Localized Energy Levels Research Articles

Ion Leakage Current Control for Polycrystalline Metal Halide Perovskite Direct X-ray Detectors.

Metal halide perovskites have emerged as promising materials for X-ray detection due to their high X-ray attenuation coefficients, defect tolerance, and suitability for large-area, low-temperature fabrication. However, the intrinsic high ion conductivity of these materials presents challenges, such as high dark current density and current drift, which impair the stability and sensitivity of perovskite X-ray detectors. This study introduces an approach to mitigating these issues by incorporating 2,2,3,3,3-pentafluoropropylamine hydrochloride (PFH) into polycrystalline MAPbI3-xClx films using a one-step blade-coating method. PFH aggregates at grain boundaries, raising local vacuum energy levels and passivating surface defects, thereby reducing ion conductivity without affecting electron conductivity. As a result, this approach significantly reduces the dark current and enhances sensitivity, achieving a low detection limit of 14.7 nGyair/s. Additionally, it improves signal stability, consistency, and response speed of the detector. These findings suggest that PFH is a promising additive for advancing the performance and practical application of polycrystalline metal halide perovskite-based X-ray detectors.

An energy‐efficient method using PSO clustering and fuzzy routing to reduce energy consumption in IoT

SummaryIn “Internet of Things” (IoT) technology, all objects can connect to the Internet with a unique Internet address. The sensors have limited energy resources due to their use of batteries in supplying energy, and since battery replacement in these sensors is not usually feasible, the longevity of wireless sensor networks is limited. Therefore, reducing the energy consumption of the used sensors in IoT networks to increase the network lifetime is one of the crucial challenges and parameters in such networks. These networks are subject to a variety of errors. Errors in wireless communication channels, network dynamics due to the mobility of nodes, and the potential for mistakes in mobile nodes are among the causes of errors in these networks. Despite the above failures, the development of routing algorithms in IoT‐based networks has become a significant challenge for researchers, so it is essential to provide routing algorithms to increase network lifespan and reduce energy consumption. In this study, a two‐dimensional network‐based architecture for the Internet of Things is presented. The proposed algorithm first organizes the nodes into logical cells and selects nodes in each cell as the cluster head. The cluster head is selected based on the binary Particle Swarm Optimization algorithm. Then, each node sends its collected data to the cluster head. The cluster heads first aggregate the received data and then use a fuzzy method to send the data to the base station. The proposed algorithm uses the remaining energy level parameter, cluster density, and location of each cell using fuzzy system capabilities and the particle swarm algorithm to try to route data with less energy consumption and increase network lifespan. The proposed method is simulated in ns2 software, and for a more accurate evaluation, we compare it with LEACH, Ant‐C, PSO, EABC, and SOA‐CH algorithms. We see that the proposed method performs better than other methods in terms of energy consumption and network lifespan.

Deuteration-Induced Energy Level Structure Reconstruction of Carbon Dots for Enhancing Photoluminescence.

Constrained by a limited understanding of the structure and luminescence mechanisms of carbon dots (CDs), achieving precise enhancement of their photoluminescence (PL) performance without altering the emission wavelength and color remains a challenge. In this work, a deuterated CD is first achieved by simply replacing the reaction solvent from H2O to D2O. The substitution of D atoms for H atoms is not limited on the surface but also within the internal structure of CDs. Deuteration affects the formation of the π-conjugated network structure by altering the content of sp2 carbon and sp3 carbon, ultimately inducing a reconstruction for energy level structure of CDs. Both the intrinsic state and surface state emission, including quantum yield, emission intensity and lifetime, are significantly enhanced after deuteration. It benefits from the reduction in non-radiative transitions, since the lowered vibrational frequencies of D atoms and optimized local energy level distribution in CDs structure. The deuterated CDs are applied in the fabrication of white-light-emitting diodes to show their application potential. This work provides a highly versatile route for improving and controlling photoluminescence performance of CDs and has opportunities to guide the development of CDs for practical applications.

