Energy Level Structure Research Articles

Rare earth oxide based electrocatalysts: synthesis, properties and applications.

As an important strategic resource, rare earths (REs) constitute 17 elements in the periodic table, namely 15 lanthanides (Ln) (La-Lu, atomic numbers from 57 to 71), scandium (Sc, atomic number 21) and yttrium (Y, atomic number 39). In the field of catalysis, the localization and incomplete filling of 4f electrons endow REs with unique physical and chemical properties, including rich electronic energy level structures, variable coordination numbers, etc., making them have great potential in electrocatalysis. Among various RE catalytic materials, rare earth oxide (REO)-based electrocatalysts exhibit excellent performances in electrocatalytic reactions due to their simple preparation process and strong structural variability. At the same time, the electronic orbital structure of REs exhibits excellent electron transfer ability, which can reduce the band gap and energy barrier values of rate-determining steps, further accelerating the electron transfer in the electrocatalytic reaction process; however, there is a lack of systematic review of recent advances in REO-based electrocatalysis. This review systematically summarizes the synthesis, properties and applications of REO-based nanocatalysts and discusses their applications in electrocatalysis in detail. It includes the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), hydrogen oxidation reaction (HOR), oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO2RR), methanol oxidation reaction (MOR), nitrogen reduction reaction (NRR) and other electrocatalytic reactions and further discusses the catalytic mechanism of REs in the above reactions. This review provides a timely and comprehensive summary of the current progress in the application of RE-based nanomaterials in electrocatalytic reactions and provides reasonable prospects for future electrocatalytic applications of REO-based materials.

Free electron laser prepared high-intensity metastable helium and helium-like ions

In the precision spectroscopy of few-electron atoms, the generation of high-intensity metastable helium atoms and helium-like ions is crucial for implementing experimental studies as well as a critical factor for improving the signal-to-noise ratio of experimental measurements. With the rapid development of free-electron laser (FEL) and technology, FEL wavelengths extend from hard X-rays to soft X-rays and even vacuum ultraviolet bands. Meanwhile, laser pulses with ultra-fast, ultra-intense and high repetition frequencies are realized, thus making it possible for FEL to prepare single-quantum state atoms/ions with high efficiency. In this work, we propose an experimental method for obtaining high-intensity single-quantum state helium atoms and helium-like ions by using FEL. The preparation efficiency can be calculated by solving the master equation of light-atom interaction. Considering the experimental parameters involved in this work, we predict that the efficiencies of preparing metastable 2<sup>3</sup>S He, Li<sup>+</sup> and Be<sup>2+</sup> are about 3%, 6% and 2%, respectively. Compared with the common preparation methods such as gas discharge and electron bombardment, a state-of-the-art laser excitation method can not only increase the preparation efficiency, but also reduce the effects of high-energy stray particles such as electrons, ions, and photons generated during discharge. Furthermore, combined with the laser preparation technique, the sophisticated ion confinement technique, which can ensure a long interaction time between the ions and laser, increases the efficiency of metastable Li<sup>+</sup> and Be<sup>2+</sup> by several orders of magnitude. Therefore, the preparation of high-intensity metastable helium and helium-like ions can improve the measurement accuracy of precision spectroscopy of atoms and ions. A new experimental method, based on FEL, to study the fine structure energy levels 2<sup>3</sup>P of helium, has the potential to obtain the results with an accuracy exceeding the sub-kHz level. Thus, the high-precision fine structure constants can be determined with the development of high-order quantum electrodynamics theory. In order to measure energy levels with higher accuracy, a new detection technique, which can reduce or even avoid more systematic effects, must be developed. For example, the quantum interference effect, which has been proposed in recent years, seriously affects the accuracy of fine-structure energy levels. If the interference phenomenon of spontaneous radiation between different excited states can be avoided in the detection process, the measurement accuracy will not be affected by this quantum interference effect. High-intensity metastable atoms or ions in chemical reaction dynamics studies also have better chances to investigate reaction mechanisms. In summary, the FEL preparation of high-intensity metastable helium atoms and helium-like ions proposed in this work will lay an important foundation for developing cold atom physics and chemical reaction dynamics.

Molecular Engineering of Perylene Diimide Polymers with a Robust Built-in Electric Field for Enhanced Solar-Driven Water Splitting.

