Exciton Binding Energy Research Articles

Energy Transfer-Dominated Quasi-2D Blue Perovskite Light-Emitting Diodes.

The bromide-chloride mixed quasi-two-dimensional (2D) perovskite, with a natural quantum well structure and tunable exciton binding energy, has gained significant attention for high-performance blue perovskite light-emitting diodes (PeLEDs). However, the relative importance of having a low trap state density or efficient exciton transfer for high-efficiency electroluminescence (EL) performance remains elusive. Here, two molecules with the benzoic acid group, sodium 4-fluorobenzoate (SFB) and 3,5-dibromobenzoic acid (DBA), are used to modulate the phase distribution and trap state to explore the effect between energy transfer and defect passivation. As a result, when the n = 1 phase is inhibited in both films, the DBA@SFB-modified perovskite films achieve a higher photoluminescence quantum yield (PLQY) than the SFB-modified perovskite films due to effective defect passivation. However, DBA@SFB-modified PeLEDs exhibit lower external quantum efficiency (EQE) compared to SFB-modified PeLEDs due to the poor exciton transfer between the low-dimensional phase. This demonstrates that passivation strategies may enhance photoluminescence through reducing nonradiative recombination, but the effect of phase distribution is pivotal for EL performance by efficient energy transfer in quasi-2D perovskites. Femtosecond time-resolved transient absorption measurements confirm the fastest carrier dynamics in SFB-modified perovskite films, further corroborating the above result. This work provides useful information about phase modulation and defect passivation for high-efficiency blue quasi-2D PeLEDs.

Arising 2D Perovskites for Ionizing Radiation Detection.

2D perovskites have greatly improved moisture stability owing to the large organic cations embedded in the inorganic octahedral structure, which also suppresses the ions migration and reduces the dark current. The suppression of ions migration by 2D perovskites effectively suppresses excessive device noise and baseline drift and shows excellent potential in the direct X-ray detection field. In addition, 2D perovskites have gradually emerged with many unique properties, such as anisotropy, tunable bandgap, high photoluminescence quantum yield, and wide range exciton binding energy, which continuously promote the development of 2D perovskites in ionizing radiation detection. This review aims to systematically summarize the advances and progress of 2D halide perovskite semiconductor and scintillator ionizing radiation detectors, including reported alpha (α) particle, beta (β) particle, neutron, X-ray, and gamma (γ) ray detection. The unique structural features of 2D perovskites and their advantages in X-ray detection are discussed. Development directions are also proposed to overcome the limitations of 2D halide perovskite radiation detectors.

Decoding Excimer Formation in Covalent-Organic Frameworks Induced by Morphology and Ring Torsion.

A thorough and quantitative understanding of the fate of excitons in covalent-organic frameworks (COFs) after photoexcitation is essential for their augmented optoelectronic and photocatalytic applications via precise structure tuning. The synthesis of a library of COFs having identical chemical backbone with impeded conjugation, but varied morphology and surface topography to study the effect of these physical properties on the photophysics of the materials is herein reported. The variation of crystallite size and surface topography substantified different aggregation pattern in the COFs, which leads to disparities in their photoexcitation and relaxation properties. Depending on aggregation, an inverse correlation between bulk luminescence decay time and exciton binding energy of the materials is perceived. Further transient absorption spectroscopic analysis confirms the presence of highly localized, immobile, Frenkel excitons (of diameter 0.3-0.5nm) via an absence of annihilation at high density, most likely induced by structural torsion of the COF skeletons, which in turn preferentially relaxes via long-lived (nanosecond to microsecond) excimer formation (in femtosecond scale) over direct emission. These insights underpin the importance of structural and topological design of COFs for their targeted use in photocatalysis.

Elucidating Solvatochromic Shifts in Two-Dimensional Photocatalysts by Solving the Bethe-Salpeter Equation Coupled with Implicit Solvation Method.

