Excitonic Transitions Research Articles

Transient Optical Modulation in Vanadium and Selenium Doped MoS2 by Carrier–Carrier and Carrier–Phonon Interactions

AbstractDoping and alloying induce defect states in atomically thin transition metal dichalcogenides (TMDCs), leading to strong carrier–phonon interactions. The robust excitonic behavior of these layered materials can be modified by injecting a high density of charge carriers. However, comprehending the influence of carrier–phonon and carrier–carrier interactions on the optical properties of 2D materials is crucial for their optoelectronic and photonic applications. Here, transient absorption (TA) spectroscopy is employed to demonstrate the modulation of the transient optical behavior of TMDCs through doping and excitation near Mott density. The TA spectra reveal broadening attributed to carrier–carrier and carrier–phonon interactions, with the broadening being particularly pronounced in vanadium (V) doped TMDCs due to the hybridization of defect and exciton transitions. Analysis of TA kinetics suggests the involvement of various carrier species in the carrier dynamics of TMDCs, with the influence of mid‐gap carriers dominating at higher excitation densities. Nonetheless, the presence of strong carrier–phonon coupling in V‐doped TMDCs is demonstrated by temperature‐dependent Raman and photoluminescence spectroscopy. The results reveal that the enhanced coupling between acoustic phonons and carriers can lead to multiphonon emission. The findings of this study hold promise for controlling the optical response of TMDCs in ultrafast optoelectronic applications.

Visualizing Triplet Energy Transfer in Organic Near-Infrared Phosphorescent Host-Guest Materials.

Limited by the energy gap law, purely organic materials with efficient near-infrared room temperature phosphorescence are rare and difficult to achieve. Additionally, the exciton transition process among different emitting species in host-guest phosphorescent materials remains elusive, presenting a significant academic challenge. Herein, using a modular nonbonding orbital-π bridge-nonbonding orbital (n-π-n) molecular design strategy, we develop a series of heavy atom-free phosphors. Systematic modification of the π-conjugated cores enables the construction of a library with tunable near-infrared phosphorescence from 655 to 710 nm. These phosphors exhibit excellent performance under ambient conditions when dispersed into a 4-bromobenzophenone host matrix, achieving an extended lifetime of 11.25 ms and a maximum phosphorescence efficiency of 4.2 %. Notably, by eliminating the interference from host phosphorescence, the exciton transition process in hybrid materials can be visualized under various excitation conditions. Spectroscopic analysis reveals that the improved phosphorescent performance of the guest originates from the triplet-triplet energy transfer of abundant triplet excitons generated independently by the host, rather than from enhanced intersystem crossing efficiency between the guest singlet state and the host triplet state. The findings provide in-depth insights into constructing novel near-infrared phosphors and exploring emission mechanisms of host-guest materials.

Visualizing Triplet Energy Transfer in Organic Near‐Infrared Phosphorescent Host‐Guest Materials

AbstractLimited by the energy gap law, purely organic materials with efficient near‐infrared room temperature phosphorescence are rare and difficult to achieve. Additionally, the exciton transition process among different emitting species in host–guest phosphorescent materials remains elusive, presenting a significant academic challenge. Herein, using a modular nonbonding orbital‐π bridge‐nonbonding orbital (n‐π‐n) molecular design strategy, we develop a series of heavy atom‐free phosphors. Systematic modification of the π‐conjugated cores enables the construction of a library with tunable near‐infrared phosphorescence from 655 to 710 nm. These phosphors exhibit excellent performance under ambient conditions when dispersed into a 4‐bromobenzophenone host matrix, achieving an extended lifetime of 11.25 ms and a maximum phosphorescence efficiency of 4.2 %. Notably, by eliminating the interference from host phosphorescence, the exciton transition process in hybrid materials can be visualized under various excitation conditions. Spectroscopic analysis reveals that the improved phosphorescent performance of the guest originates from the triplet‐triplet energy transfer of abundant triplet excitons generated independently by the host, rather than from enhanced intersystem crossing efficiency between the guest singlet state and the host triplet state. The findings provide in‐depth insights into constructing novel near‐infrared phosphors and exploring emission mechanisms of host–guest materials.