The built-in electric field of the polymer semiconductors could be regulated by the dipole moment of its building blocks, thereby promoting the separation of photogenerated carriers and achieving efficient solar-driven water splitting. Herein, three perylene diimide (PDI) polymers, namely oPDI, mPDI and pPDI, are synthesized with different phenylenediamine linkers. Notably, the energy level structure, light-harvesting efficiency, and photogenerated carrier separation and migration of polymers are regulated by the orientation of PDI unit. Among them, oPDI enables a large dipole moment and robust built-in electric field, resulting in enhanced solar-driven water splitting performance. Under simulated sunlight irradiation, oPDI exhibits the highest photocurrent of 115.1 μA cm-2 for photoelectrochemical oxygen evolution, which is 11.5 times that of mPDI, 26.8 times that of pPDI and 104.6 times that of its counterparts PDI monomer at the same conditions. This work provides a strategy for designing polymers by regulating the orientation of structural units to construct efficient solar energy conversion systems.

Molecular Engineering of Perylene Diimide Polymers with a Robust Built‐in Electric Field for Enhanced Solar‐Driven Water Splitting

AbstractThe built‐in electric field of the polymer semiconductors could be regulated by the dipole moment of its building blocks, thereby promoting the separation of photogenerated carriers and achieving efficient solar‐driven water splitting. Herein, three perylene diimide (PDI) polymers, namely oPDI, mPDI and pPDI, are synthesized with different phenylenediamine linkers. Notably, the energy level structure, light‐harvesting efficiency, and photogenerated carrier separation and migration of polymers are regulated by the orientation of PDI unit. Among them, oPDI enables a large dipole moment and robust built‐in electric field, resulting in enhanced solar‐driven water splitting performance. Under simulated sunlight irradiation, oPDI exhibits the highest photocurrent of 115.1 μA cm−2 for photoelectrochemical oxygen evolution, which is 11.5 times that of mPDI, 26.8 times that of pPDI and 104.6 times that of its counterparts PDI monomer at the same conditions. This work provides a strategy for designing polymers by regulating the orientation of structural units to construct efficient solar energy conversion systems.

All-optical modulation by continuous wave light using two-color excited-state absorption at visible wavelengths.

We demonstrated all-optical modulation with a nonlinear medium, i.e., indigo carmine, an aromatic conjugated structure with delocalized π-electrons, using non-high power continuous wave light for pump and probe of different visible wavelengths. Pump-induced probe transmission increase occurred through absorption saturation of probe light by pump-induced linear and nonlinear absorption including two-color excited-state absorption (ESA). The two-color ESA occurred only when both pump light and probe light co-propagated through a medium, leading to nearly pump power-independent increase in probe transmission for appropriately chosen wavelengths of pump and probe light, given the optical transition structure of electronic energy levels in the medium.

Construction of n-type homogeneous to improve interfacial carrier transfer for enhanced photoelectrocatalytic hydrolysis

Photoelectrocatalyzed hydrogen production plays an important role in the path to carbon neutrality. The construction of heterojunctions provides an ideal example of an oxygen precipitation reaction. In this work, the performance of the n-n type heterojunction CeBTC@FeBTC/NIF in the photoelectronically coupled catalytic oxygen evolution reaction (OER) reaction is presented. The efficient transfer of carriers between components enhances the catalytic activity. Besides, the construction of heterojunctions optimizes the energy level structure and increases the absorption of light, and the microstructure forms holes with a blackbody effect that also enhances light absorption. Consequently, CeBTC@FeBTC/NIF has excellent photoelectric coupling catalytic properties and requires an overpotential of only 300 mV to drive a current density of 100 mA cm−2 under illumination. More importantly, the n-n heterojunction was found to be effective in enhancing charge and photogenerated electron migration by examining the carrier density of each component and carrier diffusion at the interface.

Boosting Cu─In─Zn─S-based Quantum-Dot Light-Emitting Diodes Enabled by Engineering Cu─NiOx/PEDOT:PSS Bilayered Hole-Injection Layer.

