the dopant and carrier concentrations in diverse semiconductor materials. However, the influence of anisotropic nanocrystal shape and of intrinsic crystal structure on LSPR remain poorly explored. Here, we illustrate how these two factors collaborate to determine LSPR characteristics in hexagonal cesium-doped tungsten oxide nanocrystals. The effect of shape anisotropy is systematically analyzed via synthetic control of nanocrystal aspect ratio (AR), from disks to nanorods. We demonstrate the dominant influence of crystalline anisotropy, which uniquely causes strong LSPR band-splitting into two distinct peaks with comparable intensities. Modeling typically used to rationalize particle shape effects is refined by taking into account the anisotropic dielectric function due to crystalline anisotropy, thus fully accounting for the AR-dependent evolution of multiband LSPR spectra. This new insight into LSPR of semiconductor nanocrystals provides a novel strategy for an exquisite tuning of LSPR line shape.

Localized Surface Plasmon Resonance in Semiconductor Nanocrystals

Localized surface plasmon resonance (LSPR) in semiconductor nanocrystals (NCs) that results in resonant absorption, scattering, and near field enhancement around the NC can be tuned across a wide optical spectral range from visible to far-infrared by synthetically varying doping level, and post synthetically via chemical oxidation and reduction, photochemical control, and electrochemical control. In this review, we will discuss the fundamental electromagnetic dynamics governing light matter interaction in plasmonic semiconductor NCs and the realization of various distinctive physical properties made possible by the advancement of colloidal synthesis routes to such NCs. Here, we will illustrate how free carrier dielectric properties are induced in various semiconductor materials including metal oxides, metal chalcogenides, metal nitrides, silicon, and other materials. We will highlight the applicability and limitations of the Drude model as applied to semiconductors considering the complex band structures and crystal structures that predominate and quantum effects that emerge at nonclassical sizes. We will also emphasize the impact of dopant hybridization with bands of the host lattice as well as the interplay of shape and crystal structure in determining the LSPR characteristics of semiconductor NCs. To illustrate the discussion regarding both physical and synthetic aspects of LSPR-active NCs, we will focus on metal oxides with substantial consideration also of copper chalcogenide NCs, with select examples drawn from the literature on other doped semiconductor materials. Furthermore, we will discuss the promise that LSPR in doped semiconductor NCs holds for a wide range of applications such as infrared spectroscopy, energy-saving technologies like smart windows and waste heat management, biomedical applications including therapy and imaging, and optical applications like two photon upconversion, enhanced luminesence, and infrared metasurfaces.

Resonant Coupling between Molecular Vibrations and Localized Surface Plasmon Resonance of Faceted Metal Oxide Nanocrystals

Doped metal oxides are plasmonic materials that boast both synthetic and postsynthetic spectral tunability. They have already enabled promising smart window and optoelectronic technologies and have been proposed for use in surface enhanced infrared absorption spectroscopy (SEIRA) and sensing applications. Herein, we report the first step toward realization of the former utilizing cubic F and Sn codoped In2O3 nanocrystals (NCs) to couple to the C-H vibration of surface-bound oleate ligands. Electron energy loss spectroscopy is used to map the strong near-field enhancement around these NCs that enables localized surface plasmon resonance (LSPR) coupling between adjacent nanocrystals and LSPR-molecular vibration coupling. Fourier transform infrared spectroscopy measurements and finite element simulations are applied to observe and explain the nature of the coupling phenomena, specifically addressing coupling in mesoscale assembled films. The Fano line shape signatures of LSPR-coupled molecular vibrations are rationalized with two-port temporal coupled mode theory. With this combined theoretical and experimental approach, we describe the influence of coupling strength and relative detuning between the molecular vibration and LSPR on the enhancement factor and further explain the basis of the observed Fano line shape by deconvoluting the combined response of the LSPR and molecular vibration in transmission, absorption and reflection. This study therefore illustrates various factors involved in determining the LSPR-LSPR and LSPR-molecular vibration coupling for metal oxide materials and provides a fundamental basis for the design of sensing or SEIRA substrates.

