Exciton Binding Energy Research Articles

Organic device fabrication and characterizations: DFT support

In this study, the effects of introducing a zinc cation into a zinc-phthalocyanine (ZnPc) cluster are examined in relation to organic phthalocyanine material. The Au/ZnPc/Si-based organic diode is made using the thermal evaporation method. The optical properties of the filter are checked and a selected wavelength of 360[Formula: see text]nm is recorded. Au/ZnPc/Si/Al exhibits high rectifying performance, and the organic device’s primary conduction mechanism is Space Charge Limited Current. ZnPc film’s superior transparency is shown in the visible spectrum, and its optical bandgap of 3.32[Formula: see text]eV is found. According to this result, ZnPc is a semiconductor. ZnPc has a weak exciton binding energy (600[Formula: see text]meV), a high chemical stability, and non-zero value of second hyperpolarizability (4.73[Formula: see text]10[Formula: see text][Formula: see text]esu). These features can offer our ZnPc-based organic device a wide range of applications, including microelectronics, solar cells, and nonlinear optical devices.

Nonlinear Absorption in 2D Ruddlesden-Popper Perovskites: Pathways to Ultrafast Optical Applications.

Owing to their distinctive photophysical properties resulting from their larger exciton binding energy and the influence of dielectric and quantum confinement effects, considerable research interest has been directed toward two-dimensional Ruddlesden-Popper halide perovskites (2D RP-HPs). Particularly, 2D RP-HPs exhibit exceptional multiphoton absorption (MPA) effects that reveal versatile applications. In this work, two-photon absorption (2PA) and three-photon absorption (3PA) in 2D RP-HPs, specifically (PEA)2PbBr4 and (BA)2PbBr4 platelets, have been demonstrated through their photoluminescence spectra under multiphoton excitation, revealing a power law relationship with excitation energy. On the other hand, polarization-dependent MPA measurements are also conducted to obtain their anisotropy properties. The excellent 2PA and 3PA effects of 2D RP-HPs have found applications in ultrafast optics to construct fringe-resolved autocorrelation traces, enabling the retrieval of pulse duration not only passively mode-locked Ti:sapphire at 800 nm but also Yb-doped fiber lasers at 1030 nm.

Mixed Crystalline Covalent Heptazine Frameworks with Built‐in Heterojunction Structures towards Efficient Photocatalytic Formic Acid Dehydrogenation

AbstractCovalent heptazine frameworks (CHFs) are widely utilized in the recent years as potential photocatalysts. However, their limited conjugated structures, low crystallinity and small surface areas have restricted the practical photocatalysis performance. Along this line, we report herein the synthesis of a kind of mixed crystalline CHF (m‐CHF‐1) with built‐in heterojunction structure, which can efficiently catalyze the formic acid dehydrogenation by visible light driven photocatalysis. The m‐CHF‐1 is synthesized from 2,5,8‐triamino‐heptazine and dicyanobenzene (DCB) in the molten salts, in which DCB plays as organic molten co‐solvent to promote the rapid and ordered polymerization of 2,5,8‐triamino‐heptazine. The m‐CHF‐1 is formed by embedding phenyl‐linked heptazine (CHF−Ph) units in the poly(heptazine imide) (PHI) network similar to doping. The CHF−Ph combined with PHI form an effective type II heterojunction structure, which promote the directional transfer of charge carriers. And the integration of CHF−Ph makes m‐CHF‐1 have smaller exciton binding energy than pure PHI, the charge carriers are more easily dissociated to form free electrons, resulting in higher utilization efficiency of the carriers. The largest hydrogen evolution rate reaches a value of 42.86 mmol h−1 g−1 with a high apparent quantum yield of 24.6 % at 420 nm, which surpasses the majority of other organic photocatalysts.

