Optical Excitation Research Articles

Appearance of spectral dip in the cathodoluminescence spectrum of negatively charged nitrogen-vacancy centers in diamonds

Negatively charged nitrogen-vacancy (NV−) centers in diamond produce a characteristic optical zero-phonon line (ZPL) at 637 nm. This emission line can be observed under optical excitation (i.e. photoluminescence), but is rarely observed under electron excitation (i.e. cathodoluminescence). This study reports that low-temperature (80 K) and low energy (5 keV) cathodoluminescence spectroscopy is able to detect emission peak or spectral dip at the ZPL of NV− centers. The spectral dip was observed in the diamond samples with high concentration of NV− centers produced by high-energy (2 MeV) e-beam (EB) irradiation. The effects of EB irradiation fluence, NV− centers concentration and substitutional nitrogen concentration on the formation of spectral dip were discussed, and a model based on the NV− absorption of NV0 emission sideband is proposed.

(Invited) Optical Excitations and Growth in Layered Organic Metal Halide Semiconductors

Hybrid organic metal halides, such as CH3NH3PbI3, have garnered attention because they are earth-abundant, solution-processable materials that can be used to form solar cells with high power conversion efficiency (>20%). There are significant questions about the unusual electronic properties of this class of materials because of the coupling between excitations and the lattice. We will present our work investigating the optoelectronic properties of layered organic metal halide systems and the relationship to structure and growth conditions. We will discuss the nature of optical excitations in layered compounds of the class R2PbX4 where R is an organic cation and X is a halide. These systems show signatures of unusually strong optical frequency magnetic dipole transitions that can be understood through self-trapped exciton formation. We will then discuss how mechanical strain during growth influences broad photoluminescence in a model layered system based on the large cation ethylammonium (EA) with the structure (EA)2(EA)n-1PbnBr3n+1. In this system the emission is strongly impacted by growth-induced strain in thin films quantified using X-ray scattering. Our results suggest that broad emission, relevant for LEDs, can be tuned in thin films. Recent work on how growth impacts the behavior of low dimensional system will also be presented.

(Invited) Resonant Exciton Transfer in Mixed-Dimensional Heterostructures for Overcoming Dimensional Restrictions in Optical Processes

Nanomaterials exhibit unique optical phenomena, in particular excitonic quantum processes occurring at room temperature. The low dimensionality, however, imposes strict requirements for conventional optical excitation, and an approach for bypassing such restrictions is desirable. Here we report on exciton transfer in carbon-nanotube/tungsten-diselenide heterostructures, where band alignment can be systematically varied. The mixed-dimensional heterostructures display a pronounced exciton reservoir effect where the longer-lifetime excitons within the two-dimensional semiconductor are funneled into carbon nanotubes through diffusion. This new excitation pathway presents several advantages, including larger absorption areas, broadband spectral response, and polarization-independent efficiency. When band alignment is resonant, we observe substantially more efficient excitation via tungsten diselenide compared to direct excitation of the nanotube. We further demonstrate simultaneous bright emission from an array of carbon nanotubes with varied chiralities and orientations. Our findings show the potential of mixed-dimensional heterostructures and band alignment engineering for energy harvesting and quantum applications through exciton manipulation.Parts of this study are supported by JSPS (KAKENHI JP22K14624, JP22K14625, JP21K14484, JP22F22350, JP22K14623, JP21H05233, JP23H00262, JP20H02558) and MEXT (ARIM JPMXP1222UT1135). Y.R.C. is supported by JSPS (International Research Fellow). N.F. and C.F.F. are supported by RIKEN Special Postdoctoral Researcher Program. We thank the Advanced Manufacturing Support Team at RIKEN for technical assistance.[1] N. Fang, D. Yamashita, S. Fujii, M. Maruyama, Y. Gao, Y. R. Chang, C. F. Fong, K. Otsuka, K. Nagashio, S. Okada, Y. K. Kato, "Resonant exciton transfer in mixed-dimensional heterostructures for overcoming dimensional restrictions in optical processes," Nature Commun., accepted (2023). Preprint at arXiv:2307.07124.

