Progress in the Light Emission of Colloidal Semiconductor Nanocrystals

Some 25 years ago it was found that semiconductor nanocrystals emitted light. Since then tremendous progress has been made with respect to increasing the emission quantum yields, extending the spectral range that may be addressed, from the UV across to the near infrared, and improving the color purity. Here some major lines in these developments are reviewed, touching on milestones as well as on the principles of the most successful preparative approaches.     

Core/Shell Semiconductor Nanocrystals

Colloidal core/shell nanocrystals contain at least two semiconductor materials in an onionlike structure. The possibility to tune the basic optical properties of the core nanocrystals, for example, their fluorescence wavelength, quantum yield, and lifetime, by growing an epitaxial‐type shell of another semiconductor has fueled significant progress on the chemical synthesis of these systems. In such core/shell nanocrystals, the shell provides a physical barrier between the optically active core and the surrounding medium, thus making the nanocrystals less sensitive to environmental changes, surface chemistry, and photo‐oxidation. The shell further provides an efficient passivation of the surface trap states, giving rise to a strongly enhanced fluorescence quantum yield. This effect is a fundamental prerequisite for the use of nanocrystals in applications such as biological labeling and light‐emitting devices, which rely on their emission properties. Focusing on recent advances, this Review discusses the fundamental properties and synthesis methods of core/shell and core/multiple shell structures of II–VI, IV–VI, and III–V semiconductors.

     

Laser-Controlled Magnetization in a Single Magnetic Semiconductor Quantum Dot

The photoluminescene signal of individual semimagnetic CdSe–Zn_0.75Mn_0.25Se quantum dots is used to study the magnetization of the Mn²⁺ spin system in the exchange field of a single exciton. We demonstrate that by increasing the laser excitation power a significant blue shift of the photoluminescence signal occurs. This is attributed to a laser-induced demagnetization, i.e. the laser-generated carriers heat the Mn²⁺ spin system via spin–flip exchange scattering.     

应变GaN量子点中激子态的研究

利用有效质量方法和变分原理,考虑内建电场效应和量子点的三维约束效应,研究了约束在GaN/AlxGa1-xN圆柱形量子点中的激子特性与量子点的结构参数以及势垒层中Al含量之间的关系.结果表明:对给定大小的量子点,随其高度的增加激子结合能出现一最大值,此时载流子被最有效的约束在量子点内;内建电场使量子点的有效带隙减小,电子、空穴产生明显分离,从而影响量子点的光学性质.理论计算的光跃迁能和实验结果一致.     

Facet‐Dependent Optical Properties of Semiconductor Nanocrystals

Recent observations of facet‐dependent electrical conductivity and photocatalytic activity of various semiconductor crystals are presented. Then, the discovery of facet‐dependent surface plasmon resonance absorption of metal–Cu₂O core–shell nanocrystals with tunable sizes and shapes is discussed. The Cu₂O shells also exhibit a facet‐specific optical absorption feature. The facet‐dependent electrical conductivity, photocatalytic activity, and optical properties are related phenomena, resulting from the presence of an ultrathin surface layer with different band structures and thus varying degrees of band bending for the {100}, {110}, and {111} faces of Cu₂O to absorb light of somewhat different wavelengths. Recently, it is shown that the light absorption and photoluminescence properties of pure Cu₂O cubes, octahedra, and rhombic dodecahedra also display size and facet effects because of their tunable band gaps. A modified band diagram of Cu₂O can be constructed to incorporate these optical effects. Literature also provides examples of facet‐dependent optical behaviors of semiconductor nanostructures, indicating that optical properties of nanoscale semiconductor materials are intrinsically facet‐dependent. Some applications of semiconductor optical size and facet effects are considered.     

Nanocrystal Skins with Exciton Funneling for Photosensing

Highly photosensitive nanocrystal (NC) skins based on exciton funneling are proposed and demonstrated using a graded bandgap profile across which no external bias is applied in operation for light‐sensing. Four types of gradient NC skin devices (GNS) made of NC monolayers of distinct sizes with photovoltage readout are fabricated and comparatively studied. In all structures, polyelectrolyte polymers separating CdTe NC monolayers set the interparticle distances between the monolayers of ligand‐free NCs to <1 nm. In this photosensitive GNS platform, excitons funnel along the gradually decreasing bandgap gradient of cascaded NC monolayers, and are finally captured by the NC monolayer with the smallest bandgap interfacing the metal electrode. Time‐resolved measurements of the cascaded NC skins are conducted at the donor and acceptor wavelengths, and the exciton transfer process is confirmed in these active structures. These findings are expected to enable large‐area GNS‐based photosensing with highly efficient full‐spectrum conversion.     

