CdS Arms Research Articles

Defect-mediated Fermi level modulation boosting photo-activity of spatially-ordered S-scheme heterojunction

Spatially-ordered S-scheme photocatalysts are intriguing due to their enhanced light harvesting, spatially isolated redox sites, and strong redox abilities. Nonetheless, heightening the performance of S-scheme photocatalysts via controllable defect engineering is still challenging to now. In this work, multi-armed MoSe2/CdS S-scheme heterojunction with intimate Mo-S bond coupling and adjustable Se vacancies (VSe) and Mo5+ concentrations was constructed, which consisted of few- or even single-layered MoSe2 growing on the {11–20} facets of wurtzite CdS arms. The S-scheme charge transmission mechanism of MoSe2/CdS heterojunction was validated by density functional theory calculation combined with in situ photo-irradiated X-ray photoelectron spectroscopy, surface photovoltage, and radical measurements. Moreover, the Fermi level gap between CdS and MoSe2 was enlarged by regulating the contents of donor (VSe) and acceptor (Mo5+) impurities with synthesis temperature, which strengthens the built-in electric field and carriers transfer driving force of MoSe2/CdS composites, contributing to an outstanding H2 evolution activity of 52.62 mmol·g−1·h−1 (corresponding to an apparent quantum efficiency of 34.8 % at 400 nm) under visible-light irradiation (λ > 400 nm), 25.8 times that of Pt-loaded CdS counterpart and a substantial amount of reported CdS-containing photocatalysts. Our study results are anticipated to facilitate the rational design of advanced semiconductor nanostructures for efficient solar conversion and utilization.

Electric-Field-Enhanced Electroluminescence Color Tuning of Colloidal Type-II Tetrapods.

Color-tunable electroluminescence (EL) from a single emitting material can be used to develop single-pixel multicolor displays. However, finding materials capable of broad EL color tuning remains challenging. Herein, we report the observation of broad voltage-tunable EL in colloidal type-II InP/ZnS quantum-dot-seeded CdS tetrapod (TP) LEDs. The EL color can be tuned from red to bluish white by varying the red and blue emission intensities from type-II interfaces and arms, respectively. The capacitor device proves that an external electric field can enhance the color tuning in type-II TPs. COMSOL simulations, numerical calculations, and transient absorption measurements are performed to understand the underlying photophysical mechanism. Our results indicate that the reduced hole relaxation rate from the arm to the quantum dot core can enhance the emission from the CdS arms, which is favorable for EL color tuning. This study provides a novel method to realize voltage-tunable EL colors with potential in display and micro-optoelectronic applications.

The effect of computer decision support on optimizing appropriate dosing of novel oral anticoagulant therapy in the IMPACT-AF study

Abstract Background Guidelines favour use of the non-vitamin K oral anticoagulants (NOACs) over vitamin-K antagonists for stroke prevention in atrial fibrillation (AF). However, studies have shown these agents are being under-dosed relative to the doses recommended in the product labels. Purpose To assess the ability of a CDS tool, employed to support management of patients with AF in primary care, to optimize NOAC prescribing. Methods The Integrated Management Program Advancing Community Treatment of Atrial Fibrillation (IMPACT-AF) study was a cluster randomized controlled trial that assessed the ability of a CDS tool to optimize care of community-based AF patients. Between September 2014 and December 2016, 203 primary care providers (104 randomized to CDS use, 99 to usual care [UC]) and 1133 of their patients (n=597 CDS, n=548 UC) were enrolled. Among other functions, 9 CDS program rules provided recommendations on NOAC prescribing based upon a given patient's clinical profile, as per product labels. Appropriate NOAC prescribing within the IMPACT-AF study population was compared between patients managed with the CDS versus UC at baseline and 12-months. Results Of those patients prescribed a NOAC, a high proportion (approximately 70%) were managed as per NOAC prescribing recommendations at baseline (Fig. 1). At 12 months, this proportion did not appreciably change in the UC arm (Fig. 1). In the CDS arm, an 8.2% absolute/11.8% relative improvement in appropriate NOAC prescribing over baseline was seen at 12-months (Fig. 1). A comparison of patients at baseline and 12-months within each arm revealed a non-significant decline in the level of appropriate NOAC prescribing in the UC group (p=0.53). In the CDS arm, a significant improvement was observed in appropriate NOAC prescribing over time (p<0.001). Conclusion Even prior to any quality improvement efforts, appropriate NOAC prescribing was higher than anticipated in this contemporary cohort of community-based AF patients. At 12-months, significant further improvements were seen in the CDS but not the UC arm. These findings suggest that physician decision support can help enhance appropriate NOAC prescribing in the primary care setting. Figure 1. Appropriate NOAC prescribing Funding Acknowledgement Type of funding source: Private grant(s) and/or Sponsorship. Main funding source(s): Bayer Inc.

