Excitonic Features Research Articles

Semiconducting biomass-based amorphous carbon films and their potential application in photovoltaic devices

Amorphous carbon (aC) is highly appealing because of its unique structure, electrical and optical properties, making it appropriate for various applications, especially in energy conversion. This work presents a comprehensive study on the synthesis of aC materials, including both intrinsic (i-type) and doped conditions (p- and n-type), to enhance the performance of photovoltaic films. Carbon materials are derived from biomass using a straightforward and environmentally conscious technique. The obtained carbon compound demonstrates an amorphous state with a substantial prevalence of the sp2 C=C component. Raman spectroscopy and electron microscopy confirmed the stacking of 2D layers forming a multilayer graphene structure. The carbon compound prepared AC films deposited onto a quartz glass surface via spray coating. The films have a thickness ranging from 247 to 478 nm. The dielectric constants of the optical parameters reveal resonant exciton features at a photon energy of ∼3.8 eV, whereas the real component exhibits semiconductive properties. The refractive indices of the p-, i-, and n-layers, which have gap energies in decreasing order, demonstrate a decline. The optical conductivity of aC is higher than that of amorphous silicon, specifically 0.54 × 103Ω−1cm−1, 0.48 × 103 Ω−1cm−1, and 0.53 × 103 Ω−1cm−1 for the p-, i-, and n-type films, respectively. Based on this outcome, it is reasonable to suggest that the recently developed material is potentially important as a photovoltaic device.

Controlled synthesis of branched 2D polytypic CdS quantum nanostructures

Colloidal two-dimensional (2D) semiconductor quantum nanostructures have attracted substantial interest owing to their atomically uniform thickness and spectrally sharp luminescence, exhibiting potential for optoelectronic and electronic device applications. Despite recent advancements in chemical synthesis enabling better control over lateral shapes and heterostructures, achieving morphological complexity in 2D semiconductor nanocrystals remains challenging. In this study, we report the controlled synthesis of branched 2D CdS quantum nanostructures, facilitating the realization of polytypism by growing zinc blende nano-domains within wurtzite-structured quantum nanoplates. The synthesized structures comprise multi-branched 2D quantum nanoplate arms with a precisely controlled thickness of ∼1.8 nm, joined at the zinc blende nano-domain junctions. The reaction conditions enable controlled variation in the length and complexity of these structures, while maintaining their sharp excitonic features of quantum-confined 2D semiconductor nanocrystals. In-situ small- and wide-angle X-ray scattering analysis, combined with spectroscopic and microscopic analyses, reveals that a discontinuous increase in thickness beyond a certain threshold is necessary to form zinc blende crystals within wurtzite nanoplates, upon which additional 2D quantum nanoplates subsequently grow. This study advances our understanding of 2D nanocrystal synthesis mechanisms and provides pathways for designing and fabricating branched 2D nanostructures with tailored properties.

Multiconfigurational Excitonic Couplings in Homo- and Heterodimer Stacks of Azobenzene-Derived Dyes.

Molecular excitons play a major role within dye aggregates and hold significant potential for (opto)electronic and photovoltaic applications. Numerous studies have documented alterations in the spectral properties of dye homoaggregates, but only limited work has been reported for heteroaggregates. In this article, dimeric dye stacks were constructed from azobenzene-like dyes with identical or distinct structures, and their excitonic features were computationally investigated. Our results show that strong exciton coupling is not limited to identical chromophores, as often assumed, based on a recently made available Frenkel Exciton Hamiltonian and multiconfigurational plus second-order perturbation theory energetics methodology. Heteroaggregate stacks were found to exhibit different absorption features from the corresponding interacting monomers, indicating considerable coupling interactions between units. We analyzed how such coupling may vary according to various aspects, such as the relative positions of the interacting monomers or the differences in their energetics. Such qualitative and semiquantitative analyses allow the evaluation of the excitonic behavior of these dye aggregates to encourage further efforts toward a deeper understanding of the excitonic properties of tailored dye heteroaggregate systems.

Direct extraction of optical constants of organic semiconductors in ultrastrongly coupled microcavities and their application in antireflection design for polariton devices.

