Optical gain and lasing from bulk cadmium sulfide nanocrystals through bandgap renormalization.

Strongly confined colloidal quantum dots have been investigated for low-cost light emission and lasing for nearly two decades. However, known materials struggle to combine technologically relevant metrics of low-threshold and long inverted-state lifetime with a material gain coefficient fit to match cavity losses, particularly under electrical excitation. Here we show that bulk nanocrystals of CdS combine an exceptionally large material gain of 50,000 cm-1 with best-in-class gain thresholds below a single exciton per nanocrystal and 3 ns gain lifetimes not limited by non-radiative Auger processes. We quantitatively account for these findings by invoking a strong bandgap renormalization effect, unobserved in nanocrystals to date, to the best of our knowledge. Next, we demonstrate broadband amplified spontaneous emission and lasing under quasi-continuous-wave conditions. Our results highlight the prospects of bulk nanocrystals for lasing from solution-processable materials.

Efficient Synergistic Antibacterial Activity of α-MSH Using Chitosan-Based Versatile Nanoconjugates.

The application of antimicrobial peptides has emerged as an alternative therapeutic tool to encounter against multidrug resistance of different pathogenic organisms. α-Melanocyte stimulating hormone (α-MSH), an endogenous neuropeptide, is found to be efficient in eradicating infection of various kinds of Staphylococcus aureus, including methicillin-resistant Staphylococcus aureus (MRSA). However, the chemical stability and efficient delivery of these biopharmaceuticals (i.e., α-MSH) to bacterial cells with a significant antibacterial effect remains a key challenge. To address this issue, we have developed a chitosan-cholesterol polymer using a single-step, one-pot, and simple chemical conjugation technique, where α-MSH is loaded with a significantly high amount (37.7%), and the final product is obtained as chitosan-cholesterol α-MSH polymer-drug nanoconjugates. A staphylococcal growth inhibition experiment was performed using chitosan-cholesterol α-MSH and individual controls. α-MSH and chitosan-cholesterol both show bacterial growth inhibition by a magnitude of 50 and 79%, respectively. The killing efficiency of polymer-drug nanoconjugates was very drastic, and almost no bacterial colony was observed (∼100% inhibition) after overnight incubation. Phenotypic alternation was observed in the presence of α-MSH causing changes in the cell structure and shape, indicating stress on Staphylococcus aureus. As a further consequence, vigorous cell lysis with concomitant release of the cellular material in the nearby medium was observed after treatment of chitosan-cholesterol α-MSH nanoconjugates. This vigorous lysis of the cell structure is associated with extensive aggregation of the bacterial cells evident in scanning electron microscopy (SEM). The dose-response experiment was performed with various concentrations of chitosan-cholesterol α-MSH nanoconjugates to decipher the degree of the bactericidal effect. The concentration of α-MSH as low as 1 pM also shows significant inhibition of bacterial growth (∼40% growth inhibition) of Staphylococcus aureus. Despite playing an important role in inhibiting bacterial growth, our investigation on hemolytic assay shows that chitosan-cholesterol α-MSH is significantly nontoxic at a wide range of concentrations. In a nutshell, our analysis demonstrated novel antimicrobial activity of nanoparticle-conjugated α-MSH, which could be used as future therapeutics against multidrug-resistant Staphylococcus aureus and other types of bacterial cells.

Optical and Scintillation Properties of Record-Efficiency CdTe Nanoplatelets toward Radiation Detection Applications.

Colloidal CdTe nanoplatelets featuring a large absorption coefficient and ultrafast tunable luminescence coupled with heavy-metal-based composition present themselves as highly desirable candidates for radiation detection technologies. Historically, however, these nanoplatelets have suffered from poor emission efficiency, hindering progress in exploring their technological potential. Here, we report the synthesis of CdTe nanoplatelets possessing a record emission efficiency of 9%. This enables us to investigate their fundamental photophysics using ultrafast transient absorption, temperature-controlled photoluminescence, and radioluminescence measurements, elucidating the origins of exciton- and defect-related phenomena under both optical and ionizing excitation. For the first time in CdTe nanoplatelets, we report the cumulative effects of a giant oscillator strength transition and exciton fine structure. Simultaneously, thermally stimulated luminescence measurements reveal the presence of both shallow and deep trap states and allow us to disclose the trapping and detrapping dynamics and their influence on the scintillation properties.

