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 

Localized Surface Plasmon Resonance in Semiconductor Nanocrystals

Quantum dots (QDs) have received great interest for diverse applications due to their distinct advantages, such as narrow and symmetric emission with tunable colors, broad and strong absorption, reasonable stability, and solution processibility Doped QDs not only potentially retain almost all of the above advantages, but also avoid the self-quenching problem due to their substantial ensemble Stokes shift Two obvious advantages of doped QDs, especially doped ZnS QDs, over typical CdSe@ZnS and CdTe QDs are longer dopant emission lifetime and potentially lower cytotoxicity The lifetime of dopant emission from transition-metal ion or lanthanide ion-doped QDs is generally longer than that of the bandgap or defect-related emission of host, and that of biological background fluorescence, providing great opportunities to eliminate background fluorescence for biosensing and bioimaging For bioimaging applications, fluorescent dopants may mitigate toxicity problems by producing visible or infrared emission in nanocrystals made from less-harmful elements than those currently used In this review, recent advances in utilizing doped QDs for chemo/biosensing and bioimaging are discussed, and the synthetic routes and optical properties of doped QDs that make them excellent probes for various strategies in chemo/biosensing and bioimaging are highlighted Moreover, perspectives on future exploration of doped QDs for chemo/biosensing and bioimaging are also given

Doped quantum dots for chemo/biosensing and bioimaging

We review the field of multinary metal chalcogenide nanocrystals, which has gained strongly increasing interest in the quest for novel narrow band gap semiconductors. Small (2–4 nm) CuInS2 and CuInSe2 nanocrystals, for example, exhibit size dependent luminescence in the visible and near infrared range. Their quantum yield can exceed 50% after growth of a ZnS shell, which makes them appealing emitters for lighting, displaying and biological imaging applications. Cu2ZnSnS4 (CZTS) nanocrystals, on the other hand, can be used as solution processed absorbing materials in thin film solar cells showing high power conversion efficiencies (currently around 8–10%). These examples illustrate that multinary metal chalcogenide nanocrystals have high potential for replacing classical cadmium and lead chalcogenide quantum dots in many fields. We give an overview of the chemical synthesis methods of the different systems reported to date, classifying them according to the obtained crystal structure. Next, we discuss their photophysical properties and give a brief description of the main fields of application. Finally, we conclude by outlining current challenges and related future directions of this exponentially growing domain.

Ternary and quaternary metal chalcogenide nanocrystals: synthesis, properties and applications

Semiconductor nanocrystals possess size-dependent properties, which make them interesting candidates for a variety of applications, e.g., in solar energy conversion, lighting, display technology, or biolabelling. However, many of the best studied nanocrystalline materials contain toxic heavy metals; this seriously limits their potential for widespread application. One of the possible less toxic alternatives to cadmium- or lead-containing semiconductors is copper indium disulfide (CIS), a direct semiconductor with a bandgap in the bulk of 1.45 eV and a Bohr exciton radius of 4.1 nm. This Review gives an overview of the methods developed during the last years to synthesize CIS nanocrystals and summarizes the possibilities to influence their shape, composition and crystallographic structure. Also the potential of the application of CIS nanocrystals in biolabellling, photocatalysis, solar energy conversion, and light-emitting devices is discussed.

Synthesis and Application of Colloidal CuInS2 Semiconductor Nanocrystals

In the past 5 years, colloidal I–III–VI nanocrystals such as CuInS2, CuInSe2, and AgInS2 have been intensively investigated for the potential to replace commonly available colloidal nanocrystals containing toxic elements in light-emitting and solar-harvesting applications. Many researchers from different disciplines are working on developing new synthetic protocols, performing spectroscopic studies to understand the luminescence mechanisms, and exploring various applications. To achieve enhanced performance, it is very desirable to obtain high-quality materials with tunable luminescence properties. In this Perspective, we highlight the current progress on tuning the luminescence properties of I–III–VI nanocrystals, especially focusing on the advances in the synthesis, spectroscopic properties, as well as the primary applications in light-emitting devices and bioimaging techniques. Finally, we outline the challenges concerning luminescent I–III–VI NCs and list a few important research tasks in this field.

Tuning the Luminescence Properties of Colloidal I-III-VI Semiconductor Nanocrystals for Optoelectronics and Biotechnology Applications.

Au-Bi2S3 heteronanostructure photocatalysts were designed in which the coupling of a metal plasmon and a semiconductor exciton aids the absorption of solar light, enhances charge separation, and results in improved catalytic activity. Furthermore, these nanostructures show a unique pattern of structural combination, with Au nanoparticles positioned at the center of Bi2S3 nanorods. The chemistry of formation of these nanostructures, their epitaxy at the junction, and their photoconductance were studied, as well as their photoresponse properties.

Photocatalytic Au-Bi2S3 heteronanostructures.

Multinary nanocrystals (CuInS2, CIS, and AgInS2, AIS) are widely known for their strong defect state emission. On alloying with Zn (CIZS and AIZS), stable and intense emission tunable in visible and NIR windows has already been achieved. In these nanocrystals, the photogenerated hole efficiently moves to the defect-induced state and recombines with the electron in the conduction band. As a result, the defect state emission is predominantly observed without any band edge excitonic emission. Herein, we report the doping of the transition-metal ion Mn in these nanocrystals, which in certain compositions of the host nanocrystals quenches this strong defect state emission and predominantly shows the spin-flip Mn emission. Though several Mn-doped semiconductor nanocrystals are reported in the literature, these nanocrystals are of its first kind that can be excited in the visible window, do not contain the toxic element Cd, and provide efficient emission. Hence, when Mn emission is required, these multinary nanocrystals can be the ideal versatile materials for widespread technological applications.

Mn-Doped Multinary CIZS and AIZS Nanocrystals

Semiconducting and plasmonic copper phosphide platelets.

Adopting the concept of one dopant for one color, all the prominent emitting colors in the visible windows are obtained by doping selective dopants (Ag, Cu, Ni, and Cu) in an appropriate host (alloy of Cdx Zn1-x S) with fixed size/composition and bandgap. Analyzing the origin of these emissions the relative position of respective dopant states are correlated.

Goutam Manna

Papers

Photocatalytic Au-Bi2S3 heteronanostructures.

Mn-Doped Multinary CIZS and AIZS Nanocrystals

Semiconducting and plasmonic copper phosphide platelets.

Tuning the emission colors of semiconductor nanocrystals beyond their bandgap tunability: all in the dope.

Ag2S-AgInS2: p-n junction heteronanostructures with quasi type-II band alignment.