Exciton Energy Research Articles

Creating chromaticity palettes and identifying white light emitters through nanocrystal megalibraries.

Halide perovskites are used to fabricate energy-efficient optoelectronic devices. Determining which compositions yield desired chromatic responses is challenging, especially when doping strategies are used. Here, we report a way of mapping the compositional space of halide perovskites to generate a light emission or "chromaticity" palette. Megalibraries consisting of millions of Mn2+-doped PEA2PbX4 (PEA: phenethylammonium, X: halide anions) perovskite nanocrystals were synthesized to screen the compositions that led to specific emission profiles. The chromaticity palette allows one to identify single-composition white light emitters [PEA2Pb1-yMny(Br1-xIx)4 (0 ≤ x ≤ 1, 0 ≤ y ≤ 1)], eliminating the need for trilayer structures in conventional white light-emitting diodes, which are prone to instability and complex device designs. Optical studies reveal that the dual-wavelength photoluminescence emission originates from exciton recombination and energy transfer processes. This study shows how emerging megalibrary capabilities can rapidly advance our understanding of the complex composition-structure-function relationships and be used to accelerate the discovery of next-generation optoelectronic materials.

Phonon-mediated renormalization of exciton energies and absorption spectra in polar semiconductors

Phonon-mediated renormalization of exciton energies and absorption spectra in polar semiconductors

Accuracy of approximate methods for the calculation of fluorescence-type linear spectra with a complex system-bath coupling.

Much can be learned about molecular aggregates by modeling their fluorescence-type spectra. In this study, we systematically describe the accuracy of various methods for simulating fluorescence-type linear spectra in a dimer system with a complex system-environment interaction, which serves as a model for various molecular aggregates, including most photosynthetic light-harvesting complexes (LHCs). We consider the approximate full cumulant expansion (FCE), complex time-dependent Redfield (ctR), time-independent Redfield, and modified Redfield methods and calculate their accuracy as a function of the site energy gap and coupling, excitonic energy gap, and dipole factor (i.e., type of spectrum). We find that the FCE method is the most accurate method for couplings smaller than 300cm-1 at 300K, but this method fails for very strong couplings or low temperatures due to inaccurate modeling of the equilibrium initial state. The ctR method performs well for the calculation of fluorescence and linear anisotropy spectra but poorer for circularly polarized fluorescence spectra or for all spectra when the coupling is strong (∼100cm-1). The Redfield and modified Redfield methods generally perform much more poorly than the ctR and FCE methods-especially for small excitonic energy gaps and strong couplings. We show that accurate modeling of the Stokes shift is crucial and present a version of the ctR method that treats both the Stokes shift and initial state correctly for the parameter ranges in plant LHCs. Apart from the application to LHCs, our results will be useful for the spectral characterization and design of organic molecular aggregates.

A High Throughput Platform to Minimize Voltage and Fill Factor Losses

AbstractOrganic photovoltaics (OPV) now can exceed 20% power conversion efficiency in single junction solar cells. To close the remaining gap to competing technologies, both fill factor and open‐circuit voltage must be optimized. The Langevin reduction factor is a well‐known concept that measures the degree to which charge extraction is favored over charge recombination. It is therefore ideally suited as an optimization target in high‐throughput workflows; however, its evaluation so far requires expert interaction. Here, an integrated high‐throughput workflow is presented, able to obtain the Langevin reduction factor within a few seconds with high accuracy without human intervention and thus suited for autonomous experiments. This is achieved by combining evidence from UV–vis spectra, current–voltage curves, and a novel implementation of microsecond transient absorption kinetics allowing, for the first time, the intrinsic determination of charge absorption cross‐sections, which is crucial to reporting stationary charge densities. The method is demonstrated by varying the donor:acceptor ratio of the high performance OPV blend PM6:Y12. The high reproducibility of the method allows to find a strictly exponential relationship between the PM6 exciton energy and the Langevin reduction factor.

Compositionally Tunable Magneto-optical Properties of Lead-Free Halide Perovskite Nanocrystals.

Inorganic lead-free metal halide perovskites have garnered much attention as low-toxicity alternatives to lead halide perovskites for luminescence and photovoltaic applications. However, the electronic structure and properties of these materials, including the composition dependence of the band structure, spin-orbit coupling, and Zeeman effects, remain poorly understood. Here, we investigated vacancy-ordered Cs3Bi2X9 (X= Cl, Br) perovskite nanocrystals using magnetic circular dichroism spectroscopy. Our results indicate that the excitonic spectra are predominantly composed of direct and indirect band gap transitions and that the Zeeman splitting energy of the direct exciton increases from 0.50 to 0.63 meV at 7 T by substituting Br for Cl. Comparison with analogous results for Cs2AgBiCl6 nanocrystals, obtained by cation substitution, suggests an important effect of charge distribution within electronic bands on the excitonic Zeeman splitting. This work demonstrates that the magneto-optical properties of these materials can be effectively manipulated via chemical composition, suggesting promising applications in photonics, spintronics, and optoelectronics.

