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Focused ion beam (FIB) techniques have been frequently used to section metal-halide perovskites for microstructural investigations. However, the ion beams directly irradiated to the sample surface may alter the properties far different from pristine, potentially leading to modified deterioration mechanisms under aging stressors. Here, we combine complementary approaches to measure the subsurface characteristics of polished perovskite and identify the chemical species responsible for the measured properties. Analysis of the experimental results in conjunction with Monte Carlo simulations indicates that atomic displacements and local heating occur in the subsurface of methylammonium lead iodide (MAPbI3) by glazing Ar+ beam irradiation (15 nm by 4 kV at 3 degree). The lead-rich, iodine-deficient surface promotes rapid phase segregation under thermal aging conditions. On the other hand, despite the subsurface modification, our experiments confirm the rest of the MAPbI3 bulk retains the material integrity. Our observation supports that polished perovskites could serve in studying the properties of bulk or buried junctions far away from the altered subsurface with care., Comment: six figures

Solid-state single-photon sources are essential building blocks for quantum photonics and quantum information technologies. This study demonstrates promising single-photon emission from quantum defects generated in single-wall carbon nanotubes (SWCNTs) by covalent reaction with guanine nucleotides in their single-stranded DNA coatings. Low-temperature photoluminescence spectroscopy and photon-correlation measurements on individual guanine-functionalized SWCNTs (GF-SWCNTs) indicate that multiple, closely spaced guanine defect sites within a single ssDNA strand collectively form an exciton trapping potential that supports a localized quantum state capable of room-temperature single-photon emission. In addition, exciton traps from adjacent ssDNA strands are weakly coupled to give cross-correlations between their separate photon emissions. Theoretical modeling identifies coupling mechanism as a capture of band-edge excitons. Because the spatial pattern of nanotube functionalization sites can be readily controlled by selecting ssDNA base sequences, GF-SWCNTs should become a versatile family of quantum light emitters with engineered properties.

The cross-electrophile coupling of either twisted-amides or heteroaryl halides with alkyl halides, enabled by ball-milling, is herein described. The operationally simple nickel-catalyzed process has no requirement for inert atmosphere or dry solvents and delivers the corresponding acylated or heteroarylated products across a broad range of substrates. Key to negating the necessity of inert reaction conditions is the mechanical activation of the raw metal terminal reductant: manganese in the case of twisted amides and zinc for heteroaryl halides.

Chemical reactions between semiconducting single-wall carbon nanotubes (SWCNTs) and single-stranded DNA (ssDNA) achieve spatially patterned covalent functionalization sites and create coupled fluorescent quantum defects on the nanotube surface, tailoring SWCNT photophysics for applications such as single-photon emitters in quantum information technologies. The evaluation of relaxation dynamics of photoluminescence (PL) from those coupled quantum defects is essential for understanding the nanotube electronic structure and beneficial to the design of quantum light emitters. Here, we measured the PL decay for ssDNA-functionalized SWCNTs as a function of the guanine content of the ssDNA oligo that dictates the red-shifting of their PL emission peaks relative to the band-edge exciton. We then correlate the observed dependence of PL decay dynamics on energy red-shifts to the exciton potential energy landscape, which is modeled using first-principles approaches based upon the morphology of ssDNA-altered SWCNTs obtained by atomic force microscopy (AFM) imaging. Our simulations illustrate that the multiple guanine defects introduced within a single ssDNA strand strongly interact to create a deep exciton trapping well, acting as a single hybrid trap. The emission decay from the distinctive trapping potential landscape is found to be biexponential for ssDNA-modified SWCNTs. We attributed the fast time component of the biexponential PL decay to the redistribution of exciton population among the lowest energy bright states and a manifold of dark states emerging from the coupling of multiple guanine defects. The long lifetime component in the biexponential decay, on the other hand, is attributed to the redistribution of exciton population among different exciton trapping sites that arise from the binding of multiple ssDNA strands along the nanotube axis. AFM measurements indicate that those trapping sites are separated on average by ∼8 nm along the nanotube axis.