Excitonic properties and solar harvesting performance of Cs2ZnY2X2 as quasi-2D mixed-halide perovskites

Due to their low toxicity and high-temperature stability, lead-free quasi-2D metal halide perovskites (MHPs) are promising materials for optoelectronic applications. However, understanding their structural and optoelectronic properties, especially excitonic effects (electron-hole pair, e-h), is challenging due to their quantum well topology. We propose an efficient protocol for band gap correction of Cs2ZnX (X = Cl4, Br2Cl2, and I2Cl2) and Cs2PbI2Cl2 (used as a benchmark) quasi-2D MHPs. This protocol is based on a relativistic quasiparticle approach (DFT-1/2) using density functional theory (DFT). We first examined the hybrid contributions of the halide alloys, leading to excitonic characterization using the Bethe–Salpeter equation within the maximally localized Wannier functions tight-binding method. This method provides a cost-effective approach for describing e-h quasiparticle effects. Additionally, we analyzed the crystal structure, thermodynamic stability, and optoelectronic properties of the newly synthesized Zn-based systems, focusing on their structural stability mechanisms. We found a correlation between the allocation of Cs+ cations in the crystal structure and the formation of two distinct stabilization patterns, influenced by the radii of the metal (Zn or Pb) and halide components. The relativistic correction of the band gap energies yielded results within 10 % of the experimental values. Furthermore, incorporating e-h quasiparticle effects for Cs2PbI2Cl2 resulted in an exciton binding energy of 0.160 eV, in excellent agreement with experimental data. This work represents a significant advance in the optoelectronic characterization of Cs2ZnX systems, previously unexplored for their excitonic properties.

Graphene with suitable-size nitrogen-doped cavity being an excellent photocatalyst for proton-coupled electron transfer in water splitting

Aiming to attain porous carbon nitride photocatalysts with high specific surface area, abundant active sites, broad absorption range and effective electron-hole separation, we remove carbon rings from graphene and replace all the edge carbon atoms of the cavity with nitrogen atoms. The accurate electronic structures and exciton properties of the proposed materials are revealed by the ab initio many-body Green's function theory. Computational results show that the absorption of the designed materials can cover both the visible and the near-infrared light region. The exciton binding energies of the materials are one order of magnitude lower than those of the typical two-dimensional photocatalyst graphitic carbon nitride. Due to the formation of hydrogen bonds between pyridinic nitrogen atoms and water molecules during water splitting, the key excited-state proton-coupled electron transfer reactions are barrierless. These findings could serve as guidelines for the realization of high-performance metal-free two-dimensional photocatalysts.

High-performing organic/quantum dot hybrid upconversion device based on a single-component near-infrared-sensitive layer

A donor/acceptor (D/A) heterojunction with an interfacial energetic offset is demonstrated to enable efficient exciton dissociation in organic photodetectors and upconversion devices (UCDs). Unfortunately, this approach usually encounters complicated optimization procedures and interfacial instability. Herein, we present an alternative strategy for achieving high-performing UCDs by utilizing an organic single-component near-infrared (NIR)-sensitive layer instead of a D/A heterojunction. The showcased UCD is constructed by vertically stacking an organic single-component Y6 NIR-detection unit and a quantum dot light-emitting unit. Due to the high dielectric constant and low exciton binding energy of the non-fullerene acceptor Y6, free carriers are directly and spontaneously generated upon NIR light excitation. As a result, the single-component UCD achieves a low light detection capability of 2.5 μW/cm2, a fast refresh rate of >3.8 × 104, and a high resolution exceeding 1100 dpi, providing a stable optical response to high-frequency NIR signals and high-quality NIR imaging.

Unveiling the optoelectronic features and physical stability of novel Cs2HgPdI6: Computational insights

In recent years, researchers have been devoted to search for novel stable halide perovskite materials with outstanding photovoltaic performance. Herein, through density functional theory (DFT) calculations, we uncover for the first time the crystal stability, structural parameters, optoelectronic features, and photovolatic performance of Cs2HgPdI6. The Jahn−Teller-distorted Cs2HgPdI6 is detected by its structural feature. The stability of novel Cs2HgPdI6 is completely ensured by means of the DFT calculations. Accurate electronic structure calculations show that Cs2HgPdI6 exhibits an appropriate fundamental gap (1.278 eV). This band gap is mainly determined by the interaction between the I-5p and Pd-4d orbitals. Additionally, Cs2HgPdI6 has good carrier mobility and an ultra-low exciton binding energy. Meanwhile, it also exhibits relatively weak anisotropic optical properties and strong visible-light absorption. The large theoretical conversion efficiency of 31.7 % is illustrated for Cs2HgPdI6. Overall, our research highlights the great potential of this novel compound for photovoltaic applications.

