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.

Platelet-shaped copper sulfide nanocrystals (NCs) with tunable Cu stoichiometry were prepared from Cu-rich covellite (Cu1.1S) nanoplates through their reaction with a Cu(I) complex ([Cu(CH3CN)4]PF6) at room temperature. Starting from a common sample, by this approach it is possible to access a range of compositions in these NCs, varying from Cu1.1S up to Cu2S, each characterized by a different optical response: from the metallic covellite, with a high density of free carriers and strong localized surface plasmon resonance (LSPR), up to Cu2S NCs with no LSPR. In all these NCs the valency of Cu in the lattice stays always close to +1, while the average -1 valency of S in covellite gradually evolves to -2 with increasing Cu content; i.e., sulfur is progressively reduced. The addition of copper to the starting covellite NCs is similar to the intercalation of metal species in layered transition metal dichalcogenides (TMDCs); i.e., the chalcogen-chalcogen bonds holding the layers are progressively broken to make room for the intercalated metals, while their overall anion sublattice does not change much. However, differently from the TMDCs, the intercalation in covellite NCs is sustained by a change in the redox state of the anion framework. Furthermore, the amount of Cu incorporated in the NCs upon reaction is associated with the formation of an equimolar amount of Cu(II) species in solution. Therefore, the reaction scheme can be written as: Cu1.1S + 2γCu(I) → Cu1.1+γS + γCu(II).

Over the years, scientists have identified various synthetic “handles” while developing wet chemical protocols for achieving a high level of shape and compositional complexity in colloidal nanomaterials. Halide ions have emerged as one such handle which serve as important surface active species that regulate nanocrystal (NC) growth and concomitant physicochemical properties. Halide ions affect the NC growth kinetics through several means, including selective binding on crystal facets, complexation with the precursors, and oxidative etching. On the other hand, their presence on the surfaces of semiconducting NCs stimulates interesting changes in the intrinsic electronic structure and interparticle communication in the NC solids eventually assembled from them. Then again, halide ions also induce optoelectronic tunability in NCs where they form part of the core, through sheer composition variation. In this review, we describe these roles of halide ions in the growth of nanostructures and the physical changes introduced by them and thereafter demonstrate the commonality of these effects across different classes of nanomaterials.

We describe the colloidal hot-injection synthesis of phase-pure nanocrystals (NCs) of a highly abundant mineral, chalcopyrite (CuFeS2). Absorption bands centered at around 480 and 950 nm, spanning almost the entire visible and near-infrared regions, encompass their optical extinction characteristics. These peaks are ascribable to electronic transitions from the valence band (VB) to the empty intermediate band (IB), located in the fundamental gap and mainly composed of Fe 3d orbitals. Laser-irradiation (at 808 nm) of an aqueous suspension of CuFeS2 NCs exhibited significant heating, with a photothermal conversion efficiency of 49%. Such efficient heating is ascribable to the carrier relaxation within the broad IB band (owing to the indirect VB–IB gap), as corroborated by transient absorption measurements. The intense absorption and high photothermal transduction efficiency (PTE) of these NCs in the so-called biological window (650–900 nm) make them suitable for photothermal therapy as demonstrated by tumor cell annihilation upon laser irradiation. The otherwise harmless nature of these NCs in dark conditions was confirmed by in vitro toxicity tests on two different cell lines. The presence of the deep Fe levels constituting the IB is the origin of such enhanced PTE, which can be used to design other high performing NC photothermal agents.

The quest for materials with metal-like properties as alternatives to noble metals is an intense area of research that is set to lead to dramatic improvements in technologies based on plasmonics. Here, we present intermediate band (IB) semiconductor nanocrystals (NCs) as a class of all-dielectric nanomaterials providing quasi-static optical resonances. We show that IB NCs can display a negative permittivity in a broad range of visible wavelengths, enabling a metal-like optical response despite the absence of free carriers in the NC ground state. Using a combination of spectroscopy measurements and ab initio calculations, we hereby provide a theoretical model for both the linear and nonlinear optical properties of chalcopyrite CuFeS NCs, as a case study of IB semiconductor nanomaterials. Our results rationalize the high performance of IB nanomaterials as photothermal agents and suggest the use of IB semiconductors as alternatives to noble metals for technologies based on plasmonic materials.

We report a low-temperature colloidal synthesis of single-layer, five-atom-thick, β-In2Se3 nanosheets with lateral sizes tunable from ∼300 to ∼900 nm, using short aminonitriles (dicyandiamide or cyanamide) as shape controlling agents. The phase and the monolayer nature of the nanosheets were ascertained by analyzing the intensity ratio between two diffraction peaks from two-dimensional slabs of the various phases, determined by diffraction simulations. These findings were further backed-up by comparing and fitting the experimental X-ray diffraction pattern with Debye formula simulated patterns and with side-view high-resolution transmission electron microscopy imaging and simulation. The β-In2Se3 nanosheets were found to be indirect band gap semiconductors (Eg = 1.55 eV), and single nanosheet photodetectors demonstrated high photoresponsivity and fast response times.

We studied cation exchange (CE) in core/shell Cu2–xSe/Cu2–xS nanorods with two cations, Ag+ and Hg2+, which are known to induce rapid exchange within metal chalcogenide nanocrystals (NCs) at room temperature. At the initial stage of the reaction, the guest ions diffused through the Cu2–xS shell and reached the Cu2–xSe core, replacing first Cu+ ions within the latter region. These experiments prove that CE in copper chalcogenide NCs is facilitated by the high diffusivity of guest cations in the lattice, such that they can probe the whole host structure and identify the preferred regions where to initiate the exchange. For both guest ions, CE is thermodynamically driven as it aims for the formation of the chalcogen phase characterized by the lower solubility under the specific reaction conditions.

Transition metal oxide nanocrystals with dual-mode electrochromism hold promise for smart windows enabling spectrally selective solar modulation. We have developed the colloidal synthesis of anisotropic monoclinic Nb12O29 nanoplatelets (NPLs) to investigate the dual-mode electrochromism of niobium oxide nanocrystals. The precursor for synthesizing NPLs was prepared by mixing NbCl5 and oleic acid to form a complex that was subsequently heated to form an oxide-like structure capped by oleic acid, denoted as niobium oxo cluster. By initiating the synthesis using niobium oxo clusters, preferred growth of NPLs over other polymorphs was observed. The structure of the synthesized NPLs was examined by X-ray diffraction in conjunction with simulations, revealing that the NPLs are monolayer monoclinic Nb12O29, thin in the [100] direction and extended along the b and c directions. Besides having monolayer thickness, NPLs show decreased intensity of Raman signal from Nb-O bonds with higher bond order when compared to bulk monoclinic Nb12O29, as interpreted by calculations. Progressive electrochemical reduction of NPL films led to absorbance in the near-infrared region (stage 1) followed by absorbance in both the visible and near-infrared regions (stage 2), thus exhibiting dual-mode electrochromism. The mechanisms underlying these two processes were distinguished electrochemically by cyclic voltammetry to determine the extent to which ion intercalation limits the kinetics, and by verifying the presence of localized electrons following ion intercalation using X-ray photoelectron spectroscopy. Both results support that the near-infrared absorption results from capacitive charging and the onset of visible absorption in the second stage is caused by ion intercalation. File list (2) download file view on ChemRxiv Maintext-04-09-2020.pdf (5.47 MiB) download file view on ChemRxiv SuppResults-04-09-2020.pdf (7.23 MiB)