Trapping Dynamics Research Articles

An Irradiance-Adaptable Near-Infrared Vertical Heterojunction Phototransistor.

Bioinspired artificial visual perception devices with the optical environment-adaptable function have attracted significant attention for their promising potential in applications like robotics and machine vision. In this regard, a photodetector with in-sensor adaptability is longed for in terms of complexity, efficiency, and cost. Here, a near-infrared phototransistor with a benign light irradiance-adaptability is presented. The phototransistor uses a vertically stacking graphene/lead sulfide quantum dots/graphene heterojunction as the conductive channel. Compared with ordinary lead sulfide quantum dots-decorated graphene phototransistors, the present device demonstrates a faster photoresponse speed and an abnormal transfer characteristic. The latter characteristic is induced by the gate voltage-tunable Fermi level in the heterojunction and the abundant electron trap states in the quantum dot film, which jointly results in an intense dependence of the photoresponse on the gate voltage. The dynamic trapping and de-trapping processes in the quantum dot film enable the inhibition or potentiation of the photoresponse, based on which the photopic or scotopic adaptation behavior of the human retina is successfully mimicked, respectively. By providing an irradiance-adaptable photodetector with a spectral response beyond visible light, this work should inspire future research on artificial environment-adaptable perception devices.

Efficient polysulfides trapping and redox enabled by Co/N-carbon implanted Li+-montmorillonite for advanced lithium-sulfur batteries

Li-S batteries are very promising next-generation energy storage systems due to their high theoretical capacity and energy density, but suffer from sluggish redox kinetics and serious polysulfides (PS) shuttle. Herein, Co/N-carbon implanted Li+-montmorillonite (Co/NC@Li-MMT) is designed to inhibit PS shuttle and maximize PS redox kinetics in Li-S battery. The Co/NC@Li-MMT 2D nanomaterial is fabricated by exfoliation of the Li-MMT nanosheets using melamine and Co(II)(acac)2, followed by one-step thermal reduction. The exfoliated Co/NC@Li-MMT with high Li+ and electrical conductivity can expose abundant active sites for efficient PS adsorption via Co-S and Si-S and Li bonds and for fast PS electrocatalytic conversion via Co and CoNC catalytic active sites. The Co/NC@Li-MMT modified PP (Co/NC@Li-MMT@PP) separator with a thin Co/NC@Li-MMT layer of 2.2 μm (0.3 mg cm−2 mass loading) features high Li+ conductivity, fast Li+ diffusion, superior electrolyte wettability as well as efficient PS trapping and fast PS redox kinetics as verified by various analytical techniques. Consequently, the Li-S battery with the Co/NC@Li-MMT@PP separator shows high initial capacity (1447 mAh/g), good rate performance, excellent cycling stability (0.027 % capacity fade per cycle at 1C over 300 cycles) and ultralow self-discharge.

High Photoreactivity on a Reconstructed Anatase TiO2(001) Surface Predicted by Ab Initio Nonadiabatic Molecular Dynamics.

Anatase TiO2(001) surface with (4 × 1) reconstruction is proposed to be a highly active catalytic surface. In this work, using time-domain ab initio nonadiabatic molecular dynamics, we reveal that the ridge structure formed by anatase(001) surface reconstruction is the photoreactive site for hole migration and trapping. Moreover, the ridge structure is destroyed by low-coverage CH3OH adsorption, leading to the suppression of its high photoreactivity. However, when the CH3OH coverage is increased and intermolecular hydrogen bonds (H-bonds) form, the ridge structure and its high photoreactivity are restored. Furthermore, the hole trapping dynamics is strongly coherent with intermolecular proton transfer in structures with intermolecular H-bonds. Our study proves that anatase TiO2(001)-(4 × 1) is a highly photoreactive surface where the ridge is the photoreactive site for hole trapping, which is coherent with the proton transfer process.

Implications of Microstructure in Helium-Implanted Nanocrystalline Metals.