Self-Assembly of Chiral Ligands on 2D Semiconductor Nanoplatelets for High Circular Dichroism.

Group II-VI semiconductor nanoplatelets (NPLs) with atomically defined thicknesses and extended atomically flat (001) facets are used for ligand binding and chiro-optical effects. In this study, we demonstrate that tartrate ligands, anchored by two carboxylate groups, chelate the (001) facets of NPLs at an average ratio of one tartrate molecule to two cadmium (Cd) surface atoms. This assembly of chiral molecules on inorganic nanocrystals generates a circular dichroism g-factor as high as 1.3 × 10-2 at the first excitonic transition wavelength of NPLs. Tartrate ligands induce an orthorhombic distortion of the initially "cubic" crystal structure, classifying the NPLs within the 222-point group. Unlike spherical nanocrystals, where it is difficult to discern whether chiral ligands affect only the surface atoms or the entire crystal structure, our findings unequivocally show that the crystal structure of NPLs is modified due to their thinness and atomically precise thickness. The in-plane lattice parameters experience compressive and tensile stresses, significantly splitting the heavy-hole and light-hole bands. Additionally, tartrate ligands adopt different conformations on the NPL surface over time, resulting in dynamic changes in the circular dichroism signal, including an inversion of its sign.

Determination of the particle size distribution of cube-shaped colloidal perovskite quantum dots from photoluminescence spectra: A combined theoretical-experimental approach.

A theoretical-experimental approach is proposed to convert the photoluminescence spectra of colloidal perovskite quantum dot ensembles into accurate estimates for their intrinsic particle size distribution functions. Two main problems were addressed and properly correlated: the size dependence of the first excitonic transition in a single cube-shaped quantum dot and the inhomogeneous broadening of the fluorescence line shape due to the size nonuniformity of the chemically prepared quantum dot suspension in addition to the single-dot homogeneous broadening. By applying the reported methodology to CsPbBr3 quantum dot samples belonging to the strong and intermediate confinement regimes, the calculated size distributions exhibited close agreement with those obtained from transmission electron microscopy, with precise estimates for the average particle size and standard deviation. Specifically for strongly confined ultrasmall CsPbBr3 quantum dots, the presented spectroscopic model for size distribution computation is based on a new analytical expression for the size-dependent bandgap, which was developed within the framework of the finite-depth square-well effective mass approximation accounting for band nonparabolicity effects. Such a quantum mechanical approach correctly predicts the expected transition to the intermediate confinement regime in sufficiently large quantum dots, which are traditionally described by the well-known bandgap equation in the infinite potential barrier limit with a spatially correlated electron-hole wavefunction and nonparabolic carrier effective masses. The proposed calculation scheme originates from general theoretical considerations so that it can be readily adapted to semiconductor quantum dots of many other systems, from all inorganic metal halides to hybrid perovskite materials, regardless of the adopted chemical synthesis route.

Polariton-assisted incoherent to coherent excitation energy transfer between colloidal nanocrystal quantum dots.

We explore the dynamics of energy transfer between two nanocrystal quantum dots placed within an optical microcavity. By adjusting the coupling strength between the cavity photon mode and the quantum dots, we have the capacity to fine-tune the effective coupling between the donor and acceptor. Introducing a non-adiabatic parameter, γ, governed by the coupling to the cavity mode, we demonstrate the system's capability to shift from the overdamped Förster regime (γ ≪ 1) to an underdamped coherent regime (γ ≫ 1). In the latter regime, characterized by swift energy transfer rates, the dynamics are influenced by decoherence time. To illustrate this, we study the exciton energy transfer dynamics between two closely positioned CdSe/CdS core/shell quantum dots with sizes and separations relevant to experimental conditions. Employing an atomistic approach, we calculate the excitonic level arrangement, exciton-phonon interactions, and transition dipole moments of the quantum dots within the microcavity. These parameters are then utilized to define a model Hamiltonian. Subsequently, we apply a generalized non-Markovian quantum Redfield equation to delineate the dynamics within the polaritonic framework.

Achieving Efficient X-ray Scintillation of Purely Organic Phosphorescent Materials by Chromophore Confinement.

