Shallow States Research Articles

Engineering Dual Carbon and Nitrogen Vacancies in g-C3N4 for Enhanced Photodegradation of Tetracycline Hydrochloride.

Ultrathin g-C3N4 nanosheets with specific nitrogen vacancies and combined carbon and nitrogen dual vacancies were created by annealing g-C3N4 under different atmospheric conditions. The nanosheets with dual vacancies showed significant improvements in the photodegradation of tetracycline hydrochloride (TC-HCl) compared with both the pristine g-C3N4 and its nitrogen-deficient version. Various techniques, such as Raman spectroscopy, electron spin resonance (ESR), X-ray photoelectron spectroscopy, wavelength-dependent studies, electrochemical methods, and photoluminescence measurements, were used to identify vacancy defects, revealing that performance enhancement was particularly notable under visible light. Density functional theory calculations indicated that dual vacancies introduced a shallow defect state above the valence band, enhancing visible light absorption and reducing electron-hole pair recombination. Conversely, nitrogen vacancies alone formed a deep defect state, which extended light absorption but potentially trapped photoelectrons, limiting their contribution to photoreactions. Radical-scavenging experiments and ESR spin-trap spectra identified the superoxide radical (·O2-) as the primary reactive oxygen species responsible for TC-HCl degradation. A comprehensive degradation pathway for TC-HCl was proposed using liquid chromatography-mass spectrometry data. This research highlights a strategic approach to boost TC-HCl photodegradation by engineering the vacancies in g-C3N4.

Roles of shallow energy level defect states on amplified spontaneous emission enhancement of CH3NH3PbBr3 perovskite crystals

Abstract In this work, we demonstrated the role of shallow energy level defect states on the emission of CH3NH3PbBr3 perovskite polycrystals under laser excitation. The perovskite polycrystals were synthesized by a simple, one-step, low-cost solution self-assembled method. By adjusting the sample preparation temperature from 303 to 373 K, we could manipulate the number of shallow energy level defect states, which were evaluated through low-temperature photoluminescence measurement. This led to an evolution of the CH3NH3PbBr3 perovskite polycrystals’ emission from amplified spontaneous emission to random lasing emission. As a result, the most efficient lasing threshold of 4 μJ mm−2 was achieved with the CH3NH3PbBr3 perovskite polycrystals synthesized at the optimum temperature of 333 K. Furthermore, the surface morphologies and the crystal structure of the CH3NH3PbBr3 perovskite polycrystals were also taken into consideration to unravel the role of defects in the CH3NH3PbBr3 perovskite polycrystals.

Controlling the luminescence of CdSe quantum dots in the fluorinephosphate glass

A series of fluorophosphate glasses with CdSe and CdSe+ZnSe are successfully synthesized. After heat treatment above the glass transition temperature, CdSe quantum dots with sizes 1.5–5.5 nm are formed. The luminescence spectra of CdSe quantum dots are analyzed at various temperatures, excitation energies and chemical composition of glass. The influence of selenium content on the growth features of quantum dots is shown. The size dependence of luminescence quantum yield on the QDs size is found. The 2.0–2.5 nm-sized QDs demonstrate trap emission in the region of 1.7–1.85 eV with a maximum quantum yield of 60 %. It is found that only a broad band due to the transition from the low state of the conduction band and the shallow donor trap states to the deep accepter trap levels is observed. This broad emission band is observed at any selenium cadmium ratio and zinc introduction.

Solution-processed Tb: Zr co-doped In2O3 thin film transistor and its dual effect on improving photostability

In this paper, Tb: Zr co-doped In2O3 TFTs were fabricated using an aqueous route. The dual effect of Tb: Zr co-doping on improving photostability was addressed. At a 5 mol% co-doping concentration, the ΔVth under NBIS first decreased and then increased as Tb: Zr ratio increased. The optimized co-doped sample (1: 2) showed a ΔVth of −3.22 V, compared to the undoped sample of −9.5 V and the single-doped samples (1: 0 and 0: 1) of −4.4 V and −4.15 V respectively. The defect state was evaluated using μ-PCD. The peak value and τ2 first decreased and then increased with an increase in Zr ratio, and reached their minimum values when the Tb: Zr co-doping ratio was 2: 1 and 1: 2, respectively. This suggested that co-doping can introduce more deep level states for the rapid recombination of photogenerated carriers and reduce shallow level states, leading to superior photostability of the co-doped devices. Further characterization by UV-Vis and XPS indicated that the increase in band gap and the decrease in oxygen vacancy were also contributing factors to improved device stability. These results highlight the great potential of solution-processed Tb: Zr co-doped In2O3 TFT for applications in low-cost and high-stability electronics.

