Chirality dependence of the absorption cross-section of carbon nanotubes

The variation of the optical absorption of carbon nanotubes with their geometry has been a long standing question at the heart of both metrological and applicative issues, in particular because optical spectroscopy is one of the primary tools for the assessment of the chiral species abundance of samples. Here, we tackle the chirality dependence of the optical absorption with an original method involving ultra-efficient energy transfer in porphyrin/nanotube compounds that allows uniform photo-excitation of all chiral species. We measure the absolute absorption cross-section of a wide range of semiconducting nanotubes at their S22 transition and show that it varies by up to a factor of 2.2 with the chiral angle, with type I nanotubes showing a larger absorption. In contrast, the luminescence quantum yield remains almost constant

Mechanistic insight into the chemical treatments of monolayer transition metal disulfides for photoluminescence enhancement.

There is a growing interest in obtaining high quality monolayer transition metal disulfides for optoelectronic applications. Surface treatments using a range of chemicals have proven effective to improve the photoluminescence yield of these materials. However, the underlying mechanism for the photoluminescence enhancement is not clear, which prevents a rational design of passivation strategies. Here, a simple and effective approach to significantly enhance the photoluminescence is demonstrated by using a family of cation donors, which we show to be much more effective than commonly used p-dopants. We develop a detailed mechanistic picture for the action of these cation donors and demonstrate that one of them, bis(trifluoromethane)sulfonimide lithium salt (Li-TFSI), enhances the photoluminescence of both MoS2 and WS2 to a level double that of the currently best performing super-acid trifluoromethanesulfonimide (H-TFSI) treatment. In addition, the ionic salts used in our treatments are compatible with greener solvents and are easier to handle than super-acids, providing the possibility of performing treatments during device fabrication. This work sets up rational selection rules for ionic chemicals to passivate transition metal disulfides and increases their potential in practical optoelectronic applications

Structural and spectroscopic studies of a nanostructured silicon-perovskite interface.

While extensively investigated in thin film form for energy materials applications, this work investigates the formation of APbBr3 structures (A = CH3NH3+ (MA), Cs+) in silicon and oxidized silicon nanotubes (SiNTs) with varying inner diameter. We carefully control the extent of oxidation of the nanotube host and correlate the relative Si/Si oxide content in a given nanotube host with the photoluminescence quantum efficiency (PLQE) of the perovskite. Complementing these measurements is an evaluation of average PL lifetimes of a given APbBr3 nanostructure, as evaluated by time-resolved confocal photoluminescence measurements. Increasing Si (decreasing oxide) content in the nanotube host results in a sensitive reduction of MAPbBr3 PLQE, with a concomitant decrease in average lifetime (τave). We interpret these observations in terms of decreased defect passivation by a lower concentration of oxide species surrounding the perovskite. In addition, we show that the use of selected nanotube templates leads to more stable perovskite PL in air over time (weeks). Taken in concert, such fundamental observations have implications for interfacial carrier interactions in tandem Si/perovskite photovoltaics.This work was supported by the Robert A. Welch Foundation (Grant P-1212 to JLC). This project has also received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement number 756962). GD would like to acknowledge the Royal Society for funding through a Newton International Fellowship. K. F. acknowledges a George and Lilian Schiff Studentship, Winton Studentship, the Engineering and Physical Sciences Research Council (EPSRC) studentship, Cambridge Trust Scholarship, and Robert Gardiner Scholarship. R. L. Z. H. acknowledges funding from the Royal Academy of Engineering under the Research Fellowships scheme (no.: RF\201718\17101). The authors acknowledge the EPSRC (EP/R023980/1) for funding

Visualizing Buried Local Carrier Diffusion in Halide Perovskite Crystals via Two-Photon Microscopy.

Halide perovskites have shown great potential for light emission and photovoltaic applications due to their remarkable electronic properties. Although the device performances are promising, they are still limited by microscale heterogeneities in their photophysical properties. Here, we study the impact of these heterogeneities on the diffusion of charge carriers, which are processes crucial for efficient collection of charges in light-harvesting devices. A photoluminescence tomography technique is developed in a confocal microscope using one- and two-photon excitation to distinguish between local surface and bulk diffusion of charge carriers in methylammonium lead bromide single crystals. We observe a large dispersion of local diffusion coefficients with values between 0.3 and 2 cm2·s-1 depending on the trap density and the morphological environment-a distribution that would be missed from analogous macroscopic or surface measurements. This work reveals a new framework to understand diffusion pathways, which are extremely sensitive to local properties and buried defects

Controlling the Growth Kinetics and Optoelectronic Properties of 2D/3D Lead–Tin Perovskite Heterojunctions

