Excitonic Edge Research Articles

Electron Dynamics at the Surface of Semiconductor Nanocrystals

Semiconductor nanocrystals emit light from excitons confined to their core, as well as from their surfaces. Time-resolving the emission from the core yields information on the band edge exciton, which is now well understood. In contrast, the emission from the surface is ill-characterized and remains poorly understood, especially on long time scales. In order to understand the kinetics of charge trapping to the surface and electronic relaxation within the surface, we perform time-resolved emission spectroscopy on CdSe nanocrystals with strong surface emission. The time-resolved spectra reveal a time scale of electron transfer from core to surface much slower than previously thought. These spectra also unveil electron dynamics in the surface band, which gives rise to an average lifetime spectrum. These dynamics are explained by invoking two surface states. This simple model further rationalizes the role of ligands in tuning the surface emission of nanocrystals. These experimental results provide a critical ...

Chiral topological excitons in a Chern band insulator

A family of semiconductors called as Chern band insulator are shown to host exciton bands with non-zero topological Chern integers and chiral exciton edge modes. Using a prototypical two-band Chern insulator model, we calculate a cross-correlation function to obtain the exciton bands and their Chern integers. The lowest exciton band acquires Chern integers such as $\pm 1$ and $\pm 2$ in electronic Chern insulator phase. The non-trivial topology can be experimentally observed both by non-local optoelectronic response of exciton edge modes and by a phase shift in the cross-correlation response due to the bulk mode. Our result suggests that magnetically doped HgTe, InAs/GaSb quantum wells and $\text{(Bi,Sb)}_{2} \text{Te}_{3}$ thin film are promising candidates for a platform of topological excitonics.

Large array fabrication of high performance monolayer MoS2 photodetectors

Large array fabrication of high quality photodetectors derived from synthetically grown monolayer transition metal dichalcogenides is highly desired and important for a wide range of nanophotonic applications. We present here large array fabrication of monolayer MoS2 photodetectors on sapphire substrates through an efficient process, which includes growing large scale monolayer MoS2 via chemical vapor deposition (CVD) and multi-step optical lithography for device patterning and high quality metal electrode fabrication. In every measured device, we observed the following universal features: (i) negligible dark current (Idark≤10 fA), (ii) sharp peaks in photocurrent at ∼1.9 eV and ∼2.1 eV attributable to the optical transitions due to band edge excitons, and (iii) a rapid onset of photocurrent above ∼2.5 eV peaked at ∼2.9 eV due to an excitonic absorption originating from the van Hove singularity of MoS2. We observe a low (≤300%) device-to-device variation of photoresponsivity. Furthermore, we observe a very fast DC time response of ∼0.5 ms, which is two orders of magnitude faster than other reported CVD grown 1L-MoS2 based photodetectors. The combination of large-array device fabrication, high sensitivity, and high speed offers great potential for applications in photonics.

Long valley relaxation time of free carriers in monolayer WSe2

Monolayer transition metal dichalcogenides (TMDs) feature a valley degree of freedom, giant spin-orbit coupling, and spin-valley locking. These exotic natures have stimulated efforts of exploring potential applications in conceptual spintronics, valleytronics, and quantum computing. Among all the exotic directions, a long relaxation time of spin and/or valley polarization is critical. The present valley dynamics studies concentrate on the band edge excitons which predominate the optical response due to an enhanced Coulomb interaction in two dimensions. The valley relaxation time of free carriers remains ambiguous. In this Rapid Communication, we use time-resolved Kerr rotation spectroscopy to probe the valley dynamics of excitons and free carriers in monolayer tungsten diselenide. The valley relaxation time of free carriers is found around 2 ns at 70 K, about three orders of magnitude longer than the excitons of about 2 ps, and 15 times larger than that of trions (130 ps). The extended valley relaxation time of free carriers evidences that an exchange interaction dominates the valley relaxation in optical excitations. The pump-probe spectroscopy also reveals an exciton binding energy of 0.60 eV in monolayer ${\mathrm{WSe}}_{2}$.