Gelation of plasmonic metal oxide nanocrystals by polymer-induced depletion attractions

Significance Self-supported gelation of optically active nanocrystals offers a modular pathway to harness optoelectronic functionality in multiscale materials by directly controlling volume fraction, bonding, and structure during assembly. We combine depletion attractions that emerge from the incorporation of small polymer chains and electrostatic repulsions to induce the gelation of isotropic metal oxide nanocrystals. We develop a theoretical model to assess our experimental fluid-to-gel-phase progression observations. By preventing nanocrystal fusion during network assembly, we achieve gels with a strong near-infrared absorption, reminiscent of the inherent near-infrared localized surface plasmon resonance of the nanocrystal building blocks. Gelation of colloidal nanocrystals emerged as a strategy to preserve inherent nanoscale properties in multiscale architectures. However, available gelation methods to directly form self-supported nanocrystal networks struggle to reliably control nanoscale optical phenomena such as photoluminescence and localized surface plasmon resonance (LSPR) across nanocrystal systems due to processing variabilities. Here, we report on an alternative gelation method based on physical internanocrystal interactions: short-range depletion attractions balanced by long-range electrostatic repulsions. The latter are established by removing the native organic ligands that passivate tin-doped indium oxide (ITO) nanocrystals while the former are introduced by mixing with small PEG chains. As we incorporate increasing concentrations of PEG, we observe a reentrant phase behavior featuring two favorable gelation windows; the first arises from bridging effects while the second is attributed to depletion attractions according to phase behavior predicted by our unified theoretical model. Our assembled nanocrystals remain discrete within the gel network, based on X-ray scattering and high-resolution transmission electron microscopy. The infrared optical response of the gels is reflective of both the nanocrystal building blocks and the network architecture, being characteristic of ITO nanocrystals’ LSPR with coupling interactions between neighboring nanocrystals.

Impacts of surface depletion on the plasmonic properties of doped semiconductor nanocrystals

Degenerately doped semiconductor nanocrystals (NCs) exhibit a localized surface plasmon resonance (LSPR) in the infrared range of the electromagnetic spectrum. Unlike metals, semiconductor NCs offer tunable LSPR characteristics enabled by doping, or via electrochemical or photochemical charging. Tuning plasmonic properties through carrier density modulation suggests potential applications in smart optoelectronics, catalysis and sensing. Here, we elucidate fundamental aspects of LSPR modulation through dynamic carrier density tuning in Sn-doped In2O3 (Sn:In2O3) NCs. Monodisperse Sn:In2O3 NCs with various doping levels and sizes were synthesized and assembled in uniform films. NC films were then charged in an in situ electrochemical cell and the LSPR modulation spectra were monitored. Based on spectral shifts and intensity modulation of the LSPR, combined with optical modelling, it was found that often-neglected semiconductor properties, specifically band structure modification due to doping and surface states, strongly affect LSPR modulation. Fermi level pinning by surface defect states creates a surface depletion layer that alters the LSPR properties; it determines the extent of LSPR frequency modulation, diminishes the expected near-field enhancement, and strongly reduces sensitivity of the LSPR to the surroundings.Degenerately doped semiconductor nanocrystals exhibit localized surface plasmon resonance in the infrared. Semiconducting properties such as band structure modification due to doping and surface states are now shown to strongly affect plasmonic modulation.

Tuning Nanocrystal Surface Depletion by Controlling Dopant Distribution as a Route Toward Enhanced Film Conductivity

Electron conduction through bare metal oxide nanocrystal (NC) films is hindered by surface depletion regions resulting from the presence of surface states. We control the radial dopant distribution in tin-doped indium oxide (ITO) NCs as a means to manipulate the NC depletion width. We find in films of ITO NCs of equal overall dopant concentration that those with dopant-enriched surfaces show decreased depletion width and increased conductivity. Variable temperature conductivity data show electron localization length increases and associated depletion width decreases monotonically with increased density of dopants near the NC surface. We calculate band profiles for NCs of differing radial dopant distributions and in agreement with variable temperature conductivity fits find NCs with dopant-enriched surfaces have narrower depletion widths and longer localization lengths than those with dopant-enriched cores. Following amelioration of NC surface depletion by atomic layer deposition of alumina, all films of equal overall dopant concentration have similar conductivity. Variable temperature conductivity measurements on alumina-capped films indicate all films behave as granular metals. Herein, we conclude that dopant-enriched surfaces decrease the near-surface depletion region, which directly increases the electron localization length and conductivity of NC films.