Reducing Dielectric Confinement Effect Enhances Carrier Separation in Two‐Dimensional Hybrid Perovskite Photocatalysts

AbstractTwo‐dimensional organic–inorganic hybrid perovskites (OIHPs) with alternating structure of the organic and inorganic layers have a natural quantum well structure. The difference of dielectric constants between organic and inorganic layers in this structure results in the enhancement of dielectric confinement effect, which exhibits a large exciton binding energy and hinders the separation of electron‐hole pairs. Herein, a strategy to reduce the dielectric confinement effect by narrowing the dielectric difference between organic amine molecule and [PbBr6]4− octahedron is put forward. The Ethanolamine (EOA) contains hydroxyl groups, resulting in the positive and negative charge centers of O and H non‐overlapping, which generated a larger polarity and dielectric constant. The reduced dielectric constant produces a smaller exciton binding energy (71.03 meV) of (C2H7NO)2PbBr4 ((EOA)2PbBr4) than (C8H11N)2PbBr4 ((PEA)2PbBr4 (156.07 meV), and promotes the dissociation of electrons and holes. The increasing of lifetime of photogenerated carrier in (EOA)2PbBr4 are proved by femtosecond transient absorption spectra. Density functional theory (DFT) calculations have also indicated that the small energy shift of the total density of states (DOS) between the C/H/N and the Pb/Br in (EOA)2PbBr4 favors the separation of electrons and holes. In addition, this work demonstrates the application of (PEA)2PbBr4 and (EOA)2PbBr4 in the field of photocatalytic CO2 reduction.

A Dibenzo[g,p]chrysene-Based Organic Semiconductor with Small Exciton Binding Energy via Molecular Aggregation.

Exciton binding energy (Eb) is understood as the energy required to dissociate an exciton in free-charge carriers, and is known to be an important parameter in determining the performance of organic opto-electronic devices. However, the development of a molecular design to achieve a small level of Eb in the solid state continues to lag behind. Here, to investigate the relationship between aggregation and Eb, star-shaped π-conjugated compounds DBC-RD and TPE-RD were developed using dibenzo[g,p]chrysene (DBC) and tetraphenylethylene (TPE). Theoretical calculations and physical measurements in solution showed no apparent differences between DBC-RD and TPE-RD, indicating that these molecules possess similar properties on a single-molecule level. By contrast, pristine films incorporating these molecules showed significantly different levels of electron affinity, ionization potential, and optical gap. Also, DBC-RD had a smaller Eb value of 0.24 eV compared with that of TPE-RD (0.42 eV). However, these molecules showed similar Eb values under dispersed conditions, which suggested that the decreased Eb of DBC-RD in pristine film is induced by molecular aggregation. By comparison with TPE-RD, DBC-RD showed superior performances in single-component organic solar cells and organic photocatalysts. These results indicate that a molecular design suitable for aggregation is important to decrease the Eb in films.

A Dibenzo[g,p]chrysene‐Based Organic Semiconductor with Small Exciton Binding Energy via Molecular Aggregation

AbstractExciton binding energy (Eb) is understood as the energy required to dissociate an exciton in free‐charge carriers, and is known to be an important parameter in determining the performance of organic opto‐electronic devices. However, the development of a molecular design to achieve a small level of Eb in the solid state continues to lag behind. Here, to investigate the relationship between aggregation and Eb, star‐shaped π‐conjugated compounds DBC‐RD and TPE‐RD were developed using dibenzo[g,p]chrysene (DBC) and tetraphenylethylene (TPE). Theoretical calculations and physical measurements in solution showed no apparent differences between DBC‐RD and TPE‐RD, indicating that these molecules possess similar properties on a single‐molecule level. By contrast, pristine films incorporating these molecules showed significantly different levels of electron affinity, ionization potential, and optical gap. Also, DBC‐RD had a smaller Eb value of 0.24 eV compared with that of TPE‐RD (0.42 eV). However, these molecules showed similar Eb values under dispersed conditions, which suggested that the decreased Eb of DBC‐RD in pristine film is induced by molecular aggregation. By comparison with TPE‐RD, DBC‐RD showed superior performances in single‐component organic solar cells and organic photocatalysts. These results indicate that a molecular design suitable for aggregation is important to decrease the Eb in films.

