Unleashing the Full Potential of Electrochromic Heterostructured Nickel-Cobalt Phosphate for Optically Active High-Performance Asymmetric Quasi-Solid-State Supercapacitor Devices.

The rational design of hybrid systems that combine capacitor and battery merits is crucial to enable the fabrication of high energy and power density devices. However, the development of such systems remains a significant barrier to overcome. Herein, we report the design of a Ni-Co phosphate (Ni3-xCox(PO4)2·8H2O) nanoplatelet-based system via a facile coprecipitation method at ambient conditions. The nanoplatelets exhibit multicomponent synergy, exceptional charge storage capabilities, rich redox active sites (ameliorating the redox reaction activity), and high ionic diffusion rate/electron transfer kinetics. The designed Ni3-xCox(PO4)2·8H2O offered a respectable gravimetric specific capacity and marvelous capability rate (966 and 595 C g-1 at 1 and 15 A g-1) over the Ni3(PO4)2·8H2O (327.3 C g-1) and Co3(PO4)2·8H2O (68 C g-1) counterparts. Additionally, the nanoplatelets showed enhanced photoactive storage performance with a 9.7% increase in the recorded photocurrent density. Upon integration of Ni3-xCox(PO4)2·8H2O as a positive pole and commercial activated carbon as a negative pole, the constructed hybrid supercapacitor device with PVA@KOH quasi-gel electrolyte exhibits great energy and power densities of 77.7 Wh kg-1 and 15998.54 W kg-1 with remarkable cycling stability of 6000 charging/discharging cycles and prominent Coulombic efficiency of 100%. Interestingly, two assembled devices are capable of glowing a red LED bulb for nearly 180 s. This research paves the way to design and fabricate electroactive species via a facile approach for boosting the design of a plethora of supercapattery devices.

Cost-Effective Face Mask Filter Based on Hybrid Composite Nanofibrous Layers with High Filtration Efficiency.

One of the main protective measures against COVID-19's spread is the use of face masks. It is therefore of the utmost importance for face masks to be high functioning in terms of their filtration ability and comfort. Notwithstanding the prevalence of the commercial polypropylene face masks, its effectiveness is under contention, leaving vast room for improvement. During the pandemic, the use of at least one mask per day for each individual results in a massive number of masks that need to be safely disposed of. Fabricating biodegradable filters of high efficiency not only can protect individuals and save the environment but also can be sewed on reusable/washable cloth masks to reduce expenses. Wearing surgical masks for long periods of time, especially in hot regions, causes discomfort by irritating sensitive facial skin and warmed inhaled air. Herein, we demonstrate the fabrication of novel electrospun composites layers as face mask filters for protection against pathogens and tiny particulates. The combinatorial filter layers are made by integrating TiO2 nanotubes as fillers into chitosan/poly(vinyl alcohol) polymeric electrospun nanofibers as the outer layer. The other two filler-free layers, chitosan/poly(vinyl alcohol) and silk/poly(vinyl alcohol) as the middle and inner composite layers, respectively, were used for controlled protection, contamination prevention, and comfort for prolonged usage. The ASTM standards evaluation tests were adopted to evaluate the efficacy of the assembled filter, revealing high filtration efficiency compared to that of commercial surgical masks. The TiO2/Cs/PVA outer layer significantly reduced Staphylococcus aureus bacteria by 44.8% compared to the control, revealing the dual effect of TiO2 and chitosan toward the infectious bacterial colonies. Additionally, molecular dynamics calculations were used to assess the mechanical properties of the filter layers.

Real-Space Mapping of Surface-Oxygen Defect States in Photovoltaic Materials Using Low-Voltage Scanning Ultrafast Electron Microscopy.