Entropy of metallic glasses and the size effect on glass transition

A statistical description of metallic glasses is proposed based on evaluation of an entropy and using the concept of potential energy landscape (PEL). The PEL is probed using nano-indentation, assuming that serrations observed are related to local energy levels. Serrations sizes follow a Poisson distribution consistent with, that their formation is a rare events. An entropy is derived revealing parameters characterizing the glass structure. The relevance of the approach is tested on the size effect on mechanical properties of metallic glass. It is noticed that the relations explain the effect of film thickness on the glass transition temperature observed for glass polymers.

Upper-branch thermal Hall effect in quantum paramagnets

Inspired by the persistent thermal Hall effects at finite temperatures in various quantum paramagnets, we explore the origin of the thermal Hall effects from the perspective of the upper branch parts by invoking dispersive and twisted crystal field excitations. It is shown that the upper branches of the local energy levels could hybridize and form dispersive bands. The observation is that, upon time-reversal symmetry breaking by the magnetic fields, these upper branch bands could acquire a Berry curvature distribution and contribute to the thermal Hall effect even in the paramagnetic regime. As a proof of principle, we consider the setting on kagomé lattice with one ground-state singlet and an excited doublet, and show this is indeed possible. We expect this effect to be universal and that it has no strong connection with the underlying lattice. Although the thermal Hall signal can be contributed from other sources such as phonons and their scattering in the actual materials, we discuss the application to the relevant quantum materials. Published by the American Physical Society 2024

First-principles study on the electronic and optical properties of pn-type SnO/MoS[formula omitted] heterojunction tuned by various intrinsic vacancy defects and layer thicknesses

The impact of various intrinsic point defects and layer thicknesses on the electronic structure and optical properties of pn-type SnO/MoS2 heterojunctions has been investigated using first-principles calculations in this study. SnO/MoS2 heterojunctions are indirect bandgap semiconductors, with a narrower bandgap compared to monolayer SnO and MoS2, which decreases with increasing thickness of SnO or MoS2 layers. Intrinsic vacancy defects with different valence states were introduced using the transfer to the real state model method, which ensures that ionized electrons or holes are placed in the real band edge states. The primary intrinsic vacancy defects in the SnO/MoS2 heterojunction are Sn vacancies, and the valence states of the defects significantly influence the defect formation energy. Under different growth conditions, the dominant defects transition between VSn2−, VSn−, VO, and VS as the Fermi level varies. The intrinsic monolayer (1/1) SnO/MoS2 heterojunction exhibits weak n-type doping characteristics, while the introduction of VSn− defects leads to a shift towards p-type doping. As the number of SnO layers increases, VSn2− and VS defects introduce defect levels of different degrees in the bandgap, acting as electron–hole recombination centers and facilitating the transition between p-type doping and metallic conductivity characteristics. Increasing the number of MoS2 layers introduces localized defect energy levels in the bandgap, leading to p-doping or n-doping characteristics. The intrinsic SnO/MoS2 heterojunction primarily absorbs in the near-ultraviolet region, while also exhibiting a certain absorption capacity in the visible and deep ultraviolet regions. The presence of Sn and S defects can enhance the response to visible light absorption.

Correlation between morphology and transport properties of Au/Co/Au/Si wedge ultra-thin film

We report the thermoelectric power (TEP) and electrical resistivity characterization supported by structural and surface morphological properties on a wedge shaped ultra-thin sample of Au/Co/Au/Si (100) with Co have varying thickness from 0.5 nm to 4 nm across the sample. The sample was prepared by Ion Beam Sputtering method, with an ultrathin layer of Co sandwiched between two layers of Au (3 nm thicknesses each). The observed TEP results showed that the system is semiconductor in nature and the concentration of the charge carrier is inversely proportional to the Seebeck coefficient (S) and also concentration of charge carrier modifies with the film thickness leading to a change in thermo power, which is found to be higher at lower thicknesses of Co sandwiched layer. The type of charge carrier was also determined to be electrons in this system. The observed results are in good agreement with the resistivity measurement carried out as a function of film thickness indicating a decrease in resistivity as a function of film thickness due to enhancement in charge carrier mobility. The thermal activation energy was seen to increase from ∼29.5 meV to ∼280.3 meV as the film thickness increased from the minimum to the highest. Corresponding Atomic Force Microscopy (AFM) measurement revealed island type grain growth with the introduction of a significant amount of roughness, while Magnetic Force Microscopy (MFM) experiments exhibit randomly oriented magnetic domain structures. The overall results suggest that lowest thickness film shows semiconducting nature, while variable range hopping phenomena due to some localized energy levels near the valence and conduction band is observed in the highest thickness film. This result is also well supported by XRD measurement, which revealed crystalline nature of the films. Such low cost, easy to fabricate materials may find applications in Peltier cooling or energy harvesting applications without the harmful carbon dioxide emission. For this, advance experiments will be done in future.