Development of Molecular Dynamics Parameters and Theoretical Analysis of Excitonic and Optical Properties in the Light-Harvesting Complex II.

The light-harvesting complex II (LHCII) in green plants exhibits highly efficient excitation energy transfer (EET). A comprehensive understanding of the EET mechanism in LHCII requires quantum chemical, molecular dynamics (MD), and statistical mechanics calculations that can adequately describe pigment molecules in heterogeneous environments. Herein, we develop MD simulation parameters that accurately reproduce the quantum mechanical/molecular mechanical energies of both the ground and excited states of all chlorophyll (Chl) molecules in membrane embedded LHCII. The present simulations reveal that Chl a molecules reside in more inhomogeneous environments than Chl b molecules. We also find a narrow gap between the exciton energy levels of Chl a and Chl b. In addition, we investigate the nature of the exciton states of Chl molecules, such as delocalization, and analyze the optical spectra of LHCII, which align with experimental results. Thus, the MD simulation parameters developed in this study successfully reproduce the excitonic and optical properties of the Chl molecules in LHCII, validating their effectiveness.

High Color Purity Deep‐Blue Multi‐Resonance TADF Material with Narrowband Emission Toward BT.2020 Standard

AbstractDue to higher exciton energy, the deep‐blue organic light‐emitting diodes (OLEDs) are the most challenging among trichromatic emitters. In this work, three novel blue emitters with multi‐resonance (MR) effects are reported based on N,N,5,9‐tetraphenyl‐5,9‐dihydro‐5,9‐diaza‐13b‐boranaphtho[3,2,1‐de]anthracen‐7‐amine (PAB) skeleton, incorporating fluorine and methyl groups. Compound 2FPAB and MePAB exhibit ultra‐pure deep‐blue emission peaks at 436 and 448 nm respectively. The device based on MePAB achieves a maximum external quantum efficiency of 19.8% with an ultralow CIEy value of 0.046 and a full‐width‐at‐half‐maximum (FWHM) of 29 nm in the bottom emitting device. Additionally, the peripheral cladding of fluorine atoms extends the conjugation framework and slightly enhances the electron acceptance character of the boron atom at the ortho‐position. This leads to a redshift in the emission spectrum and enhanced photoluminescence quantum yield (PLQY) of up to 93% for MePABF. Furthermore, the potential application of MePAB as a deep‐blue sensitizer for MePABF is examined by fabricating a TADF‐sensitized‐TADF (TST) device. The results show a significantly reduced efficiency roll‐off and improved device performance, with a maximum external quantum efficiency (EQEmax) of 25.1% and a FWHM of 29 nm.

Defect-Mediated Exciton Localization and Relaxation in Monolayer MoS2.

Defects in chemical vapor deposition (CVD)-grown monolayer MoS2 are unavoidable and provide a powerful approach to creating single-photon emitters and quantum information systems through localizing excitons. However, insight into the A- trion and B/C exciton localization in monolayer MoS2 remains elusive. Here, we investigate defect-mediated A- trion and B/C exciton localization and relaxation in CVD-grown monolayer MoS2 samples via transient absorption spectroscopy. The localization rate of A- trions is five times faster than B excitons, which is attributed to the distinctions in the Bohr radius, diffusion rate, and multiphonon emission. Furthermore, we obtain unambiguous experimental evidence for the direct excitation of localized C excitons. Varying gap energy at the band-nesting region revealed by first-principles calculations explains the anomalous dependence of localized C exciton energy on delay time. We also find that the rapid dissociation of localized C excitons features a short characteristic time of ∼0.14 ps, while the measured relaxation time is much longer. Our results provide a comprehensive picture of the defect-mediated excitonic relaxation and localization dynamics in monolayer MoS2.

Internal Electric Field Manipulates Exciton-Phonon Couplings in Single Lead Halide Perovskite Nanocrystals.

