Strong Exciton Binding Energy Research Articles

Spectrally Tunable Lead-Free Perovskite Rb2ZrCl6:Te for Information Encryption and X-ray Imaging.

A series of lead-free Rb2ZrCl6:xTe4+ (x = 0%, 0.1%, 0.5%, 1.0%, 2.0%, 3.0%, 5.0%, 10.0%) perovskite materials were synthesized through a hydrothermal method in this work. The substitution of Te4+ for Zr in Rb2ZrCl6 was investigated to examine the effect of Te4+ doping on the spectral properties of Rb2ZrCl6 and its potential applications. The incorporation of Te4+ induced yellow emission of triplet self-trapped emission (STE). Different luminescence wavelengths were regulated by Te4+ concentration and excitation wavelength, and under a low concentration of Te4+ doping (x ≤ 0.1%), different types of host STE emission and Te4+ triplet state emission could be achieved through various excitation energies. These luminescent properties made it suitable for applications in information encryption. When Te4+ was doped at high concentrations (x ≥ 1%), yellow triplet state emission of Te4+ predominated, resulting in intense yellow emission, which stemmed from strong exciton binding energy and intense electron-phonon coupling. In addition, a Rb2ZrCl6:2%Te4+@RTV scintillating film was fabricated and a spatial resolution of 3.7 lp/mm was achieved, demonstrating the potential applications of Rb2ZrCl6:xTe4+ in nondestructive detection and bioimaging.

Theoretical study of the electronic and optical properties of ZnO/MgO rock salt superlattices

An analysis of some electronic and optical properties of rock salt (RS) ZnO/MgO superlattices related to potential applications in optoelectronics and electronics is carried out.In order to find possible light emission mechanisms, the electronic band structure, projected and k-resolved projected density of states and optical parameters such as the refractive index, reflection and absorption coefficients are calculated.We show that the bandgap of the RS ZnO/MgO superlattice is indirect for all considered thicknesses of quantum wells and barriers. Despite the indirect character of the bandgap, other features of the studied superlattice, such as the flat character of the top of the valence band and the bottom of the conduction band, combined with strong electron-phonon coupling and high exciton binding energy, may indicate the possibility of light emission similar to that in hexagonal BN.

Giant excitonic effects in vacancy-ordered double perovskites

Using first-principles GW plus Bethe-Salpeter equation calculations, we identify anomalously strong excitonic effects in several vacancy-ordered double perovskites Cs2MX6 (M = Ti, Zr; X = I, Br). Giant exciton binding energies about 1 eV are found in these moderate-gap, inorganic bulk semiconductors, pushing the limit of our understanding of electron-hole (e-h) interaction and exciton formation in solids. Not only are the exciton binding energies extremely large compared with any other moderate-gap bulk semiconductors, but they are also larger than typical 2D semiconductors with comparable quasiparticle gaps. Our calculated lowest bright exciton energy agrees well with the experimental optical band gap. The low-energy excitons closely resemble the Frenkel excitons in molecular crystals, as they are highly localized in a single [MX6]2- octahedron and extended in the reciprocal space. The weak dielectric screening effects and the nearly flat frontier electronic bands, which are derived from the weakly bonded [MX6]2- units, together explain the significant excitonic effects. Spin-orbit coupling effects play a crucial role in red-shifting the lowest bright exciton by mixing up spin-singlet and spin-triplet excitons, while exciton-phonon coupling effects have minor impacts on the strong exciton binding energies.

Electron structure and exciton energy level of HgI2, CH3NH3HgI3 and (CH3NH3)2HgI4

