Anisotropic Exciton Research Articles

A non-symmetric room-temperature tristriazolotriazine liquid crystal

Tristriazolotriazine (TTT) has emerged as an easily accessible electron-deficient heterocyclic core for discotic liquid crystals (LCs). Materials that are liquid-crystalline at room temperature, i.e., do not crystallize in ambient conditions, are of particular interest when the LC state is prone to offer advantages in optoelectronic devices, e.g., for anisotropic charge or exciton transport, or anisotropic light emission. However, there has been no report of non-symmetric TTT LCs, i.e., with unequal arms. Here, we report two non-symmetric compounds derived from the TTT core. Their non-symmetry, combined with a high number of peripheral alkyl chains, is found to promote Colh mesomorphism over a broad temperature range including room temperature. The non-symmetry also induces an increase in the emission quantum yield, compared to symmetric analogs.

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.

Electronic Couplings for Triplet-Triplet Annihilation Upconversion in Crystal Rubrene.

Triplet-triplet annihilation photon upconversion (TTA-UC) is a process able to repackage two low-frequency photons into light of higher energy. This transformation is typically orchestrated by the electronic degrees of freedom within organic compounds possessing suitable singlet and triplet energies and electronic couplings. In this work, we propose a computational protocol for the assessment of electronic couplings crucial to TTA-UC in molecular materials and apply it to the study of crystal rubrene. Our methodology integrates sophisticated yet computationally affordable approaches to quantify couplings in singlet and triplet energy transfer, the binding of triplet pairs, and the fusion to the singlet exciton. Of particular significance is the role played by charge-transfer states along the b-axis of rubrene crystal, acting as both partial quenchers of singlet energy transfer and mediators of triplet fusion. Our calculations identify the π-stacking direction as holding notable triplet energy transfer couplings, consistent with the experimentally observed anisotropic exciton diffusion. Finally, we have characterized the impact of thermally induced structural distortions, revealing their key role in the viability of triplet fusion and singlet fission. We posit that our approaches are transferable to a broad spectrum of organic molecular materials, offering a feasible means to quantify electronic couplings.

Phonon-Driven Femtosecond Dynamics of Excitons in Crystalline Pentacene from First Principles.

Nonradiative exciton relaxation processes are critical for energy transduction and transport in optoelectronic materials, but how these processes are connected to the underlying crystal structure and the associated electron, exciton, and phonon band structures, as well as the interactions of all these particles, is challenging to understand. Here, we present a first-principles study of exciton-phonon relaxation pathways in pentacene, a paradigmatic molecular crystal and optoelectronic semiconductor. We compute the momentum- and band-resolved exciton-phonon interactions, and use them to analyze key scattering channels. We find that both exciton intraband scattering and interband scattering to parity-forbidden dark states occur on the same ∼100 fs timescale as a direct consequence of the longitudinal-transverse splitting of the bright exciton band. Consequently, exciton-phonon scattering exists as a dominant nonradiative relaxation channel in pentacene. We further show how the propagation of an exciton wave packet is connected with crystal anisotropy, which gives rise to the longitudinal-transverse exciton splitting and concomitant anisotropic exciton and phonon dispersions. Our results provide a framework for understanding the role of exciton-phonon interactions in exciton nonradiative lifetimes in molecular crystals and beyond.

Characterization of 2D Transition Metal Dichalcogenides Through Anisotropic Exciton Behaviors.

This study reports the first attempt to characterize the quality, defects, and strain of as-grown monolayer transition metal dichalcogenide (TMDC)-based 2D materials through exciton anisotropy. A standard ellipsometric parameter (Ψ) to observe anisotropic exciton behavior in monolayer 2D materials is used. According to the strong exciton effect from phonon-electron coupling processes, the change in the exciton in the Van Hove singularity is sensitive to lattice distortions such as defects and strain. In comparison with Raman spectroscopy, the variations in exciton anisotropy in Ψ are more sensitive for detecting slight changes in the quality and strain of monolayer TMDC films. Moreover, the optical power requirement for TMDC characterization through exciton anisotropy in Ψ is ≈10-5mWcm-2, which is significantly less than that of Raman spectroscopy (≈106mWcm-2). The standard deviation of the signals varies with strain (defects) in Raman spectra and exciton anisotropies in Ψ are 0.700 (0.795) and 0.033 (0.073), indicating that exciton anisotropy is more sensitive to slight changes in the quality of monolayer TMDC films.

