Electron-hole Pair Excitations Research Articles

Transferability of the Specific Reaction Parameter Density Functional for H2 + Pt(111) to H2 + Pt(211).

The accurate description of heterogeneously catalyzed reactions may require chemically accurate evaluation of barriers for reactions of molecules at the edges of metal nanoparticles. It was recently shown that a semiempirical density functional describing the interaction of a molecule dissociating on a flat metal surface (CHD3 + Pt(111)) is transferable to the same molecule reacting on a stepped surface of the same metal (Pt(211)). However, validation of the method for additional systems is desirable. To address the question whether the specific reaction parameter (SRP) functional that describes H2 + Pt(111) with chemical accuracy is also capable of accurately describing H2 + Pt(211), we have performed molecular beam simulations with the quasi-classical trajectory (QCT) method, using the SRP functional developed for H2 + Pt(111). Our calculations used the Born–Oppenheimer static surface model. The accuracy of the QCT method was assessed by comparison with quantum dynamics results for reaction of the ro-vibrational ground state of H2. The theoretical results for sticking of H2 and D2 on Pt(211) are in quite good agreement with the experiment, but uncertainties remain because of a lack of accuracy of the QCT simulations at low incidence energies and possible inaccuracies in the reported experimental incidence energies at high energies. We also investigated the nonadiabatic effect of electron–hole pair excitation on the reactivity using the molecular dynamics with the electron friction (MDEF) method, employing the local density friction approximation (LDFA). Only small effects of electron–hole pair excitation on sticking are found.

Dynamics of A-exciton and spin relaxation in WS<sub>2</sub> and WSe<sub>2</sub> monolayer

Two-dimensional transitional metal dichalcogenide (2D TMD) emerges as a good candidate material in optoelectronics and valleytronics due to its particular exciton effect and strong spin-valley locking. Owing to the enhancement of quantum confinement effect and the decline of dielectric shielding effect, the optical excitation of electron-hole pair is enhanced substantially, which makes large TMD exciton binding energy and makes excitons observed easily at room temperature or even higher temperature. Optical response of 2D TMD is dominated by excitons at room temperature, which provides an ideal medium for studying the generation, relaxation and interaction of excitons or trions. By employing ultrafast time resolved spectroscopy, we investigate experimentally the dynamic behaviors of A-exciton and spin relaxations for two types of TMDs, i.e. WS<sub>2</sub> and WSe<sub>2</sub> monolayers, respectively. By tuning the excitation wavelength of the degenerate pump and probe laser beam, the WS<sub>2</sub> monolayer and WSe<sub>2</sub> monolayer are excited at their A-exciton resonance transition position or near their A-exciton resonance transition position in order to compare the dynamical evolutions of band structure and exciton polarization of the two similar WS<sub>2</sub> and WSe<sub>2</sub> monolayer structures. Our experimental results reveal that the relaxation of A exciton in WS<sub>2</sub> shows biexponential decay, while that of WSe<sub>2</sub> shows triexponential decay, and the A-exciton life time in WSe<sub>2</sub> is much longer than that of WS<sub>2</sub> counterpart. The spin relaxation of A exciton in WS<sub>2</sub> shows a monoexponential feature with a lifetime of 0.35 ps, which is dominated by the electron-hole exchange interaction. For the case of WSe<sub>2</sub>, the spin relaxation can be well fitted with biexponential function, the fast component has a lifetime of 0.5 ps and the slow one has a lifetime of 28 ps. The fast relaxation is dominated by the electron-hole exchange interaction, and the slow one comes from the formation of dark exciton via spin-lattice coupling. By tuning the excitation wavelength around A-exciton transition, the formation of dark exciton in WSe<sub>2</sub> is demonstrated to be much more effective than that in WS<sub>2</sub> monolayer. Our experimental results provide qualitative physical images for an in-depth understanding of the relationship between exciton and TMD structure, and also provide reference for further designing and regulating the TMDs based optoelectronic devices.