Giant Enhancement of Defect-Bound Exciton Luminescence and Suppression of Band-Edge Luminescence in Monolayer WSe2-Ag Plasmonic Hybrid Structures.

We have investigated how the photoluminescence (PL) of WSe2 is modified when coupled to Ag plasmonic structures at low temperature. Chemical vapor deposition (CVD) grown monolayer WSe2 flakes were transferred onto a Ag film and a Ag nanotriangle array that had a 1.5 nm Al2O3 capping layer. Using low-temperature (7.5 K) micro-PL mapping, we simultaneously observed enhancement of the defect-bound exciton emission and quenching of the band edge exciton emission when the WSe2 was on a plasmonic structure. The enhancement of the defect-bound exciton emission was significant with enhancement factors of up to ∼200 for WSe2 on the nanotriangle array when compared to WSe2 on a 1.5 nm Al2O3 capped Si substrate with a 300 nm SiO2 layer. The giant enhancement of the luminescence from the defect-bound excitons is understood in terms of the Purcell effect and increased light absorption. In contrast, the surprising result of luminescence quenching of the bright exciton state on the same plasmonic nanostructure is due to a rather unique electronic structure of WSe2: the existence of a dark state below the bright exciton state.

Topological Exciton Bands in Moiré Heterojunctions.

Moiré patterns are common in van der Waals heterostructures and can be used to apply periodic potentials to elementary excitations. We show that the optical absorption spectrum of transition metal dichalcogenide bilayers is profoundly altered by long period moiré patterns that introduce twist-angle dependent satellite excitonic peaks. Topological exciton bands with nonzero Chern numbers that support chiral excitonic edge states can be engineered by combining three ingredients: (i)the valley Berry phase induced by electron-hole exchange interactions, (ii)the moiré potential, and (iii)the valley Zeeman field.

Chiral magnetic conductivity and surface states of Weyl semimetals in topological insulator ultra-thin film multilayer

We investigate an ultra-thin film of topological insulator (TI) multilayer as a model for a three-dimensional (3D) Weyl semimetal. We introduce tunneling parameters tS, , and tD, where the former two parameters couple layers of the same thin film at small and large momenta, and the latter parameter couples neighbouring thin film layers along the z-direction. The Chern number is computed in each topological phase of the system and we find that for , the tunneling parameter changes from positive to negative as the system transits from Weyl semi-metallic phase to insulating phases. We further study the chiral magnetic effect (CME) of the system in the presence of a time dependent magnetic field. We compute the low-temperature dependence of the chiral magnetic conductivity and show that it captures three distinct phases of the system separated by plateaus. Furthermore, we propose and study a 3D lattice model of Porphyrin thin film, an organic material known to support topological Frenkel exciton edge states. We show that this model exhibits a 3D Weyl semi-metallic phase and also supports a 2D Weyl semi-metallic phase. We further show that this model recovers that of 3D Weyl semimetal in topological insulator thin film multilayer. Thus, paving the way for simulating a 3D Weyl semimetal in topological insulator thin film multilayer. We obtain the surface states (Fermi arcs) in the 3D model and the chiral edge states in the 2D model and analyze their topological properties.

Edge excitons in a 2D topological insulator in a magnetic field

Exciton edge states and the microwave edge exciton absorption of a 2D topological insulator subject to the in-plane magnetic field are studied. The magnetic field forms a narrow gap in electron edge states that allows the existence of edge exciton. The exciton binding energy is found to be much smaller than the energy of a 1D Coulomb state. Phototransitions exist on the exciton states with even numbers, while odd exciton states are dark.

Optical properties of one- and two-dimensional excitons in m-plane ZnO/MgZnO multiple quantum wells

Five pairs of ZnO/Zn0.9Mg0.1O multiple quantum wells (MQWs) with fixed barrier thickness of 55 nm and three well widths of 4, 8 and 16 nm have been grown on m-plane sapphires by pulsed laser deposition. Due to 2D quantum confinement with decreasing well width, the emission of excitons bound to the basal-plane stacking faults, which are one-dimensionally confined in MQWs, encounters larger blue shift than that of the near-band edge excitons. Furthermore, remarkably reducing coupling of free excitons with A1 longitudinal optical phonons is closely correlated with increasing exciton binding energy but enhanced coupling of E2-low phonons is a result of increasing interaction with the interface phonons with decreasing well width.