Helium bubbles are known to form in nuclear reactor structural components when displacement damage occurs in conjunction with helium exposure and/or transmutation. If left unchecked, bubble production can cause swelling, blistering, and embrittlement, all of which substantially degrade materials and—moreover—diminish mechanical properties. On the mission to produce more robust materials, nanocrystalline (NC) metals show great potential and are postulated to exhibit superior radiation resistance due to their high defect and particle sink densities; however, much is still unknown about the mechanisms of defect evolution in these systems under extreme conditions. Here, the performances of NC nickel (Ni) and iron (Fe) are investigated under helium bombardment via transmission electron microscopy (TEM). Bubble density statistics are measured as a function of grain size in specimens implanted under similar conditions. While the overall trends revealed an increase in bubble density up to saturation in both samples, bubble density in Fe was over 300% greater than in Ni. To interrogate the kinetics of helium diffusion and trapping, a rate theory model is developed that substantiates that helium is more readily captured within grains in helium-vacancy complexes in NC Fe, whereas helium is more prone to traversing the grain matrices and migrating to GBs in NC Ni. Our results suggest that (1) grain boundaries can affect bubble swelling in grain matrices significantly and can have a dominant effect over crystal structure, and (2) an NC-Ni-based material can yield superior resistance to irradiation-induced bubble growth compared to an NC-Fe-based material and exhibits high potential for use in extreme environments where swelling due to He bubble formation is of significant concern.

Dynamics of Photogenerated Charge Carriers in Inorganic/Organic S-Scheme Heterojunctions.

Step-scheme heterojunctions formed between two firmly bound photocatalysts facilitate charge separation due to interfacial charge transfer, which is usually illustrated by the gain or loss of electrons in the constituent photocatalysts characterized by in situ irradiated X-ray photoelectron spectroscopy. This technique provides a steady-state view of charge distribution but overlooks the transient and complex dynamics of charge transfer, trapping, and recombination. To provide a molecular-level and dynamic view of these processes, we investigated the behaviors of photogenerated charge carriers within an inorganic/organic TiO2/polydopamine S-scheme heterojunction using ultrafast transient absorption spectroscopy and time-resolved photoluminescence spectroscopy. We found the interfacial charge transfer within the step-scheme heterojunction occurred at a smaller shorter time scale than recombination, leading to efficient charge separation. Moreover, the charge-discharge property of polydopamine induces electron backflow, which should be avoided in practical photocatalytic applications. The composite showed higher photocatalytic H2O2-production activities due to faster H2O2 formation and suppressed H2O2 decomposition.

Trap dynamics of hot electrons in metal–insulator–metal plasmonic structures for ultra-fast optoelectronics

We have calculated the time constants of the electron dynamics in traps in a metal–insulator–metal (MIM) plasmonic structure. Because of electron relaxation in metal, the surface plasmon polaritons decays into hot electrons near the surface of the metal, which facilitates the trap of electrons in the interfacial layer of the dielectric. We have calculated the capture and emission times separately as the electron does not follow the same mechanisms with the capture process when it is emitted from a trap at the metal/oxide interface. We have developed a quasi-two-dimensional treatment that has been modified from a previously used semiconductor/oxide junction by using Bardeen’s function to calculate the capture time. Various parameters including trap’s distance from the interface, temperature, voltage bias, and spectral nature of the hot electrons’ energy distribution influence the interaction between a plasmonic hot electron and a neutral near-interface trap in the capture process. On the one hand, the emission time is independent of the capture time, and it is determined by the tunneling time to the metal depending on the temperature and the energy difference between the trap energy levels (ground and excited states). We have showed that a wide range of capture times from seconds to picoseconds is possible for an interfacial trap at the room temperature due to the spectral energy distribution of hot electrons and dependence of the capture process on the losses in metals. On the other hand, the temperature plays the dominant role in the emission time. For the trap with 250 meV energy difference between its levels, the emission time is in the range of picosecond at room temperature. Therefore, the MIM plasmonic device can respond to a wide range of ac voltage frequencies including the ultra-fast domain. These interesting findings are useful to understand the ac response of the MIM plasmonic devices with applications in integrated photonics and ultra-fast optoelectronics.