Widespread Thalassinoides facies from the upper Silurian of South China: A case study from the northwestern Hunan Province, middle to upper Yangtze Block

The upper Silurian of South China records the first, and perhaps the only occurrence of widespread (spanning over 1400 km), thick to very thick bedded Thalassinoides facies (TVTFs) after the Late Ordovician mass extinction. However, the palaeobiological, palaeoecological features and potential significance of these facies are yet to be demonstrated. A case study at northwestern Hunan Province, middle to upper Yangtze Block, reports the occurrence of TVTFs in a storm dominated open marine succession of the upper Silurian Xiaoxi Formation, which can be further assigned to lower offshore, upper offshore, offshore transition to distal lower shoreface, and proximal lower to middle shoreface settings. The regular changes of bioturbation intensity and maximum penetrating depth from various settings suggest that local energy levels, especially frequency of storms could have controlled the development of Thalassinoides, while their burrow sizes were generally confined by population densities. The Thalassinoides facies could have been constructed by unknown crustaceans, which generally conducted a deposit-feeding strategy. The return of widespread TVTFs in the tropical oceans of South China during the late Silurian could reflect a restored primary productivity, an elevated oxygen level, and a final recovery of benthic ecosystem to pre-extinction level after the Late Ordovician mass extinction. TVTFs could have remarkably shaped the late Silurian benthic environment in view of their high abundance, large burrow sizes, nature of deep tiered burrow systems and a deposit-feeding strategy.

Charge carrier trapping management in Bi3+ and lanthanides doped Li(Sc,Lu)GeO4 for x-ray imaging, anti-counterfeiting, and force recording

Discovering energy storage materials with rationally controlled trapping and de-trapping of electrons and holes upon x-rays, UV-light, or mechanical force stimulation is challenging. Such materials enable promising applications in various fields, for instance in multimode anti-counterfeiting, x-ray imaging, and non-real-time force recording. In this work, photoluminescence spectroscopy, the refined chemical shift model, and thermoluminescence studies will be combined to establish the vacuum referred binding energy (VRBE) diagrams for the LiSc1−xLuxGeO4 family of compounds containing the energy level locations of Bi2+, Bi3+, and the lanthanides. The established VRBE diagrams are used to rationally develop Bi3+ and lanthanides doped LiSc1−xLuxGeO4 storage phosphors and to understand trapping and de-trapping processes of charge carriers with various physical excitation means. The thermoluminescence intensity of x-ray irradiated LiSc0.25Lu0.75GeO4:0.001Bi3+,0.001Eu3+ is about two times higher than that of the state-of-the-art x-ray storage phosphor BaFBr(I):Eu2+. Particularly, a force induced charge carrier storage phenomenon appears in Eu3+ co-doped LiSc1−xLuxGeO4. Proof-of-concept non-real-time force recording, anti-counterfeiting, and x-ray imaging applications will be demonstrated. This work not only deepens our understanding of the capturing and de-trapping processes of electrons and holes with various physical excitation sources, but can also trigger scientists to rationally discover new storage phosphors by exploiting the VRBEs of bismuth and lanthanide levels.