The imbalance of charge injection is considered to be a major factor that limits the device performance of cadmium-free quantum-dot light-emitting diodes (QLEDs). In this work, high-performance cadmium-free Cu─In─Zn─S(CIZS)-based QLEDs are designed and fabricated through tailoring interfacial energy level alignment and improving the balance of charge injection. This is achieved by introducing a bilayered hole-injection layer (HIL) of Cu-doped NiOx (Cu─NiOx)/Poly(3,4-ethylenedioxythiophene): poly (styrene sulfonate) (PEDOT:PSS). High-quality Cu─NiOx film is prepared through a novel and straightforward sol-gel procedure. Multiple experimental characterizations and theoretical calculations show that the incorporation of Cu2+ ions can regulate the energy level structure of NiOx and enhance the hole mobility. The state-of-art CIZS-based QLEDs with Cu─NiOx/PEDOT:PSS bilayered HIL exhibit the maximum external quantum efficiency of 6.04% and half-life time of 48min, which is 1.3 times and four times of the device with only PEDOT:PSS HIL. The work provides a new pathway for developing high-performance cadmium-free QLEDs.

Passivating SnZn Defect and Optimizing Energy Level Alignment via Organic Silicon Salt Incorporation toward Efficient Solution‐Processed CZTSSe Solar Cells

AbstractThe SnZn defect passivation and heterojunction interface energetics‐modification are crucial for further improvement of open‐circuit voltage (Voc) and efficiency of Cu2ZnSn(S,Se)4 (CZTSSe) solar cells. Herein, a simple but effective cation substitution strategy is reported to promote the performance of CZTSSe devices by simultaneously modifying the absorber and heterojunction interface. This is achieved by introducing the organic silicon salt C8H20O4Si into CZTSSe precursor solution as a source of silicon to partially substitute Sn with Si. Systematic studies reveal that there are two mechanisms synergistically contributing to the increase of efficiency: 1) This strategy can passivate the undesired SnZn defect in CZTSSe absorber more efficiently, leading to at least one order of magnitude lower SnZn defect density and beneficial carrier transport properties; 2) After Si incorporation, the conduction band minimum of the CZTSSe is upshifted, thus enlarging the bandgap, which ultimately optimizes the energy level structure at the CdS/CZTSSe interface and reduces interfacial energy loss by decreasing the carrier transport barrier. Consequently, the CZTSSe device with 7% Si substitution delivers a satisfactory efficiency of 13.02% owing to an increase in Voc. It is hoped the Si substitution strategy reported here can provide inspiration for developing advanced CZTSSe devices with broad application prospects.

Optimization of visible photoluminescence emission from Ni-Zn ferrite thin films

Ni-Zn ferrite films with different thicknesses were prepared by the spray method, aiming to study the relationship between the annealing effect in an oxygen rich environment and the structural, optical properties and photoluminescence emission. X-ray diffraction (XRD) analysis used with Rietveld refinement showed that all prepared samples had a single spinel phase structure. Likewise, the Fourier transform infrared (FTIR) spectra confirmed the phase formation of Ni-Zn ferrites by appearing in both of the two characteristic absorption bands which are related to the tetrahedral and octahedral sites. For annealed thin film samples of Ni-Zn ferrite, the atomic force microscope (AFM) surface morphology exhibits pinning structure on the surface in nanoscale height, whereas for un-annealed samples, there are hills and valleys cover a broad region. The different electronic transitions were estimated from the UV-visible transmission spectrum. Strong photoluminescence (PL) intensity in the visible range was observed under the excitation of UV radiation. The intensity of the PL signal was strongest at a film thickness of 750 nm then decreased for higher thicknesses. This could be interpreted by using proposed energy level structures based on the transmission spectrum of the investigated samples. The strong PL intensity introduces the samples as a direct optical detector for UV radiation.

Br-Doped BiOCl Nanosheet Exposed (001) Facet: Surface Oxygen Vacancy and Directed Electron Flow Boosting the Photocatalytic Performance.