Excitation intensity dependence of photoluminescence from monolayers of MoS2 and WS2/MoS2 heterostructures

A detailed study of the excitation dependence of the photoluminescence (PL) from monolayers of MoS2 and WS2/MoS2 heterostructures grown by chemical vapor deposition on Si substrates has revealed that the luminescence from band edge excitons from MoS2 monolayers shows a linear dependence on excitation intensity for both above band gap and resonant excitation conditions. In particular, a band separated by ∼55 meV from the A exciton, referred to as the C band, shows the same linear dependence on excitation intensity as the band edge excitons. A band similar to the C band has been previously ascribed to a trion, a charged, three-particle exciton. However, in our study the C band does not show the 3/2 power dependence on excitation intensity as would be expected for a three-particle exciton. Further, the PL from the MoS2 monolayer in a bilayer WS2/MoS2 heterostructure, under resonant excitation conditions where only the MoS2 absorbs the laser energy, also revealed a linear dependence on excitation intensity for the C band, confirming that its origin is not due to a trion but instead a bound exciton, presumably of an unintentional impurity or a native point defect such as a sulfur vacancy. The PL from the WS2/MoS2 heterostructure, under resonant excitation conditions also showed additional features which are suggested to arise from the interface states at the heteroboundary. Further studies are required to clearly identify the origin of these features.

Optical Characterization of Strong UV Luminescence Emitted from the Excitonic Edge of Nickel Oxide Nanotowers.

NiO had been claimed to have the potential for application in transparent conducting oxide, electrochromic device for light control, and nonvolatile memory device. However, the detailed study of excitonic transition and light-emission property of NiO has rarely been explored to date. In this work, we demonstrate strong exciton-complex emission of high-quality NiO nanotowers grown by hot-filament metal-oxide vapor deposition with photoluminescence as an evaluation tool. Fine and clear emission features coming from the excitonic edge of the NiO are obviously observed in the photoluminescence spectra. A main excitonic emission of ~3.25 eV at 300 K can be decomposed into free exciton, bound excitons, and donor-acceptor-pair irradiations at lowered temperatures down to 10 K. The band-edge excitonic structure for the NiO nanocrystals has been evaluated and analyzed by transmission and thermoreflectacne measurements herein. All the experimental results demonstrate the cubic NiO thin-film nanotower is an applicable direct-band-gap material appropriate for UV luminescence and transparent-conducting-oxide applications.

Optical Investigation of Broadband White-Light Emission in Self-Assembled Organic–Inorganic Perovskite (C6H11NH3)2PbBr4

The performance of hybrid organic perovskite (HOP) for solar energy conversion is driving a renewed interest in their light emitting properties. The recent observation of broad visible emission in layered HOP highlights their potential as white-light emitters. Improvement of the efficiency of the material requires a better understanding of its photophysical properties. We present in-depth experimental investigations of white-light (WL) emission in thin films of the (C6H11NH3)2PbBr4. The broadband, strongly Stokes shifted emission presents a maximum at 90 K when excited at 3.815 eV, and below this temperature coexists with an excitonic edge emission. X-rays and calorimetry measurements exclude the existence of a phase transition as an origin of the thermal behavior of the WL luminescence. The free excitonic emission quenches at low temperature, despite a binding energy estimated to 280 meV. Time-resolved photoluminescence spectroscopy reveals the multicomponent nature of the broad emission. We analyzed the...

Exciton Fine Structure of CdSe/CdS Nanocrystals Determined by Polarization Microscopy at Room Temperature.

We present a method that allows determining the band-edge exciton fine structure of CdSe/CdS dot-in-rods samples based on single particle polarization measurements at room temperature. We model the measured emission polarization of such single particles considering the fine structure properties, the dielectric effect induced by the anisotropic shell, and the measurement configuration. We use this method to characterize the band-edge exciton fine structure splitting of various samples of dot-in-rods. We show that, when the diameter of the CdSe core increases, a transition from a spherical like band-edge exciton symmetry to a rod-like band edge exciton symmetry occurs. This explains the often reported large emission polarization of such particles compared to spherical CdSe/CdS emitters.

