Electronic Relaxation Research Articles

Intrinsically Slow Cooling of Hot Electrons in CdSe Nanocrystals Compared to CdS.

The utilization of excited charge carriers in semiconductor nanocrystals (NCs) for optoelectronic technologies has been a long-standing goal in the field of nanoscience. Experimental efforts to extend the lifetime of excited carriers have therefore been a principal focus. To understand the limits of these lifetimes, in this work, we theoretically study the time scales of pure electron relaxation in negatively charged NCs composed of two prototypical materials: CdSe and CdS. We find that hot electrons in CdSe have lifetimes that are 5 to 6 orders of magnitude longer than in CdS when the relaxation is governed only by the intrinsic properties of the materials. Although these two materials are known to have somewhat different electronic structure, we elucidate how this enormous difference in lifetimes arises from relatively small quantitative differences in electronic energy gaps and phonon frequencies, as well as the crucial role of Fröhlich-type electron-phonon couplings.

Factors Affecting the Population of Excited Charge Transfer States in Adenine/Guanine Dinucleotides: A Joint Computational and Transient Absorption Study

There is compelling evidence that the absorption of low-energy UV radiation directly by DNA in solution generates guanine radicals with quantum yields that are strongly dependent on the secondary structure. Key players in this unexpected phenomenon are the photo-induced charge transfer (CT) states, in which an electric charge has been transferred from one nucleobase to another. The present work examines the factors affecting the population of these states during electronic relaxation. It focuses on two dinucleotides with opposite orientation: 5′-dApdG-3′ (AG) and 5′-dGpdA-3′ (GA). Quantum chemistry calculations determine their ground state geometry and the associated Franck–Condon states, map their relaxation pathways leading to excited state minima, and compute their absorption spectra. It has been shown that the most stable conformer is anti-syn for AG and anti-anti for GA. The ground state geometry governs both the excited states populated upon UV photon absorption and the type of excited state minima reached during their relaxation. Their fingerprints are detected in the transient absorption spectra recorded with excitation at 266 nm and a time resolution of 30 fs. Our measurements reveal that in the large majority of dinucleotides, chromophore coupling is already operative in the ground state and that the charge transfer process occurs within ~120 fs. The competition among various relaxation pathways affects the quantum yields of the CT state formation in each dinucleotide, which are estimated to be 0.18 and 0.32 for AG and GA, respectively.

Room temperature polarization-resolved Raman and photoluminescence in uniaxially strained layered MoS2

Transition metal dichalcogenides (TMDCs) are one of the material systems of choice toward achieving room temperature quantum coherence. Externally applied strain is used as a more common control mechanism to tune electro-optical properties in TMDCs like molybdenum disulfide (MoS2). However, room temperature electron–phonon interactions in the presence of strain in transition metal dichalcogenides are still not fully explored. In this work, we employ uniaxial strain dependent Raman and photoluminescence (PL) studies on monolayer and bilayer MoS2 to explore electron–phonon physics. Helicity-resolved Raman in MoS2 obeys robust selection rules. Our studies reveal clear modification in these helicity-based selection rules in the presence of moderate uniaxial strain (ϵ = 0.4%–1.2%). The selection rules are restored upon clear symmetry breaking of the in-plane vibrational mode (ϵ > 1.2%). We assign these changes to the onset of Fröhlich interaction in this moderate strain regime. The changes in Raman scattering are accompanied by changes in valley selective relaxation observed through non-resonant photoluminescence (PL). The moderate strain regime also exhibits the onset of PL polarization for indirect excitonic emission under non-resonant excitation. Our experimental observations point toward electron–phonon coupling mechanisms affecting both valley-selective electron relaxation during PL emission as well as polarization-selective Raman scattering of two-dimensional semiconductors at room temperature.

Electronic dynamics created at conical intersections and its dephasing in aqueous solution

AbstractA dynamical rearrangement in the electronic structure of a molecule can be driven by different phenomena, including nuclear motion, electronic coherence or electron correlation. Recording such electronic dynamics and identifying its fate in an aqueous solution has remained a challenge. Here, we reveal the electronic dynamics induced by electronic relaxation through conical intersections in both isolated and solvated pyrazine molecules using X-ray spectroscopy. We show that the ensuing created dynamics corresponds to a cyclic rearrangement of the electronic structure around the aromatic ring. Furthermore, we found that such electronic dynamics were entirely suppressed when pyrazine was dissolved in water. Our observations confirm that conical intersections can create electronic dynamics that are not directly excited by the pump pulse and that aqueous solvation can dephase them in less than 40 fs. These results have implications for the investigation of electronic dynamics created during light-induced molecular dynamics and shed light on their susceptibility to aqueous solvation.