The defective BiOCl nanosheet exposed (001) facet with favorable photocatalytic performance was designed. The surface microstructure analysis and theoretical calculation certified the dominant exposed (001) facet and rich surface oxygen defects of Br--doped BiOCl (B-6) nanosheets. The energy level structure analysis indicates that the band gap can be narrowed and the light absorption range can be widened by introducing Br- to BiOCl, and the presence of defective energy levels increases the photogenerated carrier transfer efficiency. Moreover, the doping of Br- in BiOCl promotes the directional flow of electrons to the surface of B-6, which improves the photocatalytic performance of the sample. Thus, the Br--doped BiOCl can degrade 96.5% RhB within 6 min under visible-light irradiation with high apparent reaction rate constants of 0.51 min-1, exhibiting the strongest photocatalytic degradation performance. This work provides guidance for the preparation of Bi-based photocatalysts with excellent performance.

Identifying Molecular Structure–Energy Level Quantitative Relationship of Thermally Activated Delayed Fluorescence Materials Using Machine Learning

Identifying Molecular Structure–Energy Level Quantitative Relationship of Thermally Activated Delayed Fluorescence Materials Using Machine Learning

Amorphous-crystalline heterostructures enable energy-level matching of cobalt sulfide/nickel iron layered double hydroxide for efficient oxygen evolution reaction

Interface engineering of heterostructures has emerged as a promising approach to enhance the catalytic activity of nonprecious electrocatalysts. Herein, a novel amorphous cobalt sulfide-crystalline nickel iron layered double hydroxide (a-CoS@NiFe-LDH) hybrid material is presented for application as an electrocatalyst for oxygen evolution reaction (OER). Benefitting from the well-matched energy level structures, the a-CoS@NiFe-LDH catalyst delivers a low overpotential of 221 ± 14 mV at an OER current density of 20 mA cm−2 and a small Tafel slope of 83.1 mV dec-1, showing good OER properties. First-principle computations reveal that the electronic interaction between amorphous cobalt sulfide (a-CoS) and crystalline nickel iron layered double hydroxide (NiFe-LDH) components within a-CoS@NiFe-LDH promotes the adsorbate evolution mechanism and reduces the adsorption energies for oxygen intermediates, thereby enhancing the activity and stability for OER. This work opens up a new avenue to enhance the OER catalytic efficiency via the construction of amorphous-crystalline heterostructures.

Heterogeneous Structures Consisting of Rod-like ZnO Interspersed with Ce2S3 Nanoparticles for Photo-Sensitive Supercapacitors with Enhanced Capacitive Performance.

Photosensitive supercapacitors incorporate light-sensitive materials on capacitive electrodes, enabling solar energy conversion and storage in one device. In this study, heterogeneous structures of rod-shaped ZnO decorated with Ce2S3 nanoparticles on nickel foam (ZnO@Ce2S3/NF) are synthesized using a two-step hydrothermal method as photosensitive supercapacitor electrodes for capacitance enhancement under visible light. The formation of ZnO@Ce2S3 heterogeneous structures is confirmed using various structural characterization techniques. The area-specific capacitance of the ZnO@Ce2S3/NF composite electrode increased from 1738.1 to 1844.0mFcm-2 after illumination under a current density of 5 mAcm-2, which is 2.4 and 2.8 times higher than that of ZnO and Ce2S3 electrodes under similar conditions, respectively, indicating the remarkable light-induced capacitance enhancement performance. The ZnO@Ce2S3/NF electrode also exhibits a higher photocurrent and photovoltage than the two single electrodes, demonstrating its excellent photosensitivity. The improved capacitance performance and photosensitivity under illumination are attributed to the well-constructed energy-level structure, which stimulates the flow of photogenerated electrons from the outer circuit and the involvement of photogenerated holes in the resulting surface-controlled capacitance. In addition, the assembled ZnO@Ce2S3/NF-based hybrid supercapacitor exhibits a great energy density of 145.0 mWhcm-2 under illumination. This study provides a novel strategy for the development of high-performance solar energy conversion/storage devices.