Many studies have focused on tailoring the photophysical properties of two-dimensional (2D) materials for photocatalytic (PC) or photoelectrochemical (PEC) applications. To understand the optical properties of 2D materials in solution, we established a computational method that combined the Bethe-Salpeter equation (BSE) calculations with our GW-GPE method, allowing for GW/BSE-level calculations with implicit solvation described using the generalized Poisson equation (GPE). We applied this method to MoS2, phosphorene (PP), and g-C3N4 and found that when the solvent dielectric increased, it reduced the exciton binding energy and quasiparticle bandgap, resulting in almost no solvatochromic shift in the excitonic peaks of MoS2 and PP, which is consistent with previous experiments. However, our calculations predicted that the solvent dielectric had a significant impact on the excitonic properties of g-C3N4, exhibiting a large solvatochromic shift. We expect that our GW/BSE-GPE method will offer insights into the design of 2D materials for PC and PEC applications.

Exciton polariton condensation from bound states in the continuum at room temperature

Exciton–polaritons (polaritons) resulting from the strong exciton–photon interaction stimulates the development of novel low-threshold coherent light sources to circumvent the ever-increasing energy demands of optical communications1–3. Polaritons from bound states in the continuum (BICs) are promising for Bose–Einstein condensation owing to their theoretically infinite quality factors, which provide prolonged lifetimes and benefit the polariton accumulations4–7. However, BIC polariton condensation remains limited to cryogenic temperatures ascribed to the small exciton binding energies of conventional material platforms. Herein, we demonstrated room-temperature BIC polariton condensation in perovskite photonic crystal lattices. BIC polariton condensation was demonstrated at the vicinity of the saddle point of polariton dispersion that generates directional vortex beam emission with long-range coherence. We also explore the peculiar switching effect among the miniaturized BIC polariton modes through effective polariton−polariton scattering. Our work paves the way for the practical implementation of BIC polariton condensates for integrated photonic and topological circuits.

Use of benzothiophene ring to improve the photovoltaic efficacy of cyanopyridinone-based organic chromophores: a DFT study.

The benzothiophene based chromophores (A1D1-A1D5) with A-π-A configuration were designed via end-capped tailoring with benzothiophene type acceptors using reference compound (A1R). Quantum chemical calculations were accomplished at M06/6-311G(d,p) level to probe optoelectronic and photophysical properties of designed chromophores. Therefore, frontier molecular orbitals (FMOs), binding energy (Eb), open circuit voltage (Voc), transition density matrix (TDM), density of state (DOS) and UV-Vis analyses of A1R and A1D1-A1D5 were accomplished. The designed compounds (A1D1-A1D5) exhibited absorption values in the visible region as 616.316-649.676 nm and 639.753-665.508 nm in gas and chloroform phase, respectively, comparing with reference chromophore. An efficient charge transference from HOMO towards LUMO was found in A1D1-A1D5 chromophores which was further supported by TDM and DOS analyses. Among all chromophores, A1D2 exhibited unique characteristics such as reduced band gap (2.354 eV), higher softness (σ = 0.424 eV), lower exciton binding energy (0.491 eV) and maximum value of open circuit voltage (Voc = 1.981 V). Consequently, A1D2 may be considered as potential candidate for the development of optoelectronic devices. These analyses revealed that the studied compounds exhibited promising findings. They may be utilized in the realm of organic solar cells.

Carbazole-containing covalent triazine frameworks for efficient hydrogen peroxide photosynthesis from natural sunlight

Hydrogen peroxide (H2O2) photosynthesis via polymer photocatalysts is an environmentally friendly and sustainable method for H2O2 production. However, their efficiency is currently unsatisfactory due to limited dissociation and insufficient migration of photogenerated charge carriers. Constructing donor–acceptor (D-A) type polymer photocatalysts has been demonstrated to be a promising approach to improve their optical and electronic properties related to charge carrier separation and migration. Herein, we design two donor–acceptor (D-A) type carbazole-containing covalent triazine frameworks (CTF-PCZs), namely CTF-BPCZ and CTF-TPCZ. These CTF-PCZs are found to reduce the exciton binding energy (Eb) and enhance charge carriers transfer ability compared to non-D-A type CTF-HUST-1. Remarkably, CTF-TPCZ exhibit excellent H2O2 photosynthesis performance, achieving a rate of up to 10331 μmol g−1 h−1 from pure water under solar simulator (AM 1.5G), and 6039 μmol g−1 h−1 from pure water under natural sunlight irradiation in scaled-up photocatalytic experiments, significantly surpass those of all previously reported polymer-based photocatalysts. In-situ experiments provide direct evidence for intermediates involved in the photocatalytic process. Both experiments and DFT calculations reveal that the triazine ring fragment plays a crucial role in H2O2 photosynthesis through a two-step single-electron oxygen reduction reaction (ORR) and the carbazolyl group plays a crucial role in one-step two-electron water oxidation reaction (WOR).