CuInS2/CdS-Heterostructured Nanotetrapods by Seeded Growth and Their Photovoltaic Properties

We investigate a seeded-growth method for the synthesis of CuInS2 (core)/CdS (arm)-heterostructured nanotetrapods (HNTs), in which wurtzite CdS arms grow on CuInS2-core quantum dot seeds with tunable lengths. The CdS arms of the nanocrystal tetrapods effectively passivate the unstable surface defects and improve the photoluminescence quantum efficiencies to above 40%. Owing to spatially separated quasi-type-II excitons, efficient electron transport along the elongated arms, and enhanced light-absorption capabilities, the CuInS2/CdS-HNT-sensitized solar-cell device exhibits a more than 3-fold increase in the power conversion efficiency compared to that of the control CuInS2@CdS (core@shell) quantum dot device. We believe that the high photoenergy conversion abilities of the quasi-type-II CuInS2/CdS HNTs make them potential candidate materials for use in cost-effective and highly efficient solar cells.

Using shape to turn off blinking for two-colour multiexciton emission in CdSe/CdS tetrapods

Semiconductor nanostructures capable of emitting from two excited states and thereby of producing two photoluminescence colours are of fundamental and potential technological significance. In this limited class of nanocrystals, CdSe/CdS core/arm tetrapods exhibit the unusual trait of two-colour (red and green) multiexcitonic emission, with green emission from the CdS arms emerging only at high excitation fluences. Here we show that by synthetic shape-tuning, both this multi-colour emission process, and blinking and photobleaching behaviours of single tetrapods can be controlled. Specifically, we find that the properties of dual emission and single-nanostructure photostability depend on different structural parameters—arm length and arm diameter, respectively—but that both properties can be realized in the same nanostructure. Furthermore, based on results of correlated photoluminescence and transient absorption measurements, we conclude that hole-trap filling in the arms and partial state-filling in the core are necessary preconditions for the observation of multiexciton multi-colour emission.

Mapping Charge Distribution in Single PbS Core - CdS Arm Nano-Multipod Heterostructures by Off-Axis Electron Holography.

We synthesized PbS core-CdS arm nanomultipod heterostructures (NMHs) that exhibit PbS{111}/CdS{0002} epitaxial relations. The PbS-CdS interface is chemically sharp as determined by aberration corrected transmission electron microscopy (TEM) and compared to density functional theory (DFT) calculations. Ensemble fluorescence measurements show quenching of the optical signal from the CdS arms indicating charge separation due to the heterojunction with PbS. A finite-element three-dimensional (3D) calculation of the Poisson equation shows a type-I heterojunction, which would prevent recombination in the CdS arm after optical excitation. To examine charge redistribution, we used off-axis electron holography (OAEH) in the TEM to map the electrostatic potential across an individual heterojunction. Indeed, a built-in potential of 500 mV is estimated across the junction, though as opposed to the thermal equilibrium calculations significant accumulation of positive charge at the CdS side of the interface is detected. We conclude that the NMH multipod geometry prevents efficient removal of generated charge carriers by the high energy electrons of the TEM. Simulations of generated electron-hole pairs in the insulated CdS arm of the NMH indeed show charge accumulation in agreement with the experimental measurements. Thus, we show that OAEH can be used as a complementary methodology to ensemble measurements by mapping the charge distribution in single NMHs with complex geometries.

