Exciton Splitting Research Articles

Revealing and Manipulating Hidden Fine-Structure Coherence of Bright Excitons in CsPbI3 Perovskite Quantum Dots.

Observation and understanding of fine-structure splitting of bright excitons in lead halide perovskite quantum dots (QDs) are crucial to their emerging applications in quantum light sources and exciton coherence manipulation. Recent studies demonstrate that ensemble-level polarization-resolved transient absorption spectroscopy can reveal the quantum beats arising from the coherence between two fine-structure levels. Here we report the observation of an extra fine-structure quantum coherence hidden in previous studies by using cryo-magnetic quantum beat spectroscopy. In ∼6 nm CsPbI3 QDs, two splitting energies of 0.25 and 1.20 meV were observed at 1.7 K, which gradually increased to 0.74 and 1.55 meV, respectively, when a longitudinal magnetic field up to 7 T was applied. The field dependence allowed us to extract two distinct nominal Landé g-factors corresponding to QDs with different orientations with respect to the external field.

Halogen-Dependent Circular Dichroism and Magneto-Photoluminescence Effects in Chiral 2D Lead Halide Perovskites.

Chiral lead halide perovskites (chiral LHPs) have emerged as one of the best candidates for opto-spintronics due to their large spin-orbit coupling (SOC) and unique chirality-induced spin selectivity (CISS) even in the absence of a magnetic field. Here, we report the impact of halide composition on circular dichroism (CD) and magneto-photoluminescence (PL) effects of chiral 2D LHPs (R/S-MBA)2PbBrxI4-x (MBA = C6H5CH2(CH3)NH3). By tuning the mixing ratio of Br/I halide anions, we find that (R/S-MBA)2PbBrxI4-x thin films exhibit tunable and wide wavelength range CD signals. Simultaneously, the main CD signals near the exciton absorption band gradually blue shift until they disappear. Moreover, the halogen-dependent negative magneto-PL effects of (R/S-MBA)2PbBrxI4-x thin films excited by left/right circularly polarized light can be detected at room temperature. We demonstrated that the halide composition can effectively modulate exciton splitting and chirality transfer in (R/S-MBA)2PbBrxI4-x owing to the chirality-induced SOC and crystalline structure transition, which lead to the adjustable CD signals. The interplay of Rashba-type band spin splitting and spin mixing among bright triplet exciton states is responsible for the halogen-dependent magneto-PL effect of chiral 2D LHPs. This study enables chiral 2D LHPs with CISS to be a new class of promising opto-spintronics materials for exploring high-performance spin-light-emitting diodes by halide engineering.

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.

Cavity Floquet engineering

Floquet engineering is a promising tool to manipulate quantum systems coherently. A well-known example is the optical Stark effect, which has been used for optical trapping of atoms and breaking time-reversal symmetry in solids. However, as a coherent nonlinear optical effect, Floquet engineering typically requires high field intensities obtained in ultrafast pulses, severely limiting its use. Here, we demonstrate using cavity engineering of the vacuum modes to achieve orders-of-magnitude enhancement of the effective Floquet field, enabling Floquet effects at an extremely low fluence of 450 photons/μm2. At higher fluences, the cavity-enhanced Floquet effects lead to 50 meV spin and valley splitting of WSe2 excitons, corresponding to an enormous time-reversal breaking, non-Maxwellian magnetic field of over 200 T. Utilizing such an optically controlled effective magnetic field, we demonstrate an ultrafast, picojoule chirality XOR gate. These results suggest that cavity-enhanced Floquet engineering may enable the creation of steady-state or quasi-equilibrium Floquet bands, strongly non-perturbative modifications of materials beyond the reach of other means, and application of Floquet engineering to a wide range of materials and applications.

Frenkel and Charge‐Transfer Excitonic Couplings Strengthened by Thiophene‐Type Solvent Enables Binary Organic Solar Cells with 19.8 % Efficiency

