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Discerning the impact of the coherent motion of the nuclei on the timing and efficiency of charge transfer at the donor-acceptor interface is essential for designing performance-enhanced optoelectronic devices. Here, we employ an experimental approach using photocurrent detection in coherent multidimensional spectroscopy to excite a donor aromatic macrocycle and collect the charge transferred to a 2D acceptor layer. For this purpose, we prepared a cobalt phthalocyanine-graphene (CoPc-Gr) interface. Unlike blends, the well-ordered architecture achieved through the physical separation of the two layers allows us to unambiguously collect the electrical signal from graphene alone and associate it with a microscopic understanding of the whole process. The CoPc-Gr interface exhibits an ultrafast electron-transfer signal, stemming from an interlayer mechanism. Remarkably, the signal presents an oscillating time evolution modulated by coherent vibrations originating from the laser-excited CoPc states. By performing Fourier analysis on the beatings and correlating it with the Raman features, along with a comprehensive first-principles characterization of the vibrational coupling in the CoPc excited states, we successfully identify both the orbitals and molecular vibrations that promote the charge transfer at the interface.

The measurement and manipulation of the coherent dynamics of excitonic states constitute a forefront research challenge in semiconductor optics and quantum-coherence-based protocols for optoelectronic technologies. Layered semiconductors have emerged as an ideal platform for the study of exciton dynamics with accessible and technologically relevant energy and time scales. Here, we investigate the subpicosecond exciton dynamics in a van der Waals semiconductor upon quasi-resonant excitation and achieve to single out an incipient coherent excitonic state. Combining broad-band transient reflectance spectroscopy and simulations based on many-body perturbation theory, we reveal a transient enhancement of the excitonic line intensity that originates from photoinduced coherent polarization that is phase-locked with the interacting electromagnetic field. This finding allows us to define the spectral signature of a coherent excitonic state and to experimentally track the dynamical crossover from coherent to incoherent exciton, unlocking the prospective optical control of an exciton population on the intrinsic quantum-coherence time scale.

Time-resolved optical spectroscopies are emerging as a go-to technique for non-destructive testing of nanomaterials. Inspecting the thermal and mechanical properties of a mesoscale device requires achieving delay times beyond the ns timescale in a nanoscopy setup, potentially in a vibration polluted environment. These requirements constitute a major challenge for traditional pump-probe techniques based on moving mechanical delay lines and lock-in detection. Asynchronous optical sampling (ASOPS) and electronically controlled optical sampling (ECOPS), avoiding any moving mechanical parts, are good alternatives. However, their detection scheme is based on fast-balanced photodiodes, which, as a technology, are not as widespread, not as developed, and lack the performance of lock-in based detection. In this study, we introduce what we believe is a novel approach that integrates ASOPS/ECOPS and lock-in detection methodologies, eliminating the necessity for a reference signal and streamlining the optical configuration. By leveraging the strengths of each technique, our approach enhances simplicity and efficiency. The scheme is first validated against standard approaches in the frame of a beam-depletion measurement in a sum frequency experiment. It is then tested in a paradigmatic case study to inspect the mechanics of a single gold nanodisk, with dimensions in the 100 nm range, nanopatterned on a sapphire substrate. These results widen the range of applicability of time-resolved optical techniques as a nano-metrology tool to industrial settings.

Holes accumulation on the surface of bismuth ferrite oxides (BFO) photoanodes for photoelectrochemical (PEC) water splitting (WS) is one of the major issues limiting the overall cell efficiency. However, among the various BFO crystal structures, no evidence of this mechanism has been reported for Bi24Fe2O39, a scarcely investigated phase. Herein we characterize the morphological, structural and PEC properties of 100 nm thick nanogranular films of a Bi24Fe2O39 single phase synthesized by supersonic cluster beam deposition. The films were tested as photoanodes for the WS reaction in KOH and Na2SO4 + Na2SO3 electrolytes. The PEC data provide direct evidence of holes accumulation on the surface of the material with increasing applied biases. The interesting performances of this material at low biases suggest a possible use as photocatalyst under visible light irradiation.