Ultrathin layers of native oxides on the surface of photovoltaic materials may act as very efficient carrier trapping/recombination centers, thus significantly affecting their interfacial photophysical properties. How ultrathin oxide layers affect the surface and interface carrier dynamics cannot be selectively accessed by conventional ultrafast transient spectroscopic methods due to the deep penetration depth (tens to thousands of nanometers) of the pump/probe laser pulses. Herein, scanning ultrafast electron microscopy (S-UEM) at a low voltage of 1 keV electrons was recently developed at KAUST to selectively map the ultrafast charge carrier dynamics of a few layers on the top surfaces of photovoltaic materials. Unlike high-voltage 30 keV experiments, at 1 keV, the depth of detected secondary electrons (SEs) underneath the surface is significantly reduced 5 times, thus making it possible to visualize the dynamics of charge carrier from the uppermost surface of photoactive layers. More specifically, this new approach has been employed to explore and decipher the tremendous impact of native oxide layers and oxygen defect states on charge carrier dynamics in space and time simultaneously at sub-nanometer levels on several photovoltaic material surfaces, including Si, GaAs, CdTe, and CdZnTe single crystals. Interestingly, the contrast in the SEs time-resolved difference images switched from a dark "energy-loss mechanism" to a bright "energy-gain mechanism" only by removing the layers of surface oxides. Moreover, the charge carrier recombination was estimated and found to be dramatically affected by the native oxide layers. The density functional theory (DFT) calculations demonstrate that the work function of oxygen-terminated Si surface also increases slightly upon optical excitation and makes for less SE intensity, providing another piece of evidence that the origin of the dark contrast observed on these material surfaces should be assigned to the surface oxide formation, mainly oxygen defect states in the band gap and/or work function increment. Our findings provide a new method and pave the way for evaluating the effect of surface morphology and defects, including but not limited to native oxide, on charge carrier dynamics, and interfacial properties of photovoltaic absorber layers.

Tuning Solute-Redistribution Dynamics for Scalable Fabrication of Colloidal Quantum-Dot Optoelectronics.

Solution-processed colloidal quantum dots (CQDs) are attractive materials for the realization of low-cost and efficient optoelectronic devices. Although impressive CQD-solar-cell performance has been achieved, the fabrication of CQD films is still limited to laboratory-scale small areas because of the complicated deposition of CQD inks. Large-area, uniform deposition of lead sulfide (PbS) CQD inks is successfully realized for photovoltaic device applications by engineering the solute redistribution of CQD droplets. It is shown experimentally and theoretically that the solute-redistribution dynamics of CQD droplets are highly dependent on the movement of the contact line and on the evaporation kinetics of the solvent. By lowering the friction constant of the contact line and increasing the evaporation rate of the droplets, a uniform deposition of CQD ink in length and width over large areas is realized. By utilizing a spray-coating process, large-area (up to 100 cm2 ) CQD films are fabricated with 3-7% thickness variation on various substrates including glass, indium tin oxide glass, and polyethylene terephthalate. Furthermore, scalable fabrication of CQD solar cells is demonstrated with 100 cm2 CQD films which exhibits a notably high efficiency of 8.10%.

Visualization of Charge Carrier Trapping in Silicon at the Atomic Surface Level Using Four-Dimensional Electron Imaging.

The ultrathin thickness (∼1-2 nm) of the native oxide layer on silicon surfaces, which acts as efficient trapping centers, precludes the possibility of studying its impact on the surface-charge carrier dynamics by conventional time-resolved laser spectroscopic techniques because of the large penetration depth of the pump and probe pulses. Here, we use four-dimensional scanning ultrafast electron microscopy (4D S-UEM) with unique surface sensitivity to directly visualize the charge carrier dynamics on Si(100) crystals before and after surface treatment (which removes the native oxide layer) in real space and time simultaneously. Our time-resolved snapshots of the top surface and Kelvin probe-force microscopy results demonstrate that the oxide layer can be formed within minutes after surface treatment, creating undesirable surface-trap states that destroy the population of photogenerated charge carriers on the surface and possibly at the device interface. This new surface observation provides critical photophysical insights into how a few atomic layers of oxide can dramatically influence charge carrier recombination dynamics in silicon solar cells.

On the relationship between rutile/anatase ratio and the nature of defect states in sub-100 nm TiO2 nanostructures: experimental insights.