Spin Alignment of NV− Centers in 4H- and 6H-SiC Crystals Induced by IR and Visible Optical Excitation

Spin Alignment of NV− Centers in 4H- and 6H-SiC Crystals Induced by IR and Visible Optical Excitation

Tailoring of the polarization-resolved second harmonic generation in two-dimensional semiconductors

Abstract Second harmonic generation is a non-linear optical phenomenon in which coherent radiation with frequency ω interacts with a non-centrosymmetric material and produces coherent radiation at frequency 2ω. Owing to the exciting physical phenomena that take place during the non-linear optical excitation at the nanoscale, there is currently extensive research in the non-linear optical responses of nanomaterials, particularly in low-dimensional materials. Here, we review recent advancements in the polarization-resolved second harmonic generation propertied from atomically thin two-dimensional (2D) crystals and present a unified theoretical framework to account for their nonlinear optical response. Two major classes of 2D materials are particularly investigated, namely metal chalcogenides and perovskites. The first attempts to tune and control the second harmonic generation properties of such materials via the application of specific nanophotonic schemes are additionally demonstrated and discussed. Besides presenting recent advances in the field, this work also delineates existing limitations and highlights emerging possibilities and future prospects in this field.

Long-Range Self-Hybridized Exciton-Polaritons in Two-Dimensional Ruddlesden-Popper Perovskites.

Lead halide perovskites have emerged as platforms for exciton-polaritonic studies at room temperature, thanks to their excellent photoluminescence efficiency and synthetic versatility. In this work, we find proof of strong exciton-photon coupling in cavities formed by the layered crystals themselves, a phenomenon known as the self-hybridization effect. We use multilayers of high-quality Ruddlesden-Popper perovskites in their 2D crystalline form, benefiting from their quantum-well excitonic resonances and the strong Fabry-Pérot cavity modes resulting from the total internal reflection at their smooth surfaces. Optical spectroscopy reveals bending of the cavity modes typical for exciton-polariton formation, and absorption and photoluminescence spectroscopy shows splitting of the excitonic resonance and thickness-dependent peak positions. Strikingly, local optical excitation with energy below the excitonic resonance of the flakes in photoluminescence measurements unveils the coupling of light to in-plane polaritonic modes with directed propagation. These exciton-polaritons exhibit high coupling efficiencies and extremely low loss propagation mechanisms, which are confirmed by finite difference time domain simulations. Thus, we prove that mesoscopic 2D Ruddlesden-Popper perovskite flakes represent an effective but simple system to study the rich physics of exciton-polaritons at room temperature.

Designable exciton mixing through layer alignment in WS2-graphene heterostructures

Optical properties of heterostructures composed of layered 2D materials, such as transition metal dichalcogenides (TMDs) and graphene, are broadly explored. Of particular interest are light-induced energy transfer mechanisms in these materials and their structural roots. Here, we use state-of-the-art first-principles calculations to study the excitonic composition and the absorption properties of WS2–graphene heterostructures as a function of interlayer alignment and the local strain resulting from it. We find that Brillouin zone mismatch and the associated energy level alignment between the graphene Dirac cone and the TMD bands dictate an interplay between interlayer and intralayer excitons, mixing together in the many-body representation upon the strain-induced symmetry breaking in the interacting layers. Examining the representative cases of the 0° and 30° interlayer twist angles, we find that this exciton mixing strongly varies as a function of the relative alignment. We quantify the effect of these structural modifications on exciton charge separation between the layers and the associated graphene-induced homogeneous broadening of the absorption resonances. Our findings provide guidelines for controllable optical excitations upon interface design and shed light on the importance of many-body effects in the understanding of optical phenomena in complex heterostructures.

Magnetization Switching of Single Magnetite Nanoparticles Monitored Optically.

Magnetic nanomaterials record information as fast as picoseconds in computer memories but retain it for millions of years in ancient rocks. This exceedingly broad range of times is covered by hopping over a potential energy barrier through temperature, ultrafast optical excitation, mechanical stress, or microwaves. As switching depends on nanoparticle size, shape, orientation, and material properties, only single-nanoparticle studies can eliminate the ensemble heterogeneity. Here, we push the sensitivity of photothermal magnetic circular dichroism down to individual 20 nm magnetite nanoparticles. Single-particle magnetization curves display superparamagnetic to ferromagnetic behaviors, depending on the size, shape, and orientation. Some nanoparticles undergo thermally activated switching on time scales of milliseconds to minutes. Surprisingly, the switching barrier varies with time, leading to dynamical heterogeneity, a phenomenon familiar in protein dynamics and supercooled liquids. Our observations will help to identify the external parameters influencing magnetization switching and, eventually, to control it, an important step for many applications.

Influence of atomistic features in plasmon-exciton coupling and charge transfer driven by a single molecule in a metallic nanocavity.