Investigation into the Exciton Binding Energy of Carbon Nitrides on Band Structure and Carrier Concentration through the Photoluminescence Effect

Carbon nitrides form a series of polymer semiconductors popular in photocatalysis. In the course of photoresponse, the separation of light-induced electron–hole pairs is one of the critical factors that affect the conversion rate from photoenergy to chemical substance. Exciton binding energy (Eb) is treated as a classical parameter to evaluate the barrier of exciton dissociation. In this work, we study the electronic and optical nature of two specific members of the carbon nitride family, polymeric carbon nitride (melon) and crystallized poly(triazine imide) (PTI/Li+Cl−) by employing the photoluminescence spectra and density functional theory (DFT) calculations based on the Wannier-Mott exciton module. The results of self-consistent GW computation were applied. The measurement of photoluminescence spectra, by which exciton binding energies are estimated, is likewise discussed. Generally, compared with the results calculated by GW-BSE, the DFT results based on the Wannier-Mott model are closer to the experimental values. From a materials perspective, on the other hand, the exciton binding energy of the melon is lower than that of PTI/Li+Cl−.

Stark Effects of Rydberg Excitons in a Monolayer WSe2 P-N Junction.

The enhanced Coulomb interaction in two-dimensional semiconductors leads to tightly bound electron-hole pairs known as excitons. The large binding energy of excitons enables the formation of Rydberg excitons with high principal quantum numbers (n), analogous to Rydberg atoms. Rydberg excitons possess strong interactions among themselves as well as sensitive responses to external stimuli. Here, we probe Rydberg exciton resonances through photocurrent spectroscopy in a monolayer WSe2 p-n junction formed by a split-gate geometry. We show that an external in-plane electric field not only induces a large Stark shift of Rydberg excitons up to quantum principal number 3 but also mixes different orbitals and brightens otherwise dark states such as 3p and 3d. Our study provides an exciting platform for engineering Rydberg excitons for new quantum states and quantum sensing.

Infrared Imaging Using Thermally Stable HgTe/CdS Nanocrystals.

Transferring nanocrystals (NCs) from the laboratory environment toward practical applications has raised new challenges. HgTe appears as the most spectrally tunable infrared colloidal platform. Its low-temperature synthesis reduces the growth energy cost yet also favors sintering. Once coupled to a read-out circuit, the Joule effect aggregates the particles, leading to a poorly defined optical edge and large dark current. Here, we demonstrate that CdS shells bring the expected thermal stability (no redshift upon annealing, reduced tendency to form amalgams, and preservation of photoconduction after an atomic layer deposition process). The electronic structure of these confined particles is unveiled using k.p self-consistent simulations showing a significant exciton binding energy of ∼200 meV. After shelling, the material displays a p-type behavior that favors the generation of photoconductive gain. The latter is then used to increase the external quantum efficiency of an infrared imager, which now reaches 40% while presenting long-term stability.

Exploring structure-property landscape of non-fullerene acceptors for organic solar cells.

We present a comprehensive analysis of the structure-property relationship in small molecule non-fullerene acceptors (NFAs) featuring an acceptor-donor-acceptor configuration employing state-of-the-art quantum chemical computational methods. Our focus lies in the strategic functionalization of halogen groups at the terminal positions of NFAs as an effective means to mitigate non-radiative voltage losses and augment photovoltaic and photophysical properties relevant to organic solar cells. Through photophysical studies, we observe a bathochromic shift in the visible region for all halogen-functionalized NFAs, except type-2, compared to the unmodified compound. Most of these functionalized compounds exhibit exciton binding energies below 0.3eV and ΔLUMO less than 0.3eV, indicating their potential as promising candidates for organic solar cells. Selected candidate structures undergo an analysis of charge transport properties using the semi-classical Marcus theory based on hopping transport formalism. Molecular dynamics simulations followed by charge transport simulations reveal an ambipolar nature of charge transport in the investigated NFAs, with equivalent hole and electron mobilities compared to the parent compound. Our findings underscore the crucial role of end-group functionalization in enhancing the photovoltaic and photophysical characteristics of NFAs, ultimately improving the overall performance of organic solar cells. This study advances our understanding of the structure-property relationships in NFAs and provides valuable insights into the design and optimization of organic solar cell materials.

