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

Plasmon resonances in metal nanostructures have been extensively harnessed for light trapping in mesoporous solar cells (MSCs), including dye-sensitized solar cells (DSSCs) and recently in perovskite solar cells (PSCs). By altering the geometry, dimension, and composition of metal nanostructures, their optical characteristics can be tuned to either overlap with the sensitizer absorption and enhance light harvesting, or absorb light at a wavelength complementary to the sensitizer enabling broadband solar light capture in MSCs. In this comprehensive review, we discuss the mechanisms of plasmonic enhancement in MSCs including far-field coupling of scattered light, near-field coupling of localized electromagnetic fields, hot electron transfer, and plasmon resonant energy transfer. We then summarize the progress in plasmon enhanced DSSCs in the past decade and decouple the impact of metal nanostructure shape, size, composition, and surface coatings on the overall efficiency. Further, we also discuss the recent advances in plasmon-enhanced perovskite solar cells. Distinct from other published reviews, we discuss the significance of femtosecond spectroscopies to probe the fundamental underpinnings of plasmon enhanced phenomena and understand the mechanisms that give rise to energy transfer between metal nanoparticles and solar materials. The review concludes with a discussion on the challenges in plasmonic device fabrication, and the promise of low-loss semiconductor nanocrystals for plasmonic enhancement in MSCs that facilitate light capture in the infrared.

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Light trapping in mesoporous solar cells with plasmonic nanostructures

The successful transition of any nanocrystal-based product from the research phase to the commercial arena hinges on the ability to produce the required nanomaterial on large scales. The synthesis of colloidal nanocrystals using a heat-up (non-injection) method is a reliable means to achieve high quality nanomaterials on large scales with little or no batch-to-batch variation. In this class of synthesis precursors are heated within a reaction medium to induce a chemical reaction that yields monomer for nucleation and growth. Use of the heat-up technique circumvents the pitfalls of mixing time and poor heat management inherent to classical “hot-injection” methods. In heat-up syntheses monomer is produced in a more continuous fashion during the heating stage, making it more difficult to separate the nucleation and growth stages of the reaction, a factor that is conventionally considered detrimental toward achieving homogeneous colloidal dispersions. However, through the judicious selection of precursors, st...

The heat-up synthesis of colloidal nanocrystals

Cadmium sulfide (CdS)-based photocatalysts have attracted extensive attention owing to their strong visible light absorption, suitable band energy levels, and excellent electronic charge transportation properties. This review focuses on the recent progress related to the design, modification, and construction of CdS-based photocatalysts with excellent photocatalytic H2 evolution performances. First, the basic concepts and mechanisms of photocatalytic H2 evolution are briefly introduced. Thereafter, the fundamental properties, important advancements, and bottlenecks of CdS in photocatalytic H2 generation are presented in detail to provide an overview of the potential of this material. Subsequently, various modification strategies adopted for CdS-based photocatalysts to yield solar H2 are discussed, among which the effective approaches aim at generating more charge carriers, promoting efficient charge separation, boosting interfacial charge transfer, accelerating charge utilization, and suppressing charge-induced self-photocorrosion. The critical factors governing the performance of the photocatalyst and the feasibility of each modification strategy toward shaping future research directions are comprehensively discussed with examples. Finally, the prospects and challenges encountered in developing nanostructured CdS and CdS-based nanocomposites in photocatalytic H2 evolution are presented.

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Nanostructured CdS for efficient photocatalytic H 2 evolution: A review

Plasmonic doped semiconductor nanocrystals: Properties, fabrication, applications and perspectives

We report a new synthesis process of colloidal indium (In) doped zinc oxide (ZIO) nanocrystals by a hot injection technique. By fine tuning the synthesis we reached the same nucleation temperature for indium oxide and zinc oxide which helped us to study a dopant precursor dependent In incorporation into the ZnO matrix by using different In sources. The dopant induced shape evolution changes the hexagonal pyramid structured ZnO to a platelet like structure upon 8% In doping. The introduction of trivalent In3+ into the ZnO lattice and consequent substitution of divalent Zn2+ generates free electrons in the conduction band which produces a plasmonic resonance in the infrared region. The electron concentration controls plasmon frequency as well as the band gap of host ZnO. The variation of the band gap and the modification of the conduction band have been explained by the Burstein–Moss effect and Mie's theory respectively. The In dopant changes the defect chemistry of pure ZnO nanocrystals which has been studied by photoluminescence and other spectroscopic measurements. The nanocrystals are highly stable in the organic medium and can be deposited as a crack free thin film on different substrates. Careful ligand exchange and thermal annealing of the spin cast film lead to a good conductive film (720 Ω per square to 120 Ω per square) with stable inherent plasmonic absorption in the infrared and 90% transmittance in the visible region. A temperature induced metal–semiconductor transition was found for doped ZnO nanocrystals. The transition temperature shifts to a lower temperature with increase of the doping concentration.

Tunable surface plasmon resonance and enhanced electrical conductivity of In doped ZnO colloidal nanocrystals.

