Excitonic Photoluminescence Spectra Research Articles

Spin chain orientation and magneto-optical coupling in twisted NiPS3 homostructures

Magnetic two-dimensional (2D) materials have garnered significant attention due to their unique electronic, magnetic, and optical properties and their potential applications in next-generation electronic and optoelectronic devices. However, the magneto-optical effects of oligolayer antiferromagnetic materials remain inadequately understood. Here, we investigate the magnetic properties of few-layer nickel phosphorus trisulfide (NiPS3) and its twisted heterostructures, emphasizing the observation of optical phenomena at low temperatures (1.65 K). By stacking few-layer NiPS3 to fabricate twisted homostructures, we probe their magnetic characteristics using photoluminescence (PL) spectroscopy. Our results reveal that sharp exciton peaks emerge at low temperatures and that the spin chain orientation in oligolayer NiPS3 can be discerned through the polarization dependence of exciton PL intensity. Notably, fewer-layered NiPS3 exhibits a significant magneto-optical effect under an applied magnetic field, allowing the modulation of the polarization angle of its exciton PL spectrum. Additionally, the polarization-dependent Raman spectrum of NiPS3 shows substantial changes under the influence of a magnetic field. These findings underscore the potential of few-layer NiPS3 for future magneto-optical device applications.

Surface optical phonon replica in photoluminescence spectroscopy of nitride nanostructures: Crystal structure and surface effects

The surface optical (SO) phonon replica in photoluminescence (PL) spectroscopy of nitride nanowires (NWs) was theoretically investigated in this study. The dispersive relationships of SO phonon mode in anisotropic wurtzite (WZ) and isotropic zinc-blende (ZB) crystal structure NWs with circular and square cross sections (CSs) were derived within the framework of the dielectric continuum model. Based on the energy and momentum conservation laws, a constraint relationship between the frequency and wave-number was constructed for SO phonon-assisted excitonic PL spectra in the NW structure. By combining the dispersive and constraint relationships, the frequency and wave-number of the SO phonon replica in the PL spectra could be determined. The WZ and ZB crystal structures of nitride semiconductor were considered. The influences of surface factors including the CS shape, dielectric medium, and environment temperature on the frequency and photon wavelength of the band-edge emission of the SO phonon replica were studied in detail. Numerical results reveal that the crystal structure, surface factors, and environment temperature greatly affect the frequency and photon wavelength of the band-edge emission of the SO phonon replica. The calculated results for the photon wavelength agree well with the experimental values of the SO phonon replica in AlN NWs. The results of the dielectric effect obtained here are also supported by previous experimental and theoretical results for nitrides and other semiconductor NWs. The present theoretical scheme and numerical results can be used to analyze and design the SO phonon replica in PL spectra of nanostructures.

Photoluminescence modal splitting via strong coupling in hybrid Au/WS2/GaP nanoparticle-on-mirror cavities.

By integrating dielectric and metallic components, hybrid nanophotonic devices present promising opportunities for manipulating nanoscale light-matter interactions. Here, we investigate hybrid nanoparticle-on-mirror optical cavities, where semiconductor WS2 monolayers are positioned between gallium phosphide (GaP) nanoantennas and a gold mirror, thereby establishing extreme confinement of optical fields. Prior to integration of the mirror, we observe an intermediate coupling regime from GaP nanoantennas covered with WS2 monolayers. Upon introduction of the mirror, enhanced interactions lead to modal splitting in the exciton photoluminescence spectra, spatially localized within the dielectric-metallic gap. Using a coupled harmonic oscillator model, we extract an average Rabi splitting energy of 22.6 meV at room temperature, at the onset of the strong coupling regime. Moreover, the characteristics of polaritonic emission are revealed by the increasing Lorentzian linewidth and energy blueshift with increasing excitation power. Our findings highlight hybrid nanophotonic structures as novel platforms for controlling light-matter coupling with atomically thin materials.