Lead halide perovskite nanocrystals (NCs) have attracted much attention as materials for light-emitting diodes and quantum light sources. A deep understanding of exciton-phonon couplings is essential for obtaining a narrow emission line, weak phonon-sideband photoluminescence (PL), and a long exciton coherence time, which are especially useful for high-color-purity quantum-light-source applications. Here, we report the PL spectra of single CsPbBr3 NCs at 5.5 K as a function of the applied electric field. The exciton peak energy shows an asymmetric parabolic shift for positive and negative biases, implying the presence of a spontaneously generated internal electric field in the NCs when no field is applied. Both the internal electric field and exciton-phonon couplings become larger in smaller NCs, and they have a positive correlation with each other. Our findings show that the exciton-phonon couplings can be manipulated with an electric field, which dominates the PL properties of perovskite NCs.

Understanding and Controlling the Formation of Nonradiative Defects in Blue Organic Triplet Emitters

Phosphorescent organic light-emitting devices (PHOLEDs) suffer from destructive molecular processes due to triplet-polaron and triplet-triplet annihilation. These processes are energetically driven and hence are particularly active in decreasing the lifetime of blue PHOLEDs. It has recently been shown that increasing triplet radiative rates via the Purcell effect effectively extends the device operational lifetime by reducing the triplet radiative lifetime, thus decreasing their density and the probability of triplet-annihilation reactions. We provide an analytical framework using Marcus theory to explain the observed, approximately exponential relationship between exciton energy and device lifetime. From transient drift-diffusion dynamics, we show that the Purcell effect reduces the exciton density in the steady state and increases the photoluminescent yield, thereby reducing defect generation rates and extending the device lifetime. We control the radiative rate of excitons in microcavities, thereby connecting the exciton energy and decay rates with the observed device lifetime. The device lifetime is shown to follow a power-law dependence on the Purcell factor (PFm) with m=1.5 to 2.5, dependent on the TTA-to-TPA ratio and photoluminescence quantum yield. From our analysis, a fivefold increase in PF has the potential to extend the blue PHOLED lifetime by up to 2 orders of magnitude, making the blue PHOLED lifetime comparable to that of state-of-the-art green PHOLEDs. Published by the American Physical Society 2024

Photoinduced charge transfer and excitonic energy transfer in the CuInS2/ZnS/MoS2 heterotrilayer

Photo-induced charge transfer is the key process of many applications such as photovoltaics, photodetection, and light-emitting devices. With the outgrowth of a new class of low-dimensional semiconductors, i.e., monolayer transition metal dichalcogenides and semiconductor nanocrystals, charge transfer at the 2D/0D heterostructures has drawn many efforts because of the outstanding optical and electrical properties. This paper studies the dynamics of excitons of the CuInS2/ZnS/MoS2 heterotrilayer through femtosecond time-resolved transient absorption spectroscopy. The electron and hole transfer are observed by selectively exciting the electrons with tunable pump wavelengths. The exciton lifetimes are obtained on the picosecond scale. This work provides clues on exploring the non-toxic optoelectronic devices based on the CuInS2/ZnS/MoS2 heterotrilayer.

Vibrational Relaxation Completes the Excitation Energy Transfer and Localization of Vibronic Excitons in Allophycocyanin α84-β84.

Phycobilisomes are light-harvesting complexes that play a key role in photosynthesis in cyanobacteria, which generate more than 40% of the world's oxygen. The near-unity excitation energy transfer efficiency from phycobilisomes to photosystems highlights its importance in understanding efficient energy transfer processes. Spectroscopic studies have shown that the 280 fs rapid excitonic downhill energy transfer within the α84-β84 chromophore dimer in allophycocyanin (APC), a subunit of phycobilisomes, is crucial to this efficiency. However, the role of strong chromophore-protein interactions and vibrational relaxation requires further exploration to fully explain this efficient downhill energy transfer. A theory is required that adequately describes exciton dynamics in an intermediate region while also incorporating vibrational relaxation mediated by protein bath modes. In this work, we incorporate vibrational relaxation into modified Redfield theory by introducing coupling fluctuation. We holistically simulate the rapid excitation energy transfer process of the α84-β84 chromophore dimer in APC and successfully model the recently observed rapid energy capture. We find that vibrational relaxation dictates capture of excitons by the localized state of the β84 chromophore. The calculated rate shows excellent agreement with previous ultrafast spectroscopic experiments. Our results show that the inclusion of vibrational relaxation is essential for systems that utilize vibronic coupling to enhance energy transfer and capture. Consequently, incorporating vibrational relaxation into Modified Redfield theory shows promise for accurately describing the excitation energy transfer process in other photosynthetic systems.

