Ultrathin CdSe in Plasmonic Nanogaps for Enhanced Photocatalytic Water Splitting.

Enhanced plasmonic fields are a promising way to increase the efficiency of photocatalytic water splitting. The availability of atomically thin materials opens up completely new opportunities. We report photocatalytic water splitting on ultrathin CdSe nanoplatelets placed in plasmonic nanogaps formed by a flat gold surface and a gold nanoparticle. The extreme field intensity created in these gaps increases the electron–hole pair production in the CdSe nanoplatelets and enhances the plasmon-mediated interfacial electron transfer. Compared to individual nanoparticles commonly used to enhance photocatalytic processes, gap-plasmons produce several orders of magnitude higher field enhancement, strongly localized inside the semiconductor sheet thus utilizing the entire photocatalyst efficiently.This work was supported by the U.K. EPSRC grant EP/G060649/1 and EPSRC grant EP/L027151/1, Defence Science and Technology Laboratory (DSTL), a Marie Curie Intra-European Fellowship (FP7-PEOPLE-2011-IEF 298012 to L.Z.) and ERC grant 320503 LINASS.This is the final version of the article. It first appeared from ACS via http://dx.doi.org/10.1021/acs.jpclett.5b0027

Halide Ligands to Release Strain in Cadmium Chalcogenide Nanoplatelets and Achieve High Brightness

International audienceZinc blende II-VI semiconductor nanoplatelets (NPLs) are defined at the atomic scale along the thickness of the nanoparticle and are initially capped with carboxylates on the top and bottom [001] facets. These ligands are exchanged on CdSe NPLs with halides that act as X-L-type ligands. These CdSe NPLs are costabilized by amines to provide colloidal stability in nonpolar solvents. The hydrogen from the amine can participate in a hydrogen bond with the lone pair electrons of surface halides. After ligand exchange, the optical features are redshifted. Thus, ligand tuning is another way, in addition to confinement, to tune the optical features of NPLs. The improved surface passivation leads to an increase in the fluorescence quantum efficiency of up to 70% in the case of bromide. However, for chloride and iodide, the surface coverage is incomplete, and thus, the fluorescence quantum efficiency is lower. This ligand exchange is associated with a decrease in stress that leads to unfolding of the NPLs, which is particularly noticeable for iodide-capped NPLs

Probing confined phonon modes in individual CdSe nanoplatelets using surface-enhanced Raman scattering.

The phonon modes of individual ultrathin CdSe nanoplatelets are investigated using surface-enhanced Raman scattering in a tightly confined plasmonic geometry. The surface-enhanced Raman scattering spectra, taken on single nanoplatelets sandwiched between a gold nanoparticle and a gold surface, reveal a phonon doublet arising from oscillations perpendicular to and within the platelet plane. The out-of-plane mode cannot be observed with conventional Raman spectroscopy. The resulting strong electric field enhancements and the field vector reorientation within such nanometer-sized plasmonic gaps reveal otherwise hidden information deep into the Brillouin zone illuminating the vibrational properties of ultrathin materials.EPSRCThis is the Author Accepted Manuscript of Daniel O. Sigle, James T. Hugall, Sandrine Ithurria, Benoit Dubertret, and Jeremy J. Baumberg which was published in Physical review letters (https://journals.aps.org/prl/abstract/10.1103/PhysRevLett.113.087402). "Copyright 2014 by the American Physical Society.

Tight-binding calculations of image charge effects in colloidal nanoscale platelets of CdSe

International audienceCdSe nanoplatelets show perfectly quantized thicknesses of few monolayers. They present a situation of extreme, yet well de ned quantum con nement. Due to large dielectric contrast between the semiconductor and its ligand environment, interaction between carriers and their dielectric images strongly renormalize bare single particle states. We discuss the electronic properties of this original system in an advanced tight-binding model, and show that Coulomb interactions, including self-energy corrections and enhanced electron-hole interaction, lead to exciton binding energies up to several hundred meVs

Monitoring morphological changes in 2D monolayer semiconductors using atom-thick plasmonic nanocavities.

Nanometer-sized gaps between plasmonically coupled adjacent metal nanoparticles enclose extremely localized optical fields, which are strongly enhanced. This enables the dynamic investigation of nanoscopic amounts of material in the gap using optical interrogation. Here we use impinging light to directly tune the optical resonances inside the plasmonic nanocavity formed between single gold nanoparticles and a gold surface, filled with only yoctograms of semiconductor. The gold faces are separated by either monolayers of molybdenum disulfide (MoS2) or two-unit-cell thick cadmium selenide (CdSe) nanoplatelets. This extreme confinement produces modes with 100-fold compressed wavelength, which are exquisitely sensitive to morphology. Infrared scattering spectroscopy reveals how such nanoparticle-on-mirror modes directly trace atomic-scale changes in real time. Instabilities observed in the facets are crucial for applications such as heat-assisted magnetic recording that demand long-lifetime nanoscale plasmonic structures, but the spectral sensitivity also allows directly tracking photochemical reactions in these 2-dimensional solids.This work was supported by the UK EPSRC grant EP/G060649/1, Defence Science and Technology Laboratory (DSTL), and ERC grant 320503 LINASS.This is the final version of the article. It first appeared from ACS via http://dx.doi.org/10.1021/nn5064198

Field effect transistor and photo transistor of narrow band gap nanocrystal arrays using ionic glasses