Exciton Binding Energy in CdSe Nanoplatelets Measured by One- and Two-Photon Absorption.

Colloidal semiconductor nanoplatelets exhibit strong quantum confinement for electrons and holes as well as excitons in one dimension, while their in-plane motion is free. Because of the large dielectric contrast between the semiconductor and its ligand environment, the Coulomb interaction between electrons and holes is strongly enhanced. By means of one- and two-photon photoluminescence excitation spectroscopy, we measure the energies of the 1S and 1P exciton states in CdSe nanoplatelets with thicknesses varied from 3 up to 7 monolayers. By comparison with calculations, performed in the effective mass approximation with account of the dielectric enhancement, we evaluate exciton binding energies of 195-315 meV, which is about 20 times greater than that in bulk CdSe. Our calculations of the effective Coulomb potential for very thin nanoplatelets are close to the Rytova-Keldysh model, and the exciton binding energies are comparable with the values reported for monolayer-thick transition metal dichalcogenides.

Van Hove Singularities and Trap States in Two-Dimensional CdSe Nanoplatelets.

Semiconductor nanoplatelets, which offer a compelling combination of the flatness of two-dimensional semiconductors and the inherent richness brought about by colloidal nanostructure synthesis, form an ideal and general testbed to investigate fundamental physical effects related to the dimensionality of semiconductors. With low temperature scanning tunnelling spectroscopy and tight binding calculations, we investigate the conduction band density of states of individual CdSe nanoplatelets. We find an occurrence of peaks instead of the typical steplike function associated with a quantum well, that rule out a free in-plane electron motion, in agreement with the theoretical density of states. This finding, along with the detection of deep trap states located on the edge facets, which also restrict the electron motion, provides a detailed picture of the actual lateral confinement in quantum wells with finite length and width.

Colloidal Synthesis of Laterally Confined Blue-Emitting 3.5 Monolayer CdSe Nanoplatelets.

The typical synthesis protocol for blue-emitting CdSe nanoplatelets (NPLs) yields particles with extended lateral dimensions and large surface areas, resulting in NPLs with poor photoluminescence quantum efficiency. We have developed a synthesis protocol that achieves an improved control over the lateral size, by exploiting a series of long-chained carboxylate precursors that vary from cadmium octanoate (C8) to cadmium stearate (C18). The length of this metallic precursor is key to tune the width and aspect ratio of the final NPLs, and for the shorter chain lengths, the synthesis yield is improved. NPLs prepared with our procedure possess significantly enhanced photoluminescence quantum efficiencies, up to 30%. This is likely due to their reduced lateral dimensions, which also grant them good colloidal stability. As the NPL width can be tuned below the bulk exciton Bohr radius, the band edge blue-shifts, and we constructed a sizing curve relating the NPL absorption position and width. Further adjusting the synthesis protocol, we were able to obtain even thinner NPLs, emitting in the near-UV region, with a band-edge quantum efficiency of up to 11%. Results pave the way to stable and efficient light sources for applications such as blue and UV light-emitting devices and lasers.

Electrical control of single-photon emission in highly charged individual colloidal quantum dots.

Electron transfer to an individual quantum dot promotes the formation of charged excitons with enhanced recombination pathways and reduced lifetimes. Excitons with only one or two extra charges have been observed and exploited for very efficient lasing or single-quantum dot light-emitting diodes. Here, by room-temperature time-resolved experiments on individual giant-shell CdSe/CdS quantum dots, we show the electrochemical formation of highly charged excitons containing more than 12 electrons and 1 hole. We report the control over intensity blinking, along with a deterministic manipulation of quantum dot photodynamics, with an observed 210-fold increase in the decay rate, accompanied by 12-fold decrease in the emission intensity, while preserving single-photon emission characteristics. These results pave the way for deterministic control over the charge state, and room-temperature decay rate engineering for colloidal quantum dot-based classical and quantum communication technologies.

CdSe/CdS/CdTe Core/Barrier/Crown Nanoplatelets: Synthesis, Optoelectronic Properties, and Multiphoton Fluorescence Upconversion.