Optoelectronic and transport properties of layer-dependent two-dimensional perovskite Cs3Bi2I9

The emergence of two-dimensional (2D) perovskite provides an ideal platform for designing and fabricating microelectronic and optoelectronic devices. Here, we present detailed ab initio calculations to comprehensively explore the layer-dependent optoelectronic and transport properties of the newly synthesized 2D perovskite Cs3Bi2I9. The calculations reveal that the indirect band gap of monolayer, bilayer, and trilayer Cs3Bi2I9 decreases from 2.41 to 2.35 eV The charge carriers of few-layered perovskite Cs3Bi2I9 are dominated by electrons, and the highest electron and hole carrier mobilities are 140 and 62 cm²V⁻¹s⁻¹ along the b axis for bilayer Cs3Bi2I9. Exciton binding energies decrease from 2.48 to 1.19 eV with an increment of layer, and the calculated exciton level drops down into the valence band to generate potential exciton insulator. 2D Cs3Bi2I9 exhibits potential in the field of ultraviolet detection and photoluminescent devices due to large exciton energy and ultraviolet absorption.

Exciton dynamics in CsPbBr3 single crystal: LT splitting energy, exciton-polariton dispersion, and biexciton binding energy.

Metal halide perovskite materials (MHPs) are promising for several applications due to their exceptional properties. Understanding excitonic properties is essential for exploiting these materials. For this purpose, we focus on CsPbBr3 single crystals, which have higher crystal quality, are more stable, and have no Rashba effect at low temperatures compared to other 3D MHPs. We have estimated exciton energy positions, longitudinal-transverse splitting energy, and damping energy using low-temperature reflection spectra. Under high excitation intensity, two biexciton emissions (M-emission) and exciton-exciton scattering emission (P-emission) were observed. We assign the two M-emissions to the emission to the states of longitudinal and transverse excitons, i.e., ML and MT emissions. From the energy position of the MT emission, the biexciton binding energy has been estimated to be ∼2meV. By analyzing P-emission obtained from the back side of the sample, we have estimated the exciton binding energy to be 17.8-23.7meV. This estimation minimizes the influence of the wavenumber distribution in the scattering process. In addition, time-resolved transmittance measurements using pulsed white light have revealed the group velocity dispersion. Comparing experimental results with theoretical calculations using the Lorentz model clarifies that exciton dynamics in CsPbBr3 can be described with a simple Lorentz model. These insights enhance the understanding of exciton behavior and support the development of exciton-based devices using MHPs.

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.

Abnormal Response of Indirect Excitons to Non‐Uniform Elastic Strain in MoS2 Flakes

AbstractRegulating the electronic structures and carrier dynamics in 2D materials via elastic strain is a fascinating avenue for tailoring their optoelectronic properties at atomic scale. Here, the abnormal response of indirect excitons to non‐uniform elastic strain in MoS2 flakes is reported. The non‐uniform elastic strain in the MoS2 flakes is introduced by transferring them to pre‐prepared convex cross structures on a SiO2/Si substrate, where the topography and strain distribution are determined by atomic force microscopy and Raman spectroscopy, respectively. It is observed that the emission energy of the indirect excitons shows an unexpected blue‐shift followed by a red‐shift with increasing the local tensile strain, which is in sharp contrast to the linear red‐shift of the direct excitons. Density functional theory calculations reveal that the abnormal energy shift of the indirect excitons in the MoS2 flakes arises from the strain‐induced competition between two indirect bandgap transitions and the spatial exciton funnel effect in the non‐uniform strain field. This work provides new insights into the elastic strain effect on the indirect excitons in 2D semiconductors, which possesses potential applications in flexible optoelectronic devices.

Engineering exciton dissociation and intermolecular charge transfer to boost superoxide radical in conjugated microporous polymers for simultaneous elimination of coexisting contaminants

Simultaneous photocatalytic elimination of coexisting contaminants with polymeric semiconductors are highly urgent for environmental purification. Nevertheless, the insufficient exciton dissociation and charge transfer in polymeric photocatalysts results in unsatisfactory photocatalytic performance. Herein, we proposed a sulfur-contained linkages engineering strategy via regulating donor–acceptor interactions to boost exciton dissociation and intermolecular charge transfer for efficient generation of superoxide radical. With the low exciton binding energy (50.11 meV) and short average lifetime (τavg‑TAS) of the photoinduced exciton (478.1 ps), the resultant BDT-Tr deriving from BDT and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine exhibited efficient exciton dissociation and charge transfer, enabling superior photocatalytic degradation of ofloxacin (∼94.0 % in 2 h) than that of TTP-Tr (∼87 %) and DTT-Tr (∼76 %) when coupled with the uranium (VI) reduction (∼96.0 % in 1 h). This is the first work highlights the photocatalytic removal of coexisting aqueous pollutants with CMPs-based photocatalysts, which might facilitate the exploration of polymeric semiconductors for wastewater purification.

