Long-lived modulation of plasmonic absorption by ballistic thermal injection.

Light-matter interactions that induce charge and energy transfer across interfaces form the foundation for photocatalysis1,2, energy harvesting3 and photodetection4, among other technologies. One of the most common mechanisms associated with these processes relies on carrier injection. However, the exact role of the energy transport associated with this hot-electron injection remains unclear. Plasmon-assisted photocatalytic efficiencies can improve when intermediate insulation layers are used to inhibit the charge transfer5,6 or when off-resonance excitations are employed7, which suggests that additional energy transport and thermal effects could play an explicit role even if the charge transfer is inhibited8. This provides an additional interfacial mechanism for the catalytic and plasmonic enhancement at interfaces that moves beyond the traditionally assumed physical charge injection9-12. In this work, we report on a series of ultrafast plasmonic measurements that provide a direct measure of electronic distributions, both spatially and temporally, after the optical excitation of a metal/semiconductor heterostructure. We explicitly demonstrate that in cases of strong non-equilibrium, a novel energy transduction mechanism arises at the metal/semiconductor interface. We find that hot electrons in the metal contact transfer their energy to pre-existing free electrons in the semiconductor, without an equivalent spatiotemporal transfer of charge. Further, we demonstrate that this ballistic thermal injection mechanism can be utilized as a unique means to modulate plasmonic interactions. These experimental results are well-supported by both rigorous multilayer optical modelling and first-principle ab initio calculations.

Polaritonic Hybrid-Epsilon-near-Zero Modes: Beating the Plasmonic Confinement vs Propagation-Length Trade-Off with Doped Cadmium Oxide Bilayers.

Polaritonic materials that support epsilon-near-zero (ENZ) modes offer the opportunity to design light-matter interactions at the nanoscale through extreme subwavelength light confinement, producing phenomena like resonant perfect absorption. However, the utility of ENZ modes in nanophotonic applications has been limited by a flat spectral dispersion, which leads to small group velocities and extremely short propagation lengths. Here, we overcome this constraint by hybridizing ENZ and surface plasmon polariton (SPP) modes in doped cadmium oxide epitaxial bilayers. This results in strongly coupled hybrid modes that are characterized by an anticrossing in the polariton dispersion and a large spectral splitting on the order of 1/3 of the mode frequency. These hybrid modes simultaneously achieve modal propagation and ENZ mode-like interior field confinement, adding propagation character to ENZ mode properties. We subsequently tune the resonant frequencies, dispersion, and coupling of these polaritonic-hybrid-epsilon-near-zero (PH-ENZ) modes by tailoring the modal oscillator strength and the ENZ-SPP spectral overlap. PH-ENZ modes ultimately leverage the most desirable characteristics of both ENZ and SPP modes, allowing us to overcome the canonical plasmonic trade-off between confinement and propagation length.

Viscoelastic optical nonlocality of low-loss epsilon-near-zero nanofilms.

Optical nonlocalities are elusive and hardly observable in traditional plasmonic materials like noble and alkali metals. Here we report experimental observation of viscoelastic nonlocalities in the infrared optical response of epsilon-near-zero nanofilms made of low-loss doped cadmium-oxide. The nonlocality is detectable thanks to the low damping rate of conduction electrons and the virtual absence of interband transitions at infrared wavelengths. We describe the motion of conduction electrons using a hydrodynamic model for a viscoelastic fluid, and find excellent agreement with experimental results. The electrons' elasticity blue-shifts the infrared plasmonic resonance associated with the main epsilon-near-zero mode, and triggers the onset of higher-order resonances due to the excitation of electron-pressure modes above the bulk plasma frequency. We also provide evidence of the existence of nonlocal damping, i.e., viscosity, in the motion of optically-excited conduction electrons using a combination of spectroscopic ellipsometry data and predictions based on the viscoelastic hydrodynamic model.

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.

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.

Switchable Materials for Smart Windows.

This article reviews the basic principles of and recent developments in electrochromic, photochromic, and thermochromic materials for applications in smart windows. Compared with current static windows, smart windows can dynamically modulate the transmittance of solar irradiation based on weather conditions and personal preferences, thus simultaneously improving building energy efficiency and indoor human comfort. Although some smart windows are commercially available, their widespread implementation has not yet been realized. Recent advances in nanostructured materials provide new opportunities for next-generation smart window technology owing to their unique structure-property relations. Nanomaterials can provide enhanced coloration efficiency, faster switching kinetics, and longer lifetime. In addition, their compatibility with solution processing enables low-cost and high-throughput fabrication. This review also discusses the importance of dual-band modulation of visible and near-infrared (NIR) light, as nearly 50% of solar energy lies in the NIR region. Some latest results show that solution-processable nanostructured systems can selectively modulate the NIR light without affecting the visible transmittance, thus reducing energy consumption by air conditioning, heating, and artificial lighting.

Redox chemistries and plasmon energies of photodoped In2O3 and Sn-doped In2O3 (ITO) nanocrystals.