Hyperbolic exciton polaritons in a van der Waals magnet

Exciton polaritons are quasiparticles of photons coupled strongly to bound electron-hole pairs, manifesting as an anti-crossing light dispersion near an exciton resonance. Highly anisotropic semiconductors with opposite-signed permittivities along different crystal axes are predicted to host exotic modes inside the anti-crossing called hyperbolic exciton polaritons (HEPs), which confine light subdiffractionally with enhanced density of states. Here, we show observational evidence of steady-state HEPs in the van der Waals magnet chromium sulfide bromide (CrSBr) using a cryogenic near-infrared near-field microscope. At low temperatures, in the magnetically-ordered state, anisotropic exciton resonances sharpen, driving the permittivity negative along one crystal axis and enabling HEP propagation. We characterize HEP momentum and losses in CrSBr, also demonstrating coupling to excitonic sidebands and enhancement by magnetic order: which boosts exciton spectral weight via wavefunction delocalization. Our findings open new pathways to nanoscale manipulation of excitons and light, including routes to magnetic, nonlocal, and quantum polaritonics.

Anisotropic excitonic absorption in SbI3 films: Theory and experiment

Structurally characterized antimony triiodide films grown by vacuum thermal evaporation exhibit anisotropic exciton formation at room temperature for different (hkl) oriented growth. Band structure of monoclinic SbI3 was calculated using Density functional Theory with appropriate functional along with the absorption spectra of different (hkl) planes for comparing with the experimental results. The indirect band gap of 2.8 eV determined by measured absorption spectra matches closely with the calculated 2.66 eV. All (hkl) oriented films show one exciton at 3.56 eV which can be interpreted as direct type along D symmetry from the band structure. Similarly, the two excitons at 2.95 eV and 3.30 eV appearing for (130) oriented films can also be direct either at D or B symmetry. All three excitonic transitions are found to be from Iodine p states to Antimony p states.

Anisotropic Excitons Reveal Local Spin Chain Directions in a van der Waals Antiferromagnet.

A long-standing pursuit in materials science is to identify suitable magnetic semiconductors for integrated information storage, processing, and transfer. Van der Waals magnets have brought forth new material candidates for this purpose. Recently, sharp exciton resonances in antiferromagnet NiPS3 have been reported to correlate with magnetic order, that is, the exciton photoluminescence intensity diminishes above the Néel temperature. Here, it is found that the polarization of maximal exciton emission rotates locally, revealing three possible spin chain directions. This discovery establishes a new understanding of the antiferromagnet order hidden in previous neutron scattering and optical experiments. Furthermore, defect-bound states are suggested as an alternative exciton formation mechanism that has yet to be explored in NiPS3 . The supporting evidence includes chemical analysis, excitation power, and thickness dependent photoluminescence and first-principles calculations. This mechanism for exciton formation is also consistent with the presence of strong phonon side bands. This study shows that anisotropic exciton photoluminescence can be used to read out local spin chain directions in antiferromagnets and realize multi-functional devices via spin-photon transduction.

Anisotropic exciton–polaritons in 2D single-crystalline PEA2PbBr4 perovskites at room temperature

Two-dimensional (2D) single-crystalline perovskites are a suitable material for investigating the strong exciton–photon interaction due to the large exciton binding energy. Here, we grow high-quality 2D single-crystalline PEA2PbBr4 thin film in situ in between a pair of distributed Bragg reflectors and construct an anisotropic exciton–polariton microcavity. Clear evidence for strong exciton–photon coupling is observed and represented by a large coupling strength of 211.8 meV. The observed transverse electric–transverse magnetic splitting at the point where the in-plane wave vector is zero indicates crystal birefringence. The effective refractive indices for these two orthogonal polarization directions are derived to have a large difference, corresponding to a material index difference of 0.28, and then an in-plane refractive index ellipse is built for the material. This work shows that the 2D anisotropic perovskite microcavity can not only behave as a platform for characterizing the anisotropic properties of a material but also as a promising room-temperature polaritonic device.

Optical properties and polaritons of low symmetry 2D materials

Low symmetry 2D materials with intrinsic in-plane anisotropic optical properties and high tunability provide a promising platform to explore and manipulate light–matter interactions. To date, dozens of in-plane anisotropic 2D materials with diverse band structures have been discovered. They exhibit rich optical properties, indicating great potential for novel applications in optics, photonics, and optoelectronics. In this paper, we thoroughly review the anisotropic optical properties and polaritons in many kinds of low symmetry 2D materials, aiming to elicit more research interest in this field. First, the optical properties of anisotropic 2D semiconductors, including interband absorption, photoluminescence, excitons, and band structure engineering for tuning optical responses, are introduced. Then fundamentals and advances in experiments of hyperbolic polaritons in anisotropic 2D materials, including phonon, plasmon, and exciton polaritons, are discussed. Finally, a perspective on promising research directions is given.