Multifunctional Roles of Iron Oxide Nanoparticles in a Reversible Shape‐Memory Composite

AbstractThe utilization of functional fillers in the development of composite materials has come a long way since its advent to improve physical, chemical, or mechanical properties of the base material. However, the heterogenous roles contributed by a single type of filler remain uncommon in this field. Here the endowment of various modifications to a 1,8‐octanediol/1,12‐dodecanedioic acid/citric acid (OD/DDA/CA) matrix through the incorporation of iron oxide nanoparticles (IONPs) is reported. Owing to the relaxation and hysteresis loss behaviors of IONPs when exposed to an alternating magnetic field (AMF), the composites demonstrate a magnetothermal response. Similarly, the excitation and relaxation of electrons in IONPs under near‐infrared light (NIR) enable photothermic‐responsiveness. In combination, two findings nurtured an observed shape‐memory effect when the samples are under actuation by these indirect stimuli, where a shape recovery ratio (≥98%) and reversible strain (≤7%) are recorded. Moreover, the catalytic role of IONPs aided transesterification in the covalent network, demonstrated by successful repeated cycles of shape reconfiguration of the samples. This work highlights the prospectives of multifunctional composite fillers in the exploration of bio‐derived composite smart materials.

Continuous-wave two-photon terahertz quantum cascade laser

We report on the implementation of a terahertz two-photon quantum cascade laser operating in a continuous wave mode. Lasers that can emit two photons as a result of the relaxation of a single electron between two states of the same parity have been discussed since the early days of the laser era, but implementation has been hampered by the lack of a suitable gain medium. The semiconductor structure of a quantum cascade laser seems to be an ideal medium for realizing such two-photon emission. Our work demonstrates dual-band laser radiation in the range of 3.1–3.9 THz (104–130 cm−1) at temperatures up to 90 K.

RPA dielectric functions: Streamlined approach to relaxation effects, binding and high momentum dispersion

The implementation of dielectric functions based on the Random Phase Approximation (RPA), including those by Lindhard, Kaneko, and Levine-Louie, is presented systematically, incorporating the effects of electron relaxation (finite width) and lattice interactions. A straightforward approach is proposed to introduce electron relaxation time and binding effects without needing Mermin corrections or Kramers–Kronig (KK) relations. This method yields the same dielectric function as the Mermin-corrected Lindhard and Kaneko models in several limiting cases (optical, high momentum transfer, and static limits). Moreover, this method adheres to the Bethe and F sum rule and the real and imaginary part are Kramers–Kronig pairs. Still, it shows some variation at intermediate energy and momentum transfer. Additionally, the description of dispersion at high momentum transfer is refined to account for relativistic effects. A small library containing the implementation of these dielectric functions is provided as supplementary material.

Time-resolved photoelectron spectroscopy at surfaces

Light is still an important spectroscopic tool for investigating the electronic structure of surfaces. Time-resolved photoelectron spectroscopy has mainly been developed in the last 30 years. It is therefore not surprising that the topic was hardly mentioned in the last issue on “The first thirty years” of surface science. In the second thirty years, however, we have seen tremendous progress in the development of time-resolved photoelectron spectroscopy on surfaces. Femtosecond light pulses and advanced photoelectron detection schemes are increasingly being used to study the electronic structure and dynamics of occupied and unoccupied electronic states and dynamic processes such as the energy and momentum relaxation of electrons, charge transfer at interfaces and collective processes such as plasmonic excitation and optical field screening. Using spin- and time-resolved photoelectron spectroscopy, we were able to study ultrafast spin dynamics, electron-magnon scattering and spin structures in magnetic and topological materials. Light also provides photon energy as well as electric and magnetic fields that can influence molecular surface processes to steer surface photochemistry and hot-electron-driven catalysis. In addition, we can consider light as a chemical reagent that can alter the properties of matter by creating non-equilibrium states and ultrafast phase transitions in correlated materials through the coupling of electrons, phonons and spins. Electric fields have also been used to temporarily change the electronic structure. This opened up new methods and areas such as high harmonic generation, light wave electronics and attosecond physics. This overview certainly cannot cover all these interesting topics. But also as a testimony to the cohesion and constructive exchange in our ultrafast community, a number of colleagues have come together to share their expertise and views on the very vital field of dynamics at surfaces. Following the introduction, the interested reader will find a list of contributions and a brief summary in Section 1.3.