The electronic structures and exciton properties of HgI2, CH3NH3HgI3 and (CH3NH3)2HgI4 are reported. Compared with HgI2, organic-inorganic hybrids CH3NH3HgI3 and (CH3NH3)2HgI4 have lower dimension and higher band gap, which show significant excitonic properties. The effective masses of electrons and holes of these three materials were predicted by their energy band structures. Their exciton binding energy at room temperature therein was calculated to be 13.77, 166.81, and 256.00 meV, respectively. HgI2 has low exciton binding energy that cannot exist stably, while CH3NH3HgI3 and (CH3NH3)2HgI4 have strong charge localization and high exciton binding energy. In addition, the UV–vis diffuse reflectance spectra reveal the presence of exciton absorption in CH3NH3HgI3 and (CH3NH3)2HgI4, and the exciton energy levels is confirmed by combining the diffuse reflectance spectra with its exciton binding energy. Importantly, the exciton luminescence peaks of CH3NH3HgI3 and (CH3NH3)2HgI4 were observed at 468 nm and 419 nm in their photoluminescence spectra at room temperature, respectively. This indicates that CH3NH3HgI3 and (CH3NH3)2HgI4 have strong exciton properties and are potential candidates for high-light-yield scintillators and light-emitter applications.

A ligand strategy retarding monovalent copper oxidation toward achieving Cs3Cu2I5 perovskite emitters with enhanced stability for lighting.

0D copper-based perovskites (Cs3Cu2I5) have fascinating optical properties, such as strong exciton binding energy, high photoluminescence quantum yield (PLQY) and large Stokes shifts from self-trapped excitons (STEs), which make them highly considerable candidates in the field of lighting. However, the stability of Cs3Cu2I5 is compromised by the oxidation of Cu+ to Cu2+ during the storage or operation process. Here, we proposed a ligand engineering strategy to improve the stability of Cs3Cu2I5via an organic molecule (ethylenediaminetetraacetic acid, EDTA) with multiple functional groups. The strong interaction between carboxyl groups and Cu+ was evidenced through FTIR and XPS, and it could retard monovalent copper oxidation. After storing for 90 days, the EDTA-engineered Cs3Cu2I5 (EDTA-Cs3Cu2I5) maintained its original crystalline structure, while the control Cs3Cu2I5 exhibited an impurity phase. Through quantitative analysis, the content of Cu2+ in EDTA-Cs3Cu2I5 was found to be 83.9% lower than that in control Cs3Cu2I5. Benefiting from the inhibition of Cu+ oxidation, EDTA-Cs3Cu2I5 exhibited improved light emission stability. For example, the optimized EDTA-Cs3Cu2I5 retained 74.7% of the initial photoluminescence (PL) intensity after 90-day storage under ambient conditions, while the pure Cs3Cu2I5 retained only 41.7%. Furthermore, EDTA could passivate defects and enhance the PL properties of the optimized Cs3Cu2I5, which showed a PLQY of 94.7%, much higher than that of 71.4% for pure Cs3Cu2I5. We further constructed a WLED based on the EDTA-engineered Cs3Cu2I5, which showed CIE at (0.3238, 0.3354), a CRI of 91.7, and a T50 of 361 h. The proposed EDTA ligand strategy provides a new way to regulate the light-emitting properties and stabilities of Cs3Cu2I5 for future industrialization.

Electronic and optical properties of the buckled and puckered phases of phosphorene and arsenene

Using first-principles calculations, we have investigated the structural, electronic, and optical properties of phosphorene and arsenene, group V two-dimensional materials. They have attracted the scientific community’s interest due to their possible applications in electronics and optoelectronics. Since phosphorene and arsenene are not planar monolayers, two types of structures were considered for each system: puckered and buckled arrangements. Computations of band gap were performed within the GW approach to overcome the underestimation given by standard DFT and predict trustable band gap values in good agreement with experimental measurements. Our calculated electronic band gaps lie in the range from near-infrared to visible light, suggesting potential applications in optoelectronics devices. The computed electronic band gaps are 2.95 eV and 1.83 eV for blue and black phosphorene systems. On the other hand, the values for buckled and puckered arsenene are 2.56 eV and 1.51 eV, respectively. Moreover, the study of the optical properties has been dealt by computing the dielectric function imaginary part, which was obtained using the Bethe–Salpeter approach. The use of this technique allows the consideration of excitonic effects. Results indicate strong exciton binding energies of 830 meV for blue phosphorene, 540 meV for black phosphorene, 690 meV for buckled arsenene, and 484 meV for puckered arsenene. The results of our study suggest the possibility of using these materials in electronic and optoelectronic devices.