Anisotropic exciton drift-diffusion in a monolayer WS2x Se(2–2x) alloy with a gradually changing composition

We demonstrate anisotropic exciton drift-diffusion in a WS2x Se(2–2x) alloy monolayer with a gradually changing exciton energy caused by the spatial variation in the chalcogen composition ratio. The photoluminescence (PL) images under isotropic laser excitation are extended toward the lower exciton energy side. Moreover, the degree of asymmetry in the PL image increases at the positions with a steep exciton energy gradient. The anisotropy in the PL images and its correlation with the exciton energy gradient are reproduced considering the exciton kinetics obeying a drift-diffusion equation. The findings may support the development of excitonic devices using transition metal dichalcogenides.

Anisotropic exciton states and excitonic absorption spectra in a freestanding monolayer black phosphorus

The anisotropic exciton states and excitonic absorption spectra in a freestanding monolayer black phosphorus (BP) are theoretically investigated by a variationally optimized diagonalization method based on a two-dimensional (2D) nonorthogonal Laguerre basis. The exciton Hamiltonian works in the anisotropic form of the kinetic term, which has an advantage of a fully analytical expression for the matrix elements of the Hamiltonian. The energy of 1 s state is in good agreement with the reported result based on the Numerov approach. The exciton states are elongated along the x direction, while their radial nodes occur in the y direction, which leads to anomalous anisotropy in some excited states. The excitonic absorption spectra of monolayer BP possess highly anisotropic features and more peaks. The large anisotropy of the effective masses leads to the mixture of exciton states with different quantum numbers n and l , which results in highly nonhydrogenic and anisotropic features. These unusual excitonic and optical properties demonstrate the potential applications of monolayer BP in optoelectronics. Compared with my proposed diagonalization method, the variational method presented in the literatures is not a good approximation. My proposed variationally optimized diagonalization method based on a 2D nonorthogonal Laguerre basis is proven to be efficient and reliable in calculating highly accurate exciton states of anisotropic 2D materials . • A fully analytical expression of the matrix elements of the Hamiltonian is obtained. • The energy of 1 s state is in good agreement with the reported result based on the Numerov approach. • The states are elongated along the x direction while radial nodes occur in the y direction. • The excitonic absorption spectra possess highly anisotropic features and more peaks. • A 2D nonorthogonal Laguerre basis is efficient and reliable in calculating exciton states of anisotropic materials.

Anisotropic exciton diffusion in atomically-thin semiconductors

Energy transport processes are critical for the efficiency of many optoelectronic applications. The energy transport in technologically promising transition metal dichalcogenides is determined by exciton diffusion, which strongly depends on the underlying excitonic and phononic dispersion. Based on a fully microscopic theory we demonstrate that the valley-exchange interaction leads to an enhanced exciton diffusion due to the emergence of a linear excitonic dispersion and the resulting decreased exciton-phonon scattering. Interestingly, we find that the application of a uniaxial strain can drastically boost the diffusion speed and even give rise to a pronounced anisotropic diffusion, which persists up to room temperature. We reveal that this behaviour originates from the highly anisotropic exciton dispersion in the presence of strain, displaying parabolic and linear behaviour perpendicular and parallel to the strain direction, respectively. Our work demonstrates the possibility to control the speed and direction of exciton diffusion via strain and dielectric engineering. This opens avenues for more efficient and exotic optoelectronic applications of atomically thin materials.

Efficient Long-Range Triplet Exciton Transport by Metal-Metal Interaction at Room Temperature.

Efficient and long-range exciton transport is critical for photosynthesis and opto-electronic devices, and for triplet-harvesting materials, triplet exciton diffusion length ( ) and coefficient ( ) are key parameters in determining their performances. Herein, we observed that PtII and PdII organometallic nanowires exhibit long-range anisotropic triplet exciton LD of 5-7 μm along the M-M direction using direct photoluminescence (PL) imaging technique by low-power continuous wave (CW) laser excitation. At room temperature, via a combined triplet-triplet annihilation (TTA) analysis and spatial PL imaging, an efficient triplet exciton diffusion was observed for the PtII and PdII nanowires with extended close M-M contact, while is absent in nanowires without close M-M contact. Two-dimensional electronic spectroscopy (2DES) and calculations revealed a significant contribution of the delocalized 1/3 [dσ*(M-M)→π*] excited state during the exciton diffusion modulated by the M-M distance.

Efficient Long‐Range Triplet Exciton Transport by Metal–Metal Interaction at Room Temperature

AbstractEfficient and long‐range exciton transport is critical for photosynthesis and opto‐electronic devices, and for triplet‐harvesting materials, triplet exciton diffusion length ( ) and coefficient ( ) are key parameters in determining their performances. Herein, we observed that PtII and PdII organometallic nanowires exhibit long‐range anisotropic triplet exciton LD of 5–7 μm along the M−M direction using direct photoluminescence (PL) imaging technique by low‐power continuous wave (CW) laser excitation. At room temperature, via a combined triplet–triplet annihilation (TTA) analysis and spatial PL imaging, an efficient triplet exciton diffusion was observed for the PtII and PdII nanowires with extended close M−M contact, while is absent in nanowires without close M−M contact. Two‐dimensional electronic spectroscopy (2DES) and calculations revealed a significant contribution of the delocalized 1/3[dσ*(M−M)→π*] excited state during the exciton diffusion modulated by the M−M distance.