Colloidal two-dimensional (2D) nanoplatelet heterostructures are particularly interesting as they combine strong confinement of excitons in 2D materials with a wide range of possible semiconductor junctions due to a template-free, solution-based growth. Here, we present the synthesis of a ternary 2D architecture consisting of a core of CdSe, laterally encapsulated by a type-I barrier of CdS, and finally a type-II outer layer of CdTe as so-called crown. The CdS acts as a tunneling barrier between CdSe- and CdTe-localized hole states, and through strain at the CdS/CdTe interface, it can induce a shallow electron barrier for CdTe-localized electrons as well. Consequently, next to an extended fluorescence lifetime, the barrier also yields emission from CdSe and CdTe direct transitions. The core/barrier/crown configuration further enables two-photon fluorescence upconversion and, due to a high nonlinear absorption cross section, even allows to upconvert three near-infrared photons into a single green photon. These results demonstrate the capability of 2D heterostructured nanoplatelets to combine weak and strong confinement regimes to engineer their optoelectronic properties.

Two-photon based pulse autocorrelation with CdSe nanoplatelets.

We investigate broadband two-photon absorption autocorrelators based on II-VI semiconductor nanoplatelets as an alternative to common second harmonic generation based techniques. As compared to bulk materials the exceptionally high enhancement of two-photon absorption in these 2D structures results in very efficient two-photon absorption based autocorrelation detected via PL emission. We compare the results with TPA autocorrelation in CdS bulk as well as SHG based autocorrelation in ß-barium borate. We show that CdSe nanoplatelet based autocorrelation can exceed the efficiency of conventional methods by two orders in magnitude, especially for short interaction length, and allows a precise pulse-width determination. We demonstrate that very high two-photon absorption cross sections of the nanoplatelets are the basis for this effective TPA autocorrelation. Based on our results with II-VI nanoplatelets efficient broadband autocorrelation with more than ∼100 nm bandwidth and very high sensitivity seems feasible.

Chloride-Induced Thickness Control in CdSe Nanoplatelets.

Current colloidal synthesis methods for CdSe nanoplatelets (NPLs) routinely yield samples that emit, in discrete steps, from 460 to 550 nm. A significant challenge lies with obtaining thicker NPLs, to further widen the emission range. This is at present typically achieved via colloidal atomic layer deposition onto CdSe cores, or by synthesizing NPL core/shell structures. Here, we demonstrate a novel reaction scheme, where we start from 4.5 monolayer (ML) NPLs and increase the thickness in a two-step reaction that switches from 2D to 3D growth. The key feature is the enhancement of the growth rate of basal facets by the addition of CdCl2, resulting in a series of nearly monodisperse CdSe NPLs with thicknesses between 5.5 and 8.5 ML. Optical characterization yielded emission peaks from 554 nm up to 625 nm with a line width (fwhm) of 9-13 nm, making them one of the narrowest colloidal nanocrystal emitters currently available in this spectral range. The NPLs maintained a short emission lifetime of 5-11 ns. Finally, due to the increased red shift of the NPL band edge photoluminescence excitation spectra revealed several high-energy peaks. Calculation of the NPL band structure allowed us to identify these excited-state transitions, and spectral shifts are consistent with a significant mixing of light and split-off hole states. Clearly, chloride ions can add a new degree of freedom to the growth of 2D colloidal nanocrystals, yielding new insights into both the NPL synthesis as well as their optoelectronic properties.

Role of Acid-Base Equilibria in the Size, Shape, and Phase Control of Cesium Lead Bromide Nanocrystals.

A binary ligand system composed of aliphatic carboxylic acids and primary amines of various chain lengths is commonly employed in diverse synthesis methods for CsPbBr3 nanocrystals (NCs). In this work, we have carried out a systematic study examining how the concentration of ligands (oleylamine and oleic acid) and the resulting acidity (or basicity) affects the hot-injection synthesis of CsPbBr3 NCs. We devise a general synthesis scheme for cesium lead bromide NCs which allows control over size, size distribution, shape, and phase (CsPbBr3 or Cs4PbBr6) by combining key insights on the acid-base interactions that rule this ligand system. Furthermore, our findings shed light upon the solubility of PbBr2 in this binary ligand system, and plausible mechanisms are suggested in order to understand the ligand-mediated phase control and structural stability of CsPbBr3 NCs.

Shape control of zincblende CdSe nanoplatelets.