AbstractOvercoming the trade‐off between short‐circuited current (Jsc) and open‐circuited voltage (Voc) is important to achieving high‐efficiency organic solar cells (OSCs). Previous works modulated the energy gap between Frenkel local exciton (LE) and charge‐transfer (CT) exciton, which served as the driving force of exciton splitting. Differently, our current work focuses on the modulation of LE‐CT excitonic coupling (tLE‐CT) via a simple but effective strategy that the 2‐chlorothiophene (2Cl−Th) solvent utilizes in the treatment of OSC active‐layer films. The results of our experimental measurements and theoretical simulations demonstrated that 2Cl−Th solvent initiates tighter intermolecular interactions with non‐fullerene acceptor in comparison with that of traditional chlorobenzene solvent, thus suppressing the acceptor's over‐aggregation and retarding the acceptor crystallization with reduced trap. Critically, the resulting shorter distances between donor and acceptor molecules in the 2Cl−Th treated blend efficiently strengthen tLE‐CT, which not only promotes exciton splitting but also reduces non‐radiative recombination. The champion efficiencies of 19.8 % (small‐area) with superior operational reliability (T80: 586 hours) and 17.0 % (large‐area) were yielded in 2Cl−Th treated cells. This work provided a new insight into modulating the exciton dynamics to overcome the trade‐off between Jsc and Voc, which can productively promote the development of the OSC field.

Frenkel and Charge-Transfer Excitonic Couplings Strengthened by Thiophene-Type Solvent Enables Binary Organic Solar Cells with 19.8 % Efficiency.

Overcoming the trade-off between short-circuited current (Jsc) and open-circuited voltage (Voc) is important to achieving high-efficiency organic solar cells (OSCs). Previous works modulated the energy gap between Frenkel local exciton (LE) and charge-transfer (CT) exciton, which served as the driving force of exciton splitting. Differently, our current work focuses on the modulation of LE-CT excitonic coupling (tLE-CT) via a simple but effective strategy that the 2-chlorothiophene (2Cl-Th) solvent utilizes in the treatment of OSC active-layer films. The results of our experimental measurements and theoretical simulations demonstrated that 2Cl-Th solvent initiates tighter intermolecular interactions with non-fullerene acceptor in comparison with that of traditional chlorobenzene solvent, thus suppressing the acceptor's over-aggregation and retarding the acceptor crystallization with reduced trap. Critically, the resulting shorter distances between donor and acceptor molecules in the 2Cl-Th treated blend efficiently strengthen tLE-CT, which not only promotes exciton splitting but also reduces non-radiative recombination. The champion efficiencies of 19.8 % (small-area) with superior operational reliability (T80: 586 hours) and 17.0 % (large-area) were yielded in 2Cl-Th treated cells. This work provided a new insight into modulating the exciton dynamics to overcome the trade-off between Jsc and Voc, which can productively promote the development of the OSC field.

Room-temperature field-free valley exciton splitting in monolayer semiconductors achieved by perpendicular magnetic proximity effect

Room-temperature field-free valley exciton splitting in monolayer semiconductors achieved by perpendicular magnetic proximity effect

In‐Situ Removable Solid Additive Optimizing Active Layer and Cathode Interlayer of Organic Solar Cells

AbstractIn situ removable (ISR) solid additive can employ cold sublimation process to optimize active layer morphology for organic solar cells (OSCs), thus remaining unique potential. Herein, a feasible guideline is proposed to discover a new ISR solid additive 1‐bromo‐4‐chlorobenzene (CBB), whose removing time (TR) is between those of reported ISR solid additives 1,4‐dichlorobenzene (DCB) and 1‐chloro‐4‐iodobenzene (CIB). The CBB with a moderate TR is beneficial for affording the optimal active layer morphology and achieving the highest power conversion efficiency (PCE) of 18.58% for D18:L8‐BO binary active layer, as supported by the most efficient exciton splitting, the fastest exciton transfer, and the most balanced carrier transports. Due to the unique ISR ability, DCB, CBB, and CIB are further proposed to optimize the aggregation of PDINN cathode interlayer. Particularly, the CBB‐ and CIB‐treated PDINN interlayers afforded the D18:L8‐BO based binary OSCs with excellent PCEs of 19.38% and 19.26%, along with remarkable fill factors of 80.98% and 81.37%, respectively. The CBB‐ and CIB‐treated PDINN interlayers can suppress non‐radiative recombination of the devices, resulting in higher open‐circuit voltage. This work not only provides an effective approach to flourish ISR solid additives but also expands the application of the ISR solid additive in OSCs.