Understanding the thermoelastic response of a nanostructure is crucial for the choice of materials and interfaces in electronic devices with improved and tailored transport properties at the nanoscale. Here, we show how the deposition of a MoS2 monolayer can strongly modify the nanoscale thermoelastic dynamics of silicon substrates close to their interface. We demonstrate this by creating a transient grating with extreme ultraviolet light, using ultrashort free-electron laser pulses, whose ≈84 nm period is comparable to the size of elements typically used in nanodevices, such as electric contacts and nanowires. The thermoelastic response, featuring coherent acoustic waves and incoherent relaxation, is tangibly modified by the presence of monolayer MoS2. Namely, we observed a major reduction of the amplitude of the surface mode, which is almost suppressed, while the longitudinal mode is basically unperturbed, aside from a faster decay of the acoustic modulations. We interpret this behavior as a selective modification of the surface elasticity, and we discuss the conditions to observe such effect, which may be of immediate relevance for the design of Si-based nanoscale devices.

A new ferroic-like phase has been discovered in highly doped superconducting cuprates. The existence of a well-defined order parameter on the supposedly disordered side of the phase diagram challenges the accepted theoretical framework.

The light-mediated interaction of fermionic and bosonic excitations governs the optoelectronic properties of condensed matter systems. In photoexcited semiconductors, the coupling of electron-hole pairs (excitons) to coherent optical phonons enables a modulation of the excitonic resonance that is phase-locked to the frequency of the coupled vibrational mode. Moreover, due to the Coulombic nature of excitons, their dynamics are sensitive to transient changes in the screening by the photoexcited carriers. Interestingly, the effect of photoinduced screening on the transient optical signal originating from the exciton dynamics coupled to phonons is not yet established. By means of broadband transient reflectance spectroscopy, we disclose how exciton-phonon coupling manifests in either the presence or absence of dynamical screening in a layered semiconductor. Furthermore, we unveil the promoting role of photoinduced screening on these exciton-phonon coupled dynamics as opposed to the case in which the unscreened exciton-exciton repulsion likely dominates the nonequilibrium optical response. These findings set a protocol to look at an excitonic resonance and its fundamental many-body interactions on the ultrafast timescale and provide new perspectives on the access to nonequilibrium coupled dynamics.

With the emergence of novel sensing materials and the increasing opportunities to address safety and life quality priorities of our society, gas sensing is experiencing an outstanding growth. Among the characteristics required to assess performances, the overall speed of response and recovery is adding to the well-established stability, selectivity, and sensitivity features. In this review, we focus on fast detection with chemiresistor gas sensors, focusing on both response time and recovery time that characterize their dynamical response. We consider three classes of sensing materials operating in a chemiresistor architecture, exposed to the most investigated pollutants, such as NH3 , NO2 , H2 S, H2 , ethanol, and acetone. Among sensing materials, we first selected nanostructured metal oxides, which are by far the most used chemiresistors and can provide a solid ground for performance improvement. Then, we selected nanostructured carbon sensing layers (carbon nanotubes, graphene, and reduced graphene), which represent a promising class of materials that can operate at room temperature and offer many possibilities to increase their sensitivities via functionalization, decoration, or blending with other nanostructured materials. Finally, transition metal dichalcogenides are presented as an emerging class of chemiresistive layers that bring what has been learned from graphene into a quite large portfolio of chemo-sensing platforms. For each class, studies since 2019 reporting on chemiresistors that display less than 10 s either in the response or in the recovery time are listed. We show that for many sensing layers, the sum of both response and recovery times is already below 10 s, making them promising devices for fast measurements to detect, e.g., sudden bursts of dangerous emissions in the environment, or to track the integrity of packaging during food processing on conveyor belts at pace with industrial production timescales.

NiFe catalysts have emerged as promising low-cost alternatives to Ir- or Ru-based anodes for water splitting. Despite their potential, their widespread adoption in commercial alkaline electrolyzers is currently hindered by instability and rapid deactivation under real operating conditions. In this study, we investigate the behavior of NiFe (90/10% at.) thin film (∼35 nm) electrodes fabricated by supersonic cluster beam deposition as electrocatalysts for the oxygen evolution reaction in alkaline media during prolonged electrochemical activity. In particular, we observed that an exfoliation process occurred, leading to the detachment and dissolution of most (∼99%) of the catalyst nanoparticles (NPs) from the electrode surface into the electrolyte. However, upon multiple potential sweeps, a partial NP redeposition occurred. Importantly, we demonstrate the establishment of an equilibrium between the dissolution and readsorption of catalyst NPs from/to the electrode surface, thereby sustaining significant residual catalytic activity.