The lateral dimensions of CdSe nanoplatelets have a strong and unique influence on their opto-electronic properties, with sizes that can be tuned from the weak to the strong exciton confinement regime. There are state-of-the-art reports on several nanoplatelet syntheses; however, at present only the thickness is well-controlled. We demonstrate here that we can achieve a control over the aspect ratio and overall nanoplate area by carefully adjusting the reagents that induce the in-plane growth. A variation of the fraction of hydrated Cd(OAc)2 in a Cd(OAc)2/Cd(OAc)2·2H2O mixture tailors the nanoplatelet aspect ratio. This occurs independently of the reaction time, which can be used to fine-tune the overall length and width. An interpretation is given by the in situ formation of a small amount of hydroxide anions that alter the surface energy of specific planes.

Insight into the mechanism revealing the peroxidase mimetic catalytic activity of quaternary CuZnFeS nanocrystals: colorimetric biosensing of hydrogen peroxide and glucose.

Artificial enzyme mimetics have attracted immense interest recently because natural enzymes undergo easy denaturation under environmental conditions restricting practical usefulness. We report for the first time chalcopyrite CuZnFeS (CZIS) alloyed nanocrystals (NCs) as novel biomimetic catalysts with efficient intrinsic peroxidase-like activity. Novel peroxidase activities of CZIS NCs have been evaluated by catalytic oxidation of the peroxidase substrate 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H2O2). CZIS NCs demonstrate the synergistic effect of elemental composition and photoactivity towards peroxidase-like activity. The quaternary CZIS NCs show enhanced intrinsic peroxidase-like activity compared to the binary NCs with the same constituent elements. Intrinsic peroxidase-like activity has been correlated with the energy band position of CZIS NCs extracted using scanning tunneling spectroscopy and ultraviolet photoelectron spectroscopy. Kinetic analyses indicate Michaelis-Menten enzyme kinetic model catalytic behavior describing the rate of the enzymatic reaction by correlating the reaction rate with substrate concentration. Typical color reactions arising from the catalytic oxidation of TMB over CZIS NCs with H2O2 have been utilized to establish a simple and sensitive colorimetric assay for detection of H2O2 and glucose. CZIS NCs are recyclable catalysts showing high efficiency in multiple uses. Our study may open up the possibility of designing new photoactive multi-component alloyed NCs as enzyme mimetics in biotechnology applications.

Efficient solid-state light-emitting CuCdS nanocrystals synthesized in air.

Semiconductor nanocrystals (NCs) possess high photoluminescence (PL) typically in the solution phase. In contrary, PL rapidly quenches in the solid state. Efficient solid state luminescence can be achieved by inducing a large Stokes shift. Here we report on a novel synthesis of compositionally controlled CuCdS NCs in air avoiding the usual complexity of using inert atmosphere. These NCs show long-range color tunability over the entire visible range with a remarkable Stokes shift up to about 1.25 eV. Overcoating the NCs leads to a high solid-state PL quantum yield (QY) of ca. 55% measured by using an integrating sphere. Unique charge carrier recombination mechanisms have been recognized from the NCs, which are correlated to the internal NC structure probed by using extended X-ray absorption fine structure (EXAFS) spectroscopy. EXAFS measurements show a Cu-rich surface and Cd-rich interior with 46% Cu(I) being randomly distributed within 84% of the NC volume creating additional transition states for PL. Color-tunable solid-state luminescence remains stable in air enabling fabrication of light-emitting diodes (LEDs).

Mechanism of versatile catalytic activities of quaternary CuZnFeS nanocrystals designed by a rapid synthesis route.

Quaternary alloyed nanocrystals (NCs) composed of earth abundant, environment friendly elements are of interest for energy-harvesting applications. These complex NCs are useful as catalysts for the degradation of multiple refractory organic pollutants as well as nitro-organic reduction at a rapid rate. Here, a remarkably fast (∼30 s) and facile synthesis of crystalline quaternary chalcopyrite copper-zinc-iron-sulfide (CZIS) NCs is reported. These NCs show excellent catalytic properties by degrading a number of refractory organic dyes and converting nitro-compounds at a rapid rate. The valence and conduction band information of the newly designed NCs are extracted using scanning tunneling spectroscopy and ultraviolet photoelectron spectroscopy, which reveal energy levels suitable for performing redox chemistry by generating reactive radicals establishing NCs as efficient catalyst with multiple uses. Rapid synthesis of high quality phase-controlled CZIS NCs with robust catalytic activities could be useful for organic waste treatment.