Advanced Anode Materials for Sodium-Ion Batteries: Confining Polyoxometalates in Flexible Metal-Organic Frameworks by the "Breathing Effect".

Polyoxometalates (POMs) have shown great potential in sodium-ion batteries (SIBs) due to their reversible multielectron redox property and high ionic conductivity. Currently, POM-based SIBs suffer from the irreversible trapping and sluggish transmission kinetics of Na+. Herein, a series of POMs/metal-organic frameworks (MOFs)/graphene oxide (GO) (MOFs = MIL-101, MIL-53, and MIL-88B; POM = [PMo12O40]3-, denoted as PMo12) composites are developed as SIB anode materials for the first time. Unlike MIL-101 with large pore structures, the pores in flexible MIL-53 and MIL-88B swell spontaneously upon the accommodation of PMo12. Particularly, the PMo12/MIL-88B/GO composites deliver an excellent specific capacity of 214.2 mAh g-1 for 600 cycles at 2.0 A g-1, with a high initial Coulombic efficiency (ICE) of 51.0%. The so-called "breathing effect" of flexible MOFs leads to the relatively tight confinement space for PMo12, which greatly modulates its electronic structure, affects the adsorption energy of Na+, and eventually reduces the trapping of sodium ions. Additionally, the straight and multidimensional channels in MIL-88B significantly accelerate ion diffusion, inducing favored energetic kinetics and thus generating high-rate performance.

Synapse and Tunable Leaky-Integrate Neuron Functions Enabled by Oxide Trapping Dynamics in a Single Logic Transistor

We show that a high-k gated n-MOSFET can embody both the memory plasticity of a synapse and leaky-integration of a neuron, by virtue of the rich temporal dynamics of charge capture/emission by gate-oxide defects. In addition, a tunable leaky-integrate function is demonstrated. The lower limit of energy per input spike is on the order of fJ, which provides room for low-power trigger circuit design and scalability. This work points to the prospect of a gate-engineered logic transistor serving as the universal building block of hardware spiking neural networks, thereby accelerating the realization of compact, energy efficient neuromorphic computers given the relative maturity of the transistor technology.

Thermodynamic trapping and diffusion model for multiple species in systems with multiple sorts of traps

This work presents a trapping and diffusion model for multiple species of solute atoms in a system with multiple sorts of traps based on irreversible thermodynamics. We use two established approaches describing the interaction between lattice and traps, i.e. transient trapping and theory based local thermodynamic equilibrium, and extend them to systems with multiple species. Consequently, the presented theory and its numerical implementations cover effectively any kinetics of exchange between the lattice and traps as well as site competition effects within traps for any system size. The presented theory can be applied for several phenomena in material science. For example, (co-) segregation of solutes at grain boundaries, trapping of interstitials during precipitation processes and hydrogen interaction with material defects and other interstitials. Simulations of charging and discharging are presented for several plate-like samples containing multiple sorts of traps occupied by multiple species. The role of trapping parameters is demonstrated and discussed for charging and discharging behavior, site competition effects and the interaction of trapping kinetics with diffusion kinetics for multiple species.

Simulation and Experiment of the Trapping Trajectory for Janus Particles in Linearly Polarized Optical Traps.

The highly focused laser beam is capable of confining micro-sized particle in its focus. This is widely known as optical trapping. The Janus particle is composed of two hemispheres with different refractive indexes. In a linearly polarized optical trap, the Janus particle tends to align itself to an orientation where the interface of the two hemispheres is parallel to the laser propagation as well as the polarization direction. This enables a controllable approach that rotates the trapped particle with fine accuracy and could be used in partial measurement. However, due to the complexity of the interaction of the optical field and refractive index distribution, the trapping trajectory of the Janus particle in the linearly polarized optical trap is still uncovered. In this paper, we focus on the dynamic trapping process and the steady position and orientation of the Janus particle in the optical trap from both simulation and experimental aspects. The trapping process recorded by a high speed camera coincides with the simulation result calculated using the T-matrix model, which not only reveals the trapping trajectory, but also provides a practical simulation solution for more complicated structures and trapping motions.