Mechanisms of Local Stress Sensing in Multifunctional Polymer Films Using Fluorescent Tetrapod Nanocrystals.

Nanoscale stress-sensing can be used across fields ranging from detection of incipient cracks in structural mechanics to monitoring forces in biological tissues. We demonstrate how tetrapod quantum dots (tQDs) embedded in block copolymers act as sensors of tensile/compressive stress. Remarkably, tQDs can detect their own composite dispersion and mechanical properties with a switch in optomechanical response when tQDs are in direct contact. Using experimental characterizations, atomistic simulations and finite-element analyses, we show that under tensile stress, densely packed tQDs exhibit a photoluminescence peak shifted to higher energies ("blue-shift") due to volumetric compressive stress in their core; loosely packed tQDs exhibit a peak shifted to lower energies ("red-shift") from tensile stress in the core. The stress shifts result from the tQD's unique branched morphology in which the CdS arms act as antennas that amplify the stress in the CdSe core. Our nanocomposites exhibit excellent cyclability and scalability with no degraded properties of the host polymer. Colloidal tQDs allow sensing in many materials to potentially enable autoresponsive, smart structural nanocomposites that self-predict impending fracture.

Light-stimulated carrier dynamics of CuInS2/CdS heterotetrapod nanocrystals.

We synthesized a heterotetrapod composed of a chalcopyrite(ch)-CuInS2 core and wurtzite(w)-CdS arms and elucidated its optical properties and light-stimulated carrier dynamics using fs-laser flash photolysis. The CuInS2/CdS heterotetrapod possessed quasi-type II band alignment, which caused much longer-lived charge separation than that in the isolated CuInS2 nanocrystal.

Dual Wavelength Electroluminescence from CdSe/CdS Tetrapods

We fabricated a single active layer quantum dot light-emitting diode device based on colloidal CdSe (core)/CdS (arm) tetrapod nanostructures capable of simultaneously producing room temperature electroluminesence (EL) peaks at two spectrally distinct wavelengths, namely, at ∼500 and ∼660 nm. This remarkable dual EL was found to originate from the CdS arms and CdSe core of the tetrapod architecture, which implies that the radiative recombination of injected charge carriers can independently take place at spatially distinct regions of the tetrapod. In contrast, control experiments employing CdSe-core-seeded CdS nanorods showed near-exclusive EL from the CdSe core. Time-resolved spectroscopy measurements on tetrapods revealed the presence of hole traps, which facilitated the localization and subsequent radiative recombination of excitons in the CdS arm regions, whereas excitonic recombination in nanorods took place predominantly within the vicinity of the CdSe core. These observations collectively highlight the role of morphology in the achievement of light emission from the different material components in heterostructured semiconductor nanoparticles, thus showing a way in developing a class of materials which are capable of exhibiting multiwavelength electroluminescence.

I Sense the Force

Materials Science Although composite materials can show enhanced properties, understanding the way these materials deform and fail is not straightforward. Besides the individual properties of the matrix and the filler, one has to worry about the distribution of the filler particles, the strength of the interfacial bonding between the filler and matrix, and the way that the combined material will deform and debond. Raja et al. show that luminescent semiconductor nanocrystal tetrapods, composed of zinc-blend CdSe cores with epitaxially grown wurtzie CdS arms, can be used as stress sensors. The tetrapods were electrospun into a matrix of poly l-lactic acid at weight fractions ranging from 3.6 to 40%. During extension of the composite fibers, both the elastic and plastic deformation regions could be tracked through shifts in the fluorescence of the nanocrystals. The authors note that because the particles tend to clump and because there is incomplete stress transfer from the polymer to the nanocrystals, they do not deform plastically when the polymer does, thus giving greater reversibility to the stress measurements, as seen in comparing the fluorescence observations with traditional tensile measurements. Nano Lett. 10.1021/nl401999t (2013).