Topologically protected excitons in porphyrin thin films

The control of exciton transport in organic materials is of fundamental importance for the development of efficient light-harvesting systems. This transport is easily deteriorated by traps in the disordered energy landscape. Here, we propose and analyse a system that supports topological Frenkel exciton edge states. Backscattering of these chiral Frenkel excitons is prohibited by symmetry, ensuring that the transport properties of such a system are robust against disorder. To implement our idea, we propose a two-dimensional periodic array of tilted porphyrins interacting with a homogeneous magnetic field. This field serves to break time-reversal symmetry and results in lattice fluxes that mimic the Aharonov-Bohm phase acquired by electrons. Our proposal is the first blueprint for realizing topological phases of matter in molecular aggregates and suggests a paradigm for engineering novel excitonic materials.

Optical absorption of Zn(V,Al)O thin films studied by spectroscopic ellipsometry from 1 to 6 eV

Aerogel nanoparticles prepared with various Al concentrations were used as a target for the deposition of (V,Al) co-doped ZnO films by rf-magnetron sputtering on glass substrates. The influence of Al content on the structural and the optical properties of the Zn(V,Al)O films was investigated by X-ray diffraction and spectroscopic ellipsometry (SE). It is found that all films exhibit one high intensity (0 0 2) peak, indicating that they have c -axis preferred orientation due to self-texturing mechanism. SE measurements, used to determine the complex pseudo dielectric functions, were carried out at room temperature in the 1–6 eV photon energy region. The excitonic edge of the fundamental band gap ( E 0) transition in the imaginary part of the dielectric function of the Zn(V,Al)O films is observed around 3.5 eV and shows a dependence on the Al content. The E 0 absorption edge of the Zn 0 . 9 −x V 0 . 1 Al x O alloys shows a blueshift from that of pure ZnO, reaching 389 meV for x = 0 . 02. This blueshift is interpreted by the Burstein-Moss effect. By analyzing the dielectric function, reduced effective mass m * of the Zn 0.9− x V 0.1 Al x O alloy is extracted and shows good agreement with literature values.

Alignment Growth Mechanisms of Rod-like ZnO on Zinc Substrates

Discontinuous films of ZnO particles were prepared on zinc substrates by air pre-oxidation process. The arrays of rod-like ZnO nano-/micro- crystals on zinc substrates were synthesized through hydrothermal processing with N2H4·H2O solution. It is found that the rod-like ZnO nano-/micro-crystals align well on the substrate surface with a unique crystallographic orientation. The experimental results suggest a free alignment growth mechanism for rod-like ZnO nano-/micro-crystals on zinc substrates. The crystallization habit of ZnO nano-/micro-crystals is to grow along with the c axis fast under hydrothermal conditions, thus the well alignment of rod-like ZnO nano-/micro-crystals only depends on the state of ZnO nuclei on the substrate surface. The states of ZnO nuclei on the substrate surface with a unique crystallographic orientation well agree with others, which regulates the align- ment of rod-like ZnO nano-/micro-crystals. In temperature-dependent photoluminescence spectra, the thermal phenomenon of near band-gap edge excitons is observed in the temperature ranging from 30 K to 60 K, which identify two non-radiative processes and one negative thermal quenching process.

Ultraviolet electroluminescence from n-ZnO/i-MgO/p+-GaN heterojunction light-emitting diodes fabricated by RF-magnetron sputtering

Based on the easily controllable radio frequency magnetron sputtering, n-ZnO and i-MgO thin films were fabricated on p+-GaN substrate to construct heterojunctional light-emitting diodes for ultraviolet emission from the near band edge exciton recombination of ZnO. Effects of the insulator MgO layer on the electroluminescent performance of the n-ZnO/i-MgO/p+-GaN light-emitting diodes have been investigated. It was found that the light-emitting diode presented stronger near band-edge emission with blue shift emission peak under the lower working current when i-MgO layer was inserted. The fabrication process, characteristics and the mechanism were discussed in detail.