Crossover from trion-hole complex to exciton-polaron inn-doped two-dimensional semiconductor quantum wells

We present a theoretical study of photoabsorption in $n$-doped two-dimensional (2D) and quasi-2D semiconductors that takes into account the interaction of the photocreated exciton with Fermi-sea (FS) electrons through (i) Pauli blocking, (ii) Coulomb screening, and (iii) excitation of FS electron-hole pairs---that we here restrict to one. The system we tackle is thus made of one exciton plus zero or one FS electron-hole pair. At low doping, the system ground state is predominantly made of a ``trion-hole''---a trion (two opposite-spin electrons plus a valence hole) weakly bound to a FS hole---with a small exciton component. As the trion is poorly coupled to photon, the intensity of the lowest absorption peak is weak; it increases with doping, thanks to the growing exciton component, due to a larger coupling between two-particle and four-particle states. Under a further doping increase, the trion-hole complex is less bound because of Pauli blocking by FS electrons, and its energy increases. The lower peak then becomes predominantly due to an exciton dressed by FS electron-hole pairs, that is, an exciton-polaron. As a result, the absorption spectra of $n$-doped semiconductor quantum wells show two prominent peaks, the nature of the lowest peak turning from trion-hole to exciton-polaron under a doping increase. Our work also nails down the physical mechanism behind the increase with doping of the energy separation between the trion-hole peak and the exciton-polaron peak, even before the anticrossing, as experimentally observed.

Accelerated Carrier Relaxation through Reduced Coulomb Screening in Two-Dimensional Halide Perovskite Nanoplatelets

For high-speed optoelectronic applications relying on fast relaxation or energy-transfer mechanisms, understanding of carrier relaxation and recombination dynamics is critical. Here, we compare the differences in photoexcited carrier dynamics in two-dimensional (2D) and quasi-three-dimensional (quasi-3D) colloidal methylammonium lead iodide perovskite nanoplatelets via differential transmission spectroscopy. We find that the cooling of excited electron–hole pairs by phonon emission progresses much faster and is intensity-independent in the 2D case. This is due to the low dielectric surrounding of the thin perovskite layers, for which the Fröhlich interaction is screened less efficiently leading to higher and less density-dependent carrier-phonon scattering rates. In addition, rapid dissipation of heat into the surrounding occurs due to the high surface-to-volume ratio. Furthermore, we observe a subpicosecond dissociation of resonantly excited 1s excitons in the quasi-3D case, an effect which is suppressed in the 2D nanoplatelets due to their large exciton binding energies. The results highlight the importance of the surrounding environment of the inorganic nanoplatelets on their relaxation dynamics. Moreover, this 2D material with relaxation times in the subpicosecond regime shows great potential for realizing devices such as photodetectors or all-optical switches operating at THz frequencies.

Analysis of Energy Dissipation Channels in a Benchmark System of Activated Dissociation: N2 on Ru(0001).

The excitation of electron–hole pairs in reactive scattering of molecules at metal surfaces often affects the physical and dynamical observables of interest, including the reaction probability. Here, we study the influence of electron–hole pair excitation on the dissociative chemisorption of N2 on Ru(0001) using the local density friction approximation method. The effect of surface atom motion has also been taken into account by a high-dimensional neural network potential. Our nonadiabatic molecular dynamics simulations with electronic friction show that the reaction of N2 is more strongly affected by the energy transfer to surface phonons than by the energy loss to electron–hole pairs. The discrepancy between the computed reaction probabilities and experimental results is within the experimental error both with and without friction; however, the incorporation of electron–hole pairs yields somewhat better agreement with experiments, especially at high collision energies. We also calculate the vibrational efficacy for the N2 + Ru(0001) reaction and demonstrate that the N2 reaction is more enhanced by exciting the molecular vibrations than by adding an equivalent amount of energy into translation.

Optimization of nonhomogeneous indium-gallium-nitride Schottky-barrier thin-film solar cells

A two-dimensional model was developed to simulate the optoelectronic characteristics of indium-gallium-nitride (InGaN), thin-film, Schottky-barrier solar cells. The solar cells comprise a window, designed to reduce the reflection of incident light, Schottky-barrier and ohmic front electrodes, an n-doped InGaN wafer, and a metallic periodically corrugated back-reflector (PCBR). The ratio of indium to gallium in the wafer varies periodically throughout the thickness of the absorbing layer of the solar cell. Thus, the resulting InGaN wafer's optical and electrical properties are made to vary periodically. This material nonhomogeneity could be physically achieved by varying the fractional composition of indium and gallium during deposition. Empirical models for indium nitride and gallium nitride were combined using Vegard's law to determine the optical and electrical constitutive properties of the alloy. The nonhomogeneity of the electrical properties of the InGaN aids in the separation of the excited electron-hole pairs, while the periodicities of optical properties and the back-reflector enable the incident light to couple to multiple guided wave modes. The profile of the resulting charge-carrier-generation rate when the solar cell is illuminated by the AM1.5G spectrum was calculated using the rigorous coupled-wave approach. The steady-state drift-diffusion equations were solved using COMSOL, which employs finite-volume methods, to calculate the current density as a function of the voltage. Mid-band Shockley-Read-Hall, Auger, and radiative recombination rates were taken to be the dominant methods of recombination. The model was used to study the effects of the solar-cell geometry and the shape of the periodic material nonhomogeneity on efficiency. The solar-cell efficiency was optimized using the differential evolution algorithm.