Defect Engineering Simultaneously Regulating Exciton Dissociation in Carbon Nitride and Local Electron Density in Pt Single Atoms Toward Highly Efficient Photocatalytic Hydrogen Production.

The high exciton binding energy (Eb) and sluggish surface reaction kinetics have severely limited the photocatalytic hydrogen production activity of carbon nitride (CN). Herein, a hybrid system consisting of nitrogen defects and Pt single atoms is constructed through a facile self-assembly and photodeposition strategy. Due to the acceleration of exciton dissociation and regulation of local electron density of Pt single atoms along with the introduction of nitrogen defects, the optimized Pt-MCT-3 exhibits a hydrogen production rate of 172.0µmolh-1 (λ ≥ 420nm), ≈41 times higher than pristine CN. The apparent quantum yield for the hydrogen production is determined to be 27.1% at 420nm. The experimental characterizations and theoretical calculations demonstrate that the nitrogen defects act as the electron traps for the exciton dissociation, resulting in a decrease of Eb from 86.92 to 43.20meV. Simultaneously, the stronger interaction between neighboring nitrogen defects and Pt single atoms directionally drives free electrons to aggregate around Pt single atoms, and tailors the d-band electrons of Pt, forming a moderate binding strength between Pt atoms and H* intermediates.

Efficient Charge Transport in Inverted Perovskite Solar Cells via 2D/3D Ferroelectric Heterojunction.

While the 2D/3D heterojunction is an effective method to improve the power conversion efficiency (PCE) of perovskite solar cells (PSCs), carriers are often confined in the quantum wells (QWs) due to the unique structure of 2D perovskite, which makes the charge transport along the out-of-plane direction difficult. Here, a 2D/3D ferroelectric heterojunction formed by 4,4-difluoropiperidine hydrochloride (2FPD) in inverted PSCs is reported. The enriched 2D perovskite (2FPD)2PbI4 layer with n = 1 on the perovskite surface exhibits ferroelectric response and has oriented dipoles along the out-of-plane direction. The ferroelectricity of the oriented dipole layer facilitates the enhancement of the built-in electric field (1.06 V) and the delay of the cooling process of hot carriers, reflected in the high carrier temperature (above 1400 K) and the prolonged photobleach recovery time (139.85 fs, measured at bandgap), improving the out-of-plane conductivity. In addition, the alignment of energy levels is optimized and exciton binding energy (32.8 meV) is reduced by changing the dielectric environment of the surface. Finally, the 2FPD-treated PSCs achieve a PCE of 24.82% (certified: 24.38%) with the synergistic effect of ferroelectricity and defect passivation, while maintaining over 90% of their initial efficiency after 1000 h of maximum power point tracking.

Promoting exciton dissociation by metal ion modification in polymeric carbon nitride for photocatalysis

Carbon nitride, a typical low-dimensional conjugated polymer photocatalyst, features a high exciton binding energy due to the weak dielectric screening and the strong Coulombic attraction of photogenerated electrons and holes. The reduction of the exciton binding energy of carbon nitride to promote the conversion from excitons into free carriers is the first priority for the improvement of charge-transfer-dependent photocatalytic reaction activity. In this paper, by introducing a variety of polar metal cations to carbon nitride, it is demonstrated that the charge distribution of the heptazine ring can be improved by ion polarization, which effectively promotes the dissociation of excitons into electrons and holes. The sodium ion shows the best modification effect, which enhances the rate of both photocatalytic hydrogen and hydrogen peroxide production by about 50 %. Characterization shows that the introduction of strongly polar metal cations contributes to the reduction of the exciton dissociation energy of carbon nitride. This study provides a new perspective and a convenient method for the exciton modulation engineering of low-dimensional photocatalysts.