Effects of Growth Temperature on Morphological and Structural Properties of ZnO Films

Zinc oxide (ZnO) is one of the most promising oxide possibilities for use in a number of industries due to its unique properties. Because of its broad direct bandgap (3.37 eV) and strong exciton binding energy (60 meV) at ambient temperature, ZnO not only conducts electricity well but also transmits visible light and emits UV light. Here, we investigated the effect of growth temperature on ZnO thin films by changing the growth temperatures from 400 oC to 450 oC. Radio-frequency (RF) magnetron sputtering was used to create ZnO thin films on Si(100) substrates. The atomic force microscopy (AFM) results show that the root-mean-square (RMS) roughness decreases from 6.1 ± 1.0 nm to 4.8 ± 0.6 nm as the growth temperatures increase. XRD patterns display the enhancement of ZnO’s structure when increasing the growth temperature. Our findings indicate that controlling growth temperature is the critical factor in producing high quality ZnO thin films.

Sumanene Monolayer of Pure Carbon: A Two-Dimensional Kagome-Analogy Lattice with Desirable Band Gap, Ultrahigh Carrier Mobility, and Strong Exciton Binding Energy.

The design and synthesis of novel two-dimensional (2D) materials that possess robust structural stability and unusual physical properties may open up enormous opportunities for device and engineering applications. Herein, a 2D sumanene lattice that can be regarded as a derivative of the conventional Kagome lattice is proposed. The tight-binding analysis demonstrates sumanene lattice contains two sets of Dirac cones and two sets of flat bands near the Fermi surface, distinctively different from the Kagome lattice. Using first-principles calculations, two possible routines for the realization of stable 2D sumanene monolayers (named α phase and β phase) are theoretically suggested, and an α-sumanene monolayer can be experimentally synthesized with chemical vapor deposition using C21 H12 as a precursor. Small binding energies on Au(111) surface (e.g., -37.86eVÅ-2 for α phase) signify the possibility of their peel-off after growing on the noble metal substrate. Importantly, the GW plus Bethe-Salpeter equation calculations demonstrate both monolayers have moderate band gaps (1.94eV for α) and ultrahigh carrier mobilities (3.4 × 104 cm2 V-1 s-1 for α). In particular, the α-sumanene monolayer possesses a strong exciton binding energy of 0.73eV, suggesting potential applications in optics.

A Review on Materials and Methods for the Fabrication of Microcavity Laser

Optical microcavities are resonators that have at least one dimension on the order of a single optical wavelength. These structures enable one to control the optical emission properties of materials placed inside them. One of their most dramatic potential features is threshold-less lasing,unlike the conventional lasers. This is possible due to 2D monolayers, Heterostructures, Hybrid materials which are used as active layers for polariton-exciton strong coupling. In this review paper, a different method of Microcavity laser fabrication is reviewed, where a different type of active materials is utilized to improve the laser efficiency. Materials such as WS2, MoS2, WSe2 and MoSe2are used due to their strong exciton binding energy. These use high reflecting DBR mirrors fabricated using oxides of a higher refractive index such as SiO2, NbO2, HfO2/Al2O3, SiO2/Ta2O5 and SiO2/TiO2. In this way, the controlled spontaneous emission is expected to play a vital role in a new generation of optical devices and can have a wide range of applications in Optics, Quantum computing, high-speed signal transmission, etc.

Bose enhancement of excitation-energy transfer with molecular-exciton-polariton condensates.

Room-temperature Bose-Einstein condensates (BECs) of exciton polaritons have been realized in organic molecular systems owing to strong light-matter interaction, strong exciton binding energy, and low effective mass of a polaritonic particle. These molecular-exciton-polariton BECs have demonstrated their potential in nonlinear optics and optoelectronic applications. In this study, we first demonstrate that molecular-polariton BECs can be utilized for Bose enhancement of excitation-energy transfer (EET) in a molecular system with an exciton donor coupled to a group of exciton acceptors that are further strongly coupled to a single mode of an optical cavity. Similar to the stimulated emission of light in which photons are bosonic particles, a greater rate of EET is observed if the group of acceptors is prepared in the exciton-polariton BEC state than if the acceptors are initially either in their electronic ground states or in a normal excited state with an equal average number of molecular excitations. The Bose enhancement also manifests itself as the growth of the EET rate with an increasing number of exciton polaritons in the BEC. Finally, a generalization to the EET in many-donor-many-acceptor molecular systems is considered, and a permutation-symmetry-based approach to suppress the EET to the huge manifold of dark states in the acceptor group is proposed to facilitate the Bose-enhanced EET to the polariton BEC.

