Metal halide perovskites represent a flourishing area of research, driven by both their potential application in photo-voltaics and optoelectronics, and for the fundamental science underpinning their unique optoelectronic properties. The advent of colloidal methods for the synthesis of halide perovskite nanocrystals has brought to the attention inter-esting aspects of this new type of materials, above all their defect-tolerance. This review aims to provide an updated survey of this fast-moving field, with a main focus on their colloidal synthesis. We examine the chemistry and the ca-pability of different colloidal synthetic routes to control the shape, size and optical properties of the resulting nano-crystals. We also provide an up to date overview of their post-synthesis transformations, and summarize the various so-lution processes aimed at fabricating halide perovskite-based nanocomposites. We then review the fundamental optical properties of halide perovskite nanocrystals, by focusing on their linear optical properties, on the effects of quantum confinement and, then, on the current knowledge of their exciton binding energies. We also discuss the emergence of non-linear phenomena such as multiphoton absorption, biexcitons and carrier multiplication. At last, we provide an outlook in the field, with the most cogent open questions and possible future directions.

Metal Halide Perovskite Nanocrystals: Synthesis, Post-Synthesis Modifications and Their Optical Properties

Metal halide perovskites represent a flourishing area of research, which is driven by both their potential application in photovoltaics and optoelectronics and by the fundamental science behind their unique optoelectronic properties. The emergence of new colloidal methods for the synthesis of halide perovskite nanocrystals, as well as the interesting characteristics of this new type of material, has attracted the attention of many researchers. This review aims to provide an up-to-date survey of this fast-moving field and will mainly focus on the different colloidal synthesis approaches that have been developed. We will examine the chemistry and the capability of different colloidal synthetic routes with regard to controlling the shape, size, and optical properties of the resulting nanocrystals. We will also provide an up-to-date overview of their postsynthesis transformations, and summarize the various solution processes that are aimed at fabricating halide perovskite-based nanocomposites. Furthermore, we...

Metal Halide Perovskite Nanocrystals: Synthesis, Post-Synthesis Modifications, and Their Optical Properties.

Two-dimensional (2D) materials are a new type of materials under intense study because of their interesting physical properties and wide range of potential applications from nanoelectronics to sensing and photonics. Monolayers of semiconducting transition metal dichalcogenides MoS2 or WSe2 have been proposed as promising channel materials for field-effect transistors. Their high mechanical flexibility, stability, and quality coupled with potentially inexpensive production methods offer potential advantages compared to organic and crystalline bulk semiconductors. Due to quantum mechanical confinement, the band gap in monolayer MoS2 is direct in nature, leading to a strong interaction with light that can be exploited for building phototransistors and ultrasensitive photodetectors. Here, we report on the realization of light-emitting diodes based on vertical heterojunctions composed of n-type monolayer MoS2 and p-type silicon. Careful interface engineering allows us to realize diodes showing rectification and light emission from the entire surface of the heterojunction. Electroluminescence spectra show clear signs of direct excitons related to the optical transitions between the conduction and valence bands. Our p–n diodes can also operate as solar cells, with typical external quantum efficiency exceeding 4%. Our work opens up the way to more sophisticated optoelectronic devices such as lasers and heterostructure solar cells based on hybrids of 2D semiconductors and silicon.

http://absimage.aps.org/image/MAR14/MWS_MAR14-2013-004565.pdf

Light Generation and Harvesting in a Van der Waals Heterostructure

Monolayer MoS2 is a direct-gap two-dimensional semiconductor that exhibits strong electron-hole interactions, leading to the formation of stable excitons and trions. Here we report the existence of efficient exciton-exciton annihilation, a four-body interaction, in this material. Exciton-exciton annihilation was identified experimentally in ultrafast transient absorption measurements through the emergence of a decay channel varying quadratically with exciton density. The rate of exciton-exciton annihilation was determined to be (4.3 ± 1.1) × 10(-2) cm(2)/s at room temperature.

http://absimage.aps.org/image/MAR15/MWS_MAR15-2014-006549.pdf

Observation of Rapid Exciton-Exciton Annihilation in Monolayer Molybdenum Disulfide

Ultrafast fiber lasers have significant applications in ultra-precision manufacturing, medical diagnostics, medical treatment, precision measurement and astronomical detection, owing to their ultra-short pulse width and ultra-high peak-power. Since graphene was first explored as an optical saturable absorber for passively mode-locked lasers in 2009, many other 2D materials beyond graphene, including phosphorene, antimonene, bismuthene, transition metal dichalcogenides (TMDs), topological insulators (TIs), metal–organic frameworks (MOFs) and MXenes, have been successively explored, resulting in rapid development of novel 2D materials-based saturable absorbers. Herein, we review the latest progress of the emerging 2D materials beyond graphene for passively mode-locked fiber laser application. These 2D materials are classified into mono-elemental, dual-elemental and multi-elemental 2D materials. The atomic structure, band structure, nonlinear optical properties, and preparation methods of 2D materials are summarized. Diverse integration strategies for applying 2D materials into fiber laser systems are introduced, and the mode-locking performance of the 2D materials-based fiber lasers working at 1–3 μm are discussed. Finally, the perspectives and challenges facing 2D materials-based mode-locked fiber lasers are highlighted.

Emerging 2D materials beyond graphene for ultrashort pulse generation in fiber lasers.