Correlated Dynamics of Free and Self‐Trapped Excitons and Broadband Photodetection in BEA2PbBr4 Layered Crystals

AbstractSelf‐trapped excitons (STEs) exert a profound impact on the optical properties and device applications of 2D halide perovskites. Particularly distinct exciton self‐trapping and detrapping processes can facilitate the intelligent design of perovskite optoelectronic devices with emerging functionalities. Thus, a comprehensive understanding and regulation of exciton trapping and detrapping dynamics are highly desired. Herein, the authors report a 2D lead halide perovskite (BEA2PbBr4 where BEA is 2‐bromine ethylamine) with exceptional broadband photoluminescence (PL), which originates from multiple STE states. In particular, the unique energy‐level configuration of STEs with respect to free excitons is revealed by exploiting optical spectroscopy. Consequently, these distinct phenomena empower the broadband photodetection capability of BEA2PbBr4 photodetectors over a wide range from ultraviolet to near‐infrared wavelengths. These results provide an essential understanding of the intriguing photophysics of STEs and shed new light on the future development of single‐component perovskite broadband optoelectronic devices.

Design considerations for gallium arsenide pulse compression photoconductive switch

In this paper, we present the physics and design-space exploration of a novel pulse compression photoconductive switch (PCPS) using semi-insulating gallium arsenide (GaAs) operating in the negative differential mobility (NDM) regime of electron transport. We systematically quantify the relationship between the PCPS performance and various design options, including contact separation, laser energy and placement, and trap dynamics. Specifically, we report the full-width at half-maximum and the peak output current generated by the PCPS as a function of applied electrical and optical bias. We discuss the optimal spacing between the electrodes and the distance of the laser spot to the anode to achieve higher electron confinement and superior radio-frequency (RF) metrics. Reducing the laser energy is important to prevent the appearance of secondary peaks due to diffusive transport, but there exists a trade-off between the bandwidth and the maximum current of the PCPS. We also compare the PCPS response with and without trap dynamics and find that the electrostatic screening from the trap-induced space charge is time-independent when the trapping time constant is set larger than the recombination lifetime. Overall, trap dynamics are detrimental to performance, unless the compensation doping scheme to achieve semi-insulating GaAs is carefully selected. Results presented in this paper can be used by experimentalists to fine-tune the PCPS design parameters to meet the specifications of various RF applications. Moreover, our results will provide a strong theoretical basis to the measurements of PCPS devices using GaAs and other NDM materials under investigation.

Deciphering single- and multi-particle trapping dynamics under femtosecond pulsed excitation with simultaneous spatial and temporal resolution

Recent theoretical and experimental studies have shed light on how laser trapping dynamics under femtosecond pulsed excitation are fine-tuned by optical and thermal nonlinearities. Here, we present experimental results of trapping of single and multiple polystyrene beads (of 1 μm diameter). We show how integration and synchronization of bright-field video microscopy with confocal detection of backscatter provide both spatial and temporal resolution required to capture intricate details of nonlinear trapping dynamics. Such spatiotemporal detection is promising to have far-reaching applications in exploring controlled laser trapping and manipulations harnessed by optical and thermal nonlinearities.