Interface engineering of charge-transfer excitons in 2D lateral heterostructures

The existence of bound charge transfer (CT) excitons at the interface of monolayer lateral heterojunctions has been debated in literature, but contrary to the case of interlayer excitons in vertical heterostructure their observation still has to be confirmed. Here, we present a microscopic study investigating signatures of bound CT excitons in photoluminescence spectra at the interface of hBN-encapsulated lateral MoSe2-WSe2 heterostructures. Based on a fully microscopic and material-specific theory, we reveal the many-particle processes behind the formation of CT excitons and how they can be tuned via interface- and dielectric engineering. For junction widths smaller than the Coulomb-induced Bohr radius we predict the appearance of a low-energy CT exciton. The theoretical prediction is compared with experimental low-temperature photoluminescence measurements showing emission in the bound CT excitons energy range. We show that for hBN-encapsulated heterostructures, CT excitons exhibit small binding energies of just a few tens meV and at the same time large dipole moments, making them promising materials for optoelectronic applications (benefiting from an efficient exciton dissociation and fast dipole-driven exciton propagation). Our joint theory-experiment study presents a significant step towards a microscopic understanding of optical properties of technologically promising 2D lateral heterostructures.

Effect of interface quality on photoluminescence of encapsulated MoSe<sub>2</sub> monolayers

Photoluminescence spectra of excitons and trions in MoSe2 monolayers encapsulated with hexagonal boron nitride under nonresonant laser excitation were studied. When the size of the laser excitation spot decreases from 8 to 3 nm, individual peaks with a line width of ~2 meV emerge in the photoluminescence spectra, which were unresolved with a larger spot. Studies of the sample surface using a scanning electron microscope revealed the existence of a large number of features at the interfaces of structures with characteristic sizes ranging from submicron to micron and more. It was expected that the lines appearing in the spectrum at small excitation spot sizes were associated with similar submicron inhomogeneities. A study of a specially made heterostructure covered by a metal mask with holes of 1.6 microns in diameter confirmed this assumption.

Controlling exciton spontaneous emission of quantum dots by Au nanoparticles

As an ideal single-photon source, quantum dots (QDs) can play a unique role in the field of quantum information. Controlling QD exciton spontaneous emission can be achieved by anti-phase coupling between QD exciton dipole field and Au dipole field after QD film has been transferred onto the Si substrate covered by Au nanoparticles. In experiment, the studied InAs/GaAs QDs are grown by molecular beam epitaxy (MBE) on a (001) semi-insulation substrate. The films containing QDs with different GaAs thickness values are separated from the GaAs substrate by etching away the AlAs sacrificial layer and transferring the QD film to the silicon wafer covered by Au nanoparticles with a diameter of 50 nm. The distance <i>D</i> (thickness of GaAs) from the surface of the Au nanoparticles to the QD layer is 10, 15, 19, 25, and 35 nm, separately. A 640-nm pulsed semiconductor laser with a 40-ps pulse length is used to excite the QD samples for measuring QD exciton photoluminescence and time-resolved photoluminescence spectra at 5 K. It is found that when the distance <i>D</i> is 15–35 nm the spontaneous emission rate of exciton is suppressed. And when <i>D</i> is close to 19 nm, the QD spontaneous emission rate decreases to <inline-formula><tex-math id="M2">\begin{document}$ ~{10}^{-3} $\end{document}</tex-math><alternatives><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="6-20211863_M2.jpg"/><graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="6-20211863_M2.png"/></alternatives></inline-formula>, which is consistent with the theoretical calculations. The physical mechanism of long-lived exciton luminescence observed in experiment lies in the fact that Au nanoparticles scatter the light field of the exciton radiation in the QD wetting layer, and the phase of the scattered field is opposite to the phase of the exciton radiation field. Therefore, the destructive interference between the exciton radiation field and scattering field of Au nanoparticles results in long-lived exciton emission observed in experiment.