First principles study of the structural stability, lattice dynamics, optical and thermoelectric properties of NaSrX(X = As, Sb and Bi)

First principles methods are utilized in exploring the structural stability, electronic, optical, phonon, thermal properties and electronic transport coefficients of NaSrX materials. Based on the calculated cohesive and formation energies, NaSrX compounds are found to be energetically stable. NaSrX materials are also shown to be direct band gap semiconductors with strong exciton binding energies between ∼0.13 and 0.20 eV. The dynamical and mechanical stabilities of NaSrX materials are further confirmed from their phonon dispersion curves and elastic constants. The calculated lattice thermal conductivities, κL, for NaSrX compounds exhibit anisotropic behaviour with the lowest value of κL found in the a-direction. Moreover, NaSrBi is shown to possess the lowest average value of κL (1.29 Wm−1K−1) as compared to NaSrAs and NaSrSb at 300 K. p-doped NaSrX compounds are shown to record large values of thermoelectric figure of merits. For instance, the highest calculated figure of merit (ZT) for p-doped NaSrAs is estimated to be 1.66 at 1200 K when p = 1020 cm−3 whereas those of NaSrSb and NaSrBi are 2.78 (at 1000 K) and 3.16 (at 900 K) respectively when p = 1019 cm−3. The large ZT values obtained in these calculations indicate that NaSrX compounds are promising candidates for thermoelectric applications.

Molding 2D Exciton Flux toward Room Temperature Excitonic Devices

AbstractDevices operating with excitons have promising prospects for overcoming the dilemma of response time and integration in current generation of electron‐ or/and photon‐based elements and devices. In combination with the advantages of emerging twistronics and valleytronics, the atomically thin transition metal dichalcogenide semiconductors open up new opportunities for pursuing practical excitonic devices, where the strong exciton binding energy enables operating exciton at room temperature. The essential and foremost step toward exciton devices is the control of spatiotemporal exciton flux, which is density‐dependent and affected by the complex many‐body interactions. It can be effectively controlled by the strain, electric field, electron‐doping, and local dielectric environment. Intriguingly, exotic phenomena such as exciton condensation, electron‐hole liquid, exciton Hall effects, and exciton halo effects can be occurred in 2D exciton system, providing new possibilities for excitonic devices. Up to now, the proof‐of‐principle of room temperature exciton devices, including excitonic switching and transistor, exciton guides, and excitonic nanolaser, have been realized. Here the authors review the recent advances in molding 2D exciton flux from basic principle, manipulation, exotic phenomena to promising applications and discuss the opportunities and challenges in pushing the frontiers of room temperature excitonic devices.

Quasiparticle energies and optical response of RbTiOPO4 and KTiOAsO4

Many-body perturbation theory based on density-functional theory calculations is used to determine the quasiparticle band structures and the dielectric functions of the isomorphic ferroelectrics rubidium titanyl phosphate (RbTiOPO4) and potassium titanyl arsenide (KTiOAsO4). Self-energy corrections of more than 2 eV are found to widen the transport band gaps of both materials considerably to 5.3 and 5.2 eV, respectively. At the same time, both materials are characterized by strong exciton binding energies of 1.4 and 1.5 eV, respectively. The solution of the Bethe–Salpeter equation based on the quasiparticle energies results in onsets of the optical absorption within the range of the measured data.