Herein, we report a new electrochemical method for alkoxy radical generation from alcohols using a proton-coupled electron transfer (PCET) approach, showcased via the deconstructive functionalization of cycloalkanols. The electrochemical method is applicable across a diverse array of substituted cycloalkanols, accessing a broad range of synthetically useful distally functionalized ketones. The orthogonal derivatization of the products has been demonstrated through chemoselective transformations, and the electrochemical process has been performed on a gram scale in continuous single-pass flow.

Rapid and wide-ranging developments have established mechanochemistry as a powerful avenue in sustainable organic synthesis. This is primarily due to unique opportunities which have been offered in solvent-free - or highly solvent-minimised - reaction systems. Nevertheless, despite elegant advances in ball-milling technology, limitations in scale-up still remain. This tutorial review covers the first reports into the translation from "batch-mode" ball-milling to "flow-mode" reactive extrusion, using twin-screw extrusion.

Akiyama atomic force microscopy probes represent a unique means of combining several of the desirable properties of tuning fork and cantilever probe designs. As a hybridized mechanical resonator, the vibrational characteristics of Akiyama probes result from a complex coupling between the intrinsic vibrational eigenmodes of its constituent tuning fork and bridging cantilever components. Through a combination of finite element analysis modeling and experimental measurements of the thermal vibrations of Akiyama probes we identify a complex series of vibrational eigenmodes and measure their frequencies, quality factors, and spring constants. We then demonstrate the viability of Akiyama probes to perform bimodal multi-frequency force sensing by performing a multimodal measurement of a surface’s nanoscale photothermal response using photo-induced force microscopy imaging techniques. Further performing a parametric search over alternative Akiyama probe geometries, we propose two modified probe designs to enhance the capability of Akiyama probes to perform sensitive bimodal multifrequency force sensing measurements.

In 1990, after 50 years of Soviet occupation, Lithuania declared independence from the Soviet Union. The case for the restoration of Lithuanian independence was made by Juozas Urbsys, one of the la...

Defects in molecular crystals, created by non-equilibrium crystal packing, can have significant influence over the energetics and dynamics of singlet fission. Though normally thought of as detrimen...

Singlet fission, the process of splitting a singlet exciton into two triplet excitons, has been proposed as a mechanism for improving the efficiency of future photovoltaic devices. In organic semiconductors exhibiting singlet fission, the geometric relationship between molecules plays an important role by setting the intermolecular couplings that determine the system energetics. Here, we spatially image TIPS-pentacene microcrystals using ultrafast two-dimensional white-light microscopy and discover a low-energy singlet state sparsely distributed throughout the microcrystals, with higher concentrations at edges and morphological defects. The spectra of these singlet states are consistent with slip-stacked molecular geometries and increased charge-transfer couplings. The picosecond-timescale kinetics of these low-energy singlet states matches that of the correlated triplet-pair state, which we attribute to singlet/triplet-pair interconversion at these sites. Our observations support the conclusion that small populations of geometries with favourable energetics can play outsized roles in singlet fission processes. Intermolecular coupling plays a critical role in singlet fission. Now, high-resolution 2D white-light spectroscopy has been used to map the presence of non-equilibrium molecular packing in single TIPS-pentacene microcrystals and characterize its effect on the dynamics of singlet fission.

Motivated by the complexity and difficulty of engineering time-critical cloud applications, we investigated the methodology and software workbench to provide full application life cycle support to the software engineer. For this purpose we present a novel high-level concept that is concentrated on exchanging the complex, dynamic data using OASIS TOSCA standard, mainly used in static contexts. This methodology enables specifying an application logic, provisioning, deploying, monitoring, and dynamical adaptation to changing conditions. It can be applied effectively to the interchange of dynamically changing data in order to maintain Quality of Service. By extending TOSCA with dynamic mapping of Qualify of Service and runtime attributes related to the application and underlying architecture we show that TOSCA can be used to exchange data and reconfigure on-demand compute resources whilst the application is in the process of design, infrastructure provisioning, runtime or adaptation. To demonstrate that our novel research contributions can be realised, we implemented SWITCH IDE, which showcases this concept through its development workflow which offers application and underlying infrastructure description, manipulation and reconfiguration of QoS and runtime attributes. Our approach differs in that it supports the concept of dynamic TOSCA by directly enabling application runtime to be reconfigured on the fly.