Exciton landscape in van der Waals heterostructures

van der Waals heterostructures consisting of vertically stacked transition-metal dichalcogenides (TMDs) exhibit a rich landscape of bright and dark intra- and interlayer excitons. In spite of a growing literature in this field of research, the type of excitons dominating optical spectra in different van der Waals heterostructures has not yet been well established. The spectral position of exciton states depends strongly on the strength of hybridization and energy renormalization due to the periodic moir\'e potential. Combining exciton density-matrix formalism and density-functional theory, we shed light on the exciton landscape in TMD homo- and heterobilayers at different stackings. This allows us to identify on a microscopic footing the energetically lowest-lying exciton state for each material and stacking. Furthermore, we disentangle the contribution of hybridization and layer polarization-induced alignment shifts of dark and bright excitons in photoluminescence spectra. By revealing the exciton landscape in van der Waals heterostructures, our work provides the basis for further studies of the optical, dynamical, and transport properties of this technologically promising class of nanomaterials.

Optical Measurements and Theoretical Modelling of Excitons in Double ZnO/ZnMgO Quantum Wells in an Internal Electric Field.

In this paper, the photoluminescence spectra of excitons in ZnO/ZnMgO/ZnO double asymmetric quantum wells grown on a–plane substrates with internal electric-field bands structures were studied. In these structures, the electron and the hole in the exciton are spatially separated between neighbouring quantum wells, by a ZnMgO barrier with different thickness. The existence of an internal electric field generates a linear potential and, as a result, lowers the energy of quantum states in the well. For the wide wells, the electrons are spatially separated from the holes and can create indirect exciton. To help the understanding of the photoluminescence spectra, for single particle states the 8 k·p for wurtzite structure is employed. Using these states, the exciton in the self-consistent model with 2D hydrogenic 1s–like wave function is calculated.

Emergent Midgap Excitons in Large‐Size Freestanding 2D Strongly Correlated Perovskite Oxide Films

Abstract2D materials exhibit strong excitonic effects due to low dimensionality and enhanced Coulomb interactions, resulting in fascinating many‐particle phenomena like excitons. Though perovskite is a classical type of material hosting abundant correlated electronic phases, freestanding 2D perovskite oxides are not easy to fabricate and yet to be extensively studied. Here the realization of large size (1 × 1 cm2) freestanding perovskite SrTiO3 films, which show unexpected excitonic photoluminescence (PL) spectra and carrier dynamics, is reported. Two pronounced broad PL peaks emerge in 2D freestanding SrTiO3 films at 2.34–2.4 and 1.8–1.9 eV, of which the 2.34–2.4 eV emission originates from self‐trapped excitons localized within TiO6 octahedra, and the 1.8–1.9 eV peak from Ti vacancies. The time‐resolved PL shows a remarkable enhancement of nonradiative Auger recombination through three‐particle process, in which electron–hole excitons transfer their kinetic energy to other free electrons or holes. The results demonstrate unique excitonic properties in 2D perovskite SrTiO3 films and unravel their potential for high‐performance optoelectronic devices.

Long-range electron-hole exchange interaction in aluminum nitride

To resolve the discrepancies in the exciton fine structure of aluminum nitride (AlN), polarization- and angle-resolved photoluminescence (PL) spectroscopies are performed. The excitonic PL spectra strongly depend on the optical polarization and detection angle. We propose that both the long-range and short-range electron-hole exchange interaction should be used to interpret the luminescence spectra. The theoretical framework fully explains the present and previous experimental results. The large longitudinal-transverse splitting energy obtained in this study suggests that AlN has strong light-matter coupling without quantum-confined structures.

Colloidal formamidinium lead bromide quantum dots for photocatalytic CO2 reduction

With the target of bringing out a sustainable carbon–neutral system, halide perovskite materials have been explored to fulfil the requirements of solar-to-fuel conversion. Herein, formamidinium (CH(NH2)2+) lead bromide quantum dot (FAPbBr3 QD) as a novel of photocatalyst is researched, which exhibits an excellent photostability and the optimum CO yield rate of 181.25 μmol·g−1·h−1 towards photocatalytic CO2 reduction in the mixed solvent of deionized water/ethyl acetate. Furthermore, the kinetic features of exciton bleach and photoluminescence spectra infer that FAPbBr3 QDs have an enough lifetime to separate and transfer charges for adsorbing CO2 molecules, thus facilitating the photocatalytic CO2 reduction. This study puts forward a reliable avenue of organic–inorganic hybrid perovskite materials as efficient photocatalysts to convert CO2 into valuable chemical fuels.