Expanded Phase Distribution in Low Average Layer‐Number 2D Perovskite Films: Toward Efficient Semitransparent Solar Cells

AbstractThe application of low average layer‐number (〈n〉 ≤ 2) 2D perovskites in semitransparent photovoltaics (ST‐PVs) has been hindered by their strong exciton binding energy and high electrical anisotropy. Here, the phase distribution is expanded fully and orderly to enable efficient charge transport in 2D (NMA)2(MA)Pb2I7 (NMA: 1‐naphthylmethylammonium, MA: CH3NH3+) perovskite films by regulating the sedimentation dynamics of organic cation‐based colloids. Ammonium chloride is synergistically introduced to enhance the phase separation further and construct a favorable out‐of‐plane orientation. The wide and graded phase distribution well aligns the energy level to facilitate charge transfer. As a result, the first application of an average 〈n〉 = 2 2D perovskite is implemented in ST‐PVs with visible power conversion efficiency (PCE) of 7.52% and high average visible transmittance (AVT) of 40.5%. This study offers a new candidate and an effective strategy for efficient and stable ST‐PVs and is relevant to other perovskite optoelectronic devices.

Metallic phase transition metal dichalcogenide quantum dots showing different optical charge excitation and decay pathways

The charge excitation and decay pathways of two-dimensional heteroatomic quantum dots (QDs) are affected by the quantum confinement effect, bandgap structure and strong exciton binding energy. Recently, semiconducting transition metal dichalcogenides (TMDs) have been intensively studied; however, the charge dynamics of metallic phase QDs (mQDs) of TMDs remain relatively unknown. Herein, we investigate the photophysical properties of TMD-mQDs of two sizes, where the TMD-mQDs show different charge excitation and decay pathways that are mainly ascribed to the defect states and valence band splitting, resulting in a large Stokes shift and two excitation bands for maximum photoluminescence (PL). Interestingly, the dominant excitation band redshifts as the size increases, and the time-resolved PL peak redshifts at an excitation wavelength of 266 nm in the smaller QDs. Additionally, the lifetime is shortened in the larger QDs. From the structural and theoretical analysis, we discuss that the charge decay pathway in the smaller QDs is predominantly affected by edge oxidation, whereas the vacancies play an important role in the larger QDs.

Rocksalt ZnMgO alloys for ultraviolet applications: Origin of band-gap fluctuations and direct-indirect transitions

Rocksalt $\mathrm{Z}{\mathrm{n}}_{x}\mathrm{M}{\mathrm{g}}_{1\ensuremath{-}x}\mathrm{O}$ alloys are theoretically and experimentally investigated for near- and deep-UV optoelectronics with a tunable band gap of 4.2--7.8 eV. Regarding the key question about the composition $x$, at which there is a transition between the direct and indirect gaps, we performed ab initio calculations for various Zn concentrations and all possible atomic arrangements in eight- to 64-atom supercells. We show that, depending on the detailed Zn distribution (clustered, random, or uniform distribution), the alloy band gap can vary by as much as 1.27 eV. The band gap is indirect for clustered and random Zn arrangements in the supercell. For uniform Zn arrangements, the gap is also indirect, except for $x<0.5$ and atom uniform arrangements excluding Zn-O-Zn nearest neighbor bridges, for which the direct gap can be lowered below the indirect gap by about 0.1 eV. The mechanisms of band-gap fluctuation, Zn clustering, and direct-indirect band-gap transitions are analyzed and explained in terms of atomic contributions to band structures by projecting Bloch functions onto localized Wannier functions. Simultaneously, cathodoluminescence measurements were performed on a set of $\mathrm{Z}{\mathrm{n}}_{x}\mathrm{M}{\mathrm{g}}_{1\ensuremath{-}x}\mathrm{O}$ multiquantum wells grown by molecular beam epitaxy on MgO substrates. We observed strong and broad emission bands, redshifting with increasing Zn concentration but featuring no clear-cut evidence for any direct to indirect band-gap crossover. We argue that these alloys are well suited for deep-UV optoelectronics, thanks to the rare combination of strong exciton binding energy, coupling to phonons, and carrier localization, which is favored by the marked flattening of the top valence bands by both short-range and long-range Zn-Zn interactions.

Excitonic Effect Drives Ultrafast Dynamics in van der Waals Heterostructures.