Light-Mediated Growth of Noble Metal Nanostructures (Au, Ag, Cu, Pt, Pd, Ru, Ir, Rh) From Micro- and Nanoscale ZnO Tetrapodal Backbones.

Micro- and nanoscale ZnO tetrapods provide an attractive support for metallic nanostructures since they can be inexpensively produced using the flame transport method and nanoparticle synthesis schemes can take advantage of a coupled response facilitated by the formation of a semiconductor-metal interface. Here, we present a light-mediated solution-based growth mode capable of decorating the surface of ZnO tetrapods with nanostructures of gold, silver, copper, platinum, palladium, ruthenium, iridium, and rhodium. It involves two coupled reactions that are driven by the optical excitation of electron-hole pairs in the ZnO semiconductor by ultraviolet photons where the excited electrons are used to reduce aqueous metal ions onto the ZnO tetrapod as excited holes are scavenged from the surface. For the most part, the growth mode gives rise to nanoparticles with a roundish morphology that are uniformly distributed on the tetrapod surface. Larger structures with irregular shapes are, however, obtained for syntheses utilizing aqueous metal nitrates as opposed to chlorides, a result that suggests that the anion plays a role in shape determination. It is also demonstrated that changes to the molarity of the metal ion can influence the nanostructure nucleation rate. The catalytic activity of tetrapods decorated with each of the eight metals is assessed using the reduction of 4-nitrophenol by borohydride as a model reaction where it is shown that those decorated with Pd, Ag, and Rh are the most active.

Efficient charge carrier separation and excellent visible light photoresponse in Cu2O nanowires

Last decade has witnessed a surge of research pertaining to Cu2O nanowires for fields of photocatalysts, sensors, solar cells and rechargeable battery systems owing to their unique physicochemical properties. Their atomic properties, especially the size dependent electronic structures, however, remain unknown. Herein, by combining systematic first-principles calculations with material synthesis, characterization, device fabrication and measurement, we investigated physical properties of Cu2O nanowires and their applications in visible light photodiodes. We explored Cu2O nanowires with triangular and hexagonal cross sections of a series of diameter size, and found that they have favorable formation energies, indicative of facile synthesis. These nanowires have tunable direct band gap ranging from 2.2 to 5.4 eV, and a simple model is derived to effectively predict gap size. Remarkably, obvious spatially separated charge distribution of conduction and valance band edges was observed, ensuring long lifetime of excited electron-hole pairs that may greatly benefit performance of optoelectronic devices. Experimentally, we synthesized well-crystallized Cu2O nanowires and fabricated photodiodes, which exhibit a fast rise time of 9.86 ms, decay time of 27.37 ms, and high responsivity of 10 A/W. We expect these results to shed new light on Cu2O nanostructures for scalable, versatile and high-performance optoelectronic devices.

Effects of surface motion and electron-hole pair excitations in CO2 dissociation and scattering on Ni(100).

The energy transfer between different channels is an important aspect in chemical reactions at surfaces. We investigate here in detail the energy transfer dynamics in a prototypical system, i.e., reactive and nonreactive scattering of CO2 on Ni(100), which is related to heterogeneous catalytic processes with Ni-based catalysts for CO2 reduction. On the basis of our earlier nine-dimensional potential energy surface for CO2/Ni(100), dynamical calculations have been done using the generalized Langevin oscillator (GLO) model combined with local density friction approximation (LDFA), in which the former accounts for the surface motion and the latter accounts for the low-energy electron-hole pair (EHP) excitation. In spite of its simplicity, it is found that the GLO model yields quite satisfactory results, including the significant energy loss and product energy disposal, trapping, and steering dynamics, all of which agree well with the ab initio molecular dynamics ones where many surface atoms are explicitly involved with high computational cost. However, the GLO model fails to describe the reactivity enhancement due to the lattice motion because it intrinsically does not incorporate the variance of barrier height on the surface atom displacement. On the other hand, in LDFA, the energy transferred to EHPs is found to play a minor role and barely alter the dynamics, except for slightly reducing the dissociation probabilities. In addition, vibrational state-selected dissociative sticking probabilities are calculated and previously observed strong mode specificity is confirmed. Our work suggests that further improvement of the GLO model is needed to consider the lattice-induced barrier lowering.