Black TiO2 is being widely investigated due to its superior optical activity and potential applications in photocatalytic hydrogen generation. Herein, the limitations of the hydrogenation process of TiO2 nanostructures are unraveled by exploiting the fundamental tradeoffs affecting the overall efficiency of the water splitting process. To control the nature and concentration of defect states, different reduction rates are applied to sub-100 nm TiO2 nanotubes, chosen primarily for their superiority over their long counterparts. X-Ray Photoelectron Spectroscopy disclosed changes in the stoichiometry of TiO2 with the reduction rate. UV-vis and Raman spectra showed that high reduction rates promote the formation of the rutile phase in TiO2, which is inactive towards water splitting. Furthermore, electrochemical analysis revealed that such high rates induce a higher concentration of localized electronic defect states that hinder the water splitting performance. Finally, incident photon-to-current conversion efficiency (IPCE) highlighted the optimum reduction rate that attains a relatively lower defect concentration as well as lower rutile content, thereby achieving the highest conversion efficiency.

Spatiotemporal Observation of Electron-Impact Dynamics in Photovoltaic Materials Using 4D Electron Microscopy.

Understanding light-triggered charge carrier dynamics near photovoltaic-material surfaces and at interfaces has been a key element and one of the major challenges for the development of real-world energy devices. Visualization of such dynamics information can be obtained using the one-of-a-kind methodology of scanning ultrafast electron microscopy (S-UEM). Here, we address the fundamental issue of how the thickness of the absorber layer may significantly affect the charge carrier dynamics on material surfaces. Time-resolved snapshots indicate that the dynamics of charge carriers generated by electron impact in the electron-photon dynamical probing regime is highly sensitive to the thickness of the absorber layer, as demonstrated using CdSe films of different thicknesses as a model system. This finding not only provides the foundation for potential applications of S-UEM to a wide range of devices in the fields of chemical and materials research, but also has impact on the use and interpretation of electron beam-induced current for optimization of photoactive materials in these devices.

Real-Space Mapping of Surface Trap States in CIGSe Nanocrystals Using 4D Electron Microscopy.

Surface trap states in copper indium gallium selenide semiconductor nanocrystals (NCs), which serve as undesirable channels for nonradiative carrier recombination, remain a great challenge impeding the development of solar and optoelectronics devices based on these NCs. In order to design efficient passivation techniques to minimize these trap states, a precise knowledge about the charge carrier dynamics on the NCs surface is essential. However, selective mapping of surface traps requires capabilities beyond the reach of conventional laser spectroscopy and static electron microscopy; it can only be accessed by using a one-of-a-kind, second-generation four-dimensional scanning ultrafast electron microscope (4D S-UEM) with subpicosecond temporal and nanometer spatial resolutions. Here, we precisely map the collective surface charge carrier dynamics of copper indium gallium selenide NCs as a function of the surface trap states before and after surface passivation in real space and time using S-UEM. The time-resolved snapshots clearly demonstrate that the density of the trap states is significantly reduced after zinc sulfide (ZnS) shelling. Furthermore, the removal of trap states and elongation of carrier lifetime are confirmed by the increased photocurrent of the self-biased photodetector fabricated using the shelled NCs.

Nanowires: Enhanced Optoelectronic Performance of a Passivated Nanowire-Based Device: Key Information from Real-Space Imaging Using 4D Electron Microscopy (Small 17/2016).

Selective mapping of surface charge carrier dynamics of InGaN nanowires before and after surface passivation with octadecylthiol (ODT) is reported by O. F. Mohammed and co-workers on page 2313, using scanning ultrafast electron microscopy. In a typical experiment, the 343 nm output of the laser beam is used to excite the microscope tip to generate pulsed electrons for probing, and the 515 nm output is used as a clocking excitation pulse to initiate dynamics. Time-resolved images demonstrate clearly that carrier recombination is significantly slowed after ODT treatment, which supports the efficient removal of surface trap states.

Real-Space Visualization of Energy Loss and Carrier Diffusion in a Semiconductor Nanowire Array Using 4D Electron Microscopy.

A breakthrough in the development of 4D scanning ultrafast electron microscopy is described for real-time and space imaging of secondary electron energy loss and carrier diffusion on the surface of an array of nanowires as a model system, providing access to a territory that is beyond the reach of either static electron imaging or any time-resolved laser spectroscopy.