Effect of metal (Cr, Sr, Ag, Cu) doping on the performance of lead-free RbSnI3 based perovskite solar cells: A theoretical approach

Perovskite solar cells based on lead have witnessed unprecedented growth over the past decade, achieving an impressive power conversion efficiency (PCE) of 26.1%. However, lead toxicity remains a concern for commercialization. In order to resolve the matter, scientists have been investigating alternative materials; in this context, rubidium-based lead-free perovskites like RbSnI3 may be a promising alternative because it has a high optical conductivity and absorption coefficient. Density Functional Theory (DFT)-based first-principles studies are used in this work to examine the effect of metal doping (specifically Cr, Sr, Ag, and Cu) on the optoelectronic and structural characteristics of orthorhombic RbSnI3 perovskite. In addition, we conducted a comprehensive study to investigate the impact of metal doping on the formation energy, structural stability, and HOMO–LUMO energy levels of RbSnI3 perovskite. Introducing transition metal cations (Cr2+, Ag+, and Cu+) at the Rb site results in a flat band in the conduction band region, transforming the RbSnI3’s indirect band gap into a direct one and significantly affecting the optoelectronic properties. The DFT results are then integrated into the Solar Cell Capacitance Simulator (SCAPS-1D) to estimate the effectiveness of the modeled device. The Cu-doped RbSnI3 device exhibits the highest PCE of 20.2%. Furthermore, Ag and Cu doping in RbSnI3 increases bond length, which reduces exciton binding energy and helps with charge carrier generation.

Direct Observation of Circularly Polarized Nonlinear Optical Activities in Chiral Hybrid Lead Halides.

Circularly polarized light emission is a crucial application in imaging, sensing, and photonics. However, utilizing low-energy photons to excite materials, as opposed to high-energy light excitation, can facilitate deep-tissue imaging and sensing applications. The challenge lies in finding materials capable of directly generating circularly polarized nonlinear optical effects. In this study, we introduce a chiral hybrid lead halide (CHLH) material system, R/S-DPEDPb3Br8·H2O (DPED = 1,2-diphenylethylenediammonium), which can directly produce circularly polarized second harmonic generation (CP-SHG) through linearly polarized infrared light excitation, exhibiting a polarization efficiency as high as 37% at room temperature. To understand the spin relaxation mechanisms behind the high polarization efficiency, we utilized two models, so-called D'yakonov-Perel' (DP) and Bir-Aronov-Pikus (BAP) mechanisms. The unique zigzag inorganic frameworks within the hybrid structure are believed to reduce the dielectric confinement and exciton binding energy, thus enhancing spin polarization, especially in regions with a high excitation pump fluence based on the DP mechanism. In the case of low excitation pump fluence, the BAP mechanism dominates, as evidenced by the observed decrease in the polarization ratio from CP-SHG measurement. Using density functional theory analysis, we elucidate how the distinctive 8-coordination environment of lead bromide building blocks effectively suppresses spin-orbit coupling at the conduction band minimum. This suppression significantly diminishes spin-splitting, thereby slowing the spin relaxation rate.

Exploring layer thinning of exfoliated β-tellurene and room temperature photoluminescence with large exciton binding energy revealed in β-TeO2

Due to its tunable bandgap, anisotropic behavior, and superior thermoelectric properties, device applications using layered tellurene (Te) are becoming more attractive. Here, we report a thinning technique for exfoliated tellurene nanosheets using thermal annealing in an oxygen environment. We characterize different thinning parameters, including temperature and annealing time. Based on our measurements, we show that controlled layer thinning occurs in the narrow temperature range of 325–350 °C. We also show a reliable method to form β-tellurene oxide (β-TeO2), which is an emerging wide bandgap semiconductor with promising electronic and optoelectronic properties. This wide bandgap semiconductor exhibits a broad photoluminescence (PL) spectrum with multiple peaks covering the range of 1.76–2.08 eV. This PL emission, coupled with Raman spectra, is strong evidence of the formation of 2D β-TeO2. We discuss the results obtained and the mechanisms of Te thinning and β-TeO2 formation at different temperature regimes. We also discuss the optical bandgap of β-TeO2 and show the existence of pronounced excitonic effects evident by the large exciton binding energy in this 2D β-TeO2 system that reach 1.54–1.62 eV for bulk and monolayer, respectively. Our work can be utilized to have better control over the Te nanosheet thickness. It also sheds light on the formation of well-controlled β-TeO2 layered semiconductors for electronic and optoelectronic applications.