Here we investigated the dynamics of OER activity of NiFe (90/10) catalysts over 1000 potential sweep cycles as a function of their mass loading. Over twenty different films with mass loading in the 10 ng/cm2-30 mu g/cm2 range were deposited by Supersonic Cluster Beam Deposition (SCBD), allowing to study the progress of OER in sub-monolayer, monolayer and multilayer regimes. Upon prolonged potential sweeps the electrocatalytic performances of multilayers decreased, while those of monolayers were significantly improved. The best balance in terms of catalytic efficiency and stability in working conditions is found for mass loadings corresponding to a NiFe monolayer, corresponding to a mass loading around 1 mu g/cm2 and a thickness of about 3 nm.The Oxygen Evolution Activity of NiFe films with different thickness was monitored over 1000 potential sweep cycles, revealing the optimal mass loading needed to maintain catalytic activity while avoiding excessive material consumption. image

In the past decade, the emergence of ultrathin 2D films consisting of only a few atomic layers deposited on various substrates sparked new ideas and research. This Perspective provides a nonexhaustive review of utilizing ultrafast optical pump-probe microscopy and the models for fitting experimental data that emerged in the past few years. We will focus on retrieving optically induced modifications of material parameters from pump-probe data on 2D materials, involving the inversion of Maxwell’s equations and discussing new methods to localize optical interactions to capture the response of 2D films with increased resolution and sensitivity. These areas represent promising avenues for advancing our understanding of the dynamic behavior of ultrathin 2D films and their response to ultrafast optically induced transients.

The development of quantum simulators, artificial platforms where the predictions of many-body theories of correlated quantum materials can be tested in a controllable and tunable way, is one of the main challenges of condensed matter physics. Here we introduce artificial lattices made of lead halide perovskite nanocubes as a new platform to simulate and investigate the physics of correlated quantum materials. We demonstrate that optical injection of quantum confined excitons in this system realizes the two main features that ubiquitously pervade the phase diagram of many quantum materials: collective phenomena, in which long-range orders emerge from incoherent fluctuations, and the excitonic Mott transition, which has one-to-one correspondence with the insulator-to-metal transition described by the repulsive Hubbard model in a magnetic field. Our results demonstrate that time-resolved experiments provide a quantum simulator that is able to span a parameter range relevant for a broad class of phenomena, such as superconductivity and charge-density waves.

Sacrificial templates present an effective pathway for gaining high-level control over nanoscale reaction products. Atomic layer deposition (ALD) is ideally suited for such approaches due to its ability to replicate the surface topography of a template material through the deposition of an ultrathin conformal layer. Herein, metal nanostructures are demonstrated as sacrificial templates for the formation of architecturally complex and deterministically positioned oxide nanoshells, open-topped nanobowls, vertically standing half-shells, and nanorings. The three-step process sees metal nanocrystals formed in periodic arrays, coated with an ALD-deposited oxide, and hollowed out with a selective etch through nanopores formed in the oxide shell. The procedure is further augmented through the use of a directional ion beam that is used to sculpt the oxide shells into bowl- and ring-like configurations. The functionality of the so-formed materials is demonstrated through their use as substrate-confined nanoreactors able to promote the growth and confinement of nanomaterials. Taken together, the work expands the design space for substrate-based nanomaterials, creates a platform for advancing functional surfaces and devices and, from a broader perspective, advances the use of ALD in forming complex nanomaterials.The nanofabrication of periodic arrays of structurally complex oxide nanoshells is demonstrated. The so-formed structures are demonstrated as substrate-confined nanoreactors able to synthesize nanomaterials within their confines.

Managing light-matter interactions on timescales faster than the loss of electronic coherence is key for achieving full quantum control of the final products in solid-solid transformations. In this Letter, we demon-strate coherent optical control of the orbital occupation that determines the insulator-to-metal transition in the prototypical Mott insulator V2O3. Selective excitation of a specific interband transition with two phase-locked light pulses manipulates the occupation of the correlated bands in a way that depends on the coherent evolution of the photoinduced superposition of states. A comparison between experimental results and numerical solutions of the optical Bloch equations provides an electronic coherence time on the order of 5 fs. Temperature-dependent experiments suggest that the electronic coherence time is enhanced in the vicinity of the insulator-to-metal transition critical temperature, thus highlighting the role of fluctuations in determining the electronic coherence. These results open different routes to selectively switch the functionalities of quantum materials and coherently control solid-solid electronic transformations.