Progress, application and prospect of rare earth-based perovskite light-emitting diodes

Perovskites recently become star materials in light-emitting diodes (LEDs) field due to their high color purity, tunable emission spectra, and cost-effectiveness. However, the commercial applications of perovskite LEDs are hampered by inferior lattice stability of perovskite materials. Successful modification of functional materials is a promising strategy towards efficient and stable perovskite LEDs. Rare earth (RE) metals are incorporated into the perovskite lattice, including double perovskites, by occupying the B-site or A-site in perovskite such as ABX3 or A2BB'X6, forming the RE-based perovskite. Doping with RE ions enables precise control emission color of materials across a broad spectrum ranging from ultraviolet to near infrared. Moreover, this strategy reduces the energy loss in electron relaxation process and enhances electroluminescence intensity of LED device, thereby improving the potential of commercial applications of perovskite LEDs. This review provides a comprehensive and systematic summarization of recent progress and challenges in RE-based perovskite materials (structure types, luminescence mechanism and synthesis methods) and LEDs (device structures and main applications) to provide some enlightening insights for realization of efficient and stable RE-based perovskite LEDs.

Radiation-Induced Paramagnetic Centers in Meso- and Macroporous Synthetic Opals from EPR and ENDOR Data

The paramagnetic defects and radiation-induced paramagnetic centers (PCs) in silica opals can play a crucial role in determining the magnetic and electronic behavior of materials and serve as local probes of their electronic structure. Systematic investigations of paramagnetic defects are essential for advancing both theoretical and practical aspects of material science. A series of silica opal samples with different geometrical parameters were synthesized and radiation-induced PCs were investigated by means of the conventional and pulsed X- and W-band electron paramagnetic resonance, and 1H/2H Mims electron-nuclear double resonance. Two groups of PCs were distinguished based on their spectroscopic parameters, electron relaxation characteristics, temperature and time stability, localization relative to the surface of silica spheres, and their origin. The obtained data demonstrate that stable radiation-induced E’ PCs can be used as sensitive probes for the hydrogen-containing fillers of the opal pores, for the development of compact radiation monitoring equipment, and for quantum technologies.

Enhanced near-field radiative heat transfer between borophene sheets on different substrates

Abstract Near-field radiative heat transfer (NFRHT) has the potential to exceed the blackbody limit by several orders of magnitude, offering significant opportunities for energy harvesting. In this study, we have examined the NFRHT between two borophene sheets through the calculation of heat transfer coefficient (HTC). Due to the tunneling of evanescent waves, borophene sheet allows for enhanced heat flux and adjustable NFRHT by varying its electron density and electron relaxation time. Additionally, the near field coupling is further examined when the borophene is deposited on dielectric or lossy substrates. The maximum HTC is closely related to the real part of the dielectric substrate. As a case study, the HTC on the lossy substrate of MoO3, ZnSe and SiC are calculated for comparison. Our results indicate that MoO3 is the optimal substrate to get the enhanced energy transfer coefficient. It results in a remarkable value of 1737 times higher than the blackbody limit owing to the enhanced photon tunneling probability. Thus, our study reveals the effect of substrate on the HTC between borophene sheets and provides a theoretical guidance for the design of near-field thermal radiation devices.

Dielectric behavior and defects of nitrogen-containing single crystal diamond films

Single crystal diamond (SCD) film, as a new substrate material, has attracted growing attention because of its low dielectric loss. The nitrogen was usually introduced into microwave plasma chemical vapor deposition (MPCVD) process in order to enhance the growth rate of SCD films. So SCD films with nitrogen were prepared by MPCVD compared with the undoped film. The impurities and defects of diamond films were characterized by Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and photoluminescence spectroscopy (PL). The dielectric behavior of SCD films was measured using the LCR measurement in the frequency range of 1 kHz to 110 MHz. The results indicate that the primary dielectric loss in SCD films is conductivity loss and space charge polarization below 1 MHz, while the main dielectric loss is dipole orientation polarization and electronic relaxation polarization in the frequency range of 1 MHz to 110 MHz. Point defects like substitutional N+, NV− and SiV− exert a significant influence on polarization loss. This is essential to improve the growth of SCD with excellent dielectric properties.

Slowing down the hot electron cooling to activate near-infrared photocatalytic activity in potassium/carbon co-doped polymeric carbon nitride

The research on hot electron cooling in photocatalysis has been neglected. Here, taking polymeric carbon nitride as an example, a potassium/carbon (K/C) co-doping strategy is proposed to slow down hot electron cooling. The K/C co-doping reduces the specific arrangement and overlap of electronic band structures, and decreases the degeneracy of conduction band energy levels, thus exciting phonon bottleneck effect to effectively suppress the relaxation of hot electrons by reducing the interaction between hot electrons and phonons. Our work benefits to improve the efficiency of photocatalytic energy conversion.