Quadrupolar and dipolar excitons in symmetric trilayer heterostructures: insights from first principles theory

Excitons in van der Waals heterostructures come in many different forms. In bilayer structures, the electron and hole may be localized on the same layer or they may be separated forming an interlayer (IL) exciton with a finite out-of-plane dipole moment. Using first principles calculations, we investigate the excitons in a symmetric WS2/MoS2/WS2 heterostructure in the presence of a vertical electric field. The excitons exhibit a quadratic Stark shift for low field strengths and a linear Stark shift for stronger fields. This behavior is traced to the coupling of IL excitons with opposite dipole moments, which lead to the formation of quadrupolar excitons at small fields. The formation of quadrupolar excitons is determined by the relative size of the electric field-induced splitting of the dipolar excitons and the coupling between them given by the hole tunneling across the MoS2 layer. For the inverted structure, MoS2/WS2/MoS2, the dipolar excitons are coupled by electron tunneling across the WS2 layer. Because this effect is much weaker, the resulting quadrupolar excitons are more fragile and break at a weaker electric field.

Polarized Photodetectors Based on 2D 2H‐MoTe2/1T'‐MoTe2/MoSe2 Van Der Waals Heterojunction

AbstractThe van der Waals heterojunction based on transition metal dichalcogenides has broad research value and application prospects as the basic material for advanced near‐infrared polarized photodetectors. a type II heterojunction based on the 2H‐MoTe2/1T′‐MoTe2/MoSe2 structure is reported for photovoltaic photodetectors. Notably, this device generates a self‐powered photocurrent, eliminating the need for an external bias or gate voltage. This device has the ability to detect polarized light, and its photocurrent anisotropy ratio is 55. The device performance is significantly amplified due to the proficient facilitation of electron‐hole separation through the type II band structure of MoSe2 at the bottom and 2H‐MoTe2 at the top, as well as enhanced exciton splitting by 1T′‐MoTe2 situated in the middle. Consequently, the device demonstrates exceptional proficiency, presenting a noteworthy response rate of 0.76 A W−1, a high detection rate of 3 × 109 Jones, an elevated EQE of 71%, and rapid rising and falling response speeds of 13 ms/10 ms respectively. Moreover, the device's anisotropy ratio of photocurrent highlights its sensitivity to polarized light, making it a promising candidate for applications in polarized photodetection. Overall, this innovative heterostructure opens new avenues for exploring and developing advanced optoelectronic devices based on 2D van der Waals materials.

Fine structure splitting cancellation in highly asymmetric InAs/InP droplet epitaxy quantum dots

We find the fine structure splitting (FSS) of a single exciton, which splits its degenerate ground-state manifold into singlets, nearly vanishes in highly asymmetric quantum dots (QDs) due to the cancellation of splitting effects with markedly different origin. The dots simulated are those that emerge on top of etch pits through the droplet epitaxy growth process; these etch pit dots break square (C4v) spatial symmetry, which has been previously associated with small FSS. Configuration interaction calculations predict a vanishing FSS at a specific finite etch pit displacement from the center of the dot, for a structure far from square symmetry. We thus predict that highly asymmetric QDs may still display negligible FSS, providing avenues for high-fidelity generation of indistinguishable, polarization entangled photon pairs on demand. Published by the American Physical Society 2024

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.

Spin-Orbit Effects on Exciton Complexes in Diamond.

Ultrafine splittings are found in the optical absorption spectra of boron-doped diamond measured with high resolution. An analytical model of an exciton complex is developed, which permits assigning all absorption lines and sizing the interactions among the constituent charges and crystal field. We conclude that the entry of split-off holes in the acceptor-bound exciton fine structure yields two triplets separated by a spin-orbit splitting of 14.3meV. Our findings thereby resolve a long-standing controversy [R. Sauer et al., Revised fine splitting of excitons in diamond, Phys. Rev. Lett. 84, 4172 (2000).PRLTAO0031-900710.1103/PhysRevLett.84.4172; M. Cardona et al., Comment on "Revised fine splitting of excitons in diamond,", Phys. Rev. Lett. 86, 3923 (2001).PRLTAO0031-900710.1103/PhysRevLett.86.3923; R. Sauer and K. Thonke, Sauer and Thonke reply, Phys. Rev. Lett. 86, 3924 (2001).PRLTAO0031-900710.1103/PhysRevLett.86.3924], revealing the underlying physics common in diverse semiconductors, including diamond.

Two-Dimensional Electronic Spectroscopy Reveals Dynamics within the Bright Fine Structure of CdSe Quantum Dots.