First-principles study of effect of impurity compensation on optical properties of Si

Presently, impurity-compensated silicon (Si) has no clear potential applications due to high resistance and few carriers. Thus, it has received little attention from researchers. In this study, we find that impurity compensation can make localized state energy levels form in Si bandgap, which can improve the light absorption of Si in the near infrared region. In this work, in order to comprehensively and deeply understand the photoelectric properties of impurity-compensated Si, the localized state energy levels composed of P<sup>+</sup>/B<sup>–</sup> ions are constructed in Si bandgap through the co-doping of phosphorus (P) and boron (B), thereby forming impurity-compensated Si. The first-principles based on a density functional theory framework is used to study the photoelectric properties of the impurity-compensated Si (n/p-Sic) such as the density of states (DOS), dielectric function and refractive index. The DOS study reveals the following results: after the n- and p-Si with the same concentration of P and B (12.5%) are fully compensated for by impurities, the Fermi energy levels of their compensated counterparts are at the valley bottom formed by the two adjacent DOS peaks, and the DOS is not zero at the valley bottom. In the study of dielectric function and refractive index, it is found that when the doping ratio is <i>C</i><sub>B</sub>/<i>C</i><sub>P0</sub> = 0.25, n-Sic has the largest dielectric function and refractive index in the low energy region. In addition, comparing intrinsic Si with its doped counterparts in the real part (Re) of their dielectric constant, the following regularity is found: in the high energy region of <i>E</i> > 4 eV, the Re values of the intrinsic Si, n/p-Si and p-Sic are negative. In the low energy region of 0.64 eV< <i>E</i> < 1.50 eV, the Re value of n-Sic is negative for the doping ratio of <i>C</i><sub>B</sub>/<i>C</i><sub>P0</sub> = 0.25. The above comparison indicates that the n-Sic with <i>C</i><sub>B</sub>/<i>C</i><sub>P0</sub> = 0.25 can achieve good metallicity in the low energy region, indicating that the electrons in valence band are easily excited by low-energy long-wavelength light. Theoretical studies show that the good photoelectric properties of n-Sic with <i>C</i><sub>B</sub>/<i>C</i><sub>P0</sub> = 0.25 may be related to Si dangling bonds and localized state energy levels in Si bandgap. The Si dangling bonds are caused by the impurity compensation of B dopant for n-Si, leading part of Si-Si bonds to change into Si-B bonds. This study provides theoretical guidance for the application of impurity-compensated Si in the field of photodetectors such as CMOS image sensors and infrared photodetectors.

Thermally assisted optical processes in InP/ZnS quantum dots.

The utilization of InP-based biocompatible quantum dots (QDs) necessitates a comprehensive understanding of the structure-dependent characteristics influencing their optical behavior. The optimization of core/shell QDs for practical applications is of particular interest due to their reduced toxicity, enhanced photostability, and improved luminescence efficiency. This optimization involves analyzing thermally activated processes involving exciton and defect-related energy levels. This study investigates water-soluble colloidal InP/ZnS QDs with varying shell thicknesses and stabilizing coatings using temperature-dependent optical absorption (OA) and photoluminescence (PL). Our results indicate that all samples experience temperature-induced shifts in exciton absorption and luminescence peaks due to interactions with acoustic phonons. Despite the wide size distribution of nanocrystals, the halfwidth of the bands remains constant. We observe a temperature-dependent Stokes shift in InP/ZnS QDs, revealing the fine structure of exciton states across different configurations. Furthermore, our findings demonstrate common mechanisms underlying PL thermal quenching in these QDs, regardless of the shell thickness or coating type. Specifically, defect-related emissions arise from localized energy levels at the core/shell interface. At the same time, exciton PL quenching primarily occurs through thermally activated electron migration from the InP core to the ZnS shell. Overall, our study highlights the potential for tailoring the temperature response of InP/ZnS QDs by adjusting shell thickness, offering opportunities to optimize their performance for specific applications.

