Surface Chemistry Control of Colloidal Quantum Dot Band Gap

Surface chemistry modification of as-synthesized colloidal inorganic semiconductor nanocrystals (QDs), commonly referred to as ligand exchange, is mandatory toward effective QD-based optoelectronic and photocatalytic applications. The widespread recourse to ligand exchange procedures on metal chalcogenide QDs often narrows the optical band gap, although little consensus exists on explanation of this experimental evidence. This work attempts at providing a comprehensive description of such a phenomenon by exploiting rationally designed thiol ligands at the surface of colloidal PbS QDs, as archetype of material in the strong quantum confinement regime: the thiol­(ate)-induced QD optical band gap reduction almost linearly scales with the inorganic core surface-to-volume ratio and mainly depends on the sulfur binding atom, which is here suggested to contribute occupied 3p orbitals to the valence band edge of the QDs. As opposed to QD models based on the analogy with core/shell heterostructures, the indecomposable character of ligand/core adducts (the colloidal QDs themselves) arises

Colloidal Quantum Dots for Explosive Detection: Trends and Perspectives

Sensitive, accurate, and reliable detection of explosives has become one of the major needs for international security and environmental protection. Colloidal quantum dots, because of their unique chemical, optical, and electrical properties, as well as easy synthesis route and functionalization, have demonstrated high potential to meet the requirements for the development of suitable sensors, boosting the research in the field of explosive detection. Here, we critically review the most relevant research works, highlighting three different mechanisms for explosive detection based on colloidal quantum dots, namely photoluminescence, electrochemical, and chemoresistive sensing. We provide a comprehensive overview and an extensive discussion and comparison in terms of the most relevant sensor parameters. We highlight advantages, limitations, and challenges of quantum dot-based explosive sensors and outline future research directions for the advancement of knowledge in this surging research field

Charge Carrier Generation and Extraction in Hybrid Polymer/Quantum Dot Solar Cells

Here we investigate charge carrier generation and extraction processes in hybrid polymer/nanocrystal solar cells by means of time-resolved optical and photoelectrical techniques. We addressed the role of both poly­(3-hexylthiophene) and colloidal arenethiolate-capped PbS quantum dots, which constitute the hybrid composite nanomaterial, in the photoinduced processes most relevant to device operation by changing the compositional ratio and applying chemical and thermal postdeposition treatments. The carrier generation processes were found to be wavelength-dependent: excitons generated in the polymer domains led to long-lived weakly bound charge pairs upon electron transfer to PbS nanocrystals; whereas charge carrier generation in the nanocrystal domains is highly efficient, although effective separation required the application of external electric field. Overall, charge carrier generation was found efficient and almost independent of the strength of applied electric field; therefore, competition between separation of electron–hole pairs into free carriers and geminate recombination is the major factor limiting the fill factor of nanocomposite-based solar cells. Device efficiency improvements thus require faster interfacial charge transfer processes, which are deeply related to the refinement of nanocrystal surface chemistry

Role of Polymer in Hybrid Polymer/PbS Quantum Dot Solar Cells

Hybrid nanocomposites (HCs) obtained by blend solutions of conjugated polymers and colloidal semiconductor nanocrystals are among the most promising materials to be exploited in solution-processed photovoltaic applications. The comprehension of the operating principles of solar cells based on HCs thus represents a crucial step toward the rational engineering of high performing photovoltaic devices. Here we investigate the effect of conjugated polymers on hybrid solar cell performances by taking advantage from an optimized morphology of the HCs comprising lead sulfide quantum dots (PbS QDs). Uncommonly, we find that larger photocurrent densities are achieved by HCs incorporating wide-bandgap polymers. A combination of spectroscopic and electro-optical measurements suggests that wide-bandgap polymers promote efficient charge/exciton transfer processes and hinder the population of midgap states on PbS QDs. Our findings underline the key role of the polymer in HC-based solar cells in the activation/deactivation of charge transfer/loss pathways

Colloidal Arenethiolate-Capped PbS Quantum Dots: Optoelectronic Properties, Self-Assembly, and Application in Solution-Cast Photovoltaics

Suitable postsynthesis surface modification of lead-chalcogenide quantum dots (QDs) is crucial to enable their integration in photovoltaic devices. Here we exploit arenethiolate anions to completely replace pristine oleate ligands on PbS QDs in the solution phase, thus preserving the colloidal stability of QDs and allowing their solution-based processability into photoconductive thin films. Complete QD surface modification relies on the stronger acidic character of arenethiols compared to that of alkanethiols and is demonstrated by FTIR and UV–vis–NIR absorption spectroscopy analyses, which provide quantitative evaluation of stoichiometry and thermodynamic stability of the resulting system. Arenethiolate ligands induce a noticeable reduction of the optical band gap of PbS QDs, which is described and explained by charge transfer interactions occurring at the organic/inorganic interface that relax exciton confinement, and a large increase of QD molar absorption coefficient, achieved through the conjugated moiety of the replacing ligands. In addition, surface modification in the solution phase promotes switching of the symmetry of PbS QD self-assembled superlattices from hexagonal to cubic close packing, which is accompanied by further reduction of the optical band gap, ascribed to inter-QD exciton delocalization and dielectric effects, together with a drastic improvement of the charge transport properties in PbS QD solids. As a result, smooth dense-packed thin films of arenethiolate-capped PbS QDs can be integrated in heterojunction solar cells via a single solution-processing step. Such single PbS QD layers exhibit abated cracking upon thermal or chemical postdeposition treatment, and the corresponding devices generate remarkable photocurrent densities and overall efficiencies, thus representing an effective strategy toward low-cost processing for QD-based photovoltaics

Direct Band Gap Chalcohalide Semiconductors: Quaternary AgBiSCl₂ Nanocrystals

Heavy pnictogen chalcohalide semiconductors are coming under the spotlight for energy conversion applications. Here we present the colloidal synthesis of phase pure AgBiSCl2 nanocrystals. This quaternary chalcohalide compound features a quasi-two-dimensional crystal structure and a direct band gap, in contrast with the monodimensional structure and the indirect band gap peculiar to the orthorhombic, ternary Bi chalcohalides. Consistently, colloidal AgBiSCl2 nanocrystals exhibit photoinduced luminescence compatible with both band edge excitons and midgap states. This is the first observation of band edge emission in chalcohalide nanomaterials at large, although exciton recombination in our AgBiSCl2 nanocrystals mostly occurs via nonradiative pathways. This work further advances our knowledge on this class of mixed anion semiconductor nanomaterials and provides a contribution to establishing chalcohalides as a reliable alternative to metal chalcogenides and halides

Direct Band Gap Chalcohalide Semiconductors: Quaternary AgBiSCl₂ Nanocrystals

Heavy pnictogen chalcohalide semiconductors are coming under the spotlight for energy conversion applications. Here we present the colloidal synthesis of phase pure AgBiSCl2 nanocrystals. This quaternary chalcohalide compound features a quasi-two-dimensional crystal structure and a direct band gap, in contrast with the monodimensional structure and the indirect band gap peculiar to the orthorhombic, ternary Bi chalcohalides. Consistently, colloidal AgBiSCl2 nanocrystals exhibit photoinduced luminescence compatible with both band edge excitons and midgap states. This is the first observation of band edge emission in chalcohalide nanomaterials at large, although exciton recombination in our AgBiSCl2 nanocrystals mostly occurs via nonradiative pathways. This work further advances our knowledge on this class of mixed anion semiconductor nanomaterials and provides a contribution to establishing chalcohalides as a reliable alternative to metal chalcogenides and halides