Interface Engineering and Electron-Hole Wave Function Overlap of InAs/AlSb Superlattice Infrared Detectors

InAs/AlSb is a material system that can be used as a low-noise avalanche detector and operates in the short-wave infrared band. The interface parameters determine the wave function overlap (WFO). Maximizing the WFO of InAs/AlSb superlattices improves the quantum efficiency (QE) of infrared avalanche photodetectors (APDs). However, this remains a huge challenge. Here, the 8-band k·p perturbation method based on Bloch wave envelope function approximation was used to calculate the energy level structure of InAs/AlSb superlattices. The results indicate that the WFO is enhanced with increasing InSb interface thickness or when the InSb (or AlAs) interface is far from the intersection of InAs and AlSb. As the AlAs interface thickness increases, the WFO enhances and then reduces. The maximum increase in WFO is 15.7%, 93%, and 156.8%, respectively, with three different models. Based on the stress equilibrium condition, we consider the interface engineering scheme proposed for enhancing WFO with an increase of 16%, 114%, and 159.5%, respectively. Moreover, the absorption wavelength shift is less than ±0.1 μm. Therefore, the interface layer thickness and position can be designed to enhance the WFO without sacrificing other properties, thereby improving the QE of the device. It provides a new idea for the material epitaxy of APDs.

Modeling and numerical simulation optimization of gain spectrum of thulium-doped broadband fiber amplifier based on cat swarm algorithm

With the development of light technology, especially the maturation of WDM/DWDM technology, the demand for optical amplification of the S-band and S+ band (1450nm~1520nm) is increasing day by day, and the energy level structure of Tm3+ has energy level transitions to meet the requirements of S-band and S+ band amplification. Although thulium ion has a very complex energy level structure, TDFA is one of the most promising optical fiber amplifiers for S and S+ bands. At the same time, with the continuous development of computer technology and mathematical theory, the optimization algorithm has been rapidly developed and widely used in recent decades, based on genetic algorithm, simulated annealing algorithm, and other traditional optimization algorithms that have been proved to get good convergence speed and optimization results. In this paper, the thulium-doped fiber amplifier's gain is optimized by using a cat swarm intelligent optimization algorithm to obtain the maximum fiber length and doping concentration.

Construction of a Fe2O3/Ti3C2Tx heterojunction photocatalyst with oxygen-rich vacancies and its photocatalytic properties

As a class of antibiotics, tetracycline (TC) poses a serious threat to aquatic environments, thereby necessitating new demands on their restoration. Herein, a Fe2O3/Ti3C2Tx heterojunction photocatalyst with abundant surface oxygen vacancies was prepared using a solvothermal method, which can promote the migration and separation of photogenerated electron–hole pairs and improve the catalytic degradation performance of the material. The experimental results revealed that the prepared Fe2O3/Ti3C2Tx heterojunction catalysts exhibited better TC degradation performance under simulated sunlight, corresponding to 2.5 times that of Fe2O3 and 5.1 times that of Ti3C2Tx. Fe2O3 and Ti3C2Tx formed a close contact interface, and the staggered energy-level structure achieved the rapid transfer of electrons, resulting in the formation of numerous oxygen vacancies during the conversion of Fe3+ to Fe2+; these oxygen vacancies not only changed the Fe2O3/Ti3C2Tx crystal structure but also provided additional active centers for the reaction. In addition, transient fluorescence spectroscopy and photocurrent experiments revealed that the method considerably improved the separation rate of photo‐excited carriers and the corresponding optoelectronic capability. The possible degradation pathways were revealed by the determination of the TC post-degradation by-products. Moreover, toxicity modeling results revealed that most degradation intermediates were less toxic than TC. This study discusses the importance of heterojunctions with oxygen-rich vacancies for improving the performance of degraded TC and provides an effective strategy for constructing heterojunction photocatalysts, broadening the applications of Fe2O3 and Ti3C2Tx materials in environmental remediation.

Rational Design of Photocontrolled Rectifier Switches in Single-Molecule Junctions Based on Diarylethene.

The construction of multifunctional, single-molecule nanocircuits to achieve the miniaturization of active electronic devices is a challenging goal in molecular electronics. In this paper, we present an effective strategy for enhancing the multifunctionality and switching performance of diarylethene-based molecular devices, which exhibit photoswitchable rectification properties. Through a molecular engineering design, we systematically investigate a series of electron donor/acceptor-substituted diarylethene molecules to modulate the electronic properties and investigate the transport behaviors of the molecular junctions using the non-equilibrium Green's function combined with the density functional theory. Our results demonstrate that the asymmetric configuration, substituted by both the donor and acceptor on the diarylethene molecule, exhibits the highest switching ratio and rectification ratio. Importantly, this rectification function can be switched on/off through the photoisomerization of the diarylethene unit. These modulations in the transport properties of these molecular junctions with different substituents were obtained with molecule-projected self-consistent Hamiltonian and bias-dependent transmission spectra. Furthermore, the current-voltage characteristics of these molecular junctions can be explained by the molecular energy level structure, showing the significance of energy level regulation. These findings have practical implications for constructing high-performance, multifunctional molecular-integrated circuits.