An atomistic simulation study of rapid solidification kinetics and crystal defects in dilute Al–Cu alloys

Rapid solidification kinetics of dilute Al–Cu alloys is simulated using a quantum mechanics based bond-order potential (BOP), in free solidification conditions, to determine kinetic and thermodynamic properties of solidification, as well as point defects and chemical ordering of the solidified structures. We measure the anisotropic kinetic coefficient, anisotropic solid–liquid interface energy, as well as solute trapping kinetics in terms of partition coefficient versus velocity and solute drag coefficient. Furthermore, solid–liquid interface free energy and its anisotropy are measured in equilibrium simulations, showing reasonably good agreement with previous studies. We also verified the self-consistency of the MD simulations, by comparing the interfacial temperature vs. velocity to that predicted by the continuous growth model. These solid–liquid interface properties are important for quantitative parametrization of larger scale solidification modeling techniques such as phase field models. We also investigated the point defect content, local chemical ordering, and local crystalline structures in the rapidly solidified samples. We found clustering of solute with vacancies, whereas copper atoms repelled each other in these dilute alloy simulations. In addition to vacancies, a large number of interstitials were found. In solidification velocities approaching the complete solute trapping regime, we found that the vacancies and interstitials formed in conjunction, i.e. as Frenkel pairs. Finally, in addition to FCC, we detected BCC and HCP phases, where the latter two were accompanied by an increase in local copper content. Understanding the formation of point defects and their relationship to chemical ordering is an important step towards controlling the formation of pre-precipitates and precipitates, which are an important strengthening mechanism for aluminum–copper alloys.

Unique Mo2C–CdS–Co@C heterojunction integrated with redox cocatalysts and multiple active sites for efficient photocatalytic H2 generation

Photocatalytic water-splitting has encouraged great interest to obtain renewable H2 fuel via the transformation of solar energy. Although significant progress has been achieved, realizing efficient H2 evolution reaction (HER) with non-noble-metal photocatalysts is still challenging. Herein, we report a facile synthesis of Mo2C–CdS–[email protected] heterojunction by anchoring CdS and Mo2C nanoparticles onto [email protected] micro-flowers. The [email protected] micro-flowers were composed of graphitic carbon nanoflakes partially embedded with Co, CoOx, Co9S8 nanocrystals and obtained through the carbonization of metanilic-anion intercalated Co(OH)2 precursor. Due to excellent visible-light harvesting capacity, efficient charge transmission and isolation caused by the existence of superior electron mediator (graphitic carbon) together with oxidation (CoOx) and reduction (Co, Co9S8, Mo2C) cocatalysts, as well as the plentiful H2-evolving active sites originating from the metal (Co), metal sulfide (Co9S8), and metal carbide (Mo2C), the Mo2C–CdS–[email protected] hybrid micro-flowers delivered an exceptional HER (λ > 400 nm) activity of 760.58 μmol h−1 (10 mg), approximately 32 and 15 folds that of pristine CdS and platinum (3 wt%)-decorated CdS, respectively. Moreover, both the cycling and long-term photocatalytic tests confirm that the Mo2C–CdS–[email protected] possesses an outstanding durability for H2 production. The study results might inspire the rational integration of cocatalysts to simultaneously optimize the charge trapping and H2-evolving kinetics for strengthening the photocatalytic HER activity efficiently.

Unraveling the Dynamics of Charge Trapping and De-Trapping in Ferroelectric FETs

In this work, a comprehensive study of charge trapping and de-trapping dynamics is performed on n-channel ferroelectric field-effect transistors (nFeFETs) and pFeFETs. It is discovered that: 1) the degree of charge trapping depends on the substrate that nFeFETs exhibit significant electron trapping but negligible hole trapping during memory write while pFeFETs exhibit much less electron trapping but significant hole trapping when heavily stressed; 2) due to enhanced electric field in the interlayer and semiconductor, the like initial polarization states (i.e., initialized by a pulse of the same polarity as the write pulse) could exacerbate charge trapping induced by the write pulse; 3) electron trapping is fully recoverable while hole trapping shows a semi-permanent component which involves interface trap generation; and 4) less significant charge trapping in pFeFETs allows immediate read-after-write at normal operating conditions.

Highly flexible elastomer microfluidic chip for single cell manipulation.

New materials and fabrication technologies have significantly boosted the development of lab-on-a-chip technologies and functionalities. In this work, we developed a highly flexible elastomer microfluidic chip with a microchannel with a minimum width of ∼5 μm manufactured by imprinting onto an SU-8 template. We found that the deformation induced in the microstructures by manual stretching of the chip is higher than that for the chip itself, which we attribute to the stress concentration of microstructures. Here, we demonstrate that the elastomer enables the manipulation of single cells, such as dynamic trapping-releasing operations, by simply stretching and releasing the elastomer chip.