The dynamics of electronic transitions in solid-state materials are closely linked to microscopic morphology, but it is challenging to simultaneously characterize their spectral and temporal response with high spatial resolution. We present a time-resolved nonlinear microscopy system using white-light supercontinuum pulses as a broadband light source. This system is capable of correlating nanometer scale sample morphology determined from atomic force topography measurements with broadband transient absorption hyperspectral images and ultrafast 2D white-light spectra, all with a spatial resolution of ≤1 μm. The experimental apparatus is described with a focus on the dispersion management strategies necessary to minimize the duration of optical pulses when implementing an AOM based pulse-shaping system covering a broad-spectral range in the VIS/NIR. Experiments on TIPS-pentacene organic semiconductor microcrystals are used to demonstrate the unique capabilities of this technique.

Time-critical applications, such as early warning systems or live event broadcasting, present particular challenges. They have hard limits on Quality of Service constraints that must be maintained, despite network fluctuations and varying peaks of load. Consequently, such applications must adapt elastically on-demand, and so must be capable of reconfiguring themselves, along with the underlying cloud infrastructure, to satisfy their constraints. Software engineering tools and methodologies currently do not support such a paradigm. In this paper, we describe a framework that has been designed to meet these objectives, as part of the EU SWITCH project. SWITCH offers a flexible co-programming architecture that provides an abstraction layer and an underlying infrastructure environment, which can help to both specify and support the life cycle of time-critical cloud native applications. We describe the architecture, design and implementation of the SWITCH components and describe how such tools are applied to three time-critical real-world use cases.

The majority of 2D IR spectrometers operate at 1-10 kHz using Ti:Sapphire laser technology. We report a 2D IR spectrometer designed around Yb:KGW laser technology that operates shot-to-shot at 100 kHz. It includes a home-built OPA, a mid-IR pulse shaper, and custom-designed electronics with optional on-chip processing. We report a direct comparison between Yb:KGW and Ti:Sapphire based 2D IR spectrometers. Even though the mid-IR pulse energy is much lower for the Yb:KGW driven system, there is an 8x improvement in signal-to-noise over the 1 kHz Ti:Sapphire driven spectrometer to which it is compared. Experimental data is shown for sub-millimolar concentrations of amides. Advantages and disadvantages of the design are discussed, including thermal background that arises at high repetition rates. This fundamental spectrometer design takes advantage of newly available Yb laser technology in a new way, providing a straightforward means of enhancing sensitivity.

Recent advances in 3D/2D heterostructures have opened up tremendous opportunities in building highly flexible and durable optoelectronic devices. However, the inherit lack of interfacial bonding and low surface energy of van der Waals surfaces limit the nucleation and growth of 3D materials. Enhancing wettability by providing a porous buffer is effective in growing compound semiconductors on graphene while van der Waals epitaxy of Ge remains challenging. Here, the nucleation of Ge has been significantly improved from an islanded mode to granular modes by using a TiN/AlN multilayered buffer prior to Ge/graphene integration. Highly textured Ge growth with dominating (111), (220), and (311) peaks are identified by x-ray diffraction. The microstructure of the buffer TiN/AlN demonstrates a polycrystalline quality with clean interfaces between each interlayer and the substrate. Kelvin probe force microscopy measurements along the lateral TiN/AlN interface identify a potential drop corresponding to the AlN phase. This contact potential difference between TiN and AlN is the key in generating the out-of-plane dipole moment that modifies the surface energy of the monolayer graphene, resulting in enhanced wettability of the Ge adatoms nucleated on top. Surface dipole induced nucleation of 3D semiconductor thin films on 2D materials via the proper design of buffer layer is fundamentally important to enhance the 3D/2D growth toward flexible optoelectronic applications.