Scintillators have attracted significant attention due to their wide-ranging applications in both industrial and medical fields. However, one of the ongoing challenges is the efficient utilization of triplet excitons to achieve high radioluminescence efficiency. Here, a series of purely organic phosphors is presented for X-ray scintillation, employing a combined rigid and flexible host-guest doping strategy. The doped crystals exhibit a remarkable maximum phosphorescence efficiency of 99.4% under UV excitation. Furthermore, upon X-ray irradiation, the radioluminescence intensities of the doped phosphors are markedly higher compared to their single-component crystal counterparts. Through systematic investigations, it is demonstrated the crucial role of confining isolated chromophores in enhancing scintillation efficiency. Additionally, a transparent scintillator screen fabricated with the doped phosphor exhibits excellent X-ray imaging performance, achieving a high spatial resolution of 18.0 lpmm-1. This work not only offers valuable insights into suppressing non-radiative transitions of triplet excitons during scintillation but also opens a new avenue for designing highly efficient purely organic phosphorescent scintillators.

Isolation of Single Donors in ZnO.

The shallow donor in zinc oxide (ZnO) is a promising semiconductor spin qubit with optical access. Single indium donors are isolated in a commercial ZnO substrate using plasma focused ion beam (PFIB) milling. Quantum emitters are identified optically by spatial and frequency filtering. The indium donor assignment is based on the optical bound exciton transition energy and magnetic dependence. The emission stability of these single donors in terms of both intensity and frequency, alongside their transition linewidths less than twice the lifetime limit, highlight the promise of single In donors as optically accessible spin qubits. The optical stability of single donors after FIB fabrication is promising for optical device integration required for scalable quantum technologies based on single donors in direct band gap semiconductors.

Single ZnO Nanowire for Electrical and Optical NO2 Gas Sensing: Origin of Reversible and Irreversible Gas Effects Investigated by Photoluminescence Spectroscopy.

In this work, the gas sensing properties of a single ZnO nanowire (NW) are investigated, simultaneously in terms of photoluminescence (PL) and photocurrent (PC) response to NO2 gas, with the purpose of giving new insights on the gas sensing mechanism of a single 1D ZnO nanostructure. A single ZnO NW sensing device was fabricated, characterized, and compared with a sample made of bundles of ZnO NWs. UV near-band-edge PL emission spectroscopy was carried out at room temperature and by lowering the temperature down to 77 K, which allows detection of resolved PL peaks related to different excitonic transition regions. Surface effects were observed in PL maps, considering different nano and microstructures. Electrical and optical measurements were acquired at the same time during the NO2 gas exposure, allowing for the comparison of PL and PC response times and signal recovery. During NO2 gas desorption, irreversible behavior in the surface-related and donor-acceptor pair (DAP) regions is interpreted as the effect of an initial transient when electronic transfer from the gas molecules to the bulk occurs through the ZnO NW surface which acts as a channel. To the best of our knowledge, this is the first work which investigates the simultaneous PL optical and PC electrical response signals of a single ZnO NW to gas exposure.

Quantum enhanced Josephson junction field-effect transistors for logic applications

Josephson junction field-effect transistors (JJFETs) have recently re-emerged as promising candidates for superconducting computing. For JJFETs to perform Boolean logic operations, the so-called gain factor αR must be larger than 1. In a conventional JJFET made with a classical channel material, due to a gradual dependence of superconducting critical current on the gate bias, αR is much smaller than 1. In this Letter, we propose a new device structure of quantum enhanced JJFETs in a zero-energy-gap InAs/GaSb heterostructure. We demonstrate that, due to an excitonic insulator quantum phase transition in this zero-gap heterostructure, the superconducting critical current displays a sharp transition as a function of gate bias, and the deduced gain factor αR ∼ 0.06 is more than 50 times that (∼0.001) reported in a classical JJFET. Further optimization may allow achieving a gain factor larger than 1 for logic applications.

Regulation of TADF and RTP Dual Emission via Internal and External Heavy-Atom Effects.