Ligand‐Solvent Coordination Enables Comprehensive Trap Passivation for Efficient Near‐Infrared Quantum Dot Light‐Emitting Diodes

AbstractNear‐infrared light‐emitting diodes (NIR LEDs) based on perovskite quantum dots (QDs) have produced external quantum efficiency (EQE) of ~15 %. However, these high‐performance NIR‐QLEDs suffer from immediate carrier quenching because of the accumulation of migratable ions at the surface of the QDs. These uncoordinated ions and carriers—if not bound to the nanocrystal surface—serve as centers for exciton quenching and device degradation. In this work, we overcome this issue and fabricate high‐performance NIR QLEDs by devising a ligand anchoring strategy, which entails dissolving the strong‐binding ligand (Guanidine Hydroiodide, GAI) in the mediate‐polar solvent. By employing the dye‐sensitized device structure (phosphorescent indicator), we demonstrate the elimination of the interface defects. The treated QDs films exhibit an exciton binding energy of 117 meV: this represents a 1.5‐fold increase compared to that of the control (74 meV). We report, as a result, the NIR QLEDs with an EQE of 21 % which is a record among NIR perovskite QLEDs. These QLEDs also exhibit a 7‐fold higher operational stability than that of the best previously reported NIR QLEDs. Furthermore, we demonstrate that the QDs are compatible with large‐area QLEDs: we showcase 900 mm2 QLEDs with EQE approaching 20 %.

Two-photon upconversion photoluminescence in CsPbBr3 nanoplates

The utilization of solar energy by light conversion processes in both natural and artificial photosynthesis systems has become a pivotal means of sustaining a consistent power supply for our daily lives and production. In general, these reactions rely on the visible spectra region where the sun produces abundant energy according to the black body's emission. Further expanding the adoption of the near-infrared (NIR) spectral region through upconversion has become an intelligent strategy to improve the entire utilization rate of solar energy. In this work, the two-photon upconversion (TPUC) properties were discovered in CsPbBr3 nanoplates (NPs) emitted at 450 nm, and a sub-gap energy level was observed to serve as the center to facilitate the upconversion process. The excitation threshold for TPUC is drastically lower than that for the two-photon absorption, another nonlinear upconversion path that requires strengthened excitation power. Moreover, a significant negative correlation between the excitation threshold for TPUC in the CsPbBr3 NPs and the exciton binding energy was unveiled, which could be attributed to the enhanced quantum confinement effects. Our work paved the way for a feasible way to expand the utilization of the NIR spectral region in light conversion applications.

Ligand-Solvent Coordination Enables Comprehensive Trap Passivation for Efficient Near-Infrared Quantum Dot Light-Emitting Diodes.

Near-infrared light-emitting diodes (NIR LEDs) based on perovskite quantum dots (QDs) have produced external quantum efficiency (EQE) of ~15 %. However, these high-performance NIR-QLEDs suffer from immediate carrier quenching because of the accumulation of migratable ions at the surface of the QDs. These uncoordinated ions and carriers-if not bound to the nanocrystal surface-serve as centers for exciton quenching and device degradation. In this work, we overcome this issue and fabricate high-performance NIR QLEDs by devising a ligand anchoring strategy, which entails dissolving the strong-binding ligand (Guanidine Hydroiodide, GAI) in the mediate-polar solvent. By employing the dye-sensitized device structure (phosphorescent indicator), we demonstrate the elimination of the interface defects. The treated QDs films exhibit an exciton binding energy of 117 meV: this represents a 1.5-fold increase compared to that of the control (74 meV). We report, as a result, the NIR QLEDs with an EQE of 21 % which is a record among NIR perovskite QLEDs. These QLEDs also exhibit a 7-fold higher operational stability than that of the best previously reported NIR QLEDs. Furthermore, we demonstrate that the QDs are compatible with large-area QLEDs: we showcase 900 mm2 QLEDs with EQE approaching 20 %.