Correction to “Evidence for Electron–Hole Pair Excitation in the Associative Desorption of H2 and D2 from Au(111)”

Correction to “Evidence for Electron–Hole Pair Excitation in the Associative Desorption of H₂ and D₂ from Au(111)”

Quantum nonlocal theory of topological Fermi arc plasmons in Weyl semimetals

The surface of a Weyl semimetal (WSM) displays Fermi arcs, i.e. disjoint segments of a two-dimensional Fermi contour. We present a quantum-mechanical non-local theory of chiral Fermi arc plasmons in WSMs with broken time-reversal symmetry. These are collective excitations constructed from topological Fermi arc and bulk electron states and arising from electron-electron interactions, which are treated in the realm of the random phase approximation. Our theory includes quantum effects associated with the penetration of the Fermi arc surface states into the bulk and dissipation, which is intrinsically non-local in nature and arises from decay processes mainly involving bulk electron-hole pair excitations.

Shaping charge excitations in chiral edge states with a time-dependent gate voltage

We study a coherent conductor supporting a single edge channel in which alternating current pulses are created by local time-dependent gating and sent on a beam-splitter realized by a quantum point contact. The current response to the gate voltage in this setup is intrinsically linear. Based on a fully self-consistent treatment employing a Floquet scattering theory, we analyze the effect of different voltage shapes and frequencies, as well as the role of the gate geometry on the injected signal. In particular, we highlight the impact of frequency-dependent screening on the process of shaping the current signal. The feasibility of creating true single-particle excitations with this method is confirmed by investigating the suppression of excess noise, which is otherwise created by additional electron-hole pair excitations in the current signal.

Polaron Polaritons in the Integer and Fractional Quantum Hall Regimes

Elementary quasiparticles in a two-dimensional electron system can be described as exciton polarons since electron-exciton interactions ensures dressing of excitons by Fermi-sea electron-hole pair excitations. A relevant open question is the modification of this description when the electrons occupy flat bands and electron-electron interactions become prominent. Here, we perform cavity spectroscopy of a two-dimensional electron system in the strong coupling regime, where polariton resonances carry signatures of strongly correlated quantum Hall phases. By measuring the evolution of the polariton splitting under an external magnetic field, we demonstrate the modification of polaron dressing that we associate with filling factor dependent electron-exciton interactions.

Hydrogen collisions with transition metal surfaces: Universal electronically nonadiabatic adsorption.

Inelastic scattering of H and D atoms from the (111) surfaces of six fcc transition metals (Au, Pt, Ag, Pd, Cu, and Ni) was investigated, and in each case, excitation of electron-hole pairs dominates the inelasticity. The results are very similar for all six metals. Differences in the average kinetic energy losses between metals can mainly be attributed to different efficiencies in the coupling to phonons due to the different masses of the metal atoms. The experimental observations can be reproduced by molecular dynamics simulations based on full-dimensional potential energy surfaces and including electronic excitations by using electronic friction in the local density friction approximation. The determining factors for the energy loss are the electron density at the surface, which is similar for all six metals, and the mass ratio between the impinging atoms and the surface atoms. Details of the electronic structure of the metal do not play a significant role. The experimentally validated simulations are used to explore sticking over a wide range of incidence conditions. We find that the sticking probability increases for H and D collisions near normal incidence-consistent with a previously reported penetration-resurfacing mechanism. The sticking probability for H or D on any of these metals may be represented as a simple function of the incidence energy, Ein, metal atom mass, M, and incidence angle, 𝜗in. S=(S0+a⋅Ein+b⋅M)*(1-h(𝜗in-c)(1-cos(𝜗in-c)d⋅h(Ein-e)(Ein-e))), where h is the Heaviside step function and for H, S0 = 1.081, a = -0.125 eV-1, b=-8.40⋅10-4 u-1, c = 28.88°, d = 1.166 eV-1, and e = 0.442 eV; whereas for D, S0 = 1.120, a = -0.124 eV-1, b=-1.20⋅10-3 u-1, c = 28.62°, d = 1.196 eV-1, and e = 0.474 eV.

Energy dissipation to tungsten surfaces upon hot-atom and Eley-Rideal recombination of H2.

Adiabatic and nonadiabatic quasi-classical molecular dynamics simulations are performed to investigate the role of electron-hole pair excitations in hot-atom and Eley-Rideal H2 recombination mechanisms on H-covered W(100). The influence of the surface structure is analyzed by comparing with previous results for W(110). In the two surfaces, hot-atom abstraction cross sections are drastically reduced due to the efficient energy exchange with electronic excitations at low incident energies and low coverage, while the effect on Eley-Rideal reactivity is negligible. As the coverage increases, the projectile energy is more efficiently dissipated into the other adsorbates. Consequently, the effect of electronic excitations is reduced. As a result, the reactivity and final energy distributions of the formed H2 molecules are similar for both abstraction mechanisms.