Organic materials with thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP) dual emission have attracted great attention in recent years, but the regulation mechanism via internal and external heavy atoms is not clear enough. Here, we carry out a systematic theoretical investigation on the photophysical properties of the materials by introducing aliphatic or aromatic bromine atoms. The molecule with aromatic bromine atoms exhibits obvious TADF owing to the effective reverse intersystem crossing (RISC) with matchable energy levels and enhanced spin orbit couplings, the molecule with aliphatic bromine atoms shows a long RTP lifetime because of the reduced nonradiative transition of triplet excitons, and the molecule with both aliphatic and aromatic bromine atoms presents balanced TADF and RTP emissions thanks to the synergy internal and external heavy-atom effects. Besides, the internal and external heavy atoms induce multisite intermolecular interactions, effectively suppressing the nonradiative process in the solid phase. The efficient RISC process and the suppressed nonradiative process of triplet excitons should be key to regulating the dual emission property. These findings and insights are of great importance for revealing the structure-performance relationship, providing theoretical guidance for the design of TADF and RTP dual emission molecules via internal and external heavy-atom effects.

Effects of Dislocation Filtering Layers on Optical Properties of Third Telecom Window Emitting InAs/InGaAlAs Quantum Dots Grown on Silicon Substrates.

Integrating light emitters based on III-V materials with silicon-based electronics is crucial for further increase in data transfer rates in communication systems since the indirect bandgap of silicon prevents its direct use as a light source. We investigate here InAs/InGaAlAs quantum dot (QD) structures grown directly on 5° off-cut Si substrate and emitting light at 1.5 μm, compatible with established telecom platform. Using different dislocation defect filtering layers, exploiting strained superlattices, and supplementary QD layers, we mitigate the effects of lattice constant and thermal expansion mismatches between III-V materials and Si during growth. Complementary optical spectroscopy techniques, i.e. photoreflectance and temperature-, time- and polarization-resolved photoluminescence, allow us to determine the optical quality and application potential of the obtained structures by comparing them to a reference sample-state-of-the-art QDs grown on InP. Experimental findings are supported by calculations of excitonic states and optical transitions by combining multiband k•p and configuration-interaction methods. We show that our design of structures prevents the generation of a considerable density of defects, as intended. The emission of Si-based structures appears to be much broader than for the reference dots, due to the creation of different QD populations which might be a disadvantage in particular laser applications, however, could be favorable for others, e.g., in broadly tunable devices, sensors, or optical amplifiers. Eventually, we identify the overall most promising combination of defect filtering layers and discuss its advantages and limitations and prospects for further improvements.

Manipulation of anisotropic Zhang-Rice exciton in NiPS3 by magnetic field

The effect of external magnetic fields on the behavior of the Zhang-Rice exciton in NiPS3, which captures the physics of spin-orbital entanglement in 2D XY-type antiferromagnets, remains unclear. This study presents systematic study of angle-resolved and polarization-resolved magneto-optical photoluminescence spectra of NiPS3 in the Voigt geometry. We observed highly anisotropic, non-linear Zeeman splitting and polarization rotation of the Zhang-Rice exciton, which depends on the direction and intensity of the magnetic field and can be attributed to the spin-orbital coupling and field-induced spin reorientation. Furthermore, above the critical magnetic field, we detected additional splitting of the exciton peaks, indicating the coexistence of various orientations of Néel vector. This study characterizes orbital change of Zhang-Rice exciton and field-induced spin-reorientation phase transitions in a 2D hexagonal XY-type antiferromagnet, and it further demonstrates the continuous manipulation of the spin and polarization of the Zhang-Rice exciton.

Sub-picosecond, strain-tunable, polarization-selective optical switching via anisotropic exciton dynamics in quasi-1D ZrSe3