Synergistic Tri‐efficiency Enhancement Utilizing Functionalized Covalent Organic Frameworks for Photocatalytic H2O2 Production

AbstractThe overall maximization of photocatalytic H2O2 production efficiency urgently requires the comprehensive optimization of each step in multiplex photocatalysis. Despite numerous endeavors, isolated researches focusing on single efficiencies hinder further advancements in overall catalytic activity. In this work, a series of imine‐linked COFs (TT‐COF‐X), incorporating electronically tunable functional groups (X = ─H, ─OMe, ─OH, ─Br), are rationally fabricated for visible‐light‐driven H2O2 production via a dual‐channel pathway involving 2e− water oxidation and 2e− oxygen reduction. Combined simulations and characterizations reveal that the synergistic modification of functional groups for electronic conjugation and locally intramolecular polarity collectively enhanced light absorption, charge separation and transfer, and interface water–oxygen affinity efficiency. Notably, femtosecond time‐resolved transient absorption (fs‐TA) reveals that the polarity‐induced built‐in electric field play a crucial role in facilitating exciton dissociation by reacting BIEF‐mediated shallow trapping state. The simultaneously optimal tri‐efficiency ultimately results in the highest H2O2 production rate of 3406.25 µmol h−1 g−1 and apparent quantum yields of 8.1% of TT‐COF‐OH. This study offers an emerging strategy to rational design of photocatalysts from the comprehensive tri‐efficiency‐oriented perspective.

Ultrafast photoinduced charge carrier dynamics of L-cysteine and oleylamine stabilized CsPbBr3 perovskite quantum dots coupled with gold nanoparticles.

We have synthesized L-cysteine and oleylamine stabilized CsPbBr3 perovskite quantum dots (PQDs) and coupled them with gold nanoparticles (AuNPs). The PQDs and AuNPs, as well as their hybrid nanostructures (HNS), were characterized using UV-visible (UV-vis) and photoluminescence (PL) spectroscopy. The UV-vis spectra show absorption bands of the HNS at 503 and 520nm, attributed mainly to PQDs and AuNPs, respectively. The PQDs show a strong excitonic PL band peaked at 513nm from PQDs. The HR-TEM results show the formation of hybrid structures between PQDs and AuNPs, which is also supported by the PL quenching of the PQDs by the coupled AuNPs. Ultrafast dynamics of the exciton and charge carriers in the HNS and pristine PQD were studied using femtosecond transient absorption. Multiexponential fitting of the dynamic data revealed the existence of shallow and deep trap states in pristine PQDs and ultrafast electron transfer from PQDs to AuNPs in the HNS. A kinetic model was proposed to account for the key dynamic processes involved and to extract the time for electron transfer from PQDs to AuNPs in the HNS, found to be ∼2ps. Dynamic processes in pristine PQDs are largely unchanged by HNS formation with AuNPs.

Thin Film Stoichiometry and Defects Management for Low Threshold and Air Stable Near-Infrared Perovskite Laser.

While significant efforts have been devoted to optimize the thin-film stoichiometry and processing of perovskites for applications in photovoltaic and light-emitting diodes, there is a noticeable lack of emphasis on tailoring them for lasing applications. In this study, it is revealed that thin films engineered for efficient light-emitting diodes, with passivation of deep and shallow trap states and a tailored energetic landscape directing carriers toward low-energy emitting states, may not be optimal for light amplification systems. Instead, amplified spontaneous emission (ASE) is found to be sustained by shallow defects, driven by the positive correlation between the ASE threshold and the ratio of carrier injection rate in the emissive state to the recombination rate of excited carriers. This insight has informed the development of an optimized perovskite thin film and laser device exhibiting a low threshold (≈ 60 µJ cm-2) and stable ASE emission exceeding 21 hours in ambient conditions.

