Spectro-electrochemical Probing of Intrinsic and Extrinsic Processes in Exciton Recombination in I–III–VI₂ Nanocrystals

Ternary CuInS₂ nanocrystals (CIS NCs) are attracting attention as nontoxic alternatives to heavy metal–based chalcogenides for many technologically relevant applications. The photophysical processes underlying their emission mechanism are, however, still under debate. Here we address this problem by applying, for the first time, spectro-electrochemical methods to core-only CIS and core/shell CIS/ZnS NCs. The application of an electrochemical potential enables us to reversibly tune the NC Fermi energy and thereby control the occupancy of intragap defects involved in exciton decay. The results indicate that, in analogy to copper-doped II–VI NCs, emission occurs via radiative capture of a conduction-band electron by a hole localized on an intragap state likely associated with a Cu-related defect. We observe the increase in the emission efficiency under reductive electrochemical potential, which corresponds to raising the Fermi level, leading to progressive filling of intragap states with electrons. This indicates that the factor limiting the emission efficiency in these NCs is nonradiative electron trapping, while hole trapping is of lesser importance. This observation also suggests that the centers for radiative recombination are Cu²⁺ defects (preexisting and/or accumulated as a result of photoconversion of Cu¹⁺ ions) as these species contain a pre-existing hole without the need for capturing a valence-band hole generated by photoexcitation. Temperature-controlled photoluminescence experiments indicate that the intrinsic limit on the emission efficiency is imposed by multiphonon nonradiative recombination of a band-edge electron and a localized hole. This process affects both shelled and unshelled CIS NCs to a similar degree, and it can be suppressed by cooling samples to below 100 K. Finally, using experimentally measured decay rates, we formulate a model that describes the electrochemical modulation of the PL efficiency in terms of the availability of intragap electron traps as well as direct injection of electrons into the NC conduction band, which activates nonradiative Auger recombination, or electrochemical conversion of the Cu²⁺ states into the Cu¹⁺ species that are less emissive due to the need for their “activation” by the capture of photogenerated holes

Single-Particle Ratiometric Pressure Sensing Based on “Double-Sensor” Colloidal Nanocrystals

Ratiometric pressure sensitive paints (<i>r</i>-PSPs) are all-optical probes for monitoring oxygen flows in the vicinity of complex or miniaturized surfaces. They typically consist of a porous binder embedding mixtures of a reference and a sensor chromophore exhibiting oxygen-insensitive and oxygen-responsive luminescence, respectively. Here, we demonstrate the first example of an <i>r</i>-PSP based on a single two-color emitter that removes limitations of <i>r</i>-PSPs based on chromophore mixtures such as different temperature dependencies of the two chromophores, cross-readout between the reference and sensor signals and phase segregation. In our approach, we utilize a novel “double-sensor” <i>r</i>-PSP that features two spectrally separated emission bands with opposite responses to the O₂ pressure, which boosts the sensitivity with respect to traditional reference-sensor pairs. Specifically, we use two-color-emitting dot-in-bulk CdSe/CdS core/shell nanocrystals, exhibiting red and green emission bands from their core and shell states, whose intensities are respectively enhanced and quenched in response to the increased oxygen partial pressure that effectively tunes the position of the nanocrystal’s Fermi energy. This leads to a strong and reversible ratiometric response at the single particle level and an over 100% enhancement in the pressure sensitivity. Our proof-of-concept <i>r</i>-PSPs further exhibit suppressed cross-readout thanks to zero spectral overlap between the core and shell luminescence bands and a temperature-independent ratiometric response between 0 and 70 °C

Role of Nonradiative Defects and Environmental Oxygen on Exciton Recombination Processes in CsPbBr₃ Perovskite Nanocrystals

Lead halide perovskite nanocrystals (NCs) are emerging as optically active materials for solution-processed optoelectronic devices. Despite the technological relevance of tracing rational guidelines for optimizing their performances and stability beyond their intrinsic resilience to structural imperfections, no in-depth study of the role of selective carrier trapping and environmental conditions on their exciton dynamics has been reported to date. Here we conduct spectro-electrochemical (SEC) experiments, side-by-side to oxygen sensing measurements on CsPbBr₃ NCs for the first time. We show that the application of EC potentials controls the emission intensity by altering the occupancy of defect states without degrading the NCs. Reductive potentials lead to strong (60%) emission quenching by trapping of photogenerated holes, whereas the concomitant suppression of electron trapping is nearly inconsequential to the emission efficiency. Consistently, oxidizing conditions result in minor (5%) brightening due to suppressed hole trapping, confirming that electron traps play a minor role in nonradiative decay. This behavior is rationalized through a model that links the occupancy of trap sites with the position of the NC Fermi level controlled by the EC potential. Photoluminescence measurements in controlled atmosphere reveal strong quenching by collisional interactions with O₂, which is in contrast to the photobrightening effect observed in films and single crystals. This indicates that O₂ acts as a scavenger of photoexcited electrons without mediation by structural defects and, together with the asymmetrical SEC response, suggests that electron-rich defects are likely less abundant in nanostructured perovskites than in the bulk, leading to an emission response dominated by direct interaction with the environment

“Quantized” Doping of Individual Colloidal Nanocrystals Using Size-Focused Metal Quantum Clusters

The insertion of intentional impurities, commonly referred to as doping, into colloidal semiconductor quantum dots (QDs) is a powerful paradigm for tailoring their electronic, optical, and magnetic behaviors beyond what is obtained with size-control and heterostructuring motifs. Advancements in colloidal chemistry have led to nearly atomic precision of the doping level in both lightly and heavily doped QDs. The doping strategies currently available, however, operate at the ensemble level, resulting in a Poisson distribution of impurities across the QD population. To date, the synthesis of monodisperse ensembles of QDs individually doped with an identical number of impurity atoms is still an open challenge, and its achievement would enable the realization of advanced QD devices, such as optically/electrically controlled magnetic memories and intragap state transistors and solar cells, that rely on the precise tuning of the impurity states (<i>i</i>.<i>e</i>., number of unpaired spins, energy and width of impurity levels) within the QD host. The only approach reported to date relies on QD seeding with organometallic precursors that are intrinsically unstable and strongly affected by chemical or environmental degradation, which prevents the concept from reaching its full potential and makes the method unsuitable for aqueous synthesis routes. Here, we overcome these issues by demonstrating a doping strategy that bridges two traditionally orthogonal nanostructured material systems, namely, QDs and metal quantum clusters composed of a “magic number” of atoms held together by stable metal-to-metal bonds. Specifically, we use clusters composed of four copper atoms (Cu₄) capped with d-penicillamine to seed the growth of CdS QDs in water at room temperature. The elemental analysis, performed by electrospray ionization mass spectrometry, X-ray fluorescence, and inductively coupled plasma mass spectrometry, side by side with optical spectroscopy and transmission electron microscopy measurements, indicates that each Cu:CdS QD in the ensemble incorporates four Cu atoms originating from one Cu₄ cluster, which acts as a “quantized” source of dopant impurities