Spin-Dependent Exciton Quenching and Spin Coherence in CdSe/CdS Nanocrystals

Large surface-to-volume ratios of semiconductor nanocrystals cause susceptibility to charge trapping, which can modify luminescence yields and induce single-particle blinking. Optical spectroscopies cannot differentiate between bulk and surface traps in contrast to spin-resonance techniques, which in principle avail chemical information on such trap sites. Magnetic resonance detection via spin-controlled photoluminescence enables the direct observation of interactions between emissive excitons and trapped charges. This approach allows the discrimination of three radical species located in two functionally different trap states in CdSe/CdS nanocrystals, underlying the fluorescence quenching and thus blinking mechanisms: a spin-dependent Auger process in charged particles; and a charge-separated state pair process, which leaves the particle neutral. The paramagnetic trap centers offer control of the energy transfer yield from the wide-gap CdS to the narrow-gap CdSe, that is, light harvesting within the heterostructure. Coherent spin motion within the trap states of the CdS arms of nanocrystal tetrapods is reflected by spatially remote luminescence from CdSe cores with surprisingly long coherence times of >300 ns at 3.5 K, illustrating coherent control of light harvesting.

Linear polarization dependence of microwave-induced magnetoresistance oscillations in high-mobility two-dimensional systems

CdSe/CdS nanocrystal tetrapods are interesting building blocks for excitonic circuits, where the flow of excitation energy is gated by an external stimulus. The physical morphology of the nanoparticle, along with the electronic structure, which favors electron delocalization between the two semiconductors, suggests that all orientations of a particle relative to an external electric field will allow for excitons to be dissociated, stored, and released at a later time. While this approach, in principle, works, and fluorescence quenching of over 95$%$ can be achieved electrically, we find that discrete trap states within the CdS are required to dissociate and store the exciton. These states are rapidly filled up with increasing excitation density, leading to a dramatic reduction in quenching efficiency. Charge separation is not instantaneous on the CdS excitonic antennae in which light absorption occurs, but arises from the relaxed exciton following hole localization in the core. Consequently, whereas strong electromodulation of the core exciton is observed, the core multiexciton and the CdS arm exciton are not affected by an external electric field.

Nearly Temperature‐Independent Threshold for Amplified Spontaneous Emission in Colloidal CdSe/CdS Quantum Dot‐in‐Rods

Nearly Temperature‐Independent Threshold for Amplified Spontaneous Emission in Colloidal CdSe/CdS Quantum Dot‐in‐Rods

Exciton storage in CdSe/CdS tetrapod semiconductor nanocrystals: Electric field effects on exciton and multiexciton states

CdSe/CdS nanocrystal tetrapods are interesting building blocks for excitonic circuits, where the flow of excitation energy is gated by an external stimulus. The physical morphology of the nanoparticle, along with the electronic structure, which favors electron delocalization between the two semiconductors, suggests that all orientations of a particle relative to an external electric field will allow for excitons to be dissociated, stored, and released at a later time. While this approach, in principle, works, and fluorescence quenching of over 95$%$ can be achieved electrically, we find that discrete trap states within the CdS are required to dissociate and store the exciton. These states are rapidly filled up with increasing excitation density, leading to a dramatic reduction in quenching efficiency. Charge separation is not instantaneous on the CdS excitonic antennae in which light absorption occurs, but arises from the relaxed exciton following hole localization in the core. Consequently, whereas strong electromodulation of the core exciton is observed, the core multiexciton and the CdS arm exciton are not affected by an external electric field.