When an organic molecule is placed inside a plasmonic cavity formed by two metallic nanoparticles (MNP) under illumination, the electronic excitations of the molecule couple to the plasmonic electromagnetic modes of the cavity, inducing new hybrid light-matter states called polaritons. Atomistic abinitio methods accurately describe the coupling between MNPs and molecules at the nanometer scale and allow us to analyze how atomistic features influence the interaction. In this work, we study the optical response of a porphine molecule coupled to a silver nanoparticle dimer from first principles, within the linear-response time-dependent density functional theory framework, using the recently developed Python Numeric Atomic Orbitals implementation to compute the optical excitations. The optical spectra show the splitting of the resonances of the plasmonic dimer and the molecule into two distinct polaritons, a characteristic feature of the strong light-matter coupling regime. Our results stress the importance of atomistic features, such as the gap configuration in determining the plasmon-exciton coupling strength and in the emergence of molecule-mediated charge-transfer plasmon (CTP) resonances at lower frequencies. Moreover, we show that the strength of the CTP resonance can be tuned by shifting the alignment of the molecular energy levels with respect to the Fermi level of the MNPs.

Emission dynamics of optically driven aluminum nitride quantum emitters

Aluminum nitride is a technologically important wide band-gap semiconductor which has been shown to host bright quantum emitters. We use photon emission correlation spectroscopy (PECS), time-resolved photoluminescence (TRPL), and state-population dynamic simulations to probe the dynamics of emission under continuous wave (CW) and pulsed optical excitation. We infer that there are at least four dark shelving states, which govern the TRPL, bunching, and saturation of the optical transition. We study in detail the emission dynamics of two quantum emitters (QEs) with differing power-dependent shelving processes, hypothesized to result from charge ionization and recombination. These results demonstrate that photon bunching caused by shelving the system in a dark state inherently limits the saturation rate of the photon source. In emitters where increasing optical power deshelves the dark states, we observe an increased photon emission intensity. Published by the American Physical Society 2024

Impacts of electric gating and divacancies on optical absorption spectra of zigzag buckling silicene nanoribbons

In this study, by combining the tight-binding description with the gradient approximation, we investigated the impacts of electric gating and divacancies on the optical characteristics of zigzag buckling silicene nanoribbons. Our results show that the back-gate electric potential tends to shift the peak structure to higher frequencies in the free-defective structures, while the side-gate electric potentials intensify the intensity of the excitation channels obeying the selection rule ΔJ=even. In particular, applying the potentials in a suitable range can improve the optical absorption efficiency at a certain frequency with the back gate or widen the threshold absorption intensity from Jv=1 to Jc=1 with the side gates. Besides, the defective structures' absorption spectra exhibit richer features than the perfect one, with the appearance of new optical excitations due to the transitions between the local minimum or maximum in the low-energy bands around the Fermi level. Moreover, applying electric gating in defective structures can also tune the absorption spectra with additional features.

Flexible plasmonic display featuring differentiated and localized control over transmission and reflection

Structural colors using metal materials, plasmonic color generation, can confine optical excitation beyond the diffraction limit owing to nanoscale metals with high efficiency in light absorption and scattering. They have several advantages over conventional display technology, including superior resolution and long-term preservation. However, most research on plasmonic color generation has been conducted for the development of static color generation, and dynamic tuning remains a challenging issue. To develop dynamic plasmonic colors, electrochemical, liquid crystal, and electromechanical methods have been proposed; however, there have been limitations in repeatability, flexibility, and scale-up processes. To address these problems, this work proposes a flexible dynamic plasmonic display using dielectric elastomer actuators (DEAs) to isotropically control the interdistance between the metal nanostructures, which can show dynamic coloration without polarization distortion. To replace the expensive and small-scale manufacturing approach, shadow masking and transfer technique with the anodic aluminum oxide (AAO) membrane was applied to realize large-scale and uniformly distributed Au nanodisc array. The differentiated and localized color change in the transmission and reflection modes, such as Janus's face, is realized by proper design of Au nanodisc array on the patterned transparent compliant electrodes formed by silver nanowires and PEDOT:PSS composites. Apparent and locally active color changes appeared in the transmission mode, but almost no color changes were observed in the reflection model by DEA actuation. The proposed system has the potential to activate color filters, cryptographic characters, and next generation display technologies.

A near-resonant excitation strategy to achieve ultra-low threshold GaN polariton lasing.