The strongly bound Frenkel excitons in organic semiconductors enable strong or even ultrastrong exciton-photon coupling in room-temperature cavities, with the resulting polariton states typically resolved through reflectance measurements. This paper demonstrates that the distinct features of exciton and polariton modes in the reflectance spectra of strongly/ultrastrongly coupled organic microcavities can be effectively utilized to extract the optical constants and physical thickness of the embedded organic semiconductor. We investigate metal-clad microcavities based on two prototype conjugated polymers, poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and poly(3-hexylthiophene) (P3HT), both exhibiting ultrastrong coupling characteristics. The (n,k) spectra and thickness of these polymer films are determined by fitting the normal incidence reflectance spectra of organic microcavities, using Kramers-Kronig transformation and transfer-matrix calculations with varying optical and thickness parameters. We also examine the individual effects of the main fitting parameters on the spectrum, establishing a close correlation with the underlying polariton properties. Moreover, we analyze the optical admittance at exciton and polariton modes to understand reflectance variations with different parameters, which facilitates precise control of optical properties at specific modes through cavity design. Finally, using the extracted optical constants of MDMO-PPV and P3HT, we propose optimized microcavity designs that exhibit antireflection at the lower polariton mode for potential luminescence and photodetection device applications.

Structural and excitonic properties of the polycrystalline FAPbI3 thin films, and their photovoltaic responses

Faormamadinium based perovskites have been proposed to replace the methylammonium lead tri-iodide (MAPbI3) perovskite as the light absorbing layer of photovoltaic cells owing to their photo-active and chemically stable properties. However, the crystal phase transition from the photo-activeα-FAPbI3to the non-perovksiteδ-FAPbI3still occurs in un-doped FAPbI3films owing to the existence of crack defects, which degrads the photovoltaic responses. To investigate the crack ratio (CR)-dependent structure and excitonic characteristics of the polycrystalline FAPbI3thin films deposited on the carboxylic acid functionalized ITO/glass substrates, various spectra and images were measured and analyzed, which can be utilized to make sense of the different devices responses of the resultant perovskite based photovoltaic cells. Our experimental results show that the there is a trade-off between the formations of surface defects and trapped iodide-mediated defects, thereby resulting in an optimal crack density or CR of the un-dopedα-FAPbI3active layer in the range from 4.86% to 9.27%. The decrease in the CR (tensile stress) results in the compressive lattice and thereby trapping the iodides near the PbI6octahedra in the bottom region of the FAPbI3perovskite films. When the CR of the FAPbI3film is 8.47%, the open-circuit voltage (short-circuit current density) of the resultant photovoltaic cells significantly increased from 0.773 V (16.62 mA cm-2) to 0.945 V (18.20 mA cm-2) after 3 d. Our findings help understanding the photovoltaic responses of the FAPbI3perovskite based photovoltaic cells on the different days.

Small Polaron Dynamics in Transition Metal Oxide Photoelectrodes

The transition metal oxides are widely used in many optoelectronic applications, such as working as charge-transporting layers in solar cells and photoelectrodes in light-driven water-splitting. Considering the ionic bonding nature, the lattice of these oxides can be polarized by the charge carriers due to the strong electron-phonon coupling, giving rise to lattice distortion that fosters a local potential well. This lattice distortion together with the trapped carrier is regarded as a quasi-particle, i.e., a polaron. Here, the photocarrier dynamics in transition metal oxides were investigated using the transient absorption and time-resolved terahertz spectroscopies. We identified the spectral features of small polarons, self-trapped excitons, and free carriers and extracted their dynamics independently. We proposed a molecular model that could successfully explain the non-barrier self-trapping and quantitatively describe the temperature-dependent recombination of self-trapped excitons and the dopant effect on the photocarrier dynamics. Our model also suggested that the recombination of self-trapped excitons at room temperature was dominated by nuclear quantum tunneling. This model also predicted the micro-heterogeneity of the self-trapped species, and thus be able to quantitatively describe the Auger annihilation dynamics of self-trapped excitons.