The Enhancement of Interfacial Exciton Dissociation by Energetic Disorder Is a Nonequilibrium Effect.

The dissociation of excited electron–hole pairs is a microscopic process that is fundamental to the performance of photovoltaic systems. For this process to be successful, the oppositely charged electron and hole must overcome an electrostatic binding energy before they undergo ground state recombination. It has been observed previously that the presence of energetic disorder can lead to a reduction in recombination losses. Here we investigate this effect using a simple model of charge dynamics at a donor–acceptor interface. We consider the effect of spatial variations in electronic energy levels, such as those that arise in disordered molecular systems, on dissociation yield and demonstrate that it is maximized with a finite amount of disorder. We demonstrate that this is a nonequilibrium effect that is mediated by the dissipation driven formation of partially dissociated intermediate states that are long-lived because they cannot easily recombine. We present a kinetic model that incorporates these states and show that it is capable of reproducing similar behavior when it is parametrized with nonequilibrium rates.

Relaxation of Plasmon-Induced Hot Carriers

Plasmon-induced hot carrier generation has attracted much recent attention due to its promising potential in photocatalysis and other light harvesting applications. Here we develop a theoretical model for hot carrier relaxation in metallic nanoparticles using a fully quantum mechanical jellium model. Following pulsed illumination, nonradiative plasmon decay results in a highly nonthermal distribution of hot electrons and holes. Using coupled master equations, we calculate the time-dependent evolution of this carrier distribution in the presence of electron–electron, electron–photon, and electron–phonon scattering. Electron–electron relaxation is shown to be the dominant scattering mechanism and results in efficient carrier multiplication where the energy of the initial hot electron–hole pair is transferred to other multiple electron–hole pair excitations of lower energies. During this relaxation, a small but finite fraction of electrons scatter into luminescent states where they can recombine radiatively ...

Nonadiabatic Vibrational Damping of Molecular Adsorbates: Insights into Electronic Friction and the Role of Electronic Coherence.

We present a perturbation approach rooted in time-dependent density-functional theory to calculate electron-hole (e-h) pair excitation spectra during the nonadiabatic vibrational damping of adsorbates on metal surfaces. Our analysis for the benchmark systems CO on Cu(100) and Pt(111) elucidates the surprisingly strong influence of rather short electronic coherence times. We demonstrate how in the limit of short electronic coherence times, as implicitly assumed in prevalent quantum nuclear theories for the vibrational lifetimes as well as electronic friction, band structure effects are washed out. Our results suggest that more accurate lifetime or chemicurrentlike experimental measurements could characterize the electronic coherence.

Communication: Hot-atom abstraction dynamics of hydrogen from tungsten surfaces: The role of surface structure.

Adiabatic and non-adiabatic quasiclassical molecular dynamics simulations are performed to investigate the role of the crystal face on hot-atom abstraction of H adsorbates by H scattering from covered W(100) and W(110). On both cases, hyperthermal diffusion is strongly affected by the energy dissipated into electron-hole pair excitations. As a result, the hot-atom abstraction is highly reduced in favor of adsorption at low incidence energy and low coverages, i.e., when the mean free path of the hyperthermal H is typically larger. Qualitatively, this reduction is rather similar on both surfaces, despite at such initial conditions, the abstraction process involves more subsurface penetration on W(100) than on W(110).

Photo- and cathodoluminescence of Eu3+ or Tb3+ doped CaZrO3 films prepared by pulsed laser deposition

Luminescent films of Eu3+ or Tb3+ doped CaZrO3 were epitaxially grown on SrTiO3 or LaAlO3 (001) single crystal substrates by pulsed laser deposition (PLD). They showed a high transmittance in the visible region and a smooth surface. Uniform red photoluminescence (PL) was observed from Eu3+ 5% doped films, and blue and green PL was observed from Tb3+ 0.5% and 5% doped films, respectively. These PL spectra of the films turned out to be very similar to those of the powder samples. Practically, it has to be noticed the use of a LaAlO3 substrate is necessary for intense blue luminescence for Tb3+ 0.5% doped films to avoid optical absorption of emitted light by the SrTiO3 substrate. The cathodoluminescence (CL) spectra of the red and green luminescent films were almost the same as those PL spectra. In contrast, blue CL was significantly enhanced in CL compared to PL. This was attributed to the shorter lifetime of the 5D3-7FJ transitions and many excited electron-hole pairs, which were generated rapidly on high energy electron irradiation.