A near-resonant excitation strategy is proposed and implemented in a 4-µm-thick GaN microcavity to realize an exciton-polariton condensate/lasing with low threshold. Strong exciton-photon coupling is demonstrated, and polariton lasing is realized with an ultra-low threshold excitation power density of about 13.3 W/cm2 at room temperature. Such an ultra-low threshold is ascribed to the implementation of the near-resonant optical excitation strategy, which enables acceleration of the exciton and polariton relaxation and suppression of the heat generation in the cavity, thereby reducing the energy loss and enhance the cavity excitation efficiency.

The energy transfer of electronic excitations to impurities in dosimetric phosphors [formula omitted]-Dy

The formation of new radiative states from the combination of Dy2+-SO4- and SO43--SO4- electron trapping centers in the range of 2.95–3.1 eV has been investigated using VUV and thermal activation spectroscopy. During the excitation process, there is a charge transfer between the oxygen ion of the sulfate anion and Dy3+ leading to the formation of a combined emissive state SO43-→SO4-. These states can be formed from the electron-hole trapping centers of Dy2+-SO4- and SO43--SO4-. The combined radiative state at 2.95–3.1 eV and impurity emission at 2.16 eV and 2.56 eV are excited simultaneously by photons of 3.95 eV and 4.5 eV, respectively. During the thermal or optical excitation process, the Dy2+ and SO43- electronic centers are ionized. Electrons recombine with a hole trapped by the ground state of the impurity (SO4--Dy3+), and the released energy is transferred to the Dy3+ impurities.

Nature of Excitons and Their Ligand-Mediated Delocalization in Nickel Dihalide Charge-Transfer Insulators

The fundamental optical excitations of correlated transition-metal compounds are typically identified with multielectronic transitions localized at the transition-metal site, such as dd transitions. In this vein, intense interest has surrounded the appearance of sharp, below-band-gap optical transitions, i.e., excitons, within the magnetic phase of correlated Ni2+ van der Waals magnets. The interplay of magnetic and charge-transfer insulating ground states in Ni2+ systems raises intriguing questions on the roles of long-range magnetic order and of metal-ligand charge transfer in the exciton nature, which inspired microscopic descriptions beyond typical dd excitations. Here we study the impact of charge transfer and magnetic order on the excitation spectrum of the nickel dihalides (NiX2, X=Cl, Br, and I) using Ni-L3 edge resonant inelastic x-ray scattering (RIXS). In all compounds, we detect sharp excitations, analogous to the recently reported excitons, and assign them to spin-singlet multiplets of octahedrally coordinated Ni2+ stabilized by intra-atomic Hund’s exchange. Additionally, we demonstrate that these excitons are dispersive using momentum-resolved RIXS. Our data evidence a ligand-mediated multiplet dispersion, which is tuned by the charge-transfer gap and independent of the presence of long-range magnetic order. This reveals the mechanisms governing nonlocal interactions of on-site dd excitations with the surrounding crystal or magnetic structure, in analogy to ground-state superexchange. These measurements thus establish the roles of magnetic order, self-doped ligand holes, and intersite-coupling mechanisms for the properties of dd excitations in charge-transfer insulators. Published by the American Physical Society 2024

Sub-bandgap Photocurrent Spectra of p-i-n Perovskite Solar Cells with n-Doped Fullerene Electron Transport Layers and Bias Illumination.

In p-i-n perovskite solar cells optical excitation of defect states at the interface between the perovskite and fullerene electron transport layer (ETL) creates a photocurrent responsible for a distinct sub-bandgap external quantum efficiency (EQE). The precise nature of these signals and their impact on cell performance are largely unknown. Here, the effect of n-doping the fullerene on the EQE spectra is studied. The n-doped fullerene is either deposited from solution or by coevaporation. The latter method is used to create undoped-doped fullerene bilayers and investigate the effect of the proximity of the doped region on the EQE spectra. The intensity of the sub-bandgap EQE increases when the ETL is n-doped and also when the device is biased with green light. Using these results, the sub-bandgap EQE signal is attributed to originate from electron trap states in the perovskite with an energy below the conduction band that are filled by excitation with low-energy photons. The trapped electrons give rise to photocurrent when they are collected at a nearby electrode. The enhanced sub-bandgap EQE observed when the ETL is n-doped or bias light is applied, is related to a higher probability to extract trapped electrons under these conditions.