Modulating long-lived ultrafast charge carrier recombination in type-I MoS2/CdS photocatalyst achieving optimal H2 evolution

Maximizing charge carrier efficiency is crucial for enhancing photocatalyst systems’ capacity to achieve outstanding photocatalytic hydrogen evolution (PHE). Herein, an I-type CdS nanorod/MoS2 nanoflowers heterojunction was successfully fabricated and kinetic transportof charge carriers was being investigated with electron paramagnetic resonance (EPR) analysis, surface photovoltage (SPV), femtosecond transient absorption (fs-TA) measurements and related density functional theory (DFT) calculations, etc. The in-situ dynamic study conducted using fs-TA reveals that the optimal CdS/MoS2 ratio (3CM), when excited by a 380 nm pump, exhibits a quasi-discrete exciton hot carrier cooling time of 0.35 picoseconds (ps), with interfacial electron transfer occurring in approximately 21.90 ps. In this context, MoS2 enhances the efficiency of interfacial electron transfer by passivating surface shallow trapped states, which were observed to be only 8.62 ps in pure CdS. Moreover, the kinetic coupling of long-lived charge separation (approximately 4440 ps) within the 3CM heterojunction, across various ratios of CdS/MoS2, is identified as a key factor in enhancing visible-light-driven PHE. This enhancement achieves remarkable rates of up to 31.094 mmol h-1 g-1, surpassing the performance of physically mixed CdS-MoS2 without chemical bonding by an impressive factor of 31. Our findings highlight the importance of tailored cocatalyst ratios in modulating the charge recombination for enhanced photocatalytic activity.

Enhancing electrical and optical properties of anatase TiO2 nanotubes through electrochemical lithiation

In presented paper, anatase TiO2 nanotubes (NTs) were obtained by anodic oxidation of Ti-foil followed by subsequent annealing in air at 400 °C. After thermal treatment, TiO2 nanotubes (NTs) were electrochemically lithiated by means of galvanostatic (GS) discharge, as a part of GS cycling, at 25°C and 55 °C. Microstructural properties of the as-prepared material were observed by scanning and transmission electron microscopy (SEM, TEM), while changes in chemical bonding with lithiation were examined by X-ray photoelectron spectroscopy (XPS). Specific electrical conductivity, obtained by 4-point probe method, showed multifold increase after Li-ion insertion in TiO2 NTs, at both temperatures. By using diffuse reflectance spectroscopy (DRS), the decrease in energy gap, from 3.04 eV for the as-prepared TiO2 NTs to 2.81 eV for lithiated TiO2 NTs, was observed. The photoluminescence (PL) measurements suggest that Li-ion intercalation led to suppression of deep-level trap states within the bandgap, of TiO2 NTs, and promoted shallow defects associated to F-centers. Open-circuit photovoltage decay (OCVD) measurements confirm the promotion of shallow defect states. Furthermore, HER measurements indicate that the electrochemical lithiation is a promising strategy for enhancing the catalytic performance of TiO2.

Computational approach to modeling electronic properties of titanium oxynitride systems

The study presents the use of a novel on-lattice sampling approach to generate titanium oxynitride (TiNxOy) structures with potential applications in photovoltaic and water splitting. This approach presents a simple route to overcome challenges with structure-generating tools like Cluster Approach to Statistical Mechanics (CASM), and Ab initio Random Structure Search (AIRSS), CASM faces difficulty in generating ternary structures with large unit cells. With AIRSS, there is an increase in probability of sampling amorphous sample spaces with increased number of atoms in the unit cell. Here an on-lattice sampling approach was used to model the electronic structure of TiNxOy as a function of composition. We present results for Ti2N2O, Ti5N4O4 and Ti7N4O8, with 33 %, 50 % and 67 % N replaced by O via substitution relative to titanium nitride (TiN), respectively. Koopmans theorem was used correct the Kohn-Sham Density Functional Theory (KS-DFT) bandgaps with corresponding values of 2.68 eV, 3.03 eV, and 3.65 eV for 33, 50 and 67 % O doping respectively. The projected density of states (PDOS) plot for TiN shows that the Fermi level is dominated by the 3d atomic orbitals of Ti, confirming pure TiN’s metallicity. The valence bands of TiNxOy structures were dominated by 2p orbitals of O at lower energy levels, but they were dominated by 2p orbitals of N at energies close to the valence band maximum (VBM). The conduction bands were dominated by the 3d atomic orbitals of Ti, with the bandgap increasing with O composition leading to creation of shallow trap states near the VBM, which negatively impacts carrier mobility. In conclusion, the on-lattice sampling approach is an effective tool to generate highly crystalline structures of large unit cells, also keeping O substitution for N below 33 % as seen in Ti2N2O is crucial for avoiding shallow traps in TiNxOy structures.

