Deciphering hot- and multi-exciton dynamics in core-shell QDs by 2D electronic spectroscopies

Although the harnessing of multiple and hot excitons is a prerequisite for many of the groundbreaking applications of semiconductor quantum dots (QDs), the characterization of their dynamics through conventional spectroscopic techniques is cumbersome. Here, we show how a careful analysis of 2DES maps acquired in different configurations (BOXCARS and pump–probe geometry) allows the tracking and visualization of intraband Auger relaxation mechanisms, driving the hot carrier cooling, and interband bi- and tri-exciton recombination dynamics. The results obtained on archetypal core– shell CdSe/ZnS QDs suggest that, given the global analysis of the resulting datasets, 2D electronic spectroscopy techniques can successfully and efficiently dispel the intertwined dynamics of fast and ultrafast recombination processes in nanomaterials. Hence, we propose this analysis scheme to be used in future research on novel quantum confined systems

Cation-disorder engineering promotes efficient charge-carrier transport in AgBiS2 nanocrystal films

Efficient charge-carrier transport is critical to the success of emergent semiconductors in photovoltaic applications. So far, disorder has been considered detrimental for charge-carrier transport, lowering mobilities and causing fast recombination. This work demonstrates that, when properly engineered, cation disorder in a multinary chalcogenide semiconductor can considerably enhance the charge-carrier mobility and extend the charge-carrier lifetime. Here, the properties of AgBiS2 nanocrystals (NCs) are explored where Ag and Bi cation-ordering can be modified via thermal-annealing. Local Ag-rich and Bi-rich domains formed during hot-injection synthesis are transformed to induce homogeneous disorder (random Ag-Bi distribution). Such cation engineering results in a six-fold increase in the charge-carrier mobility, reaching ∼2.7 cm2V−1s−1 in AgBiS2 NC thin films. It is further demonstrated that homogeneous cation disorder reduces charge-carrier localisation, a hallmark of charge-carrier transport recently observed in silver-bismuth semiconductors. This work proposes that cation-disorder engineering flattens the disordered electronic landscape, removing tail states that would otherwise exacerbate Anderson localisation of small polaronic states. Together, these findings unravel how cation-disorder engineering in multinary semiconductors can enhance the efficiency of renewable energy applications

Self-Assembly of Oriented Antibody-Decorated Metal–Organic Framework Nanocrystals for Active-Targeting Applications

Antibody (Ab)-targeted nanoparticles are becoming increasingly important for precision medicine. By controlling the Ab orientation, targeting properties can be enhanced; however, to afford such an ordered configuration, cumbersome chemical functionalization protocols are usually required. This aspect limits the progress of Abs-nanoparticles toward nanomedicine translation. Herein, a novel one-step synthesis of oriented monoclonal Ab-decorated metal–organic framework (MOF) nanocrystals is presented. The crystallization of a zinc-based MOF, Zn2(mIM)2(CO3), from a solution of Zn2+ and 2-methylimida-zole (mIM), is triggered by the fragment crystallizable (Fc) region of the Ab. This selective growth yields biocomposites with oriented Abs on the MOF nanocrystals (MOF*Ab): the Fc regions are partially inserted within the MOF surface and the antibody-binding regions protrude from the MOF surface toward the target. This ordered configuration imparts antibody–antigen rec-ognition properties to the biocomposite and shows preserved target binding when compared to the parental antibodies. Next, the biosensing performance of the system is tested by loading MOF*Ab with luminescent quantum dots (QD). The targeting efficiency of the QD-containing MOF*Ab is again, fully preserved. The present work represents a simple self-assembly approach for the fabrication of antibody-decorated MOF nanocrystals with broad potential for sensing, diagnostic imaging, and targeted drug delivery

Silver-Bismuth Based 2D Double Perovskites (4FPEA)(4)AgBiX8 (X = Cl, Br, I): Highly Oriented Thin Films with Large Domain Sizes and Ultrafast Charge-Carrier Localization