(Invited) Manipulating the Exotic Excitons of Van Der Waals Correlated Antiferromagnet with Impurities and Size

A Van der Waals correlated antiferromagnet, metal phosphorus trichalcogenides (MPX3, M = Mn, Fe, Ni; X = S, Se), have emerged as promising candidates for next generation spintronics, and quantum information technologies. Nickel phosphorus trisulfide (NiPS3) is a most notable member of this family and has been extensively studied for its unique properties, including the emergence of an ultra-sharp photoluminescence (PL) peak at ~1.476 eV below Néel temperature of 150 Kelvin. While the highly anisotropic, linearly polarized emission of this PL peak has been shown to be directly correlated to the long-range spin order of NiPS3, its ultra-narrow linewidth of a few hundred meV has led to the speculation that it is originated from a coherent many-body exciton state. Observations of multiple phonon bounds states and formation of exciton-polaritons also creates more excitement as they present new possibilities for design and control of correlated electron systems.Aiming to achieve understanding and control of this spin-correlated exciton, we conduct temperature dependent, polarization resolved, PL studies on compounds of NiPS3 doped with different concentration of Mn (Ni1-xMnxPS3) and Se (NiPS3(1-x)Se3x). We observed systematic variation in characteristics of the spin-correlated exciton revealing their sensitive dependence on disturbance in the magnetic order of NiPS3.Next, to explore the effect of nanostructuring, we developed a novel chemical synthesis for highly crystalline NiPS3 nano flakes. We observed an activation of a new exciton state that share many exciting properties of bulk spin-correlated exciton.

Ligand-Induced Size-Dependent Circular Dichroism in Quantum Dots.

Recent experiments have probed the chiral properties of semiconductor nanocrystal (NC) quantum dots (QDs), but understanding the circular dichroism line shape, excitonic features, and chirality induction mechanism remains a challenge. We propose an atomistic pseudopotential method to model chiral ligand passivated QDs, computing circular dichroism (CD) spectra for CdSe QDs (2.6-3.8 nm). We find strong agreement between calculated and measured line shapes, predicting consistent bisignate line shapes with decreasing CD magnitude as size increases. Our analysis reveals the origin of bisignate line shapes, arising from nondegenerate excitons with opposing angular momenta. We also explore the impact of chiral ligand orientation on QD surfaces, observing changes in the optical activity magnitude and sign. This orientation sensitivity offers the means to distinguish ordered from disordered ligand configurations, facilitating the study of order-disorder transitions at ligand-QD interfaces.

Strong Electrostatic Control of Excitonic Features in MoS2 by a Free‐Standing Ultrahigh‐κ Ferroelectric Perovskite

AbstractIntegrating free‐standing complex oxides with two‐dimensional (2D) materials has recently attracted great interest, due to the rich physics evolving from such structures. Enhancing and tuning the opto–electronic properties of these systems is of high importance for a multitude of applications, such as sensors, memory devices or optical communications. The electrostatic control of photoluminescence of monolayer MoS2 at room temperature via integration of free‐standing BaTiO3 (BTO), a ferroelectric perovskite oxide is presented. It is shown that the use of BTO leads to highly tunable exciton emission of MoS2 in a minimal range of gate voltages. Due to BTO's ferroelectric polarization‐induced doping, large peak emission shifts as well as a large and tunable A trion binding energy in the range of 40–100 meV are observed. These measurements are compared with those carried out when the BTO is replaced by a hexagonal boron nitride (hBN) dielectric layer, confirming BTO's superior gating properties and thus lower power consumption. Additionally, advantage of the ferroelectric switching of BTO is taken by fabricating devices where the BTO layer is decoupled from the gate electrode with a SiO2 layer. Choosing to isolate the BTO allows to induce large remanent behavior of MoS2’s excitonic features.

Interfacial Charge-Transfer Excitonic Insulator in a Two-Dimensional Organic-Inorganic Superlattice.

Excitonic insulators are long-sought-after quantum materials predicted to spontaneously open a gap by the Bose condensation of bound electron-hole pairs, namely, excitons, in their ground state. Since the theoretical conjecture, extensive efforts have been devoted to pursuing excitonic insulator platforms for exploring macroscopic quantum phenomena in real materials. Reliable evidence of excitonic character has been obtained in layered chalcogenides as promising candidates. However, owing to the interference of intrinsic lattice instabilities, it is still debatable whether those features, such as the charge density wave and gap opening, are primarily driven by the excitonic effect or by the lattice transition. Herein, we develop an intercalation chemistry strategy for obtaining a novel charge-transfer excitonic insulator in organic-inorganic superlattice interfaces that serves as an ideal platform to decouple the excitonic effect from the lattice effect. In this system, we observe a narrow excitonic gap, formation of a charge density wave without periodic lattice distortion, and metal-insulator transition, providing visualized evidence of exciton condensation occurring in thermal equilibrium. Our findings identify self-assembly intercalation chemistry as a new strategy for developing novel excitonic insulators.