Ultrafast Scintillator Based on Zirconium‐Doped Cesium Zinc Chloride Single Crystals and Their Charge Carrier Dynamics

AbstractScintillators have been widely used for high‐energy radiation imaging. It is in great demand and challenge to develop scintillator materials with fast decay time, high scintillation light yield, and low detection limit for high‐resolution imaging applications such as time‐of‐flight positron emission tomography. However, it is still a challenge to develop the ultrafast carrier dynamics to achieve 100% ultrafast decay time with high scintillation light yield. To meet the demand, a series of component‐tunable Cs2ZnCl4: x%Zr single crystals as promising ultrafast scintillators is successfully developed. With 8% of Zr‐dopant (Cs2ZnCl4: 8%Zr), the single crystal exhibits high light yield (28000 photons MeV−1) and low detection limit (51 nGy s−1) under X‐ray excitation. Photo‐induced transient absorption signals on sub‐nanosecond and nanosecond scales ensure almost 100% fast decay time (≈3 ns) in nanoseconds under γ‐ray excitation. In particular, the different radiative transition processes are achieved under ultraviolet and high‐energy radiation due to the tunable carrier dynamics from the shallow trapped state to the self‐trapped exciton (STE) state.

N-n+ homojunction of S-doped SnFe2O4 to inhibit surface-state-mediated electrons adverse trapping for enhanced photocatalysis performance

How to make full use of solar energy and improve the efficiency of charges separation of photocatalysis has been a concern for scientists all along. To achieve this, this work designed an n-n+ homojunction of S-doped SnFe2O4 and applied it to near infrared driven photocatalytic degradation and sterilization. The experimental results demonstrated that S doping significantly enhanced the photocatalytic performance of SnFe2O4. The degradation rate of ciprofloxacin and the removal rate of Staphylococcus aureus (S. aureus) reached up to approximately 65 % and 100 % after 6 h irradiation, respectively. The S-doping could increase the content of shallow trap states in SnFe2O4, effectively inhibiting the recombination of photogenerated electrons and holes. Moreover, S-doping also enhances the n-type character and forms n-n+ homojunction. This n-n+ homojunction generates a built-in electric field within the sample, which causes band bending and promotes photogenerated charges transfer and separation. Consequently, more carries are available for the generation of reactive oxygen species. Free radical quenching experiments and ESR tests show that •O2− is the main free radical in the photocatalysis. In addition, DFT calculations confirmed the enhanced activation of O2 after S doping. This work provides a feasible way to effectively promote charges separation and transfer in metalloid-based photocatalysts.

An EPR study of point defects in zinc oxide thin films

We studied ZnO thin films deposited on glass slides by thermal evaporation in vacuum followed by heat treatment in open air or Ar flow. The samples were characterized using x-ray diffraction, Raman scattering, photoluminescence (PL), and electron paramagnetic resonance (EPR) spectroscopy. We observed a broad PL band in the visible region at spectral positions of 504 and 560 nm and a low-intensity band in the UV region at 390 nm. The EPR spectra display a clear first derivative structure at g=1.96 at temperatures below 200 K. The PL spectrum shows red-shifted valence to conduction band emission due to electron hole recombination through shallow surface states. We found an activation energy of E a = 4.2 meV using the Arrhenius plot and estimated concentrations of paramagnetic defects and spin–spin relaxation time constants of 1016 m−3 and 10–14 s, respectively.