Revealing the Quantum-Confined Free Exciton A Anisotropic Emission in a CdS/CdS:SnS2 Superlattice Nanocone via Angle-Resolved Photoluminescence Spectroscopy

The nanostructures with exciton anisotropic emission are important in many applications due to the directionality of the flow of photons and the exciton confinement. Moreover, it is still a challenge to observe exciton anisotropic emission directly due to the limitation of measurement techniques and materials. Here, we observed the anisotropy of free exciton A (FXA) in a CdS/CdS:SnS2 superlattice nanocone by angle-resolved photoluminescence (ARPL) spectroscopy. Raman spectra and in situ spectral mapping indicate quasi-periodic SnS2 layers perpendicular to the nanocone within the CdS/CdS:SnS2 superlattice nanocone. Polarization-dependent ARPL spectra discriminated two exciton series, namely, FXA and free exciton B (FXB). By comparing different CdS nanostructures, FXA is found to be omniscient in different samples, but it is even significant in the CdS/CdS:SnS2 superlattice nanocone due to the local dielectric confinement of SnS2 layers in the nanocone and the enhanced anisotropic exciton–phonon coupling. Meanwhile, ARPL spectra indicated that the FXA emission blue shifts with reducing cross-sectional radius, while the FXB emission does not. The comprehensive understanding of the FXA anisotropic emission and quantum confinement effect in the CdS/CdS:SnS2 superlattice nanocone may trigger the potential applications in future anisotropy-polarized devices and wavelength-tuning lasers.

Defect-engineering-enhanced electrical manipulation of anisotropic excitons in two-dimensional ReS2

Engineering the photoluminescence (PL) properties, such as emission peaks, intensity, and lifetime, is highly desirable for widespread applications. Electric control is a facile and feasible method, and electrical manipulation of the PL properties with a high efficiency becomes increasingly important. ReS2 has excellent environmental stability, distinctive interlayer decoupling, and strong anisotropic properties. Herein, taking ReS2 as a prototype material, we propose a novel strategy to enhance electrical control of anisotropic excitons in ReS2 by defect engineering. Sulfur vacancies have been introduced controllably by mild argon plasma treatment, and contribute to the anisotropic defect-related exciton emission whose polarization direction is almost the same as those of the excitons along the Re–S atomic chains. However, the conversion from the neutral excitons to the defect-related excitons significantly modulate the radiation recombination behavior under a lateral electric field. The defect-engineering-enhanced electrical manipulation of anisotropic excitons paves the way towards an exciton engineering in new 2D electronic and optoelectronic devices.

Singlet Exciton Dynamics of Perylene Diimide- and Tetracene-Based Hetero/Homogeneous Substrates via an Ab Initio Kinetic Monte Carlo Model

Luminescent solar concentrators (LSCs) are devices that trap a portion of the solar spectrum and funnel it toward photon-harvesting devices. The modeling of LSCs at a quantum chemical level, however, remains a challenge due to the complexity of exciton and photon dynamic modeling. This study examines singlet exciton dynamics occurring within a typical LSC device. To do this, we use a rejection-free kinetic Monte Carlo method to predict diffusion lengths, diffusion coefficients, substrate anisotropy, and average exciton lifetimes of perylene diimide (PDI)- and tetracene-based substrates in the low-concentration scheme. Ab initio rate constants are computed using time-dependent density functional theory-based methods. PDI-type substrates are observed to display enhanced singlet exciton transport properties compared to tetracene. Simulations show that substrates with dipole-aligned chromophores are characterized by anisotropic exciton diffusion, with slightly improved transport properties. Finally, a PDI–tetracene substrate is simulated for both disordered and dipole-aligned chromophore configurations. In this multidopant substrate, transport is predominantly mediated by PDI due to the asymmetry in the transport rates between the two dyes considered. We conclude by discussing the properties of multidopant substrates and how they can impact the design of next-generation LSCs.

Geminate exciton fusion fluorescence as a probe of triplet exciton transport after singlet fission

The geminate annihilation of two triplet excitons created by singlet exciton fission is affected by the dimensionality of transport as determined by typically anisotropic triplet exciton mobilities in organic molecular crystals. We analyze this process using a random-walk model where the time dynamics of the geminate annihilation probability is determined by the average exciton hopping times along the crystallographic directions. The model is then applied to the geminate fluorescence dynamics in rubrene, where the main channel for triplet-triplet annihilation is via triplet fusion and subsequent photon emission, and we identify the transitions between transport in one, two, and three dimensions.