Genesis of temperature-driven red-shift of charge transfer band edge for Sm3+-doped vanadate self-activated phosphor

The temperature-driven redshift of the charge transfer band (CTB) exhibits promising potential for optical temperature sensing as well as for the design of anti-thermal quenching phosphors. Therefore, it is essential to investigate the displacement mechanism in detail. In this contribution, we created LiCa2.95MV3O12:5%Sm3+ (M = Mg/Zn) phosphors with considerably red-shifted CTB edges upon temperature stimulation and outstanding anti-thermal quenching behavior. To investigate this unusual behavior, gaussian fitting was performed on the excitation spectra and emission spectra at different temperatures to investigate the redshift mechanism. By averaging the peak energy of the lowest excitation and emission peaks, the zero phonon line (Ezp) indicating the electronic energy level location of the charge transfer state (CTS) shows a downward trend is obtained. As well as the energy reduction of the 1A2(1T1)-1B1(1T2) and 1E(1T1)-1B1(1T2) absorption bands in the [VO4]3− group is observed. Therefore, the drop in the CTS electronic energy level is the dominant factor in the temperature-driven CTB redshift. Based on the redshift phenomenon and anti-thermal quenching phenomenon of CTB, the phosphor exhibited exceptional optical temperature measurement performance in all three thermometry modes of excitation intensity ratio (EIR), International Committee on Illumination (CIE) color coordinates, and fluorescence intensity ratio (FIR), demonstrating its broad application prospects in the field of optical temperature sensing as well as guiding the design of anti-thermal quenching phosphors.

Nanoscale chemical and structural investigation of solid solution polyelemental transition metal oxide nanoparticles

Although it has been shown that configurational entropy can improve the structural stability in transition metal oxides (TMOs), little is known about the oxidation state of transition metals under random mixing of alloys. Such information is essential in understanding the chemical reactivity and properties of TMOs stabilized by configurational entropy. Herein, utilizing electron energy loss spectroscopy (EELS) technique in an aberration-corrected scanning transmission electron microscope (STEM), we systematically studied the oxidation state of binary (Mn,Fe)3O4, ternary (Mn, Fe, Ni)3O4, and quinary (Mn, Fe, Ni, Cu, Zn)3O4 solid solution polyelemental transition metal oxides (SSP-TMOs) nanoparticles. Our findings show that the random mixing of multiple elements in the form of solid solution phase not only promotes the entropy stabilization but also results in stable oxidation state in transition metals spanning from binary to quinary transition metal oxide nanoparticles.

Liquid water as an adaptive information medium

Here, the internally consistent model of information medium is built from additional (helical) structural detailing of the disordered and continuous network of hydrogen bonds. In this model, the double helix (H2O)2n with strong hydrogen bonds in opposite edges of helical chains has opportunity of coherent and synchronous vibrations of n proton pairs with the resonance frequency fn in terahertz range. At the same time, the electronic band gap of liquid water has the allowed local energy levels on inherent species of liquid water as hydroxonium H3O+ and hydroxide OH-. These electron levels are disposed symmetrically relative to the middle of band gap with energy difference equal to 1.75 eV. The double helix H3O+(H2O)2n-2OH- charged by mentioned ions on its ends is considered as a LC-oscillator of protons with their locking voltage of 1.75 V. This vibrator can launch the collective motion of n proton pairs under the action of electromagnetic field with the frequency fn. Then, such coherently oscillating double helix H3O+(H2O)2n-2OH-↔OH-(H2O)2n-2H3O+ can become an information n-unit which will create in ordinary water a volumetric working memory up to 8.5 PB/l.

A Type-I Heterojunction by Anchoring Ultrafine Cu2O on Defective TiO2 Framework for Efficient Photocatalytic H2 Production

The metal–organic framework (MOF) contains abundant metal ions and organic ligands, and is an excellent self-sacrificial template or precursor for further assembly of functional composites. Herein, MOF-derived defective TiO2 anchored by ultrafine Cu2O nanoparticles has been successfully prepared. In situ formation of type-I heterojunctions between defective TiO2 and ultrafine Cu2O nanoparticles and their application in photocatalytic H2 evolution were demonstrated. Series of composites with varying amounts of Cu2O from 1% to 10% were synthesized. 5 wt % Cu2O loading leads to a H2 generation activity of 4.81 mmol g –1 h –1 under UV–visible light, which is about 3.2 times larger than that of MOF-derived defective TiO2 (1.49 mmol g –1 h –1). It is found that the existence of Ti3+ and Ov defects in the prepared Cu2O/D-TiO2 (defective TiO2) introduces a new local energy level in the forbidden band, which is responsible for effective charge separation. The uniform distribution of Cu2O nanoparticles in defective TiO2 enables close surface contact, enhanced visible light absorption, and electron-transfer efficiency through the formation of heterojunction. This work provides valuable guidelines for exploiting high-performance MOF-derived photocatalysts for the photocatalytic H2 evolution.