Multiexcitonic Dual Emission in CdSe/CdS Tetrapods and Nanorods

CdSe/CdS semiconductor nanocrystal heterostructures are currently of high interest for the peculiar electronic structure offering unique optical properties. Here, we show that nanorods and tetrapods made of such material combination enable efficient multiexcitonic emission, when the volume of the nanoparticle is maximized. This condition is fulfilled by tetrapods with an arm length of 55 nm and results in a dual emission with comparable intensities from the CdS arms and CdSe core. The relative intensities of the dual emission, originating from exciton phase-space filling and reduced Auger recombination, can be effectively modulated by the photon fluence of the pump laser. The results, obtained under steady-state detection conditions, highlight the properties of tetrapods as multiexciton dual-color emitters.

Octapod-Shaped Colloidal Nanocrystals of Cadmium Chalcogenides via “One-Pot” Cation Exchange and Seeded Growth

The growth behavior of cadmium chalcogenides (CdE = CdS, CdSe, and CdTe) on sphalerite Cu(2-x)Se nanocrystals (size range 10-15 nm) is studied. Due to the capability of Cu(2-x)Se to undergo a fast and quantitative cation exchange reaction in the presence of excessive Cd(2+) ions, no Cu(2-x)Se/CdE heterostructures are obtained and instead branched CdSe/CdE nanocrystals are built which consist of a sphalerite CdSe core and wurtzite CdE arms. While CdTe growth yields multiarmed structures with overall tetrahedral symmetry, CdS and CdSe arm growth leads to octapod-shaped nanocrystals. These results differ significantly from literature findings about the growth of CdE on sphalerite CdSe particles, which until now had always yielded tetrapod-shaped nanocrystals.

Spatio-temporal dynamics of coupled electrons and holes in nanosize CdSe-CdS semiconductor tetrapods

We report on coupled electron-hole transfer, Coulomb drag, in CdSe/CdS semiconductor nanotetrapods. We demonstrate that photoexcited holes can either be transferred to the CdSe core or become trapped in one of the CdS arms. By combining time-resolved pump-probe and photoluminescence measurements we investigate how the Coulomb potential drags the electron to the hole localization site. As supported by effective-mass calculations taking into account Coulomb effects we conclude that the hole dynamics determines the fate of the electron in a coupled dynamics.

Infrared-Active Heterostructured Nanocrystals with Ultralong Carrier Lifetimes

We present the synthesis of composite PbSe/CdSe/CdS nanocrystals with two distinct geometries: core/shell/shell structures and tetrapods. These novel nanostructures exhibit extremely long carrier decay times up to 20 micros that are combined with high emission efficiencies in the infrared. The increase in carrier lifetimes is attributed to the reduction of the electron-hole overlap as a result of delocalization of the electron wave function into the outer CdS shell or arms. The ultralong carrier lifetimes and controlled geometry render these nanocrystals attractive for a variety of applications from lasing to photocatalysis and photovoltaics.

Seeded Growth of Highly Luminescent CdSe/CdS Nanoheterostructures with Rod and Tetrapod Morphologies

We have demonstrated that seeded growth of nanocrystals offers a convenient way to design nanoheterostructures with complex shapes and morphologies by changing the crystalline structure of the seed. By using CdSe nanocrystals with wurtzite and zinc blende structure as seeds for growth of CdS nanorods, we synthesized CdSe/CdS heterostructure nanorods and nanotetrapods, respectively. Both of these structures showed excellent luminescent properties, combining high photoluminescence efficiency (approximately 80 and approximately 50% for nanorods and nanotetrapods, correspondingly), giant extinction coefficients (approximately 2 x 10(7) and approximately 1.5 x 10(8) M(-1) cm(-1) at 350 nm for nanorods and nanotetrapods, correspondingly), and efficient energy transfer from the CdS arms into the emitting CdSe core.