In Situ EPR Spin Trapping and Competition Kinetics Demonstrate Temperature-Dependent Mechanisms of Synergistic Radical Production by Ultrasonically Activated Persulfate.

Ultrasound coupled with activated persulfate can synergistically degrade aqueous organic contaminants. Here, in situ electron paramagnetic resonance spin trapping was used to compare radicals produced by ultrasonically activated persulfate (US-PS) and its individual technologies, ultrasound alone (US) and heat-activated persulfate (PS), with respect to temperature. Radicals were trapped using 5,5-dimethyl-1-pyrroline-N-oxide, DMPO, to form detectable nitroxide adducts. Using initial rates of radical adduct formation, and compared to US and PS, US-PS at 40 and 50 °C resulted in the largest synergistic production of radicals. Radicals generated from US were reasonably consistent from 40 to 70 °C, indicating that temperature had little effect on cavitational bubble collapse over this range. However, synergy indexes calculated from initial rates showed that ultrasonic activation of persulfate at the bubble interface changes with temperature. From these results, we speculate that higher temperatures enhance persulfate uptake into cavitation bubbles via nanodroplet injection. DMPO-OH was the predominant adduct detected for all conditions. However, competition modeling and spin trapping in the presence of nitrobenzene and atrazine probes showed that SO4•- predominated. Therefore, the DMPO-OH signal is derived from SO4•- trapping with subsequent DMPO-SO4- hydrolysis to DMPO-OH. Spin trapping is effective in quantifying total radical adduct formation but limited in measuring primary radical speciation in this case.

Origin of layered perovskite device efficiencies revealed by multidimensional time-of-flight spectroscopy.

Mixtures of layered perovskite quantum wells with different sizes form prototypical light-harvesting antenna structures in solution-processed films. Gradients in the bandgaps and energy levels are established by concentrating the smallest and largest quantum wells near opposing electrodes in photovoltaic devices. Whereas short-range energy and charge carrier funneling behaviors have been observed in layered perovskites, our recent work suggests that such light-harvesting processes do not assist long-range charge transport due to carrier trapping at interfaces between quantum wells and interstitial organic spacer molecules. Here, we apply a two-pulse time-of-flight technique to a family of layered perovskite systems to explore the effects that interstitial organic molecules have on charge carrier dynamics. In these experiments, the first laser pulse initiates carrier drift within the active layer of a photovoltaic device, whereas the second pulse probes the transient concentrations of photoexcited carriers as they approach the electrodes. The instantaneous drift velocities determined with this method suggest that the rates of trap-induced carrier deceleration increase with the concentrations of organic spacer cations. Overall, our experimental results and model calculations suggest that the layered perovskite device efficiencies primarily reflect the dynamics of carrier trapping at interfaces between quantum wells and interstitial organic phases.

Trap-state mapping to model GaN transistors dynamic performance

Trapping phenomena degrade the dynamic performance of wide-bandgap transistors. However, the identification of the related traps is challenging, especially in presence of non-ideal defects. In this paper, we propose a novel methodology (trap-state mapping) to extract trap parameters, based on the mathematical study of stretched exponential recovery kinetics. To demonstrate the effectiveness of the approach, we use it to identify the properties of traps in AlGaN/GaN transistors, submitted to hot-electron stress. After describing the mathematical framework, we demonstrate that the proposed methodology can univocally describe the properties of the distribution of trap states. In addition, to prove the validity and the usefulness of the model, the trap properties extracted mathematically are used as input for TCAD simulations. The results obtained by TCAD closely match the experimental transient curves, thus confirming the accuracy of the trap-state mapping procedure. This methodology can be adopted also on other technologies, thus constituting a universal approach for the analysis of multiexponential trapping kinetics.