LiTaO3:Bi3+,Tb3+,Ga3+,Ge4+: A Smart Perovskite with High Charge Carrier Storage Capacity for X‐Ray Imaging, Stress Sensing, and Non‐Real‐Time Recording

AbstractDeveloping X‐ray or UV‐light charged storage and mechanoluminescence (ML) materials with high charge carrier storage capacity is challenging. Such materials have promising utilization in developing new applications, for example, in flexible X‐ray imaging, stress sensing, or non‐real‐time recording. Herein, the study reports on such materials; Bi3+, Tb3+, Ga3+, or Ge4+ doped LiTaO3 perovskite storage and ML phosphors. Their photoluminescence, thermoluminescence (TL), and ML properties are studied. The charge carrier trapping and release processes in the Bi3+, Tb3+, Ga3+, or Ge4+ doped LiTaO3 are explained by using the constructed vacuum referred binding energy diagram of LiTaO3 including the energy level locations of unintended defects, Tb3+, Bi3+, and Bi2+. The ratio of the TL intensity after X‐ray charging of the optimized LiTaO3:0.005Bi3+,0.006Tb3+,0.05Ga3+, or LiTaO3:0.005Bi3+,0.006Tb3+,0.05Ge4+ to that of the state‐of‐the‐art BaFBr(I):Eu2+ is ≈1.2 and 2.7, respectively. Force induced charge carrier storage phenomena is studied in the Tb3+, Bi3+, Ga3+, or Ge4+ doped LiTaO3. Proof‐of‐concept compression force distribution sensing and X‐ray imaging is demonstrated by using optimized LiTaO3:0.005Bi3+,0.006Tb3+,0.05Ga3+ dispersed in a hard epoxy resin disc and in a silicone gel film. Proof‐of‐concept color‐tailorable ML for anti‐counterfeiting is demonstrated by admixing commercial ZnS:Cu+,Mn2+ with optimized LiTaO3:0.005Bi3+,0.006Tb3+,0.05Ge4+ in an epoxy resin disc.

Z-scheme TiO2−x@ZnIn2S4 architectures with oxygen vacancies-mediated electron transfer for enhanced catalytic activity towards degradation of persistent antibiotics

In photocatalysis as a “green chemistry” technology, the development of efficient strategies to fabricate high-performance micro-nano photocatalysts with robust solar light utilization to deal with persistent pharmaceutical products in the wastewater system is crucially important. In order to improve the photoelectric activity, interfacial charge transfer, and reduce the recombination rate of photo-generated electron-hole pair, a Z-scheme TiO2−x @ZnIn2S4 heterojunction was prepared by hydrothermal method. The morphological structure and optical properties of the prepared catalysts were extensively characterized. Experimental results show that the rich of oxygen vacancies in TiO2−x benefits the formation of local defect energy levels at the bottom of the CB, which can be advantageous to broaden the light absorption range. Likewise, the TiO2−x @ZnIn2S4 showed 12.4-fold and 7.70-fold higher photocatalytic performance pristine TiO2−x and ZnIn2S4 towards the degradation of tetracycline hydrochloride (TCH) and nitrofurantoin (NFT) in real water matrix and solution water. Furthermore, the photo-decomposition pathway of NFT was proposed by HPLC-MS, and the Z-scheme electron transfer mechanism in TiO2−x @ZnIn2S4 heterojunction was proposed and discussed in detail. This work emphasizes a facile method for designing high-efficiency oxygen vacancy mediated titanium-based photocatalysts with excellent photoactivity in environmental remediation.

Superimposed Effect of La Doping and Structural Engineering to Achieve Oxygen-Deficient TiNb2O7 for Ultrafast Li-Ion Storage.