Strategies to Enhance the Stability of Non‐Fullerene Acceptor‐Based Organic Solar Cells

AbstractThrough comprehensive density functional theory calculations, the photodegradation mechanisms, including cis–trans isomerization, electrocyclization, and sigmatropic rearrangement reactions are investigated in indacenodithieno [3,2‐b] thiophene (IT)‐based non‐fullerene acceptors (NFAs). Various functional group substitutions on the core (fluorine, ethyl, and cyano groups) and end groups (fluorine) of NFA are introduced to elucidate the influence of chemical modifications on photodegradation pathways. The findings reveal that the core substitution can effectively suppress electrocyclization and 1,5‐sigmatropic shift reactions, which are major contributors to photodegradation. Furthermore, the electronic, excited‐state, and charge transport properties of pristine and degraded products are studied to gain insights into the impact of degradation on photovoltaic parameters. The results suggest that photodegradation leads to the formation of shallow energy trap states, hindering charge transport and increasing charge recombination, ultimately affecting the power conversion efficiency of organic solar cells (OSCs). The study not only provides a comprehensive understanding of photodegradation mechanisms but also offers valuable molecular design strategies to enhance the stability of NFAs for future large‐scale applications of OSCs. By establishing a clear connection between the chemical structure and photostability of NFA, this research represents a pivotal contribution to the field of organic electronics and sustainable energy technologies.

Electronic relaxation in PLD TiO2 films processed with femtosecond UV-laser

Modifications of shallow electron trap states near conduction band was analyzed after surface structuring of TiO2 thin films prepared via pulsed laser deposition method. Laser-induced periodic surface structures (LIPSS) were produced on the large-area films after irradiation with femtosecond KrF laser (λ = 248 nm). While spatial period of LIPSS Λ ≈ 190 ± 10 nm was not affected by laser fluence, coherence was increased with an increase of laser dose. Time-resolved microwave conductivity measurements accompanied by theoretical modelling revealed energetic positions of shallow electron trap states, connected to LIPSS. A possibility to alter the trap states energy via surface structuring of the material was shown.

Defect‐Expedited Photocarrier Separation in Zn2In2S5 for High‐Efficiency Photocatalytic C─C Coupling Synchronized with H2 Liberation from Benzyl Alcohol

AbstractPhotocatalytic carbon‐carbon (C─C) coupling of benzyl alcohol is a promising means to coproduce the value‐added chemicals with H2 but is generally subject to low efficiency in terms of photon utilization. Here, efficient benzyl alcohol C─C coupling is achieved over Zn2In2S5 containing a tunable content of Zn vacancies (VZn). The VZn tends to form shallow defect states below the conduction band that can expedite photocarrier separation by collecting the photo‐generated electrons. The VZn‐collected electrons are essential for a high selectivity of the C─C coupling reactions because they enable a fast elimination of the byproduct benzaldehyde by catalyzing its reduction back to the ketyl radicals. Under simulated sunlight, the VZn‐containing Zn2In2S5 accomplishes ≈100% conversion of benzyl alcohol for merely 1 h and attains ≈100% selectivity for the C─C coupling compounds for 2 h, delivering an apparent quantum yield as high as 7.7% at 420 ± 20 nm. The benefits of VZn have also been verified by the theoretical calculations that indicate reduced energy barriers for various surface reactions in the presence of VZn. This work brings fresh mechanistic insights into the role of VZn and can serve as a useful guideline in the design of efficient photocatalysts.

Analysis of the Optical Properties and Electronic Structure of Semiconductors of the Cu2NiXS4 (X = Si, Ge, Sn) Family as New Promising Materials for Optoelectronic Devices

In this work, the optoelectronic characteristics of kesterites of the Cu2NiXS4 system (X = Si, Ge, Sn) were studied. The electronic properties of the Cu2NiXS4 (X = Si, Ge, Sn) system were studied using first-principles calculations within the framework of density functional theory. For calculations, ab initio codes VASP and Wien2k were used. The high-precision modified Beke-Jones (mBJ) functional and the hybrid HSE06 functional were used to estimate the bandgap, electronic, and optical properties. Calculations have shown that when replacing Si with Ge and Sn, the band gap decreases from 2.58 eV to 1.33 eV. Replacing Si with Ge and Sn reduces the overall density of electronic states. In addition, new deep (shallow) states are formed in the band gap of these crystals, which is confirmed by the behavior of their optical properties. The obtained band gap values are compared with existing experimental measurements, demonstrating good agreement between HSE06 calculations and experimental data. The nature of changes in the dielectric constant, absorption capacity, and optical conductivity of these systems depending on the photon energy has also been studied. The statistical dielectric constant and refractive index of these materials were found. The results will help increase the amount of information about the properties of the materials under study and will allow the use of these compounds in a wider range of optoelectronic devices, in particular, in solar cells and other devices that use solar radiation to generate electric current.