Electronic and nanoscale structures of metal oxyhalide intergrowth photocatalysts

Multimetal oxyhalide intergrowths show promise for photocatalytic water splitting. However, the relationships between intergrowth stoichiometry and their electronic and nanoscale structures are yet to be identified. This study investigates Bi4TaO8Cl–Bi2GdO4Cl intergrowths and demonstrates that stoichiometry controls the tilting of [TaO6] octahedra, influencing the bandgap of the photocatalyst and its valence and conduction band positions. To determine how the [TaO6] octahedral tilting in the intergrowths manifests as a function of intergrowth stoichiometry, we investigated changes in crystal symmetry by analyzing features arising at the higher order Laue zone (HOLZ) of convergent-beam electron diffraction patterns. Higher Ta content intergrowths displayed a more intense outer HOLZ ring compared to lower Ta content intergrowths, indicating transformation from P21cn (orthorhombic) to P4/mmm (tetragonal). This finding suggests that more distortion occurs along the ⟨001⟩ directions of the crystal than the ⟨100⟩ and ⟨010⟩ directions. This variation directly impacts the electronic structure, affecting both conduction and valence band energy levels. By combining ultraviolet photoelectron spectroscopy, UV-visible diffuse reflectance spectroscopy, and electron energy loss spectroscopy, the absolute band positions of the intergrowths were determined. Agreement between the bandgaps obtained via ensemble and nanoscale measurements indicates nanoscale homogeneity of the electronic structure. Overall, the integrated approach establishes that the bandgap energy increases with increasing Ta content, which is correlated with the crystal symmetry and [TaO6] octahedral tilting. Broadly, the modular nature of intergrowths provides building block layers to tune octahedral tilting within perovskite layers for manipulation of optoelectronic properties.

Enhanced Hole Injection in Blue Quantum‐Dot Light‐emitting Diodes Utilizing Dual Hole Injection Layer of PEDOT:PSS/Ti3C2Tx

AbstractThe low hole injection efficiency severely constrains the operational capability of blue quantum‐dot light‐emitting diodes (QLEDs). Constructing the structure of stepped energy levels is an effective approach to enhance the hole injection efficiency. Here, the dual hole injection structure is fabricated through the introduction of Ti3C2Tx film, in which its function is modulated by controlling the size of Ti3C2Tx nanosheets. Benefitting from a matched Fermi energy of Ti3C2Tx film, the Ti3C2Tx‐modified devices achieve a peak external quantum efficiency (EQE) of 15.89%, exhibiting a 67% increase compared to the reference devices with an EQE of 9.72%. The enhanced EQE can be attributed to the reduced energy barrier between indium tin oxide (ITO) and PEDOT:PSS, resulting from the incorporation of a Ti3C2Tx hole injection layer. In addition, the Ti3C2Tx layer effectively avoids the corrosion of the ITO electrode by acidic PEDOT:PSS, thereby enhancing the electrical stability of the ITO/PEDOT:PSS interface. The results provide a new approach to realize the high‐performance blue QLEDs devices.

Study on optical absorption of silicene nanodisks under strain modulation

Using the tight-binding Hamiltonian approach, we theoretically study the position of energy level structures and optical absorption peaks by applying stress forces laterally or longitudinally of triangular zigzag silicene nanodisks (TZSN). We consider the effect of strain on the structure. We found that by applying a lateral force similar to that applied to the stretched structure (the force applied to the compressed structure), all absorption peaks can be observed to move to the left or to the right as a whole in the optical absorption spectrum, and this shift is more pronounced at the main absorption peaks, indicating the possibility of TZSN as a strain sensor, and we also considered which size of TZSN would be more suitable as a sensor. On the other hand, it is found that the compressive strain can effectively reduce the light absorption intensity when the incident energy is less than 1.4 eV (0.89 µm). The work described in the system can be used as new material is applied to the sensor and imaging equipment, etc.