Semiconductor quantum dots are characterized by a discrete excitonic structure featuring coarse as well as fine structure. The lowest fine structure states have splittings into bright-dark states which are now well confirmed by single dot spectroscopy. In contrast, the splitting of the lowest coarse exciton into bright-bright fine structure states has not been observed nor the dynamics between these states. Here, we use the unique combination of time and energy resolution of two-dimensional electronic spectroscopy to directly observe the fine structure splittings into a bright-bright doublet. These splittings are strongly size dependent, with population relaxation on the <100 fs time scale.

TD‐DFT analysis of the excitation of H‐dimers of cationic dyes in an aqueous solution using functionals without additional dispersion correction

AbstractThis work is a development and extension of the previous one (DOI: 10.1039/d3cp00882g). Here, H‐dimers of acridine (acridine orange—AO and proflavine—PF), thiazine (methylene blue—MB and thionine—TH), and oxazine (brilliant cresyl blue—BCB and Nile blue—NB) dyes were modeled using hybrid functionals with a large proportion of exact Hartree–Fock exchange and long‐range correction. It turned out that nine functionals (LC‐ωHPBE, M06HF, M052X, M062X, M08HX, M11, MN15, SOGGA11X, and ωB97XD) reliably stabilize these molecular aggregates in both the ground and excited states. In addition, these functionals ensure that the conditions for transition moments (M(dimer) ≈ M(monomer) from strong coupling theory for H‐aggregates) and absorption maxima (λmax(dimer) &lt; λmax(monomer) from Kasha exciton theory) are met. The S2 excited state stabilizes the H‐dimers more strongly than the ground state, while the S1 state stabilizes even more than S2. This is due to the large overlap between the corresponding molecular orbitals (LUMO &gt; HOMO−1 &gt; HOMO). When calculating the vibronic absorption spectra, the best agreement with the experiment for AO2, PF2, and NB2 showed the M08HX functional, and M11—for MB2 and BCB2. For dye monomers, these functionals gave the worst agreement, and MN15 demonstrated the closest similarity to the experiment. Vibronic absorption spectra for AO2, MB2, BCB2, and NB2 were calculated for the first time. The exciton splitting is calculated, which for MB2 is in good agreement with the experimental value.

Exciton interactions of chlorophyll tetramer in water-soluble chlorophyll-binding protein BoWSCP

The exciton interaction of four chlorophyll a (Chl a) molecules in a symmetrical tetrameric complex of the water-soluble chlorophyll-binding protein BoWSCP was analyzed in the pH range of 3–11. Exciton splitting ΔE = 232 ± 2 cm−1 of the Qy band of Chl a into two subcomponents with relative intensities of 78.1 ± 0.7 % and 21.9 ± 0.7 % was determined by a joint decomposition of the absorption and circular dichroism spectra into Gaussian functions. The exciton coupling parameters were calculated based on the BoWSCP atomic structure in three approximations: the point dipole model, the distributed atomic monopoles, and direct ab initio calculations in the TDDFT/PCM approximation. The Coulomb interactions of monomers were calculated within the continuum model using three values of optical permittivity. The models based on the properties of free Chl a in solution suffer from significant errors both in estimating the absolute value of the exciton interaction and in the relative intensity of exciton transitions. Calculations within the TDDFT/PCM approximation reproduce the experimentally determined parameters of the exciton splitting and the relative intensities of the exciton bands. The following factors of pigment-protein and pigment–pigment interactions were examined: deviation of the macrocycle geometry from the planar conformation of free Chl; the formation of hydrogen bonds between the macrocycle and water molecules; the overlap of wave functions of monomers at close distances. The most significant factor is the geometrical deformation of the porphyrin macrocycle, which leads to an increase in the dipole moment of Chl monomer from 5.5 to 6.9 D and to a rotation of the dipole moment by 15° towards the cyclopentane ring. The contributions of resonant charge-transfer states to the wave functions of the Chl dimer were determined and the transition dipole moments of the symmetric and antisymmetric charge-transfer states were estimated.

Multiexciton spectra of molecular aggregates: application to photosynthetic antenna complexes.

We perform theoretical studies of nonlinear spectral responses of molecular aggregates upon multiple electronic excitations. It is shown that the transient absorption (TA) spectra exhibit gradual shifting to short wavelengths upon an increase in excitation energy accompanied by population of higher-order exciton manifolds. This transformation of the TA profile reflects a character of the exciton splitting and, therefore, is strongly dependent on the aggregate shape and size as well as on the exciton couplings and disorder of the site energies. The theory is applied for modeling of the intensity-dependent TA spectra of a light-harvesting LH1 antenna from a photosynthetic purple bacterium. Fitting of the data allowed verification of the exciton model of the complex (enabling us to differentiate between the correlated (elliptical) and uncorrelated energetic disorder). We found that the difference between the TA spectra corresponding to the absorption of one and two quanta suggests the presence of strong uncorrelated disorder (in agreement with earlier models of bacterial LH1/LH2 antennas). Nonlinear spectroscopy with multiple excitations may also be useful for exploring the exciton structure of other photosynthetic antennas and similar molecular systems.