Intrinsic Chiroptical Activity and Excitonic Properties of Group II-VI Magic-Size Clusters.

Semiconductor magic-size clusters (MSCs), lying in the local minima of the potential landscape, are important intermediates that emerge during the synthesis of colloidal quantum dots. They have definite geometrical and electronic structures, thus serving as atomically precise building blocks for assembling supramolecular structures and devices with unprecedented functionalities. Here we report the intrinsic chiroptical activity in the magic-size cadmium and zinc chalcogenide clusters with magic numbers of 13, 33, and 34 possessing unique core-shell structures. They are responsive to circularly polarized light from the ultraviolet to visible region, with size-tunable energy gap, absorption wavelength, and excitonic characteristics. The origin of the chiroptical activity and the evolution of excitonic states with magic size are disclosed by time-dependent density functional theory calculations within a correlated electron-hole picture. This molecular-level understanding of the photophysical properties of group II-VI MSCs provides essential guidelines for utilizing them for chiral optoelectronics and photonics.

Distinct Valley Polarization in Vertical Heterobilayers: Difference between Edge- and Center-Nucleated WS2/MoS2.

Structural imperfections can cause both beneficial and detrimental consequences on the excitonic characteristics of transition metal dichalcogenides (TMDs). Regarding valley selection, structural defects typically promote valley depolarization in monolayer TMDs, but defect healing via an additional growth process can restore valley polarization in vertical heterobilayers (VHs). In this study, we analyzed the valley polarization of center-nucleated and edge-nucleated VHs (WS2/MoS2) grown using a controlled growth process and discovered that defect-related photoluminescence (PL) is strongly suppressed in the center-nucleated VHs due to defect healing. Additionally, we demonstrated that the valley polarization of lower-lying intralayer excitons is more sensitive to the defect density of the sample than to higher-lying intralayer excitons. Despite defect healing in the center-nucleated VHs, the temperature-dependent PL study indicated that valley depolarization of the lower-lying intralayer excitons becomes significant below 100 K because of stronger hybridization of defect states. Also, we conducted a comprehensive study on the excitation intensity dependence to investigate the electron-doping-induced Auger recombination mechanism, which also contributes to valley depolarization of intralayer excitons via regeneration of intervalley trions. Our findings provide valuable insight into the development of VH-based valleytronic devices.

Rise and fall of patterns in driven-dissipative Rydberg polaritons

In this study, we present an exploration of spontaneous symmetry breaking and pattern formation in the driven-dissipative system of Rydberg exciton polaritons with long-range interactions. Our investigation unravels the pattern formations through modulational instability, characterized by scales in the micron range. We observe the dynamics of the polariton ensemble, studying the emergence of metastable patterns and their eventual collapse in the long-time limit. This phenomenon is attributed to the destructive interference between the polariton state and the external drive within the ensemble. Further, we delineate conditions conducive to the stable formation of patterns under incoherent pumping. These findings open up various avenues for delving into the burgeoning realm of driven-dissipative and long-range interacting gases through the unique characteristics of Rydberg excitons. Published by the American Physical Society 2024

Strain-induced changes of electronic and optical properties of Zr-based MXenes

Zr-based MXenes recently attracted attention because of its experimental preparation showing temperature stability, mechanical strength, and promising energy, sensoric, and electrochemistry applications. However, necessary theoretical predictions at a precise/predictive level are complicated due to essential excitonic features and strong electron correlation (i.e., a necessity to go beyond standard density functional theory, DFT). Contrary to the prevailing focus on oxygen-terminated MXenes and standard predictions of other Zr-based MXenes as conductors, based on the hybrid DFT and GW many-body perturbational theory, we were able to find seven different semiconductors (five of them for their equilibrium geometry and two others under slight tensile biaxial strain) in the case of two- and three-layered Zr2CT2 and Zr3C2T2 configurations with various terminations (T = O, F, S, Cl). We observed semiconductor-to-conductor transition induced by strain in the majority of such Zr-based MXenes at an experimentally achievable strain range. Furthermore, using the Bethe–Salpeter equation (BSE), we demonstrated that selected semiconducting Zr-based MXenes possess high optical absorption efficiency (20%–30%) in the visible light range, underscoring their potential in photonic applications. The high sensitivity of Zr-based MXenes to external conditions and functionalization combined with the thermal stability makes the materials promising for applications at operational temperatures in electronic and optical technologies.