International audienceGating of nanocrystal films is currently driven by two approaches: either the use of a dielectric such as SiO2 or the use of electrolyte. SiO2 allows fast bias sweeping over a broad range of temperatures but requires a large operating bias. Electrolyte, thanks to a large capacitance, leads to significantly reduce operating bias but is limited to slow speed and quasi room temperature operation. None of these operating conditions are optimal for narrow band gap nanocrystal-based phototransistors for which the need of a large capacitance gate has to be combined with low temperature operation. Here we explore the use of a LaF3 ionic glass as a high capacitance gating alternative. We demonstrate for the first time the use of such ionic glasses to gate thin films made of HgTe and PbS nanocrystals. This gating strategy allows operation in the 180 to 300 K range of temperatures with capacitance as high as 1 µF·cm-2. We unveil the unique property of ionic glass gate to enable unprecedented tunability of both magnitude and dynamics of the photocurrent, thanks to high charge doping capability within an operating temperature window relevant for infrared photodetection. We demonstrate that by carefully choosing the operating gate bias, the signal to noise ratio can be improved by a factor 100 and the time response accelerated by a factor 6. Moreover, the good transparency of LaF3 substrate allows back side illumination in the infrared which is highly valuable for the design of phototransistor

Double-crowned 2D semiconductor nanoplatelets with bicolor power-tunable emission

Nanocrystals (NCs) are now established building blocks for optoelectronics and their use as down converters for large gamut displays has been their first mass market. NC integration relies on a combination of green and red NCs into a blend, which rises post-growth formulation issues. A careful engineering of the NCs may enable dual emissions from a single NC population which violates Kasha’s rule, which stipulates that emission should occur at the band edge. Thus, in addition to an attentive control of band alignment to obtain green and red signals, non-radiative decay paths also have to be carefully slowed down to enable emission away from the ground state. Here, we demonstrate that core/crown/crown 2D nanoplatelets (NPLs), made of CdSe/CdTe/CdSe, can combine a large volume and a type-II band alignment enabling simultaneously red and narrow green emissions. Moreover, we demonstrate that the ratio of the two emissions can be tuned by the incident power, which results in a saturation of the red emission due to non-radiative Auger recombination that affects this emission much stronger than the green one. Finally, we also show that dual-color, power tunable, emission can be obtained through an electrical excitation

Exciton-Phonon Interactions Govern Charge-Transfer-State Dynamics in CdSe/CdTe Two-Dimensional Colloidal Heterostructures.

CdSe/CdTe core-crown type-II nanoplatelet heterostructures are two-dimensional semiconductors that have attracted interest for use in light-emitting technologies due to their ease of fabrication, outstanding emission yields, and tunable properties. Despite this, the exciton dynamics of these complex materials, and in particular how they are influenced by phonons, is not yet well understood. Here, we use a combination of femtosecond vibrational spectroscopy, temperature-resolved photoluminescence (PL), and temperature-dependent structural measurements to investigate CdSe/CdTe nanoplatelets with a thickness of four monolayers. We show that charge-transfer (CT) excitons across the CdSe/CdTe interface are formed on two distinct time scales: initially from an ultrafast (∼70 fs) electron transfer and then on longer time scales (∼5 ps) from the diffusion of domain excitons to the interface. We find that the CT excitons are influenced by an interfacial phonon mode at ∼120 cm-1, which localizes them to the interface. Using low-temperature PL spectroscopy we reveal that this same phonon mode is the dominant mechanism in broadening the CT PL. On cooling to 4 K, the total PL quantum yield reaches close to unity, with an ∼85% contribution from CT emission and the remainder from an emissive sub-band-gap state. At room temperature, incomplete diffusion of domain excitons to the interface and scattering between CT excitons and phonons limit the PL quantum yield to ∼50%. Our results provide a detailed picture of the nature of exciton-phonon interactions at the interfaces of 2D heterostructures and explain both the broad shape of the CT PL spectrum and the origin of PL quantum yield losses. Furthermore, they suggest that to maximize the PL quantum yield both improved engineering of the interfacial crystal structure and diffusion of domain excitons to the interface, e.g., by altering the relative core/crown size, are required.We acknowledge financial support from the EPSRC [EP/M005143/1] and Winton Program for the Physics of Sustainability. The work of SI is supported by the program ANR JCJC NannoDoSe

Emission State Structure and Linewidth Broadening Mechanisms in Type-II CdSe/CdTe Core–Crown Nanoplatelets: A Combined Theoretical–Single Nanocrystal Optical Study

Type-II heterostructures are key elementary components in optoelectronic, photovoltaic, and quantum devices. The staggered band alignment of materials leads to the stabilization of indirect excitons (IXs), i.e., correlated electron–hole pairs experiencing spatial separation with novel properties, boosting optical gain and promoting strategies for the design of information storage, charge separation, or qubit manipulation devices. Planar colloidal CdSe/CdTe core–crown type-II nested structures, grown as nanoplatelets (NPLs), are the focus of the present work. By combining low temperature single NPL measurements and electronic structure calculations, we gain insights into the mechanisms impacting the emission properties. We are able to probe the sensitivity of the elementary excitations (IXs, trions) with respect to the appropriate structural parameter (core size). Neutral IXs, with binding energies reaching 50 meV, are shown to dominate the highly structured single NPL emission. The large broadening linewidth that persists at the single NPL level clearly results from strong exciton–LO phonon coupling (Eph = 21 meV) whose strength is poorly influenced by trapped charges. The spectral jumps (≈10 meV) in the photoluminescence recorded as a function of time are explained by the fluctuations in the IX electrostatic environment considering fractional variations (≈0.2 e) of the noncompensated charge defects

Investigating the n- and p-Type Electrolytic Charging of Colloidal Nanoplatelets

We investigate the ion gel gating of 2D colloidal nanoplatelets. We propose a simple, versatile, and air-operable strategy to build electrolyte-gated transistors. We provide evidence that the charges are injected in the quantum states of the nanocrystals. The gating is made possible by the presence of large voids into the NPL films and is sensitive to the availability of the nanocrystals surface