Photocatalytic benzylamine coupling dominated by modulation of linkers in donor-acceptor covalent organic frameworks

The strong excitonic effect is widely prevalent in covalent organic frameworks (COFs)-based catalysts, while the high exciton binding energies (Eb) of COFs seriously limit their photocatalytic performance. Herein, theoretical calculations are conducted to evaluate the Eb values of potential COFs derived from benzo[1,2-b:3,4-b'-b'']trithiophene-2,5,8-tricarbaldehyde (BTT) and 2,4,6-trihydroxybenzene-1,3,5-tricarbaldehyde (Bp) as aldehyde monomers. Diverse aromatic amine linkers including dipyridine diamine (BPy), biphenyl diamine (BPh), and p-phenylenediamine (MPh) with different molecular lengths and N-sites are used as linker models to regulate the excitonic effect. The obtained BTT-BPy-COF with a long BPy linker and the lowest calculated Eb value possesses the best photocatalytic performance for benzylamine coupling, with conversion and selectivity up to 99% accompanied by a high oxidation rate, outperforming most of the reported works. Further mechanistic investigation reveals that the bipyridine-N sites in BTT-BPy-COF exhibit strong electron transfer as well as enhanced O2 adsorption and activation that is beneficial to photocatalytic benzylamine coupling.

Highly efficient deep-blue emitting CsPbBr3 nanoplatelets synthesized via surface ligand-mediated strategy

Two-dimensional (2D) CsPbBr3 nanoplatelets (NPLs) have attracted great attention as one of promising semiconductor nanomaterials due to their large exciton binding energy and narrow emission spectra. However, the labile ionic and weakly bound surfaces of deep-blue emitting CsPbBr3 NPLs with wide bandgap result in their colloidal instability, thus degrading their optical properties. It is challenging to obtain deep-blue emitting CsPbBr3 NPLs with excellent optical properties. In this study, high-quality blue-emitting CsPbBr3 NPLs with tunable thickness were prepared adopting the DBSA-mediated confinement effect based on the hot-injection method. Thanks to the coordination interaction of − SO3− of DBSA ligand and the Pb2+ on the surface of the CsPbBr3 NPLs, as well as the effective passivation of Br vacancy defects on the surface of NPLs by OAm-Br, the obtained pure-blue CsPbBr3 NPLs and deep-blue CsPbBr3 NPLs show high photoluminescence quantum yield (PLQY) of 92 % and 81.2 %, respectively. To the best of our knowledge, this is the highest PLQY recorded for deep-blue emitting CsPbBr3 NPLs with two monolayers [PbBr6]4− octahedra. Furthermore, the agglomeration of CsPbBr3 NPLs due to ligand loss induced by moisture, oxygen, and irradiation was also suppressed by the dual passivation effect of DBSA and OAm-Br. Our work provided a new approach to developing high-performance and stable deep-blue emitting CsPbBr3 perovskite nanoplatelets.

Carrier Transport in Low‐Dimensional Tin Perovskite Solar Cells

Recently, the emerging of low‐dimensional tin perovskite solar cells (TPSCs) by introducing bulky organic spacers has attracted extensive attention. It can not only inhibit the oxidation of Sn2+, but also reduce the ion migration and self‐doping effect. Thanks to these advantages, the TPSCs have achieved an impressive power conversion efficiency (PCE) of over 15% recently. However, the introduction of organic spacers impedes the carrier transport and thus limits the attainable PCE. Therefore, it is important to understand the carrier‐transport mechanism in low‐dimensional perovskite to develop more efficient and stable TPSCs. In this review, the latest progress of carrier transport in low‐dimensional TPSCs is summarized in detail. First, the characteristics of carrier transport in low‐dimensional tin perovskites are discussed. Then, the strategies to improve carrier transport are discussed, mainly from the aspects of crystal orientation, crystallization kinetics, defects, interface energy level alignment, quantum well effect, and exciton binding energy. Finally, the future challenges and prospects are expounded to prepare high‐performance and stable low‐dimensional TPSCs.