Graphitic carbon nitride (gCN) is a promising n-type semiconductor widely investigated for photo-assisted water splitting, but less studied for the (photo)electrochemical degradation of aqueous organic pollutants. In these fields, attractive perspectives for advancements are offered by a proper engineering of the material properties, e.g., by depositing gCN onto conductive and porous scaffolds, tailoring its nanoscale morphology, and functionalizing it with suitable cocatalysts. The present study reports on a simple and easily controllable synthesis of gCN flakes on Ni foam substrates by electrophoretic deposition (EPD), and on their eventual decoration with Co-based cocatalysts [CoO, CoFe2O4, cobalt phosphate (CoPi)] via radio frequency (RF)-sputtering or electrodeposition. After examining the influence of processing conditions on the material characteristics, the developed systems are comparatively investigated as (photo)anodes for water splitting and photoelectrocatalysts for the degradation of a recalcitrant water pollutant [potassium hydrogen phthalate (KHP)]. The obtained results highlight that while gCN decoration with Co-based cocatalysts boosts water splitting performances, bare gCN as such is more efficient in KHP abatement, due to the occurrence of a different reaction mechanism. The related insights, provided by a multi-technique characterization, may provide valuable guidelines for the implementation of active nanomaterials in environmental remediation and sustainable solar-to-chemical energy conversion.

Following recent literature work, an interesting result on hydrogen sorption by Ag–Rh clusters was reported which do not follow the common understanding of hydrogen absorption in bulk alloys. Thus, nanostructured Ag–Rh films with a composition of 75% Ag–25% Rh were grown by supersonic cluster beam deposition onto microbalance quartz crystals in order to measure hydrogen absorption. The films were exposed to H2 gas to study hydrogen absorption at different partial pressure. The Ag–Rh films were then characterized by XPS and AFM. The Ag/Rh atomic ratio was found to be 75/25 by XPS. Surface roughness was determined by AFM to be 3 nm RMS in all the films. In disagreement with the quoted literature report, no hydrogen absorption was observed in our Ag–Rh films up to 5.3×103Pa of hydrogen pressure. The response of the balance was checked and validated by measuring hydrogen absorption on 10 and 100 nm Pd films. The hydrogen absorption by Pd yielded an atomic H/Pd ratio of ∼0.65 in agreement with our prior measurements.

Electronic noses (e-noses) have received considerable interest in the past decade as they can match the emerging needs of modern society such as environmental monitoring, health screening, and food quality tracking. For practical applications of e-noses, it is necessary to collect large amounts of data from an array of sensing devices that can detect interactions with molecules reliably and analyze them via pattern recognition. The use of graphene (Gr)-based arrays of chemiresistors in e-noses is still virtually missing, though recent reports on Gr-based chemiresistors have disclosed high sensing performances upon functionalization of the pristine layer, opening up the possibility of being implemented into e-noses. In this work, with the aim of creating a robust and chemically stable interface that combines the chemical properties of metal phthalocyanines (M-Pc, M = Fe, Co, Ni, Zn) with the superior transport properties of Gr, an array of Gr-based chemiresistor sensors functionalized with drop-cast M-Pc thin layers has been developed. The sensing capability of the array was tested towards biomarkers for breathomics application, with a focus on ammonia (NH3). Exposure to NH3 has been carried out drawing the calibration curve and estimating the detection limit for all the sensors. The discrimination capability of the array has then been tested, carrying out exposure to several gases (hydrogen sulfide, acetone, ethanol, 2-propanol, water vapour and benzene) and analysing the data through principal component analysis (PCA). The PCA pattern recognition results show that the developed e-nose is able to discriminate all the tested gases through the synergic contribution of all sensors.