An Intrinsically Fluorescent Recognition Ligand Scaffold Based on Chaperonin Protein and Semiconductor Quantum‐Dot Conjugates

Genetic engineering of a novel protein–nanoparticle hybrid system with great potential for biosensing applications and for patterning of various types of nanoparticles is described. The hybrid system is based on a genetically modified chaperonin protein from the hyperthermophilic archaeon Sulfolobus shibatae. This chaperonin is an 18‐subunit double ring, which self‐assembles in the presence of Mg ions and ATP. Described here is a mutant chaperonin (His‐β‐loopless, HBLL) with increased access to the central cavity and His‐tags on each subunit extending into the central cavity. This mutant binds water‐soluble semiconductor quantum dots, creating a protein‐encapsulated fluorescent nanoparticle. The new bioconjugate has high affinity, in the order of strong antibody–antigen interactions, a one‐to‐one protein–nanoparticle stoichiometry, and high stability. By adding selective binding sites to the solvent‐exposed regions of the chaperonin, this protein–nanoparticle bioconjugate becomes a sensor for specific targets.     

Physicochemical evaluation of the hot-injection method, a synthesis route for monodisperse nanocrystals

The quintessence of the hot-injection method, a synthesis route for monodisperse, highly luminescent semiconductor nanocrystals, is reviewed. The separate stages of nucleation and growth of the nanocrystals are discussed in the framework of classical nucleation theory and an equilibrium model proposed by Debye. We also review the numerous adaptations of the original synthesis that currently provide colloidal nanocrystals with well-defined, size-dependent optical, electrical, and magnetic properties. The availability of these remarkable materials is one of the most promising developments in nanoscience and nanotechnology.     

Shape control of II-VI semiconductor nanomaterials

Anisotropic II-VI semiconductor nanocrystals and nanoparticles have become important building blocks for (potential) nanotechnological applications. Even though a wide variety of differently shaped nanoparticles of this class can be prepared, the underlying mechanisms are mostly not fully understood. This Review article provides a brief overview of the currently studied shape-evolution mechanisms and the most prominent synthesis methods for such particles, with an aim to provide a fundamental understanding on how different morphologies evolve, and to function as a tool to aid in the preparation of specific nanocrystals.     

Direct Visualization of Exciton Transport in Defective Few-Layer WS2 by Ultrafast Microscopy

As defects usually limit the exciton diffusion in 2D transition metal dichalcogenides (TMDCs), the interaction knowledge of defects and exciton transport is crucial for achieving efficient TMDC-based devices. A direct visualization of defect-modulated exciton transport is developed in few-layer WS₂ by ultrafast transient absorption microscopy. Atomic-scale defects are introduced by argon plasma treatment and identified by aberration-corrected scanning transmission electron microscopy. Neutral excitons can be captured by defects to form bound excitons in 7.75–17.88 ps, which provide a nonradiative relaxation channel, leading to decreased exciton lifetime and diffusion coefficient. The exciton diffusion length of defective sample has a drastic reduction from 349.44 to 107.40 nm. These spatially and temporally resolved measurements reveal the interaction mechanism between defects and exciton transport dynamics in 2D TMDCs, giving a guideline for designing high-performance TMDC-based devices.     

Polyvalent Display and Packing of Peptides and Proteins on Semiconductor Quantum Dots: Predicted Versus Experimental Results

Quantum dots (QDs) are loaded with a series of peptides and proteins of increasing size, including a <20 residue peptide, myoglobin, mCherry, and maltose binding protein, which together cover a range of masses from <2.2 to ≈44 kDa. Conjugation to the surface of dihydrolipoic acid‐functionalized QDs is facilitated by polyhistidine metal affinity coordination. Increasing ratios of dye‐labeled peptides and proteins are self‐assembled to the QDs and then the bioconjugates are separated and analyzed using agarose gel electrophoresis. Fluorescent visualization of both conjugated and unbound species allows determination of an experimentally derived maximum loading number. Molecular modeling utilizing crystallographic coordinates or space‐filling structures of the peptides and proteins also allow the predicted maximum loadings to the QDs to be estimated. Comparison of the two sets of results provides insight into the nature of the QD surface and reflects the important role played by the nanoparticle's hydrophilic solubilizing surface ligands. It is found that for the larger protein molecules steric hindrance is the major packing constraint. In contrast, for the smaller peptides, the number of available QD binding sites is the principal determinant. These results can contribute towards an overall understanding of how to engineer designer bioconjugates for both QDs and other nanoparticle materials.