Recent experiments revealed stacking-configuration-independent and ultrafast charge transfer in transition metal dichalcogenides van der Waals (vdW) heterostructures, which is surprising given strong exciton binding energies and large momentum mismatch across the heterojunctions. Previous theories failed to provide a comprehensive physical picture for the charge transfer mechanisms. To address this challenge, we developed a first-principles framework which can capture exciton-phonon interaction in extended systems. We find that excitonic effect does not impede, but actually drives ultrafast charge transfer in vdW heterostructures. The many-body electron-hole interaction affords cooperation among the electrons, which relaxes the constraint on momentum conservation and reduces energy gaps for charge transfer. We uncover a two-step process in exciton dynamics: ultrafast hole transfer followed by much longer relaxation of intermediate "hot" excitons. This work establishes that many-body excitonic effect is crucial to the ultrafast dynamics and provides a basis to understand relevant phenomena in vdW heterostructures.

Nonradiative Energy Transfer between Thickness-Controlled Halide Perovskite Nanoplatelets.

Despite showing great promise for optoelectronics, the commercialization of halide perovskite nanostructure-based devices is hampered by inefficient electrical excitation and strong exciton binding energies. While transport of excitons in an energy-tailored system via Förster resonance energy transfer (FRET) could be an efficient alternative, halide ion migration makes the realization of cascaded structures difficult. Here, we show how these could be obtained by exploiting the pronounced quantum confinement effect in two-dimensional CsPbBr3-based nanoplatelets (NPls). In thin films of NPls of two predetermined thicknesses, we observe an enhanced acceptor photoluminescence (PL) emission and a decreased donor PL lifetime. This indicates a FRET-mediated process, benefitted by the structural parameters of the NPls. We determine corresponding transfer rates up to kFRET = 0.99 ns–1 and efficiencies of nearly ηFRET = 70%. We also show FRET to occur between perovskite NPls of other thicknesses. Consequently, this strategy could lead to tailored energy cascade nanostructures for improved optoelectronic devices.

Co‐Interlayer Engineering toward Efficient Green Quasi‐Two‐Dimensional Perovskite Light‐Emitting Diodes

AbstractWith respect to three‐dimensional (3D) perovskites, quasi‐two‐dimensional (quasi‐2D) perovskites have unique advantages in light‐emitting devices (LEDs), such as strong exciton binding energy and good phase stability. Interlayer ligand engineering is a key issue to endow them with these properties. Rational design principles for interlayer materials and their processing techniques remain open to investigation. A co‐interlayer engineering strategy is developed to give efficient quasi‐2D perovskites by employing phenylbutylammonium bromide (PBABr) and propylammonium bromide (PABr) as the ligand materials. Preparation of these co‐interlayer quasi‐2D perovskite films is simple and highly controllable without using antisolvent treatment. Crystallization and morphology are readily manipulated by tuning the ratio of co‐interlayer components. Various optical techniques, including steady and ultrafast transient absorption and photoluminescence spectroscopies, are used to investigate their excitonic properties. Photoluminescence quantum yield (PLQY) of the perovskite film is dramatically improved to 89% due to the combined optimization of exciton binding energy and suppression of trap state formation. Accordingly, a high current efficiency of 66.1 cd A−1 and an external quantum efficiency of 15.1% are achieved for green co‐interlayer quasi‐2D perovskite LEDs without using any light out‐coupling techniques, indicating that co‐interlayer engineering is a simple and effective approach to develop high‐performance perovskite electroluminescence devices.

Room-Temperature Electron-Hole Liquid in Monolayer MoS2.

Excitons in semiconductors are usually noninteracting and behave like an ideal gas, but may condense to a strongly correlated liquid-like state, i.e., electron-hole liquid (EHL), at high density and appropriate temperature. An EHL is a macroscopic quantum state with exotic properties and represents the ultimate attainable charge excitation density in steady states. It bears great promise for a variety of fields such as ultra-high-power photonics and quantum science and technology. However, the condensation of gas-like excitons to an EHL has often been restricted to cryogenic temperatures, which significantly limits the prospect of EHLs for use in practical applications. Herein we demonstrate the formation of an EHL at room temperature in monolayer MoS2 by taking advantage of the monolayer's extraordinarily strong exciton binding energy. This work demonstrates the potential for the liquid-like state of charge excitations to be a useful platform for the studies of macroscopic quantum phenomena and the development of optoelectronic devices.