Two-dimensional (2D) hybrid double perovskites are a promising emerging class of materials featuring superior intrinsic and extrinsic stability over their 3D parent structures, while enabling additional structural diversity and tunability. Here, we expand the Ag-Bi-based double perovskite system, comparing structures obtained with the halides chloride, bromide, and iodide and the organic spacer cation 4-fluorophenethylammonium (4FPEA) to form the n = 1 Ruddlesden-Popper (RP) phases (4FPEA)(4)AgBiX8 (X = Cl, Br, I). We demonstrate access to the iodide RP-phase through a simple organic spacer, analyze the different properties as a result of halide substitution and incorporate the materials into photodetectors. Highly oriented thin films with very large domain sizes are fabricated and investigated with grazing incidence wide angle X-ray scattering, revealing a strong dependence of morphology on substrate choice and synthesis parameters. First-principles calculations confirm a direct band gap and show type Ib and IIb band alignment between organic and inorganic quantum wells. Optical characterization, temperature-dependent photoluminescence, and optical-pump terahertz-probe spectroscopy give insights into the absorption and emissive behavior of the materials as well as their charge-carrier dynamics. Overall, we further elucidate the possible reasons for the electronic and emissive properties of these intriguing materials, dominated by phonon-coupled and defect-mediated polaronic states

Chalcohalide Antiperovskite Thin Films with Visible Light Absorption and High Charge-Carrier Mobility Processed by Solvent-Free and Low-Temperature Methods

Silver chalcohalide antiperovskites represent a rather unexplored alternative to lead halide perovskites and other semiconductors based on toxic heavy metals. All synthetic approaches reported so far for Ag3SI and Ag3SBr require long synthesis times (typically days, weeks, or even months) and high temperatures. Herein, we report the synthesis of these materials using a fast and low-temperature method involving mechanochemistry. Structural and optical properties are examined experimentally and supported by first-principles calculations. Furthermore, we deposit Ag3SI as thin films by pulsed laser deposition and characterize its optoelectronic properties using optical-pump-terahertz-probe measurements, revealing a high charge-carrier mobility of 49 cm2 V-1 s-1. This work paves the way to the implementation of chalcohalide antiperovskites in various optoelectronic applications

Contrasting Ultra-Low Frequency Raman and Infrared Modes in Emerging Metal Halides for Photovoltaics

Lattice dynamics are critical to photovoltaic material performance, governing dynamic disorder, hot-carrier cooling, charge-carrier recombination, and transport. Soft metal-halide perovskites exhibit particularly intriguing dynamics, with Raman spectra exhibiting an unusually broad low-frequency response whose origin is still much debated. Here, we utilize ultra-low frequency Raman and infrared terahertz time-domain spectroscopies to provide a systematic examination of the vibrational response for a wide range of metal-halide semiconductors: FAPbI3, MAPbI x Br3–x , CsPbBr3, PbI2, Cs2AgBiBr6, Cu2AgBiI6, and AgI. We rule out extrinsic defects, octahedral tilting, cation lone pairs, and “liquid-like” Boson peaks as causes of the debated central Raman peak. Instead, we propose that the central Raman response results from an interplay of the significant broadening of Raman-active, low-energy phonon modes that are strongly amplified by a population component from Bose–Einstein statistics toward low frequency. These findings elucidate the complexities of light interactions with low-energy lattice vibrations in soft metal-halide semiconductors emerging for photovoltaic applications

Optical Nanostructures for Excitonic Devices

Unrelenting advances in the field of nanoscience are fostering the progress in diverse research fields, ranging from light-emitting to medicine and diagnostics, from energy conversion to communication technologies. Besides representing the most paradigmatic example of nanoscience, semiconductor quantum dots (QDs) avowedly brought revolutions in many of the research fields mentioned above. Nowadays, some QDs-based devices and applications reported efficiencies almost as good as current state-of-the-art technologies. The founding concept of QDs is the application of quantum confinement effects on excitons, i.e., the main players of optical properties in bulk semiconductors. Among the wealth of ensuing properties, the size- and shape- tunability of the electronic excitations and increased coupling with light field aroused much interest. Also, the colloidal approach endows QDs with high processability and low cost, thereby encouraging their implementation in existing technologies and extending their impact to other fields. Howbeit, despite three decades of investigations, the bottom line has not been reached yet, and researchers are still delving deeper into the photophysics of these nanosystems. Though many of the low hanging fruit of QDs have been harvested, higher-lying ones seem to be even more succulent. This thesis deals with the quest for highly performing nanostructures, as a prerequisite for some high impact optoelectronic applications, e.g., QD-Lasers and QD-Solar Cells. Within this framework, the struggle against fast Auger recombinations and trapping of either hot carriers or cold excitons was addressed mainly by sophisticated core/shell technologies. Thus, the first part of the thesis reports how tuning different shell parameters (e.g., the smoothness of the interface potential, the height of the confining potential, and the interfacial strain) it is possible to exert control on these detrimental recombination processes. Though often disregarded, even the role of organic capping ligand is reconsidered in promoting the outcoupling of QDs excited states and addressing their interaction. Besides the useful and technologically relevant advice gathered within these studies, the primary inheritance of the first part is the comprehensive photophysical scenario, portrayed by a phenomenological model that successfully describes many aspects of the exciton dynamics in QDs. This amount of knowledge was capitalized in the second part of this thesis, dealing with the quest for novel materials, potentially outpacing conventional CdSe-based QDs. Perovskite-based QDs reported promising results, whereas some pitfall in the conventional characterization of carbon-based QDs were discovered. The rationalization of both nature and dynamics of this materials is expected to expedite their development as alternative (and potentially superior) technologies concerning those studied in the first part