Demonstration of ultrarapid interfacial formation of 1D fullerene nanorods with photovoltaic properties.

We demonstrate ultrarapid interfacial formation of one-dimensional (1D) single-crystalline fullerene C60 nanorods at room temperature in 5 s. The nanorods of ∼ 11 µm in length and ∼ 215 nm in diameter are developed in a hexagonal close-pack crystal structure, contrary to the cubic crystal structure of pristine C60. Vibrational and electronic spectroscopy provide strong evidence that the nanorods are a van der Waals solid, as evidenced from the preservation of the electronic structure of the C60 molecules within the rods. Steady state optical spectroscopy reveals a dominance of charge transfer excitonic transitions in the nanorods. A significant enhancement of photogenerated charge carriers is observed in the nanorods in comparison to pristine C60, revealing the effect of shape on the photovoltaic properties. Due to their ultrarapid, large-scale, room-temperature synthesis with single-crystalline structure and excellent optoelectronic properties, the nanorods are expected to be promising for photosensitive devices applications.

Modulation of glyceraldehyde-3-phosphate dehydrogenase activity by surface functionalized quantum dots.

Enzymatic regulation is a fast and reliable diagnosis tool via identification and design of inhibitors for modulation of enzyme function. Previous reports on quantum dots (QDs)-enzyme interactions reveal a protein-surface recognition ability leading to promising applications in protein stabilization, protein delivery, bio-sensing and detection. However, the direct use of QDs to control enzyme inhibition has never been revealed to date. Here we show that a series of biocompatible surface-functionalized metal-chalcogenide QDs can be used as potent inhibitors for malignant cells through the modulation of enzyme activity, while normal cells remain unaffected. The in vitro activity of glyceraldehyde-3-phosphate dehydrogenase (GAPDH), an enzyme involved critically in the glycolysis of cancer cells, is inactivated selectively in a controlled way by the QDs at a significantly low concentration (nM). Cumulative kinetic studies delineate that the QDs undergo both reversible and irreversible inhibition mechanisms owing to the site-specific interactions, enabling control over the inhibition kinetics. These complementary loss-of-function probes may offer a novel route for rapid clinical diagnosis of malignant cells and biomedical applications.

Improved mechanical stability of acetoxypropyl cellulose upon blending with ultranarrow PbS nanowires in Langmuir monolayer matrix.

Cellulose and cellulose derivatives have long been used as membrane fabrication. Langmuir monolayer behavior, which naturally mimics membranes, of acetoxypropyl cellulose (APC) and lead sulfide (PbS) nanowire mixtures at different volume ratios is reported. Surface pressure (π)-area (A) isotherms of APC and PbS nanowires mixtures at different volume ratios show a gradual decrease in the monolayer area with increasing volume fraction of PbS nanowires. Change of surface potential with monolayer area at different volume ratios also reveals a gradual increase in the surface potential indicating incorporation of PbS nanowires within APC matrix. The compressibility and elastic constants measurements reveal an enhancement of the elasticity upon incorporation of PbS nanowires up to certain volume fractions. An enhancement in stability of the blend is observed upon PbS nanowire incorporation to the APC matrix. Rheological measurements also support the robustness of the mixture of APC and PbS nanowires in 3D bulk phase. Such robust ultrathin films of cellulose based-nanowire blend obtained by means of the Langmuir technique may lead to novel routes for designing cellulosic-based thin films and membranes.

Origin of chains of Au-PbS nano-dumbbells in space.

Self-assembled, one-dimensional (1D) nanomaterials are amenable building blocks for bottom-up nanofabrication processes. A current shortcoming in the self-assembly of 1D nanomaterials in solution phase is the need for specific linkers or templates under very precise conditions to achieve a handful of systems. Here we report on the origin of a novel self-assembly of 1D dumbbells consisting of Au tipped PbS nanorods into stable chains in solution without any linkers or templates. A realistic multi-particle model suggests that the mesophase comprises 1D dumbbells arrayed in chains formed by anisotropic van der Waals type interactions. We demonstrate an alternative recognition mechanism for directing the assembly of the 1D dumbbells, based on effective interaction between the neighboring dumbbells consisting of Au tips with complementary crystallographic facets that guides the entire assembly in space.