Surface sensing behavior and band edge properties of AgAlS2: Experimental observations in optical, chemical, and thermoreflectance spectroscopy

Optical examination of a chaocogenide compound AgAlS2 which can spontaneously transfer to a AgAlO2 oxide has been investigated by thermoreflectance (TR) spectroscopy herein. The single crystals of AgAlS2 were grown by chemical vapor transport (CVT) method using ICl3 as a transport agent sealed in evacuated quartz tubes. The as-grown AgAlS2 crystals essentially possess a transparent and white color in vacuum. The crystal surface of AgAlS2 becomes darkened and brownish when putting AgAlS2 into atmosphere for reacting with water vapor or hydrogen gas. Undergoing the chemical reaction process, oxygen deficient AgAlO2-2x with brownish and reddish-like color on surface of AgAlS2 forms. The transition energy of deficient AgAlO2-2x was evaluated by TR experiment. The value was determined to be ∼2.452 eV at 300 K. If the sample is kept dry and moved away from moisture, AgAlS2 crystal can stop forming more deficient AgAlO2-2x surface oxides. The experimental TR spectra for the surface-reacted sample show clearly two transition features at EW=2.452 eV for deficient AgAlO2-2x and EU=3.186 eV for AgAlS2, respectively. The EU transition belongs to direct band-edge exciton of AgAlS2. Alternatively, for surface-oxidation process of AgAlS2 lasting for a long time, a AgAlO2 crystal with yellowish color will eventually form. The TR measurements show mainly a ground-state band edge exciton of ${\rm E}{}_{{\rm OX}}^{\rm 1}$E OX 1 detected for AgAlO2. The energy was determined to be ${\rm E}{}_{{\rm OX}}^{\rm 1}$E OX 1=2.792 eV at 300 K. The valence-band electronic structure of AgAlS2 has been detailed characterized using polarized-thermoreflectance (PTR) measurements in the temperature range between 30 and 340 K. Physical chemistry behaviors of AgAlS2 and AgAlO2 have been comprehensively studied via detailed analyses of PTR and TR spectra. Based on the experimental analyses, optical and chemical behaviors of the AgAlS2 crystals under atmosphere are realized. A possible optical-detecting scheme for using AgAlS2 as a humidity sensor has also been proposed.

Surface exciton separation in photoexcited MgO nanocube powders

In MgO nanocube powders surface excitons can separate and the resulting charge carriers provide reactive adsorption sites at well-defined surface elements. We employed photoluminescence (PL) emission bands originating from the photoexcitation of nanocube corners and edges as quantitative probes to explore their chemical reactivity towards molecular hydrogen. Surface excitons which form at corners and edges exhibit similar cross-sections for separation in vacuum. The separation of edge excitons, however, is significantly enhanced in hydrogen atmosphere when hydrogen adsorption occurs as a simultaneous surface process. The electronic structure of MgO nanocube edges which split hydrogen heterolytically upon generation of surface hydroxyls and hydrides is unaffected by the photoexcitation of corners. Respective edges, however, are efficient absorption sites for UV photons. Transfer of exciton energy to oxygen ions in corners is followed by exciton separation which transforms corner ions into surface radicals leading to a well-defined starting point for the site selective functionalization of metal oxide nanostructures.

Exciton Localization Behaviors of Basal Stacking Faults in a-Plane AlGaN Alloys

We study the basal plane stacking faults (BSFs) related optical properties in a-plane AlGaN alloys with different Al composition ranging from 0 to 0.28. The low-temperature photoluminescence (PL) spectra for AlGaN show two dominant peaks attributed to the emission of near band edge and BSFs-bound excitons, respectively. The PL integrated intensity ratio of the BSFs to NBE is found to correlate to the density of BSFs observed by the transmission electron microscopy. Finally, the exciton localization behaviors of BSFs in a-plane AlGaN alloys is observed and discussed in this study.