Metasurface Absorber for Blood Hemoglobin Concentration.

In this study, a biosensing scenario is developed for monitoring blood quality based on the detection of blood hemoglobin concentration. The procedure involves considering the blood sample as the dielectric with different refractive indexes for different concentrations of hemoglobin. Usually, the sensitivity to design parameters is the major issue with the metasurface-based detection. To address this issue, a three-layer graphene-based wave absorber is designed and modeled using passive circuit elements. The major idea behind this work is to maximize the device sensitivity against the blood sample. The research methodology involves impedance matching between the device and the surrounding environment, while full-wave simulation is also performed and compared to ensure circuit view accuracy. The findings suggest that the proposed graphene-based absorber can efficiently monitor blood quality via dual absorption peaks. The simulation results extracted from impedance matching and the full-wave method indicate frequency shifts of the second absorption peak. These shift values are interpreted based on hemoglobin concentration. Additionally, ample analyses are provided to show the reliability of the proposed absorber against geometrical aspects, incident angle, external stimulation, and the graphene electron relaxation time.

Modulating intramolecular charge transfer via π-d conjugative effect in coordination polymers toward photo-thermo-electric conversion

The prospect of harnessing sunlight to generate cost-effective heat and electricity presents a captivating opportunity to address water scarcity and electricity shortages. Photothermal materials with a broad absorption spectrum are indispensable for effectively harnessing solar energy and converting it into heat/electricity. Herein, we developed an intramolecular charge transfer strategy via conjugated effect to regulate solar absorption and photothermal conversion ability of M-DABDT (M = Fe/Co/Ni/Cu/Zn, DABDT = 2,5-diaminobenzene-1,4-dithiol), overcoming a common limitation of narrow absorption and low photothermal efficiency in traditional metal-organic assemblies. The density functional theory calculations reveal that altering transition metal ions induces the structural torsion of organic linkers, resulting in a significant change in dihedral angle from 89.96° to 2.57°. The structural change significantly facilitates the charge transfer and electron relaxation, ultimately promoting the conversion of light to heat. Under one sun irradiation, the maximum temperature of Fe-DABDT can reach approximately 92.5 ℃. More significantly, the integration of M-DABDT CPs and thermoelectric devices under normal solar irradiation results in an extraordinary open circuit voltage (238 mV) and maximum power density (364.5 μW m−2), processing a peak output voltage density of 76.9 V m−2 at 11:00 a.m. in the presence of outdoor sunlight. This strategy presents an avenue for developing metal-organic solar absorbers for photo-thermo-electric conversion systems.

Internal Conversion Cascade in a Carbon Nanobelt: A Multiconfigurational Quantum Dynamical Study.

Carbon nanobelts feature intriguing photophysical properties, due to their high symmetry and structural rigidity. Here, we consider a (6,6) armchair carbon nanobelt, i.e., the very first carbon nanobelt to be synthesized [Povie et al., Science 2017, 356, 172] and characterize the internal conversion dynamics using multiconfigurational quantum dynamics via the multi-layer multiconfiguration time-dependent Hartree (ML-MCTDH) method. A symmetry-adapted linear vibronic coupling Hamiltonian for 26 electronic states and 210 vibrational modes is employed. Electronic excitations are found to decay through a dense manifold of excited states, which interact via multiple conical intersections, while inducing minimal geometry change. It is shown that a rapid coherent decay, exhibiting a nonvanishing quantum flux on a time scale of less than 50 fs, transitions toward a slower, decoherent decay at longer times. As previously suggested in the literature, electronic relaxation is hindered by phonon bottlenecks such that a stepwise internal conversion cascade is observed. The computed vibronic absorption spectrum is shown to be in good agreement with the experimental spectrum.

Light funneling into localized acoustic graphene plasmons for extreme infrared and terahertz field enhancement and confinement

Enhancing light-matter interaction through deep subwavelength-scale confinement is crucial for numerous applications like molecular sensing, optoelectronic devices, and non-linear optics. Here, we report the excitation of localized acoustic graphene plasmons (LAGPs) confined in a sub-micro- wide, nanometer-thick layer using a metal slit antenna. This approach enables light funneling in the infrared and terahertz regimes, leading to strong field enhancement and confinement. LAGPs exhibit broad-band excitation characteristics, with the number of excited modes adjustable via the symmetry of the relative positioning between graphene and the metal slit. Detailed analysis indicates that the local field intensities of LAGPs are critically influenced by both the periodicity of the device structure and the electron relaxation time of graphene. These findings are effectively elucidated using temporal coupled mode theory. In comparison to conventional non-localized acoustic graphene plasmons, LAGPs demonstrate significantly improved field confinement and enhancement attributed to the funneling effect. Our study presents a promising avenue for achieving robust light-matter interaction and holds potential for various applications in the infrared and terahertz domains.