Spin Crossover and Exchange Effects on Oxygen Evolution Reaction Catalyzed by Bimetallic Metal Organic Frameworks.

Bimetallic metal-organic frameworks (BMOFs) have shown a superior oxygen evolution reaction (OER) performance, attributed to the synergistic effects of dual metal sites. However, the significant role of these dual-metal synergies in the OER is not yet fully understood. In this study, we employed density functional theory to systematically investigate the OER performance of NiAl- and NiFe-based BMOFs by examining all possible spin states of each intermediate across diverse external potentials and pH environments. We found that the spin state featuring a shallow hole trap state and Ni ions with a higher oxidation state serve as strong oxidizing agents, promoting the OER. An external potential-induced spin crossover was observed in each intermediate, resulting in significant changes in the overall reaction and activation energies due to altered energy levels. Combining the constant potential method and the electrochemical nudged elastic band method, we mapped the minimum free energy barriers of the OER under varied external potential and pH by considering the spin crossover effect for both NiAl and NiFe BMOFs. The results showed that NiFe exhibits better OER thermodynamics and kinetics, which is in good agreement with experimentally measured OER polarization curves and Tafel plots. Moreover, we found that the improved OER kinetics of NiFe not only is attributed to lower barriers but also is a result of improved electrical conductivity arising from the synergistic effects of Ni-Fe dual-metal sites. Specifically, replacing the second metal Al with Fe leads to two significant outcomes: a reduction in both the band gap and the effective hole mass compared to NiAl, and the initiation of super- and double-exchange interactions within the Ni-F-Fe chain, thereby enhancing electron transfer and hopping and leading to the improved OER kinetics.

Resistance analysis of laser-welded aluminum lead and tab for electric vehicle battery: Experiment and simulation

In pouch-type Li-ion batteries used in electric vehicles, battery cell tabs are electrically connected to an external lead of the same substance. Laser welding is a promising technique for joining these materials. This study investigates the fundamental question of whether electrical resistance measurements can be used to reliably estimate the welding state. An Al lead (400 μm thick) was welded spot-by-spot to a stack of 30 Al tabs (each tab 13 μm thick) using a laser beam incident on the lead surface. By adjusting the laser irradiation conditions, three different welding states (shallow, intermediate, and deep states) were intentionally produced. However, these structures exhibited no appreciable difference in the resistance measured across the welded region. The resistance was on the order of 10−4 Ω regardless of the welding state. Simulations were conducted for various joint structures, including those with voids, to derive the current flow through the structures and joint resistances. The simulation results corresponded well with the experimental results. Our study indicates that the electrical estimation of the welding state is challenging, because extremely low resistances are obtained even if the lead and tab are locally connected with narrow current paths.

Ultrafast Exciton Dynamics of CH3NH3PbBr3 Perovskite Nanoclusters.

Exciton dynamics of perovskite nanoclusters has been investigated for the first time using femtosecond transient absorption (TA) and time-resolved photoluminescence (TRPL) spectroscopy. The TA results show two photoinduced absorption signals at 420 and 461 nm and a photoinduced bleach (PB) signal at 448 nm. The analysis of the PB recovery kinetic decay and kinetic model uncovered multiple processes contributing to electron-hole recombination. The fast component (∼8 ps) is attributed to vibrational relaxation within the initial excited state, and the medium component (∼60 ps) is attributed to shallow carrier trapping. The slow component is attributed to deep carrier trapping from the initial conduction band edge (∼666 ps) and the shallow trap state (∼40 ps). The TRPL reveals longer time dynamics, with modeled lifetimes of 6.6 and 93 ns attributed to recombination through the deep trap state and direct band edge recombination, respectively. The significant role of exciton trapping processes in the dynamics indicates that these highly confined nanoclusters have defect-rich surfaces.