Introduction: As we approach the post-antibiotic era, the development of innovative antimicrobial strategies that carry out their activities through non-specific mechanisms could limit the onset and spread of drug resistance. In this context, the use of nanogranular coatings of multielement nanoparticles (NPs) conjugated to the surface of implantable biomaterialsmight represent a strategy to reduce the systemicdrawbacks by locally confining the NPs effects against either prokaryotic or eukaryotic cells. Methods: In the present study, two new multielement nanogranular coatings combining Ag and Cu with either Ti or Mg were synthesized by a gas phase physical method and tested against pathogens isolated from periprosthetic joint infections to address their potential antimicrobial value and toxicity in an in vitro experimental setting. Results: Overall, Staphylococcus aureus, Staphylococcus epidermidis and Escherichia coli displayed a significantly decreased adhesion when cultured on Ti-Ag-Cu and Mg-Ag-Cu coatings compared to uncoated controls, regardless of their antibiotic resistance traits. A dissimilar behavior was observed when Pseudomonas aeruginosa was cultured for 30 and 120 minutes upon the surface of Ti-Ag-Cu and Mg-Ag-Cu-coated discs. Biofilm formation was mainly reduced by the active effect of Mg-Ag-Cu compared to Ti-Ag-Cu and, again, coatings had a milder effect on P. aeruginosa, probably due to its exceptional capability of attachment and matrix production. These data were further confirmed by the evaluation of bacterial colonization on nanoparticle-coated discs through confocal microscopy. Finally, to exclude any cytotoxic effects on eukaryotic cells, the biocompatibility of NPs-coated discs was studied. Results demonstrated a viability of 95.8% and 89.4% of cells cultured in the presence of Ti-Ag-Cu and Mg-Ag-Cu discs, respectively, when compared to negative controls. Conclusion: In conclusion, the present study demonstrated the promising antiadhesive fe

Sensor arrays are currently attracting the interest of researchers due to their potential of overcoming the limitations of single sensors regarding selectivity, required by specific applications. Among the materials used to develop sensor arrays, graphene has not been so far extensively exploited, despite its remarkable sensing capability. Here we present the development of a graphene-based sensor array prepared by dropcasting nanostructure and nanocomposite graphene solution on interdigitated substrates, with the aim to investigate the capability of the array to discriminate several gases related to specific applications, including environmental monitoring, food quality tracking, and breathomics. This goal is achieved in two steps: at first the sensing properties of the array have been assessed through ammonia exposures, drawing the calibration curves, estimating the limit of detection, which has been found in the ppb range for all sensors, and investigating stability and sensitivity; then, after performing exposures to acetone, ethanol, 2-propanol, sodium hypochlorite, and water vapour, chemometric tools have been exploited to investigate the discrimination capability of the array, including principal component analysis (PCA), linear discriminant analysis (LDA), and Mahalanobis distance. PCA shows that the array was able to discriminate all the tested gases with an explained variance around 95%, while with an LDA approach the array can be trained to accurately recognize unknown gas contribution, with an accuracy higher than 94%.

A novel strategy for the improvement in the sensing performance of p-type NiO is developed by employing the unique functional properties of self-assembled monolayers. Specifically, hole concentration near the surface of NiO nanowires (NWs) is modulated by terminal epoxy groups of the organosilane. This modulation leads to the increase in electron transfer from reducing gases to NWs surface. As a result, SAM-functionalized sensors showed 9-times higher response at low-temperature as compared to bare NiO NWs.

Boosted by the emerging need for highly integrated gas sensors in the internet of things (IoT) ecosystems, electronic noses (e-noses) are gaining interest for the detection of specific molecules over a background of interfering gases. The sensing of nitrogen dioxide is particularly relevant for applications in environmental monitoring and precision medicine. Here we present an easy and efficient functionalization procedure to covalently modify graphene layers, taking advantage of diazonium chemistry. Separate graphene layers were functionalized with one of three different aryl rings: 4-nitrophenyl, 4-carboxyphenyl and 4-bromophenyl. The distinct modified graphene layers were assembled with a pristine layer into an e-nose for NO2 discrimination. A remarkable sensitivity to NO2 was demonstrated through exposure to gaseous solutions with NO2 concentrations in the 1-10 ppm range at room temperature. Then, the discrimination capability of the sensor array was tested by carrying out exposure to several interfering gases and analyzing the data through multivariate statistical analysis. This analysis showed that the e-nose can discriminate NO2 among all the interfering gases in a two-dimensional principal component analysis space. Finally, the e-nose was trained to accurately recognize NO2 contributions with a linear discriminant analysis approach, thus providing a metric for discrimination assessment with a prediction accuracy above 95 %.