Halide perovskites are emerging as valid alternatives to conventional photovoltaic active materials owing to their low cost and high device performances. This material family also shows exceptional tunability of properties by varying chemical components, crystal structure, and dimensionality, providing a unique set of building blocks for new structures. Here, highly stable self-assembled lead–tin perovskite heterostructures formed between low bandgap 3D and higher bandgap 2D components are demonstrated. A combination of surface-sensitive X-ray diffraction, spatially resolved photoluminescence, and electron microscopy measurements is used to reveal that microstructural heterojunctions form between high bandgap 2D surface crystallites and lower bandgap 3D domains. Furthermore, in situ X-ray diffraction measurements are used during film formation to show that an ammonium thiocyanate additive delays formation of the 3D component and thus provides a tunable lever to substantially increase the fraction of 2D surface crystallites. These novel heterostructures will find use in bottom cells for stable tandem photovoltaics with a surface 2D layer passivating the 3D material, or in energy transfer devices requiring controlled energy flow from localized surface crystallites to the bulk.- EPSRC Departmental Graduate Studentship - Royal Society - Polish Ministry of Science and Higher Education within the Mobilnosc Plus program (Grant no. 1603/ 2 MOB/V/2017/0). - Jardine Foundation - Cambridge Trus

Enhancing Photoluminescence and Mobilities in WS2 Monolayers with Oleic Acid Ligands.

Many potential applications of monolayer transition metal dichalcogenides (TMDs) require both high photoluminescence (PL) yield and high electrical mobilities. However, the PL yield of as prepared TMD monolayers is low and believed to be limited by defect sites and uncontrolled doping. This has led to a large effort to develop chemical passivation methods to improve PL and mobilities. The most successful of these treatments is based on the nonoxidizing organic "superacid" bis(trifluoromethane)sulfonimide (TFSI) which has been shown to yield bright monolayers of molybdenum disulfide (MoS2) and tungsten disulfide (WS2) but with trap-limited PL dynamics and no significant improvements in field effect mobilities. Here, using steady-state and time-resolved PL microscopy we demonstrate that treatment of WS2 monolayers with oleic acid (OA) can greatly enhance the PL yield, resulting in bright neutral exciton emission comparable to TFSI treated monolayers. At high excitation densities, the OA treatment allows for bright trion emission, which has not been demonstrated with previous chemical treatments. We show that unlike the TFSI treatment, the OA yields PL dynamics that are largely trap free. In addition, field effect transistors show an increase in mobilities with the OA treatment. These results suggest that OA serves to passivate defect sites in the WS2 monolayers in a manner akin to the passivation of colloidal quantum dots with OA ligands. Our results open up a new pathway to passivate and tune defects in monolayer TMDs using simple "wet" chemistry techniques, allowing for trap-free electronic properties and bright neutral exciton and trion emission

Revealing Nanomechanical Domains and Their Transient Behavior in Mixed‐Halide Perovskite Films

Abstract: Halide perovskites are a versatile class of semiconductors employed for high performance emerging optoelectronic devices, including flexoelectric systems, yet the influence of their ionic nature on their mechanical behavior is still to be understood. Here, a combination of atomic‐force, optical, and compositional X‐ray microscopy techniques is employed to shed light on the mechanical properties of halide perovskite films at the nanoscale. Mechanical domains within and between morphological grains, enclosed by mechanical boundaries of higher Young's Modulus (YM) than the bulk parent material, are revealed. These mechanical boundaries are associated with the presence of bromide‐rich clusters as visualized by nano‐X‐ray fluorescence mapping. Stiffer regions are specifically selectively modified upon light soaking the sample, resulting in an overall homogenization of the mechanical properties toward the bulk YM. This behavior is attributed to light‐induced ion migration processes that homogenize the local chemical distribution, which is accompanied by photobrightening of the photoluminescence within the same region. This work highlights critical links between mechanical, chemical, and optoelectronic characteristics in this family of perovskites, and demonstrates the potential of combinational imaging studies to understand and design halide perovskite films for emerging applications such as photoflexoelectricity

Revealing Nanomechanical Domains and Their Transient Behavior in Mixed‐Halide Perovskite Films

Abstract: Halide perovskites are a versatile class of semiconductors employed for high performance emerging optoelectronic devices, including flexoelectric systems, yet the influence of their ionic nature on their mechanical behavior is still to be understood. Here, a combination of atomic‐force, optical, and compositional X‐ray microscopy techniques is employed to shed light on the mechanical properties of halide perovskite films at the nanoscale. Mechanical domains within and between morphological grains, enclosed by mechanical boundaries of higher Young's Modulus (YM) than the bulk parent material, are revealed. These mechanical boundaries are associated with the presence of bromide‐rich clusters as visualized by nano‐X‐ray fluorescence mapping. Stiffer regions are specifically selectively modified upon light soaking the sample, resulting in an overall homogenization of the mechanical properties toward the bulk YM. This behavior is attributed to light‐induced ion migration processes that homogenize the local chemical distribution, which is accompanied by photobrightening of the photoluminescence within the same region. This work highlights critical links between mechanical, chemical, and optoelectronic characteristics in this family of perovskites, and demonstrates the potential of combinational imaging studies to understand and design halide perovskite films for emerging applications such as photoflexoelectricity