Room temperature polariton spin switches based on Van der Waals superlattices

Transition-metal dichalcogenide monolayers possess large exciton binding energy and a robust valley degree of freedom, making them a viable platform for the development of spintronic devices capable of operating at room temperature. The development of such monolayer TMD-based spintronic devices requires strong spin-dependent interactions and effective spin transport. This can be achieved by employing exciton-polaritons. These hybrid light-matter states arising from the strong coupling of excitons and photons allow high-speed in-plane propagation and strong nonlinear interactions. Here, we demonstrate the operation of all-optical polariton spin switches by incorporating a WS2 superlattice into a planar microcavity. We demonstrate spin-anisotropic polariton nonlinear interactions in a WS2 superlattice at room temperature. As a proof-of-concept, we utilize these spin-dependent interactions to implement different spin switch geometries at ambient conditions, which show intrinsic sub-picosecond switching time and small footprint. Our findings offer new perspectives on manipulations of the polarization state in polaritonic systems and highlight the potential of atomically thin semiconductors for the development of next generation information processing devices.

Rational Strategies to Improve the Efficiency of 2D Perovskite Solar Cells.

In the quest for durable photovoltaic devices, 2D halide perovskites have emerged as a focus of extensive research. However, the reduced dimension in structure is accompanied by inferior optical-electrical properties, such as widened band gap, enhanced exciton binding energy, and obstructed charge transport. As a result, the efficiency of 2D perovskite solar cells (PSCs) lags significantly behind their 3D counterparts. To overcome these constraints, extensive investigations into materials and processing techniques are pursued rigorously to augment the efficiency of 2D PSCs. Herein, The cutting-edge delve into developments in 2D PSCs, with a focus on chemical and material engineering, as well as their structure and photovoltaic properties. The review starts with an introduction of the crystal structure, followed by the key evaluation criteria of 2D PSCs. Then, the strategies around solution chemical engineering, processing technique, and interface optimization, to simultaneously boost efficiency and stability are systematically discussed. Finally, the challenges and perspectives associated with 2D perovskites to provide insights into potential improvements in photovoltaic performance will be outlined.

Donor polarization engineering of conjugated microporous polymers to boost exciton dissociation for photocatalytic degradation of tetracycline

The misuse and inevitable release of antibiotics can cause significant harm to both human health and the environment, and the use of polymeric semiconductors for photodegradation of antibiotics in aqueous environments is one of the most effective strategies to alleviate the current dilemma. Nevertheless, the inherently high exciton binding energy (Eb) and low photogenerated carrier transfer efficiency for most photocatalysts results in unsatisfactory photodegradation performance. Hence, this work proposes a donor polarization strategy to regulate the exciton dissociation of conjugated microporous polymers (CMPs) by minimizing their Eb. Results exhibited that the introduction of the strong donor unit 3,4-ethylenedioxythiophene (EDOT) not only reduces the Eb and effectively promotes exciton dissociation, but also broadens the visible light absorption of CMP. Among them, EdtTz-CMP with the lowest Eb (99 meV) delivered an efficiency of 94.6% in photocatalytic degradation of tetracycline (TC) with in 90 min, significantly higher than those of its analogues. This work provides a viable approach to design CMPs by tuning the intrinsic dipole of the donor for efficient environmental purification.

Dynamically Tunable Circularly Polarized Selectivity in Plasmon-Enhanced Halide Perovskite Nanocrystal Glasses.