We report the preparation of monolayer (n = 1), few-layer (n = 2–5) and 3D (n = ∞) organic lead bromide perovskite nanoplatelets (NPLs) by tuning the molar ratio of methylammonium bromide (MABr) and hexadecammonium bromide (HABr). The absorption spectrum of the monolayer (HA)2PbBr4 perovskite NPLs shows about 138 nm blue shift from that of 3D MAPbBr3 perovskites, which is attributed to strong quantum confinement effect. We further investigate the two-photon photoluminescence (PL) of the NPLs and measure the exciton binding energy of monolayer perovskite NPLs using linear absorption and two-photon PL excitation spectroscopy. The exciton binding energy of monolayer perovskite NPLs is about 218 meV, which is far larger than tens of meV in 3D lead halide perovskites.

Quantum confinement effect and exciton binding energy of layered perovskite nanoplatelets

Plasmon-mediated energy transfer is highly desirable in photo-electronic nanodevices, but the direct injection efficiency of "hot electrons" in plasmonic photo-detectors and plasmon-sensitized solar cells (plasmon-SSCs) is poor. On another front, Fano resonance induced by strong plasmon-exciton coupling provides an efficient channel of coherent energy transfer from metallic plasmons to molecular excitons, and organic dye molecules have a much better injection efficiency in exciton-SSCs than "hot electrons". Here, we investigate enhanced light-harvesting of chlorophyll-a molecules strongly coupled to Au nanostructured films via Fano resonance. The enhanced local field and plasmon resonance energy transfer are experimentally revealed by monitoring the ultrafast dynamical processes of the plexcitons and the photocurrent flows of the assembled plexciton-SSCs. By tuning the Fano factor and anti-resonance wavelengths, we find that the local field is largely enhanced and the efficiency of plexciton-SSCs consisting of ultrathin TiO2 films is significantly improved. Most strikingly, the output power of the plexciton-SSCs is much larger than the sum of those of the individual plasmon- and exciton-SSCs. Our observations provide a practical approach to monitor energy and electron transfer in plasmon-exciton hybrids at a strong coupling regime and also offer a new strategy to design photovoltaic nanodevices.

Plasmon resonance energy transfer and plexcitonic solar cell

The magnetic plasmons of three-dimensional nanostructures have unique optical responses and special significance for optical nanoresonators and nanoantennas. In this study, we have successfully synthesized colloidal Au and AuAg nanocups with a well-controlled asymmetric geometry, tunable opening sizes, and normalized depths (h/b, where h is depth and b is the height of the templating PbS nanooctahedrons), variable magnetic plasmon resonance, and largely enhanced second-harmonic generation (SHG). The most-efficient SHG of the bare Au nanocups is experimentally observed when the normalized depth h/b is adjusted to ∼0.78–0.79. We find that the average magnetic field enhancement is maximized at h/b = ∼0.65 and reveal that the maximal SHG can be attributed to the joint action of the optimized magnetic plasmon resonance and the “lightning-rod effect” of the Au nanocups. Furthermore, we demonstrate for the first time that the AuAg heteronanocups prepared by overgrowth of Ag on the Au nanocups can synergize the m...

Magnetic Plasmon-Enhanced Second-Harmonic Generation on Colloidal Gold Nanocups.

Here, we prepared silver (Ag) dendrite fractal nanostructures by a facile electrochemical deposition method. The silver dendrite fractal nanostructures exhibit multiple plasmon resonances, which leads to an enhanced second harmonic generation (SHG). Interestingly, the prepared thin film can be used as plasmonic substrates. As an example application, we selected surface-enhanced Raman scattering (SERS) spectroscopy with tunable sensitivity. Using 1,4-benzenedithiol (1,4-BDT) as a probe molecule, the SERS intensity of dendrite fractal nanostructures is approximately 77 times larger than that of the flower-like nanoplates (one of the structures that appears during the growth), and a low detection limit of 10−14 M 1,4-BDT can be achieved. Our results offer a low-cost and easy strategy in fabricating nonlinear photonic nanodevices and SERS chips.

Fabrication of silver dendrite fractal structures for enhanced second harmonic generation and surface-enhanced Raman scattering

Substantial effort has been devoted to synthesizing plasmonic metal/semiconductor heteronanostructures with controlled morphology owing to their excellent performance ranging from photocatalysis to optical information processing. However, growing semiconductor heterojunctions with both counterparts in direct contact with the plasmonic metal nanostructures remains challenging. Herein, we report a three-step method to grow CdS–Cu2−xS lateral heteroshells on Au nanoparticles with all components directly connected with each other. Ag2S semi shells are initially grown on the Au nanoparticles as an interim layer, Cu2−xS semi shells are then grown on the uncovered surface of the Au nanoparticles, and CdS is generated by replacing Ag2S and the Au core complex with CdS–Cu2−xS lateral heteroshells Au/CdS–Cu2−xS is finally obtained. These complexes integrate the plasmon resonances of Au in the visible region and that of Cu2−xS in the near-infrared region, and therefore show improved photocatalytic activity and high photothermal efficiency. This study offers a synthetic approach to grow metal sulfides on Au nanostructures which have diverse applications in photocatalysis and photothermal therapy.

Yun-Hang Qiu

Papers

Quantum confinement effect and exciton binding energy of layered perovskite nanoplatelets

Plasmon resonance energy transfer and plexcitonic solar cell

Magnetic Plasmon-Enhanced Second-Harmonic Generation on Colloidal Gold Nanocups.

Fabrication of silver dendrite fractal structures for enhanced second harmonic generation and surface-enhanced Raman scattering

Controlled growth of CdS–Cu2−xS lateral heteroshells on Au nanoparticles with improved photocatalytic activity and photothermal efficiency