Direct Synthesis of Zinc-Blende ZnSe Nanoplatelets.

The distinct optical properties and electronic structures of two-dimensional colloidal nanoplatelets (NPLs) have garnered significant scientific and practical interest. However, concerns regarding the toxicity of cadmium-based NPLs and their limited spectral coverage show the importance of developing nontoxic alternatives. In this study, we devised a new synthetic approach for the direct synthesis of zinc-blende (ZB) ZnSe NPLs. By introducing two different zinc precursors, short-chain metal carboxylate- zinc acetate, and metal halide-zinc chloride, we successfully synthesized two-dimensional ZB ZnSe NPLs. By modifying the reaction parameters, we obtained two different populations of ZnSe NPLs, characterized by the first absorption peak at "343" and "367 nm". Ostwald ripening experiments further confirmed the formation of 2D ZnSe NPLs by the observed discrete growth mechanism. Lastly, we investigated the impact of surface ligands on the excitonic properties of ZB ZnSe NPLs by treating their initially carboxylic acid-capped surface with oleylamine. Remarkably, we observed significant red-shifting in the first excitonic peaks, up to 130 meV, in a reversible manner, demonstrating further tunability of excitonic features in ZnSe NPLs. We anticipate that our findings will serve as a catalyst for further exploration of nontoxic two-dimensional materials, fostering their investigation and application in various fields.

Molten glass-mediated conditional CVD growth of MoS2 monolayers and effect of surface treatment on their optical properties

In the rapidly developing field of optoelectronics, the utilization of transition-metal dichalcogenides with adjustable band gaps holds great promise. MoS2, in particular, has garnered considerable attention owing to its versatility. However, a persistent challenge is to establish a simple, reliable and scalable method for large-scale synthesis of continuous monolayer films. In this study, we report the growth of continuous large-area monolayer MoS2 films using a glass-assisted chemical vapor deposition (CVD) process. High-quality monolayer films were achieved by precisely controlling carrier gas flow and sulfur vaporization with a customized CVD system. Additionally, we explored the impact of chemical treatment using lithium bistrifluoromethylsulfonylamine (Li-TFSI) salt on the optical properties of monolayer MoS2 crystals. To investigate the evolution of excitonic characteristics, we conditionally grew monolayer MoS2 flakes by controlling sulfur evaporation. We reported two scenarios on MoS2 films and flakes based on substrate-related strain and defect density. Our findings revealed that high-quality monolayer MoS2 films exhibited lower treatment efficiency due to substrate-induced surface strain. whereas defective monolayer MoS2 flakes demonstrated a higher treatment sensitivity due to the p-doping effect. The Li-TFSI-induced changes in exciton density were elucidated through photoluminescence, Raman, and x-ray photoelectron spectroscopy results. Furthermore, we demonstrated treatment-related healing in flakes under variable laser excitation power. The advancements highlighted in our study carry significant implications for the scalable fabrication of diverse optoelectronic devices, potentially paving the way for widespread real-world applications.

Excited-State Dynamics of MAPbBr3: Coexistence of Excitons and Free Charge Carriers at Ultrafast Times.

Methylammonium lead tribromide perovskite (MAPbBr3) is an important material, for example, for light-emitting applications and tandem solar cells. The relevant photophysical properties are governed by a plethora of phenomena resulting from the complex and relatively poorly understood interplay of excitons and free charge carriers in the excited state. In this study, we combine transient spectroscopies in the visible and terahertz range to investigate the presence and evolution of excitons and free charge carriers at ultrafast times upon excitation at various photon energies and densities. For above- and resonant band-gap excitation, we find that free charges and excitons coexist and that both are mainly promptly generated within our 50-100 fs experimental time resolution. However, the exciton-to-free charge ratio increases upon decreasing the phonon energy toward resonant band gap excitation. The free charge signatures dominate the transient absorption response for above-band-gap excitation and low excitation densities, masking the excitonic features. With resonant band gap excitation and low excitation densities, we find that although the exciton density increases, free charges remain. We show evidence that the excitons localize into shallow trap and/or Urbach tail states to form localized excitons (within tens of picoseconds) that subsequently get detrapped. Using high excitation densities, we demonstrate that many-body interactions become pronounced and effects such as the Moss-Burstein shift, band gap renormalization, excitonic repulsion, and the formation of Mahan excitons are evident. The coexistence of excitons and free charges that we demonstrate here for photoexcited MAPbBr3 at ultrafast time scales confirms the high potential of the material for both light-emitting diode and tandem solar cell applications.