Colloidal trivalent gallium (Ga) doped zinc oxide (ZnO) hexagonal nanocrystals have been prepared to introduce more carrier concentration into the wide band gap of ZnO. The dopant (Ga) modifies the morphology and size of ZnO nanocrystals. Low content of Ga enhances the optical band gap of ZnO due to excess carrier concentration in the conduction band of ZnO. The interaction among free carriers arising from higher concentration of Ga gives rise to narrowing of the band gap. Surface plasmon resonance absorption appears in the infrared region due to excessive carrier concentration. A broad emission band consists of blue, yellow and green colors associated with different native defects of ZnO. Intrinsic defects and extrinsic dopant Ga control the defect related emission spectrum in the visible region. Replacement of Zn by Ga induces a room temperature metallic state in a degenerate semiconductor. Cationic disorder leads to metal–semiconductor transition at low temperature strongly dependent on the concentration of Ga. Pure semiconducting behavior up to about 80 K is observed for the highest amount of Ga. Temperature dependent metal–semiconductor transition has been interpreted by localization of charge carriers due to disorder arising from random Ga substitution.

Carrier concentration dependent optical and electrical properties of Ga doped ZnO hexagonal nanocrystals.

High quality nearly monodisperse colloidal WO3-x nanorods with an aspect ratio ∼18 were synthesized using the thermal decomposition technique. The effects of a capping agent and an activating agent on the nanorod aspect ratio have been studied. Excess carrier concentration due to large oxygen vacancy and smaller width of the nanorods compared to the Bohr exciton radius gives rise to an increase of the band gap. Shape anisotropy in nanorods results in two plasmonic absorbance bands at about 890 nm and 5900 nm corresponding to short axis and long axis plasmon modes. The short axis mode reveals an excellent plasmonic sensitivity of ∼345 nm per refractive index. A plasmonic photocatalysis process based on WO3-x nanorods has been developed to synthesize Ag/WO3-x heterostructures consisting of multiple Ag dots with ∼2 nm size, randomly decorated on the surface of the WO3-x nanorods. Long time irradiation leads to an increase in the size (5 nm) of Ag nanocrystals concomitant with decrease in the number of Ag nanocrystals attached per WO3-x nanorod. Plasmonic photocatalysis followed by thermal annealing produces only one Ag nanocrystal of size ∼10 nm on each WO3-x nanorod. Red shifting and broadening of plasmon bands of Ag nanocrystals and WO3-x nanorods confirm the formation of heterostructures between the metal and semiconductor. Detailed transmission electron micrograph analysis indicates the epitaxial growth of Ag nanocrystals onto WO3-x nanorods. A high photocurrent gain of about 4000 is observed for Ag (10 nm)/WO3-x heterostructures. The photodegradation rate for Rhodamine-B and methylene blue is maximum for Ag (10 nm)/WO3-x heterostructures due to efficient electron transfer from WO3-x nanorods to Ag nanocrystals. Metal plasmon-semiconductor exciton coupling, prominent plasmon absorbance of metal nanoparticles, and formation of an epitaxial interface are found to be the important factors to achieve the maximum photocatalytic activity and fabrication of a high speed photodetector device by employing the heterostructures.

Maximizing the photo catalytic and photo response properties of multimodal plasmonic Ag/WO3−x heterostructure nanorods by variation of the Ag size

Aliovalent ion doped n-type semiconductor nanocrystals (NC) have presently gained high interest in semiconductor research for their potential applications in plasmonics, transparent conducting oxid...

Tunable Surface Plasmon Resonance in Sn-Doped Zn–Cd–O Alloyed Nanocrystals

The synthesis of different anisotropic shaped (eight different shapes) Sn4+ doped CdO (Sn:CdO) colloidal nanocrystals (NCs) by precise tuning of precursor reactivity and proper choice of capping agent is reported. In all these systems, formation of Sn:CdO quantum dots (QDs) of 2-3 nm is identified at very early stage of reaction. The colloidally stable QDs act as a continuous source for the formation of primary nanoparticles that can be transformed selectively into specific type of nanoparticle morphology. The specific facet stabilization of fcc (face centered cubic)CdO is predicted by particular choice of ligand. Fine tuning of plasmonic absorbance band can be achieved by variation of Sn4+ doping concentration. Different anisotropic Sn:CdO NCs exhibit interesting shape dependent plasmonic absorbance features in NIR region. High quality crack free uniform dense thin film has been deposited on glass substrate to make high quality transparent conducting oxide (TCO) coatings. figure of merit of TCO can be maximized as high as 0.523 Ω-1 with conductivity of 43 600 S cm-1 and visible transmittance of ≈85% which is much higher than commercially available tin doped indium oxide and other transparent electrodes.

Manas Saha

Papers

Tunable surface plasmon resonance and enhanced electrical conductivity of In doped ZnO colloidal nanocrystals.

Carrier concentration dependent optical and electrical properties of Ga doped ZnO hexagonal nanocrystals.

Maximizing the photo catalytic and photo response properties of multimodal plasmonic Ag/WO3−x heterostructure nanorods by variation of the Ag size

Tunable Surface Plasmon Resonance in Sn-Doped Zn–Cd–O Alloyed Nanocrystals

Shape Controlled Plasmonic Sn Doped CdO Colloidal Nanocrystals: A Synthetic Route to Maximize the Figure of Merit of Transparent Conducting Oxide.