Interaction of Hermite–Gaussian Beams with a Macroscopic Atomic Target

AbstractA theoretical analysis is presented on the photoexcitation of a macroscopic atomic target by a Hermite–Gaussian (HG) beam within the framework of density matrix theory. Special emphasis is paid to the influence of the incoming HG mode on the population of an excited state and the emitted fluorescence radiation. In particular, a general expression for the alignment parameter of the excited state is derived, which depends on the beam parameters of the HG mode. Although the developed theory can be applied to any atomic system, here the electric dipole transition in neutral sodium atoms is investigated when driven by three , and modes. For this optical (valence‐shell) excitation, it is demonstrated that the population of the excited state is sensitive to the beam waist and the mode index of the HG beam. Furthermore, the influence of beam parameters on the angular distribution and linear polarization of the emitted fluorescence radiation is discussed.

Optical Control of Adaptive Nanoscale Domain Networks.

Adaptive networks can sense and adjust to dynamic environments to optimize their performance. Understanding their nanoscale responses to external stimuli is essential for applications in nanodevices and neuromorphic computing. However, it is challenging to image such responses on the nanoscale with crystallographic sensitivity. Here, the evolution of nanodomain networks in (PbTiO3)n/(SrTiO3)n superlattices (SLs) is directly visualized in real space as the system adapts to ultrafast repetitive optical excitations that emulate controlled neural inputs. The adaptive response allows the system to explore a wealth of metastable states that are previously inaccessible. Their reconfiguration and competition are quantitatively measured by scanning x-ray nanodiffraction as a function of the number of applied pulses, in which crystallographic characteristics are quantitatively assessed by assorted diffraction patterns using unsupervised machine-learning methods. The corresponding domain boundaries and their connectivity are drastically altered by light, holding promise for light-programable nanocircuits in analogy to neuroplasticity. Phase-field simulations elucidate that the reconfiguration of the domain networks is a result of the interplay between photocarriers and transient lattice temperature. The demonstrated optical control scheme and the uncovered nanoscopic insights open opportunities for the remote control of adaptive nanoscale domain networks.

Photoinduced Charge Injection from Shallow Point Defects in Diamond into Water.

Thanks to its low or negative surface electron affinity and chemical inertness, diamond is attracting broad attention as a source material of solvated electrons produced by optical excitation of the solid-liquid interface. Unfortunately, its wide bandgap typically imposes the use of wavelengths in the ultraviolet range, hence complicating practical applications. Here, we probe the photocurrent response of water surrounded by single-crystal diamond surfaces engineered to host shallow nitrogen-vacancy (NV) centers. We observe clear signatures of diamond-induced photocurrent generation throughout the visible range and for wavelengths reaching up to 594 nm. Experiments as a function of laser power suggest that NV centers and other coexisting defects─likely in the form of surface traps─contribute to carrier injection, though we find that NVs dominate the system response in the limit of high illumination intensities. Given our growing understanding of near-surface NV centers and adjacent point defects, these results open new perspectives in the application of diamond-liquid interfaces to photocarrier-initiated chemical and spin processes in fluids.

Electroluminescence from pure resonant states in hBN-based vertical tunneling junctions

Defect centers in wide-band-gap crystals have garnered interest for their potential in applications among optoelectronic and sensor technologies. However, defects embedded in highly insulating crystals, like diamond, silicon carbide, or aluminum oxide, have been notoriously difficult to excite electrically due to their large internal resistance. To address this challenge, we realized a new paradigm of exciting defects in vertical tunneling junctions based on carbon centers in hexagonal boron nitride (hBN). The rational design of the devices via van der Waals technology enabled us to raise and control optical processes related to defect-to-band and intradefect electroluminescence. The fundamental understanding of the tunneling events was based on the transfer of the electronic wave function amplitude between resonant defect states in hBN to the metallic state in graphene, which leads to dramatic changes in the characteristics of electrons due to different band structures of constituent materials. In our devices, the decay of electrons via tunneling pathways competed with radiative recombination, resulting in an unprecedented degree of tuneability of carrier dynamics due to the significant sensitivity of the characteristic tunneling times on the thickness and structure of the barrier. This enabled us to achieve a high-efficiency electrical excitation of intradefect transitions, exceeding by several orders of magnitude the efficiency of optical excitation in the sub-band-gap regime. This work represents a significant advancement towards a universal and scalable platform for electrically driven devices utilizing defect centers in wide-band-gap crystals with properties modulated via activation of different tunneling mechanisms at a level of device engineering.