Plasmonic doped semiconductor nanocrystals promise exciting opportunities for new technologies, but basic features of the relationships between their structures, compositions, electronic structures, and optical properties remain poorly understood. Here, we report a quantitative assessment of the impact of composition on the energies of localized surface plasmon resonances (LSPRs) in colloidal tin-doped indium oxide (Sn:In2O3, or ITO) nanocrystals. Using a combination of aliovalent doping and photodoping, the effects of added electrons and impurity ions on the energies of LSPRs in colloidal In2O3 and ITO nanocrystals have been evaluated. Photodoping allows electron densities to be tuned post-synthetically in ITO nanocrystals, independent of their Sn content. Because electrons added photochemically are easily titrated, photodoping also allows independent quantitative determination of the dependence of the LSPR energy on nanocrystal composition and changes in electron density. The data show that ITO LSPR energies are affected by both electron and Sn concentrations, with composition yielding a broader plasmon tuning range than achievable by tuning carrier densities alone. Aspects of the photodoping energetics, as well as magneto-optical properties of these ITO LSPRs, are also discussed.

Nanostructured electrochromic smart windows: traditional materials and NIR-selective plasmonic nanocrystals.

Electrochromic devices, which dynamically change colour under applied potential, are widely studied for use in energy-efficient smart windows. To improve the viability of smart windows, many researchers are utilizing nanomaterials, which can provide electrochromic devices with improved colouration efficiencies, faster switching times, longer cycle lives, and potentially reduced costs. In an effort to demonstrate a new type of electrochromic device that goes beyond the capabilities of commonly used electrochromic materials, researchers have turned to plasmonic transparent conductive oxide (TCO) nanocrystals. Electrochemical injection of electrons into plasmonic TCO nanocrystal films induces a shift in the plasmon frequency and gives rise to the new functionality of selective optical modulation in the near-infrared region of the solar spectrum. These nanocrystals can be used as building blocks to enable creation of advanced electrochromic devices containing mesoporous electrodes or nanocrystal-in-glass composites. Such devices have been important in advancing the field towards achieving the ideal smart window with independent control over visible and NIR transmittance.

Influence of dopant distribution on the plasmonic properties of indium tin oxide nanocrystals.

Doped metal oxide nanocrystals represent an exciting frontier for colloidal synthesis of plasmonic materials, displaying unique optoelectronic properties and showing promise for a variety of applications. However, fundamental questions about the nature of doping in these materials remain. In this article, the strong influence of radial dopant distribution on the optoelectronic properties of colloidal indium tin oxide nanocrystals is reported. Comparing elemental depth-profiling by X-ray photoelectron spectroscopy (XPS) with detailed modeling and simulation of the optical extinction of these nanocrystals using the Drude model for free electrons, a correlation between surface segregation of tin ions and the average activation of dopants is observed. A strong influence of surface segregation of tin on the line shape of the localized surface plasmon resonance (LSPR) is also reported. Samples with tin segregated near the surface show a symmetric line shape that suggests weak or no damping of the plasmon by ionized impurities. It is suggested that segregation of tin near the surface facilitates compensation of the dopant ions by electronic defects and oxygen interstitials, thus reducing activation. A core-shell model is proposed to explain the observed differences in line shape. These results demonstrate the nuanced role of dopant distribution in determining the optoelectronic properties of semiconductor nanocrystals and suggest that more detailed study of the distribution and structure of defects in plasmonic colloidal nanocrystals is warranted.

Defect Chemistry and Plasmon Physics of Colloidal Metal Oxide Nanocrystals.

Plasmonic nanocrystals of highly doped metal oxides have seen rapid development in the past decade and represent a class of materials with unique optoelectronic properties. In this Perspective, we discuss doping mechanisms in metal oxides and the accompanying physics of free carrier scattering, both of which have implications in determining the properties of localized surface plasmon resonances (LSPRs) in these nanocrystals. The balance between activation and compensation of dopants limits the free carrier concentration of the most common metal oxides, placing a ceiling on the LSPR frequency. Furthermore, because of ionized impurity scattering of the oscillating plasma by dopant ions, scattering must be treated in a fundamentally different way in semiconductor metal oxide materials when compared with conventional metals. Though these effects are well-understood in bulk metal oxides, further study is needed to understand their manifestation in nanocrystals and corresponding impact on plasmonic properties, and to develop materials that surpass current limitations in free carrier concentration.

Dynamically modulating the surface plasmon resonance of doped semiconductor nanocrystals.

Localized surface plasmon absorption features arise at high doping levels in semiconductor nanocrystals, appearing in the near-infrared range. Here we show that the surface plasmons of tin-doped indium oxide nanocrystal films can be dynamically and reversibly tuned by postsynthetic electrochemical modulation of the electron concentration. Without ion intercalation and the associated material degradation, we induce a > 1200 nm shift in the plasmon wavelength and a factor of nearly three change in the carrier density.