Ultrafast spin manipulation for optical spin-logic applications requires material systems with strong spin-selective light-matter interactions. The optical Stark effect can realize spin-selective light-matter interactions by breaking the degeneracy of spin-selective transitions with an external electric field. Halide perovskites have large exciton binding energies, which enable a room-temperature optical Stark effect. However, halide perovskites are prone to degradation when interacting with light and polar solvents, limiting further integration with nanophotonic structures. We demonstrate a hybrid material system consisting of CsPbBr3 nanocrystal glass weakly coupled to resonant plasmonic silver nanoparticles, showing ultrafast tunable spin-based polarization selectivity at room temperature. We performed circularly polarized pump-probe characterizations to investigate the optical Stark effect in this material system, which resulted in a maximum energy shift of ∼3.67 meV (detuning energy of 0.11 eV and pump intensity of 0.62 GW/cm2). We show that halide perovskite nanocrystal glasses have excellent resistance to heat and moisture, which may be favorable for integration with nanophotonic structures for further engineering polarization states, energy tuning, and coherence time.

Influence of Growth Temperature on Morphological and Structural Properties of Sputtered- Zinc Oxide Nanorods

Zinc oxide is highly sought after for several applications in biology, optoelectronics, electronics, and sensing. Zinc oxide nanorods exhibit a high exciton binding energy and a wide direct band gap, making them an attractive material for ultraviolet optoelectronic devices in the compound semiconductor field. This investigation focuses mainly on the influence of growing temperature on the crystal structure and surface morphology of ZnO nanorods, specifically for their application as UV photodetectors. Si (100) substrates were utilized for the growth of ZnO nanorods using radio frequency magnetron sputtering. The ZnO nanorods are grown at temperatures of 350 °C, 375 °C, and 400 °C, respectively. The crystal structure and surface morphology were examined using X-ray diffraction and scanning electron microscopy. The samples exhibited a same crystal orientation of the (002) diffraction peak at all growth temperatures. The growth temperatures show a direct influence on the density and length of nanorods, as evidenced by the scanning electron microscopy photographs. The results revealed the significant influence of substrate temperature on the regulation of nanorod length and crystal formation.

Halide Mixing in Cs2AgBi(I x Br1-x )6 Double Perovskites: A Pathway to Tunable Excitonic Properties.

Cs2AgBiBr6 is an emerging double perovskite semiconductor with robust stability. However, its potential for photovoltaics is limited by its indirect band gap and localized electronic structure featuring a resonant exciton with a large binding energy. Cs2AgBi(I x Br1-x )6 nanocrystals with iodide concentrations of up to 100% were recently demonstrated, but an atomistic understanding of how halide mixing affects the electronic and excited-state structure is missing. Here, we use first-principles GW and Bethe-Salpeter Equation calculations to show that halide mixing leads to a pronounced change in the band gap and character of optical excitations. Exciton binding energies are reduced by up to a factor of 5, with significantly more delocalized excitons in I-rich compounds. We further show that phase-pure bulk alloys with x ≤ 0.11 can be fabricated using mechanosynthesis and measure a red-shifted absorption in line with our calculations. Our study highlights that halide mixing in double perovskites can not only lead to significant band gap changes but may also be used for tuning excitonic properties.

Advantages of Ultrathin AlN/GaN/AlN Quantum Wells for Excitonic Population Distribution and Transition Features Studied by Phononic–Excitonic–Radiative Model

Excitons are expected to be a high‐efficiency emission source in UV light‐emitting devices. However, the damping of the excitonic laser oscillation has been reported under conditions where the excitonic states are expected to be populated in the conventional theory. In order to understand the exciton dynamics under the thermal nonequilibrium state, a theoretical model including various energy species in semiconductors such as electrons, phonons, and photons is required. Herein, a 2D phononic–excitonic–radiative model is constructed to analyze the exciton dynamics in a 2D system. 2D excitons with four principal quantum number states and the continuum in the lowest energy level of the AlN/GaN/AlN quantum wells are considered. It is found that the 2D phonon significantly augments the excitation transition rate. When the high recombination rate corresponding to stimulated emission is considered, the exciton binding energy of 108 meV is not enough to reduce the population in the high‐order discreet states and the continuum states, while the binding energy of 215 meV corresponding to the one monolayer GaN has an advantage of reducing these populations. The analysis of population flux has an advantage in discussing the increase in the kinetic energy transfer to the 1S exciton.