Enhanced Optoelectronic Performance of a Passivated Nanowire-Based Device: Key Information from Real-Space Imaging Using 4D Electron Microscopy.

Managing trap states and understanding their role in ultrafast charge-carrier dynamics, particularly at surface and interfaces, remains a major bottleneck preventing further advancements and commercial exploitation of nanowire (NW)-based devices. A key challenge is to selectively map such ultrafast dynamical processes on the surfaces of NWs, a capability so far out of reach of time-resolved laser techniques. Selective mapping of surface dynamics in real space and time can only be achieved by applying four-dimensional scanning ultrafast electron microscopy (4D S-UEM). Charge carrier dynamics are spatially and temporally visualized on the surface of InGaN NW arrays before and after surface passivation with octadecylthiol (ODT). The time-resolved secondary electron images clearly demonstrate that carrier recombination on the NW surface is significantly slowed down after ODT treatment. This observation is fully supported by enhancement of the performance of the light emitting device. Direct observation of surface dynamics provides a profound understanding of the photophysical mechanisms on materials' surfaces and enables the formulation of effective surface trap state management strategies for the next generation of high-performance NW-based optoelectronic devices.

Mapping Carrier Dynamics on Material Surfaces in Space and Time using Scanning Ultrafast Electron Microscopy.

Selectively capturing the ultrafast dynamics of charge carriers on materials surfaces and at interfaces is crucial to the design of solar cells and optoelectronic devices. Despite extensive research efforts over the past few decades, information and understanding about surface-dynamical processes, including carrier trapping and recombination remains extremely limited. A key challenge is to selectively map such dynamic processes, a capability that is hitherto impractical by time-resolved laser techniques, which are limited by the laser's relatively large penetration depth and consequently these techniques record mainly bulk information. Such surface dynamics can only be mapped in real space and time by applying four-dimensional (4D) scanning ultrafast electron microscopy (S-UEM), which records snapshots of materials surfaces with nanometer spatial and subpicosecond temporal resolutions. In this method, the secondary electron (SE) signal emitted from the sample's surface is extremely sensitive to the surface dynamics and is detected in real time. In several unique applications, we spatially and temporally visualize the SE energy gain and loss, the charge carrier dynamics on the surface of InGaN nanowires and CdSe single crystal and its powder film. We also discuss the mechanisms for the observed dynamics, which will be the foundation for future potential applications of S-UEM to a wide range of studies on material surfaces and device interfaces.

Molecular-structure Control of Ultrafast Electron Injection at Cationic Porphyrin-CdTe Quantum Dot Interfaces.

Charge transfer (CT) at donor (D)/acceptor (A) interfaces is central to the functioning of photovoltaic and light-emitting devices. Understanding and controlling this process on the molecular level has been proven to be crucial for optimizing the performance of many energy-challenge relevant devices. Here, we report the experimental observations of controlled on/off ultrafast electron transfer (ET) at cationic porphyrin-CdTe quantum dot (QD) interfaces using femto- and nanosecond broad-band transient absorption (TA) spectroscopy. The time-resolved data demonstrate how one can turn on/off the electron injection from porphyrin to the CdTe QDs. With careful control of the molecular structure, we are able to tune the electron injection at the porphyrin-CdTe QD interface from zero to very efficient and ultrafast. In addition, our data demonstrate that the ET process occurs within our temporal resolution of 120 fs, which is one of the fastest times recorded for organic photovoltaics.

Layered tantalum oxynitride nanorod array carpets for efficient photoelectrochemical conversion of solar energy: experimental and DFT insights.

Anodically fabricated tantalum oxide (Ta2O5) nanorod array carpets are converted into the corresponding tantalum oxynitride (TaON) through nitridation in an ammonia atmosphere. The measured optical bandgap energy of TaON is ∼2.3 eV, which is also confirmed via the density functional theory calculations. When used to photoelectrochemically split water (AM 1.5G illumination, 1 M KOH, and 0.6 V applied DC bias), the multilayer nanorod films show visible-light incident photon conversion efficiencies (IPCE) as high as 7.5%. The enhanced photochemical activity is discussed in terms of the ordered one-dimensional morphology as well as the electron effective mass in TaON and Ta2O5.