Optical Nanostructures for Excitonic Devices

Unrelenting advances in the field of nanoscience are fostering the progress in diverse research fields, ranging from light-emitting to medicine and diagnostics, from energy conversion to communication technologies. Besides representing the most paradigmatic example of nanoscience, semiconductor quantum dots (QDs) avowedly brought revolutions in many of the research fields mentioned above. Nowadays, some QDs-based devices and applications reported efficiencies almost as good as current state-of-the-art technologies. The founding concept of QDs is the application of quantum confinement effects on excitons, i.e., the main players of optical properties in bulk semiconductors. Among the wealth of ensuing properties, the size- and shape- tunability of the electronic excitations and increased coupling with light field aroused much interest. Also, the colloidal approach endows QDs with high processability and low cost, thereby encouraging their implementation in existing technologies and extending their impact to other fields. Howbeit, despite three decades of investigations, the bottom line has not been reached yet, and researchers are still delving deeper into the photophysics of these nanosystems. Though many of the low hanging fruit of QDs have been harvested, higher-lying ones seem to be even more succulent. This thesis deals with the quest for highly performing nanostructures, as a prerequisite for some high impact optoelectronic applications, e.g., QD-Lasers and QD-Solar Cells. Within this framework, the struggle against fast Auger recombinations and trapping of either hot carriers or cold excitons was addressed mainly by sophisticated core/shell technologies. Thus, the first part of the thesis reports how tuning different shell parameters (e.g., the smoothness of the interface potential, the height of the confining potential, and the interfacial strain) it is possible to exert control on these detrimental recombination processes. Though often disregarded, even the role of organic capping ligand is reconsidered in promoting the outcoupling of QDs excited states and addressing their interaction. Besides the useful and technologically relevant advice gathered within these studies, the primary inheritance of the first part is the comprehensive photophysical scenario, portrayed by a phenomenological model that successfully describes many aspects of the exciton dynamics in QDs. This amount of knowledge was capitalized in the second part of this thesis, dealing with the quest for novel materials, potentially outpacing conventional CdSe-based QDs. Perovskite-based QDs reported promising results, whereas some pitfall in the conventional characterization of carbon-based QDs were discovered. The rationalization of both nature and dynamics of this materials is expected to expedite their development as alternative (and potentially superior) technologies concerning those studied in the first part.--

Bridging Energetics and Dynamics of Exciton Trapping in Core\u2013Shell Quantum Dots

The widespread application of quantum dots greatly profits from their broad absorption band. However, the variable nature of excitations within these bands is expected to result in undesired excitation energy dependence of steady state emission properties. We demonstrate the different role played by hot and cold carrier trapping in determining fluorescence quantum yields. Our analysis relates the energetic parameters with the available knowledge on the dynamics of charge trapping. It turns out that detrapping processes play a pivotal role in determining steady state emission properties. We studied excitation dependent photoluminescence quantum yields (PLQY) in different CdSe/CdxZn1–xS (x = 0, 0.5, and 1) quantum dots to identify best performing heterostructures in terms of shell thickness and composition. Our rationalization of the observed behavior is focused on the modulation of trapping and detrapping rates. The combination of experimental results and PLQY kinetics modeling reveals the need to consider hot-carrier trapping, supporting recent dynamics observations. This work provides a deeper insight into the trapping process in quantum dots, relating its energetics and dynamics