Unraveling the electronic properties in SiO2 under ultrafast laser irradiation

First-principles simulations were conducted to explore various electronic properties of crystalline SiO2 (α-quartz) under ultrafast laser irradiation. Employing Density Functional Perturbation Theory and the many-body (GW) approximation, we calculated the impact of thermally excited electrons on the electronic specific heat, electron pressure, effective mass, deformation potential, electron-phonon coupling and electron relaxation time of quartz, covering a wide range of electron temperatures, up to 100,000 K. We show that the electron-phonon relaxation time of highly-excited quartz becomes twice faster compared to low-excited states. The deformation potential, which dictates atomic displacement, has a non-monotonic behavior with a well-pronounced minimum at around 16,000 K (2.7 × 1021 cm−3 of excited electrons) where the bond ionicity of the Si-O starts decreasing followed by a cohesion loss at 35,000 K due to the pressure exerted by the excited electrons on the lattice. Consequently, our calculated data, illustrating the evolution of physical parameters, can facilitate simulations of laser-matter interactions and provide predictive insights into the behavior of quartz under experimental conditions.

Influence of Aliphatic versus Aromatic Ligand Passivation on Intersystem Crossing in Au25(SR)18.

The electronic relaxation dynamics of gold monolayer protected clusters (MPCs) are influenced by the hydrocarbon structure of thiolate protecting ligands. Here, we present ligand-dependent electronic relaxation for a series of Au25(SR)18- (SR = SC8H9, SC6H13, SC12H25) MPCs using femtosecond time-resolved transient absorption spectroscopy. Relaxation pathways included a ligand-independent femtosecond internal conversion and a competing ligand-dependent picosecond intersystem crossing process. Intersystem crossing was accelerated for the aliphatic (SC6H13, SC12H25) thiolate MPCs compared to the aromatic (SC8H9) thiolate MPCs. Additionally, a 1.2 THz quadrupolar acoustic mode and a 2.4 THz breathing acoustic mode was identified in each cluster, which indicated that differences in ligand structure did not result in significant structural changes to the metal core of the MPCs. Considering that the difference in relaxation rates did not result from ligand-induced core deformation, the accelerated intersystem crossing was attributed to greater electron-vibrational coupling to Au-S vibrational modes. The results suggested that the organometallic semiring was less rigid for the aliphatic thiolate MPCs due to reduced steric effects, and in turn, increases in nonradiative decay rates were observed. Overall, these results imply that the protecting ligand structure can be used to modify carrier relaxation in MPCs.

Effect of high-temperature annealing on terahertz optoelectronic properties of nitrogen-doped polycrystalline diamond

Nitrogen-doped polycrystalline diamond (N-PCD) is one of the most important carbon-based electronic materials. Here we present a systmatic investigation of the effect of high-temperature annealing (HTA) on basic physical properties of N-PCD wafer grown by microwave plasma-enhanced chemical vapor deposition (MPECVD). The metallographic and optical microscopes, X-ray diffraction,Raman spectroscopy and X-ray photoelectron spectroscopy are applied for the characterization of N-PCD before and after HTA. Particularly, we study the optoelectrnic properties of N-PCD before and after HTA by using terahertz (THz) time-domain spectroscopy. THz transmittance, dynamical and static dielectric constants and optical conductivity for N-PCD are measured. For N-PCD before HTA, we can observe a THz absorption peak induced by weak H-bonds in N-PCD, which was predicted theoretically in 1999. For N-PCD after HTA, we find that the corresponding optical conductivity can be rightly descriped by the Drude-Lorentz formula. Thus, via fitting the experimental results with the theoretical formula, we can determine optically the key electronic parameters of N-PCD after HTA, such as the electron density, the electronic relaxation time and the Lorentz frequency. The temperature dependence of these parameters is examined in the range of 80–300 K. This work demondtrates that HTA is a practical and efficient way in improving the electronic and optoelectronic properties of N-PCD. The results obtained from this research can benefit an in-depth understanding of the effect of HTA on physical properties of N-PCD from a viewpoint of semiconductor physics.