In cutting-edge optical technologies, polarization is a key for encoding and transmitting vast information, highlighting the importance of selectively switching and modulating polarized light. Recently, anisotropic two-dimensional materials have emerged for ultrafast switching of polarization-multiplexed optical signals, but face challenges with low polarization ratios and limited spectral ranges. Here, we apply strain to quasi-one-dimensional layered ZrSe3 to enhance polarization selectivity and tune operational energies in ultrafast all-optical switching. Initially, transient absorption on unstrained ZrSe3 reveals a sub-picosecond switching response in polarization along a specific crystal axis, attributed to shifting-recovery dynamics of an anisotropic exciton. However, its polarization selectivity is weakened by a slow non-excitonic response in the perpendicular polarization. To overcome this limitation, we apply strain to ZrSe3 by bending its flexible substrate. The compressive strain spectrally decouples the excitonic and non-excitonic components, doubling the polarization selectivity of the sub-picosecond switching and tripling it compared to that in the tensile-strained ZrSe3. It also effectively tunes the switching energy at a shift rate of ~93 meV %-1. This strain-tunable switching is repeatable, reversible, and robustly maintains the sub-picosecond operation. First-principles calculations reveal that the strain control is enabled by momentum- and band-dependent modulations of the electronic band structure, causing opposite shifts in the excitonic and non-excitonic transitions. Our findings offer a novel approach for high-performance, wavelength-tunable, polarization-selective ultrafast optical switching.

Pressure-controlled free exciton and self-trapped exciton emission in quasi-one-dimensional hybrid lead bromides

Hybrid metal halides represent a novel type of semiconductor light emitters with intriguing excitonic emission properties, including free exciton emission and self-trapped exciton emission. Achieving precise control over these two excitonic emissions in hybrid metal halides is highly desired yet remains challenging. Here, the complete transformation from intrinsically broadband self-trapped exciton emission to distinctively sharp free exciton emission in a quasi-one-dimensional hybrid metal halide (C2H10N2)8[Pb4Br18]·6Br with a ribbon width of n = 4, is successfully achieved based on high-pressure method. During compression, pressure-induced phonon hardening continuously reduces exciton–phonon coupling, therefore suppressing excitonic localization and quenching the original self-trapped exciton emission. Notably, further compression triggers excitonic delocalization to induce intense free exciton emission, accompanied with reduced carrier effective masses and improved charge distribution. Controlled high-pressure investigations indicate that the ribbon width of n > 2 is necessary to realize excitonic delocalization and generate free exciton emissions in similar quasi-one-dimensional hybrid metal halides. This work presents an important photophysical process of excitonic transitions from self-trapped exciton emission to free exciton emission in quasi-one-dimensional hybrid metal halides without chemical regulation, promoting the rational synthesis of hybrid metal halides with desired excitonic emissions.

Advantages of Ultrathin AlN/GaN/AlN Quantum Wells for Excitonic Population Distribution and Transition Features Studied by Phononic–Excitonic–Radiative Model

Excitons are expected to be a high‐efficiency emission source in UV light‐emitting devices. However, the damping of the excitonic laser oscillation has been reported under conditions where the excitonic states are expected to be populated in the conventional theory. In order to understand the exciton dynamics under the thermal nonequilibrium state, a theoretical model including various energy species in semiconductors such as electrons, phonons, and photons is required. Herein, a 2D phononic–excitonic–radiative model is constructed to analyze the exciton dynamics in a 2D system. 2D excitons with four principal quantum number states and the continuum in the lowest energy level of the AlN/GaN/AlN quantum wells are considered. It is found that the 2D phonon significantly augments the excitation transition rate. When the high recombination rate corresponding to stimulated emission is considered, the exciton binding energy of 108 meV is not enough to reduce the population in the high‐order discreet states and the continuum states, while the binding energy of 215 meV corresponding to the one monolayer GaN has an advantage of reducing these populations. The analysis of population flux has an advantage in discussing the increase in the kinetic energy transfer to the 1S exciton.

One-dimensional Dexter-type excitonic topological phase transition

The concept of the Su-Schrieffer-Heeger model, which was successfully introduced in topological photonics, can also be applied to the study of topological excitonics. Here we study the topological properties of a one-dimensional excitonic tight-binding model formed by two-level systems by taking into account the charge transfer and local excitations. The interactions between the two types of excitons give rise to a rich spectrum of physics, including the nontrivial topological phase in the uniform chain, unlike the conventional Su-Schrieffer-Heeger model, the topologically nontrivial flat bands, and, most importantly, the excitonic topological phase transition assisted by the Dexter electron exchange process. The excitonic topological phase leads to the development of “chiral superposition.” The topological edge states are robust because they are protected by the inversion symmetry. Based on our calculations, experiments for observing the edge states optically in a molecular chain are proposed. Published by the American Physical Society 2024