Tailoring Hot Exciton Dynamics in 2D Hybrid Perovskites through Cation Modification

We report a family of two-dimensional hybrid perovskites (2DHPs) based on phenethylammonium lead iodide ((PEA)2PbI4) that show complex structure in their low-temperature excitonic absorption and photoluminescence (PL) spectra as well as hot exciton PL. We replace the 2-position (ortho) H on the phenyl group of the PEA cation with F, Cl, or Br to systematically increase the cation's cross-sectional area and mass and study changes in the excitonic structure. These single atom substitutions substantially change the observable number of and spacing between discrete resonances in the excitonic absorption and PL spectra and drastically increase the amount of hot exciton PL that violates Kasha's rule by over an order of magnitude. To fit the progressively larger cations, the inorganic framework distorts and is strained, reducing the Pb-I-Pb bond angles and increasing the 2DHP band gap. Correlation between the 2DHP structure and steady-state and time-resolved spectra suggests the complex structure of resonances arises from one or two manifolds of states, depending on the 2DHP Pb-I-Pb bond angle (as)symmetry, and the resonances within a manifold are regularly spaced with an energy separation that decreases as the mass of the cation increases. The uniform separation between resonances and the dynamics that show excitons can only relax to the next-lowest state are consistent with a vibronic progression caused by a vibrational mode on the cation. These results demonstrate that simple changes to the cation can be used to tailor the properties and dynamics of the confined excitons without directly modifying the inorganic framework.

Giant Fine Structure Splitting of the Bright Exciton in a Bulk MAPbBr3 Single Crystal.

Exciton fine structure splitting in semiconductors reflects the underlying symmetry of the crystal and quantum confinement. Because the latter factor strongly enhances the exchange interaction, most work has focused on nanostructures. Here, we report on the first observation of the bright exciton fine structure splitting in a bulk semiconductor crystal, where the impact of quantum confinement can be specifically excluded, giving access to the intrinsic properties of the material. Detailed investigation of the exciton photoluminescence and reflection spectra of a bulk methylammonium lead tribromide single crystal reveals a zero magnetic field splitting as large as ∼200 μeV. This result provides an important starting point for the discussion of the origin of the large bright exciton fine structure splitting observed in perovskite nanocrystals.

Dark exciton based strain sensing in tungsten-based transition metal dichalcogenides

The trend towards ever smaller high-performance devices in modern technology requires novel materials with new functionalities. The recent emergence of atomically thin two-dimensional (2D) materials has opened up possibilities for the design of ultra-thin and flexible nanoelectronic devices. As truly 2D materials, they exhibit an optimal surface-to-volume ratio, which results in an extremely high sensitivity to external changes. This makes these materials optimal candidates for sensing applications. Here, we exploit the remarkably diverse exciton landscape in monolayer transition metal dichalcogenides to propose a novel dark-exciton-based concept for ultra sensitive strain sensors. We demonstrate that the dark-bright-exciton separation can be controlled by strain, which has a crucial impact on the activation of dark excitonic states. This results in a pronounced intensity change of dark excitons in photoluminescence spectra, when only 0.05 $\%$ strain is applied. The predicted extremely high optical gauge factors of up to 8000 are promising for the design of optical strain sensors.

Optical spin pumping induced pseudomagnetic field in two-dimensional heterostructures

Two dimensional heterostructures are likely to provide new avenues for the manipulation of magnetization that is crucial for spintronics or magnetoelectronics. Here, we demonstrate that optical spin pumping can generate a large effective magnetic field in two dimensional MoSe2/WSe2 heterostructures. We determine the strength of the generated field by polarization-resolved measurement of the interlayer exciton photoluminescence spectrum: the measured splitting exceeding 10 milli-electron volts (meV) between the emission originating from the two valleys corresponds to an effective magnetic field of ~ 30 T. The strength of this optically induced field can be controlled by the excitation light polarization. Our finding opens up new possibilities for optically controlled spintronic devices based on van der Waals heterostructures.