Phase-Selective Synthesis of Rhombohedral WS2 Multilayers by Confined-Space Hybrid Metal-Organic Chemical Vapor Deposition.

Rhombohedral polytype transition metal dichalcogenide (TMDC) multilayers exhibit non-centrosymmetric interlayer stacking, which yields intriguing properties such as ferroelectricity, a large second-order susceptibility coefficient χ(2), giant valley coherence, and a bulk photovoltaic effect. These properties have spurred significant interest in developing phase-selective growth methods for multilayer rhombohedral TMDC films. Here, we report a confined-space, hybrid metal-organic chemical vapor deposition method that preferentially grows 3R-WS2 multilayer films with thickness up to 130 nm. We confirm the 3R stacking structure via polarization-resolved second-harmonic generation characterization and the 3-fold symmetry revealed by anisotropic H2O2 etching. The multilayer 3R WS2 shows a dendritic morphology, which is indicative of diffusion-limited growth. Multilayer regions with large, stepped terraces enable layer-resolved evaluation of the optical properties of 3R-WS2 via Raman, photoluminescence, and differential reflectance spectroscopy. These measurements confirm the interfacial quality and suggest ferroelectric modification of the exciton energies.

Pyrazine-Based Aromatic Dyes as Novel Photosensitizers with Improved Conduction Band and Photovoltaic Features: DFT Insights for Efficient Dye-Sensitized Solar Cells

Dye-sensitized solar cells (DSSCs) have garnered significant attention due to their exceptional ability to convert solar energy into electricity at a relatively low cost. Novel organic photosensitizers (FZB1-FZB9) from the pyrazine-based aromatic dye (E)-3-(5-(2,3-bis(40-(diphenylamino)-[1,10-biphenyl]-4-yl)-7 (trifluoromethyl)quinoxalin-5-yl)thiophen-2-yl)-2-cyanoacrylic acid (TPPF) have been quantum chemically modeled for their application in dye-sensitized nanocrystalline TiO2 solar cells (DSSCs). The electrochemical and photovoltaic features of modeled dyes are investigated by performing DFT insights, i.e. FMOs, absorption maxima, DOS, TDM, NBO, exciton and binding energy, radiative lifetime analysis (ꚍ), electron-injection (Δ G inject ) and regeneration analysis ( Δ G dye regen )@TiO2. FMO analysis confirmed the better electron injection as HOMO of designed dyes was found to be more positive than redox potential I/I3 (-4.8 eV), and the LUMO appeared more negative than the conduction band of TiO2 (-4.0 eV). The modeled photosensitizers exhibited red shift λmax from 338-494 nm with a lower energy gap from 5.62 eV in FZB (R) to 5.17 eV in FZB9. Bridging modification reduces the exciton and binding energy for designed dye FZB9 and FZB7 compared to reference FZB. The designed dyes appeared with a lower radiative lifetime of up to 1.32 than the reference dye of 1.63, better light harvesting efficiency (LHE), and the highest NBO charge on bridges of designed photosensitizers for enhanced light emitting efficiency. The investigated dyes exhibited more negative values for electron injection, i.e. −0.003 and the highest values of dye regeneration ( Δ G regedye regen ) up to 11.717, which unveils innovative and effective injection of electrons toward semiconductor TiO2. Among all dyes, FZB8 proved best with the novel bridging modification that enables quick charge transfer as exhibited the lowest gap (5.17 eV), lowest excitation energy, better LHE, highest charge on LUMO and more negative electron injection (Δ G inject ) . The outcomes of this computational study confirmed that this research established a new benchmark for achieving novel and efficient photosensitizers, thus recommending them for future DSSC applications.

Anomalous hybridized excitons induced by combined effects of Van der Waals coupling and Rashba spin–orbit coupling

As a typical transition-metal dichalcogenide, MoS2has drawn wide attention due to its good stability and excellent physicochemical properties, making it suitable for visible-region optoelectronic devices. To expand its application, bandgap engineering via heterostructure, thus far, was conventionally employed to tune the band gap. However, this strategy has the disadvantage that energy levels of bands do not show obvious changes compared to the isolated components, limiting the range of applications. Here, we achieve hybridized excitons induced by combined effects of Van der Waals (vdW) coupling and Rashba spin-orbit coupling (SOC), with a small exciton energy of 0.65 eV. For this purpose, we design a MoS2/MoWC heterostructure, where a built-in field (due to the absence of mirror symmetry) induces the Rashba SOC and contributes to the anomalous hybridized states, combined with the vdW coupling. An effective model is proposed to demonstrate the anomalous hybridized states for the heterostructure. Our approach reveals a novel mechanics model for hybridized excitons states, providing new physical ways to achieve infrared-region devices.