(Invited) Electronic Doping in Two-Dimensional Semiconductors

Quantum-confined semiconductors provide highly tunable optical and electrical properties for a wide variety of emerging applications. Two-dimensional semiconductors possess tunable bandgaps, high charge carrier mobilities, and strong light-matter interactions that can enable applications in photovoltaics, quantum information processing, and spintronics. Electronic doping, the intentional introduction of controlled charge carrier density and type (electrons or holes) is a fundamental enabler for many emerging applications of two-dimensional semiconductors. While electrostatic doping in transistor geometries is useful for certain applications, it is important to develop additional methods based on e.g. molecular redox doping and substitutional atomic doping that can provide tunable Fermi level control in the absence of an applied bias. In this presentation, I will discuss our efforts to develop such doping strategies for a variety of two-dimensional semiconductors. I will discuss how electronic doping modulates opto-electronic properties, including ground-state absorbance, charge transport, and excited-state dynamics in these 2D semiconductors. These studies provide fundamental insights into the degree to which molecular and substitutional doping strategies can modulate Fermi level, charge transport, and excitonic optical transitions in 2D semiconductors.

In Situ Investigation of Defect Site Formation in Carbon Nanotubes

Semiconducting single-walled carbon nanotubes (SWCNTs) exhibit a photostable excitonic fluorescence in the short wave near-infrared (SWIR). Recently, the covalent functionalization of nanotubes opened new avenues to manipulate their excitonic fluorescence [1]. These “organic color centers (OCCs)” act as localized potential wells on the nanotube surface, trapping locally otherwise diffusing excitons. This effectively results in an increase in the SWCNT emission, the trapped excitons avoiding possible quenching sites along the nanotube surface (structural defects, nanotube ends) [2]. This new radiative pathway results in a shifting of the SWCNT emission towards longer wavelengths and allows SWCNT excitation on their first-order excitonic transition (ca. SWIR) [3]. Altogether, these properties make OCC-functionalized SWCNTs particularly attractive for various applications ranging from biological imaging to quantum information. Yet, the functionalization reaction of SWCNTs with OCC is still poorly understood, stochastic and, as a result, poorly controlled. To gain knowledge and control over these reactions, we developed a two-color imaging platform to image simultaneously both the SWCNT and OCC emissions in situ during the functionalization reaction [4]. We will present how this platform allows to monitor the kinetics of the functionalization reaction and further discuss our findings which provide insights on the interactions existing between OCCs and the SWCNT surface.[1] A. H. Brozena et al., Nat. Rev. Chem., vol. 3, no. 6, pp. 375–392, 2019[2] N. Danné et al., ACS Nano, vol. 12, no. 6, pp. 6059–6065, 2018[3] A. K. Mandal et al., Sci. Rep., vol. 10, no. 1, pp. 1–9, 2020[4] B.P. Lambert et al., in preparation

Tuning the electronic structure of monolayer MoS2 towards metal like via vanadium doping

Doping of two-dimensional layered semiconducting materials is becoming pivotal in tailoring their electronic properties, enabling the development of advanced electronic and optoelectronic devices, where the selection of dopant is important. Here, we demonstrate the potential of substitutional vanadium (V) doping in monolayer molybdenum disulfide (MoS2) lattice in different extents leading to tunable electronic and optoelectronic properties. We found that low-level V doping (∼1 at.%) induces p-type characteristics in otherwise n-type monolayer MoS2, whereas medium-level doping (∼5 at.%) leads to an ambipolar semiconductor. Degenerately doped MoS2 (∼9 at.%) facilitates a transition from semiconducting towards metallic (metal-like) with reduced electrical resistivity (∼4.5 Ωm of MoS2 to ∼2.2×10−5Ωm), low activation energy for transport (∼11 meV), and electric field independent drain current in field effect transistor–based transfer characteristics. A detailed temperature- and power-dependent photoluminescence study along with density functional theory–based calculations in support unravels the emergence of an excitonic transition at ∼850 nm with its intensity dependent on the amount of vanadium. This study shows the potential of V doping in MoS2 for generating multifunctional two-dimensional materials for next generation electronics, optoelectronics, and interconnects with systematic control over its electronic structure in a wide range. Published by the American Physical Society 2024