Colloidal 2D Mo1-xWxS2 nanosheets: an atomic- to ensemble-level spectroscopic study.

Composition dependent tuning of electronic and optical properties in semiconducting two-dimensional (2D) transition metal dichalcogenide (TMDC) alloys is promising for tailoring the materials for optoelectronics. Here, we report a solution-based synthesis suitable to obtain predominantly monolayered 2D semiconducting Mo1-xWxS2 nanosheets (NSs) with controlled composition as substrate-free colloidal inks. Atomic-level structural analysis by high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectroscopy (EDXS) depicts the distribution of individual atoms within the Mo1-xWxS2 NSs and reveals the tendency for domain formation, especially at low molar tungsten fractions. These domains cause a broadening in the associated ensemble-level Raman spectra, confirming the extrapolation of the structural information from the microscopic scale to the properties of the entire sample. A characterization of the Mo1-xWxS2 NSs by steady-state optical spectroscopy shows that a band gap tuning in the range of 1.89-2.02 eV (614-655 nm) and a spin-orbit coupling-related exciton splitting of 0.16-0.38 eV can be achieved, which renders colloidal methods viable for upscaling low cost synthetic approaches toward application-taylored colloidal TMDCs.

Chiroptical properties of cyanine aggregates: hierarchical modelling from monomers to bundles.

Some achiral cyanine dyes form well-ordered chiral assemblies exhibiting pronounced Circular Dichroism (CD) and Circularly Polarized Luminescence (CPL). Notably, achiral C8O3 cyanines self-assemble into tubular J-aggregates, which further organize into bundles displaying bisignate CD spectrum - hallmark of an exciton coupled system - and an unusual bisignated CPL. In contrast, the tubular aggregates display a monosignate CD spectrum. The mechanism underlying these intriguing features remains elusive. In the present work, a quantum-mechanical exciton model is proposed to elucidate the (chir)optical behaviour of C8O3 aggregates. A herringbone arrangement of C8O3 dyes within the tubular aggregates well reproduces the observed spectral signatures. The anomalous observation of a singular CD peak in tubular aggregates is ascribed to the intrinsic chirality of the monomeric units inside the aggregate, whereas the CD doublet characterizing the bundles is attributed to the exciton coupling between the constituent tubes. The bisignated CPL signal observed in bundles reveals significant anti-Kasha emission at room temperature and is quantitatively addressed accounting for a very tiny exciton splitting leading to a sizable thermal population of both exciton states. This study provides crucial insights on the complexity of C8O3 aggregation and on the origin of chiroptical response at various aggregation stages.

Band Edge Excitons and Amplified Spontaneous Emission of Mercury Chalcogenide Nanoplatelets

AbstractColloidal nanoplatelets of HgSe and HgTe prepared indirectly through cation exchange reactions can transfer many of the advantageous properties of atomically precise, 2D cadmium chalcogenides to the near‐infrared (NIR) spectral window. In this work, HgSe and HgTe nanoplatelets are studied to understand their fundamental photophysical properties, particularly those areas of similarity and difference from cadmium‐based NPLs, and to examine their potential as optical gain media. Similar to cadmium chalcogenide NPLs, low‐temperature photoluminescence of HgTe NPLs displays two‐color emission that depends on temperature, sample, fluence, excitation frequency, and irradiation time. Both HgTe and HgSe show nanosecond emission dynamics at temperatures as low as 2.5 K, with no indication that bright‐dark excitonic splitting governs the low‐temperature photoluminescence. Collectively, experimental data is most consistent with emission from a negative trion state at low temperature. Although the mercury chalcogenide nanoplatelets are shown to have broadened optical resonances compared to the cadmium chalcogenides from which they are derived, they retain slow Auger recombination and can display low‐threshold amplified spontaneous emission in the NIR spectral window. Optical pumping thresholds for HgTe NPLs are observed as low as 4.4 µJ cm−2 and highlight the potential 2D nanoplatelets as gain medium in the near‐infrared.