Multiphoton excitation and thermal activation in indirect bandgap semiconductors

The single crystals of wide- and indirect-bandgap semiconductor CdI2 were grown and their optical properties as well as the defect-induced excitonic photoluminescence (PL) spectra were studied. The multiphoton excited PL spectra, charactering the emissions from excitons in the visible region, were taken. The PL intensity (IPL) was found to vary nonlinearly with pumping power (P). The IPL was also found to decrease with increasing temperature. The temperature dependence of IPL for each P followed a fashionable relationship, from which the activation energy (∆E) of the defect-induced excitonic trapping was calculated. The ∆E was found to slightly decrease with increasing P, with an average value of 2.5 meV. The results, however, demonstrates the existence of the self-trapped excitons responsible for the characteristics broad-band emission in the visible range. This study shows that the single crystals of CdI2 might have potential in applications as thermo-luminescent dosimeters in radiation measurements.

Thermal dissociation of inter-layer excitons in MoS2/MoSe2 hetero-bilayers.

We describe photoluminescence (PL), PL excitation, and time-resolved PL spectroscopy of hetero-bilayers comprising monolayers (1L) of MoS2 and MoSe2 at cryogenic temperatures. A PL peak showing a decay time of 2.5 ns was observed below 100 K, which can be attributed to an inter-layer exciton emission in the 1L-MoS2/1L-MoSe2 hetero-bilayers. An inter-layer exciton binding energy of ∼90 meV is determined from its thermal dissociation behavior; the band offset of each layer obtained from this value is consistent with previously reported first-principles calculations. Moreover, generation of inter-layer charged excitons (trions) is implied from the gate modulation of the inter-layer exciton PL spectra.

Fine structure of electron-hole complexes in trigonal quantum dots

A theory of the Zeeman effect and fine structure of the energy spectrum of electron-hole complexes in highly symmetric quantum dots grown along the [111] direction from materials with a zinc blende lattice has been presented. In the studied quantum dots with C3v point symmetry, the Zeeman effect for a heavy hole in a magnetic field B ‖ [111] has an unusual form: in addition to the diagonal component (gh1), the effective tensor of g-factors contains the off-diagonal element (gh2). For gh2 ≠ 0, there is a magnetically induced mixing of heavy-hole states, which explains two additional lines observed in experimental photoluminescence spectra of excitons and trions. A microscopic theory of the effective g-factors gh1 and gh2 within the Luttinger Hamiltonian in the spherical approximation has been discussed, as well as additional contributions to the off-diagonal element gh2 due to the warping of the spectrum of holes. The results of theoretical calculations of the g-factors gh1 and gh2 for quantum dots based on GaAs have been compared with the experimental data.

Luminescence signature of free exciton dissociation and liberated electron transfer across the junction of graphene/GaN hybrid structure.

Large-area graphene grown on Cu foil with chemical vapor deposition was transferred onto intentionally undoped GaN epilayer to form a graphene/GaN Schottky junction. Optical spectroscopic techniques including steady-state and time-resolved photoluminescence (PL) were employed to investigate the electron transfer between graphene and n-type GaN at different temperatures. By comparing the near-band-edge excitonic emissions before and after the graphene covering, some structures in the excitonic PL spectra are found to show interesting changes. In particular, a distinct “dip” structure is found to develop at the center of the free exciton emission peak as the temperature goes up. A mechanism that the first dissociation of some freely moveable excitons at the interface was followed by transfer of liberated electrons over the junction barrier is proposed to interpret the appearance and development of the “dip” structure. The formation and evolution process of this “dip” structure can be well resolved from the measured time-resolved PL spectra. First-principles simulations provide clear evidence of finite electron transfer at the interface between graphene and GaN.

Nonlinear photoluminescence properties of trions in hole-doped single-walled carbon nanotubes

We studied the excitation density dependence of photoluminescence (PL) spectra of excitons and trions (charged excitons) in hole-doped single-walled carbon nanotubes. We found that the PL intensity of trions exhibited a strong nonlinear saturation behavior as the excitation density increased, whereas that of excitons exhibited a weak sublinear behavior. The strong PL saturation of trions is attributed to depletion of doped holes that are captured by excitons in the formation processes. Moreover, the effective radiative lifetime of a trion was evaluated to be approximately 20 ns.