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 InO (Sn:InO) NCs. Monodisperse Sn:InO 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.

Defects may tend to make crystals interesting but they do not always improve 10 performance. In doped metal oxide nanocrystals with localized surface plasmon resonance 11 (LSPR), aliovalent dopants and oxygen vacancies act as centers for ionized impurity scattering 12 of electrons. Such electronic damping leads to lossy, broadband LSPR with low quality factors,

Solution-processed films of colloidal aliovalent niobium-doped anatase TiO2 nanocrystals exhibit modulation of optical transmittance in two spectral regions-near-infrared (NIR) and visible light-as they undergo progressive and reversible charging in an electrochemical cell. The Nb-TiO2 nanocrystal film supports a localized surface plasmon resonance in the NIR, which can be dynamically modulated via capacitive charging. When the nanocrystals are charged by insertion of lithium ions, inducing a well-known structural phase transition of the anatase lattice, strong modulation of visible transmittance is observed. Based on X-ray absorption near-edge spectroscopy, the conduction electrons localize only upon lithium ion insertion, thus rationalizing the two modes of optical switching observed in a single material. These multimodal electrochromic properties show promise for application in dynamic optical filters or smart windows.

Coloration efficiency is an important figure of merit in electrochromic windows. Though it is thought to be an intrinsic material property, we tune optical modulation by effective utilization of ion intercalation sites. Specifically, we enhance the coloration efficiency of m-WO 2.72 nanocrystal films by selectively intercalating sodium ions into optically active hexagonal sites. To accurately measure coloration efficiencies, significant degradation during cycling is mitigated by introducing atomic-layer-deposited Al 2 O 3 layers. Galvanostatic spectroscopic measurement shows that the site-selective intercalation of sodium ions in hexagonal tunnels enhances the coloration efficiency compared to a nonselective lithium ion-based electrolyte. Electrochemical rate analysis shows insertion of sodium ions to be capacitive-like, another indication of occupying hexagonal sites. Our results emphasize the importance of different site occupation on spectroelectrochemical properties, which can be used for designing materials and selecting electrolytes for enhanced electrochromic performance. In this context, we suggest sodium ion-based electrolytes hold unrealized potential for tungsten oxide electrochromic applications.

Organic metal halide Ruddlesden–Popper layered perovskite phases combine the excellent optoelectronic properties of three-dimensional, bulk hybrid perovskites with superior material stability under ambient conditions. However, the thin film structure of these layered perovskites is still poorly understood, as phase purity is typically determined solely by specular X-ray diffraction. The thin film structure of these Ruddlesden–Popper phases was examined by increasingly local characterization techniques. From the comparison of grazing-incidence wide-angle X-ray scattering patterns of cast films to expected scattering from single-crystal structures, significant in-plane disorder was observed. Spatially localized photoluminescence measurements show that films do not phase separate on the micrometer scale. Selected area electron diffraction measurements show the intergrowth of different phases within the same thin film, consistent with previous observations seen in epitaxially grown Ruddlesden–Popper complex oxides. Despite the presence of phase impurities that would typically be detrimental for device performance, fits to photothermal deflection spectroscopy measurements show relatively low Urbach energies of 33 meV for (C4H9NH3)2(CH3NH3)2Pb3I10 and 32 meV for (C4H9NH3)2(CH3NH3)3Pb4I13, indicating that the electronic properties are insensitive to the phase impurities.