A Systematic Study of the Temperature Dependence of the Dielectric Function of GaSe Uniaxial Crystals from 27 to 300 K.

We report the temperature dependences of the dielectric function ε = ε1 + iε2 and critical point (CP) energies of the uniaxial crystal GaSe in the spectral energy region from 0.74 to 6.42 eV and at temperatures from 27 to 300 K using spectroscopic ellipsometry. The fundamental bandgap and strong exciton effect near 2.1 eV are detected only in the c-direction, which is perpendicular to the cleavage plane of the crystal. The temperature dependences of the CP energies were determined by fitting the data to the phenomenological expression that incorporates the Bose-Einstein statistical factor and the temperature coefficient to describe the electron-phonon interaction. To determine the origin of this anisotropy, we perform first-principles calculations using the mBJ method for bandgap correction. The results clearly demonstrate that the anisotropic dielectric characteristics can be directly attributed to the inherent anisotropy of p orbitals. More specifically, this prominent excitonic feature and fundamental bandgap are derived from the band-to-band transition between s and pz orbitals at the Γ-point.

Temperature-dependent excitonic emission characteristics of highly crystallized carbon nitride nanosheets

Highly-crystallized carbon nitride (HCCN) nanosheets exhibit significant potential for advancements in the field of photoelectric conversion. However, to fully exploit their potential, a thorough understanding of the fundamental excitonic photophysical processes is crucial. Here, the temperature-dependent excitonic photoluminescence (PL) of HCCN nanosheets and amorphous polymeric carbon nitride (PCN) is investigated using steady-state and time-resolved PL spectroscopy. The exciton binding energy of HCCN is determined to be 109.26 meV, lower than that of PCN (207.39 meV), which is attributed to the ordered stacking structure of HCCN with a weaker Coulomb interaction between electrons and holes. As the temperature increases, a noticeable reduction in PL lifetime is observed on both the HCCN and PCN, which is ascribed to the thermal activation of carrier trapping by the enhanced electron–phonon coupling effect. The thermal activation energy of HCCN is determined to be 102.9 meV, close to the value of PCN, due to their same band structures. Through wavelength-dependent PL dynamics analysis, we have identified the PL emission of HCCN as deriving from the transitions: σ*–LP, π*–π, and π*–LP, where the π*–LP transition dominants the emission because of the high excited state density of the LP state. These results demonstrate the impact of high-crystallinity on the excitonic emission of HCCN materials, thereby expanding their potential applications in the field of photoelectric conversion.

Excitons in confined molecular aggregates

AbstractOrganic optoelectronic materials have attracted extensive attention in the past decades due to their wide applications in organic light‐emitting diodes (OLEDs), organic photovoltaics (OPVs), photocatalysis, etc. Significant advancements have been obtained in the material designs based on the insight into the fundamental physics of exciton related to molecular stacking patterns in solid/condensed states. The exciton characteristics and behaviors are not only a starting point for studying photophysical and photochemical processes on a microscopic level, but also a crucial point in determining the optoelectronic properties of macroscopic aggregates. This review summarizes the historic development of exciton models, accompanied by the discoveries of special molecular stacking patterns (H‐/J‐/X‐/M‐aggregates), and the competitive de‐excitation pathways of excitons including fluorescence, energy transfer, singlet fission, excimer formation and symmetry‐breaking charge separation in the confined aggregate structures. Additionally, it highlights the capabilities of a correlation between molecular stacking modes and exciton behaviors, which provides new insights and perspectives for optimizing exciton character and behavior through the modulation of molecular arrangement in aggregate states, thereby enhancing the performance of optoelectronic materials.