TiNb2O7 (TNO) is a competitive candidate of a fast-charging anode due to its high specific capacity. However, the insulator nature seriously hinders its rate performance. Herein, the La3+-doped mesoporous TiNb2O7 materials (La-M-TNO) were first synthesized via a facile one-step solvothermal method with the assistance of polyvinyl pyrrolidone (PVP). The synergic effect of La3+ doping and the mesoporous structure enables a dual improvement on the electronic conductivity and ionic diffusion coefficient, which delivers an impressive specific capacity of 213 mAh g-1 at 30 C. The capacity retention (@30C/@1C) increases from 33 to 53 and 74% for TNO, M-TNO, and La-M-TNO (0.03), respectively, demonstrating a step-by-step improvement of rate performance by making porous structures and intrinsic conductivity enhancement. DFT calculations verify that the enhancement in electronic conductivity due to La3+ doping and oxygen vacancy, which induce localized energy levels via slight hybridization of O 2p, Ti 3d, and Nb 4d orbits. Meanwhile, the GITT result indicates that PVP-induced self-assembly of TNO accelerates the lithium ion diffusion rate by shortening the Li+ diffusion path. This work verifies the effectiveness of the porous structure and highlights the significance of electronic conductivity to rate performance, especially at >30C. It provides a general approach to low-conductivity electrode materials for fast Li-ion storage.

Charge-Transfer Process in Surface-Enhanced Raman Scattering Based on Energy Level Locations of Rare-Earth Nd3+-Doped TiO2 Nanoparticles.

Surface-enhanced Raman scattering (SERS) for semiconductor nanomaterial systems is limited due to weak Raman signal intensity and unclear charge-transfer (CT) processes for chemical enhancement. Here, rare-earth element neodymium-doped titanium dioxide (Nd-TiO2) nanoparticles (NPs) were synthesized by the sol–gel method. The characterizations show that the doping of Nd ions causes TiO2 NPs to show an increase in the concentration of defects and change in the energy level structure. The CT process between Nd-TiO2 NPs substrate and probe molecule 4-Mercaptopyridine (4-Mpy) was innovatively analyzed using the relative energy level location relationship of the Dorenbos model. The SERS signal intensity exhibits an exponential enhancement with increasing Nd doping concentration and reaches its optimum at 2%, which is attributed to two factors: (1) The increase in the defect concentration is beneficial to the CT process between the TiO2 and the probe molecule; (2) the introduction of 4f electron orbital energy levels of rare-earth ions created unique CT process between Nd3+ and 4-Mpy. Moreover, the Nd-TiO2 NPs substrate shows excellent SERS performance in Raman signal reproducibility (RSD = 5.31%), the limit of detection (LOD = 10−6 M), and enhancement factor (EF = 3.79 × 104). Our work not only improves the SERS performance of semiconductor substrates but also provides a novel approach to the development of selective detection of probe molecules.

Spatial carrier separation in cobalt phosphate deposited ZnIn2S4 nanosheets for efficient photocatalytic hydrogen evolution

Developing photocatalyst with effective charge separation and fast surface reaction kinetics is crucial to high-efficiency photocatalytic H2 evolution. Herein we spatially separate the reductive and oxidative reaction sites of ZnIn2S4 nanosheet and accelerate the hole transfer process by simply depositing cobalt phosphate (CoHxPOy, noted as Co-Pi), a non-precious co-catalyst, on its basal plane. Theoretical calculations combined with comprehensive characterizations reveal that Zn vacancies induced deep local energy levels serve as hole trap states to pin the photogenerated holes on (001) surface of ZnIn2S4. Upon Co-Pi deposition, Co atoms preferentially bond with S atoms nearby the Zn vacancies of ZnIn2S4. Taking advantage of the formation of Co-S bonds, Co-Pi acts as a hole receptor to extract the trapped holes effectively. As the photocatalytic activity of ZnIn2S4 is caused by active S atoms on its edge side, deposition of Co-Pi on planar side of nanosheets helps electron-hole migration to different facets. As a result of inert facet activation and spatial carrier separation, Co-Pi/ZnIn2S4 exhibits a superior photocatalytic H2 evolution rate of 10.19 mmol g-1h−1 under visible light, which is superior to most of reported ZnIn2S4-based photocatalysts. This work will provide novel insights into the activation of inert basal planes of two-dimensional photocatalysts.