Electron-hole Recombination Process Research Articles

Two-dimensional Fullerene-Based Ferroelectric Materials: Assembly and Effects on Charge Carrier Lifetime.

Manipulating the symmetry of fullerene-based low-dimensional materials is crucial to the development of electronic devices and modern nonvolatile memories. However, there have been few reports on studying the physicochemical properties of fullerene and its derivatives by controlling the symmetries. Herein, we demonstrate ferroelectricity in Sc3N@Ih-C80-Pd/Pt adducts with relatively strong spontaneous polarization. Polarization originates from subtle molecular interactions between Sc3N@Ih-C80 and Pd/Pt atoms, breaking the structural symmetry. Additionally, we investigate how a temperature-dependent polar-nonpolar phase transition affects the corresponding nonadiabatic electron-hole recombination process in the ferroelectric fullerene adduct Sc3N@Ih-C80-Pd. The results indicate that polarization has a greater impact than temperature effects, resulting in an extension of the carrier lifetime in the polar phase by over 3 times compared to that in the nonpolar phase. Our findings unveil new members of the ferroelectric fullerene family and provide guidance for improving the performance of optoelectronic materials.

A room-temperature ultrafast carrier dynamical study and thickness-dependent investigation of WTe2 thin films on a flexible PET substrate

In the current era of increasing demand for optoelectronic-based devices with ultra-rapid response, it is important to understand the processes associated with the relaxation dynamics of hot carriers and transient electrical properties of WTe2 material under photoexcitation of charge carriers. In this work, using femtosecond laser pump–probe spectroscopy at room temperature we performed the transient absorption measurement on sputtered deposited WTe2 thin films having four different thicknesses to study dynamics associated with the relaxation of their hot carriers. The relaxation dynamics of photoexcited charge carriers undergo three exponential decay components associated with electron–phonon thermalization in the conduction band and phonon-assisted electron–hole recombination between the electron and hole pocket. The thickness-dependent investigation of WTe2 thin films reveals that the electron–hole recombination process is more prominent in thicker films than in thinner films, supporting previously published theoretical and experimental conclusions. The Ultrafast study of WTe2 thin films suggests that it is a suitable material for future ultrafast optoelectronic-based device applications.

Improved ammonia gas sensing performance at room temperature of polypyrrole by polyoxometalate decoration

Here, we introduced polyoxometalate (POMs) into polypyrrole (PPy) gas sensitive material for the first time to restrain the electron-hole recombination process and enhance the gas sensing performances. At room temperature, the sensing response value of PPy/POMs composite nanoparticles to 100 ppm NH3 gas can be improved to 80.85 %, 2.99 times than that of pure PPy nanoparticles. PPy/3 % SiW12 sensor response-recovery time was 39 s/166 s. It had good linearity (R2 = 0.9958), the LOD of NH3 was 85 ppb. In 21 days, the sensor still maintained over 90 % of the initial ammonia response value. Selectivity, repeatability and other sensing parameters were systematically investigated. In addition, the mechanism of sensing performance enhancement was analyzed and discussed. The study proved that POMs can separate electrons and holes, finally improved gas sensing properties. This work provides a new idea for the design and construction of high sensitivity PPy-based gas sensor by introducting polyoxometalates.

Nonadiabatic Coupling-Induced Quantum Coherence in Two-Dimensional Materials.

Two-dimensional materials provide a rich platform demonstrating quantum effects, and the process of electron-hole recombination occurring in them has significant applications in the fields of the photocatalytic and optoelectronic community. Here, we present nonadiabatic coupling-induced quantum coherence and quantum beats in Al-doped blue phosphorene. The work improves our understanding and utilization of nonadiabatic coupling in low-dimensional materials from a new perspective. In addition, our investigations provide meaningful guidance for manipulating quantum coherence in low-dimensional materials and promoting their novel optoelectronic properties.

A dual-purpose photocatalytic reaction for hydrogen evolution and simultaneous organic pollutant degradation of V2O5/Ppy based composite photocatalyst

The present work reports for the facile synthesis of novel vanadium oxide/polypyrrole (V2O5/Ppy) nanohybrids using various loadings of the V2O5. This novel hybrid photocatalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman, UV–Visible absorption spectra (UV–Vis), photoluminescence spectra (PLS) and N2 adsorption-desorption analysis. XRD and TEM results suggest that V2O5 with individual spherical shaped nanoparticles of around 20–25 nm, which is uniformly wrapped on the surface of the Ppy sheets. A significant reduction in the bad gap energy (3.06–2.13 eV) and prevent the electron-hole recombination process was examined by UV and PL studies. The photocatalytic degradation efficiency was carried out for Reactive Black 31 (RB 31) and 4-chlorophenol (4-CP) dyes under visible light. The results illustrate that the optimal hybrid catalyst could reach 99 % of removal efficiency towards RB31 with visible light irradiation for 60 min. Moreover, the catalyst show high TOC efficiency (88%) high apparent constant (0.9189 min−1), and good stability with multiple cycle experiments. The improved photocatalytic mechanism was also discussed in detail. In comparison to V2O5 (425 μmol−1h−1 of H2) and PPy (151 μmol−1h−1 of H2), the optimised composite, 15 wt% V2O5 incorporated PPy showed a remarkable production rate under visible light (2255 μmol−1h−1 of H2).

Hot carrier relaxation dynamics of an aza-covalent organic framework during photoexcitation: An insight from abinitio quantum dynamics.

In order to develop an efficient metal-free solar energy harvester, we herein performed the electronic structure calculation, followed by the hot carrier relaxation dynamics of two dimensional (2D) aza-covalent organic framework by time domain density functional calculations in conjunction with non-adiabatic molecular dynamics (NAMD) simulation. The electronic structure calculation shows that the aza-covalent organic framework (COF) is a direct bandgap semiconductor with acute charge separation and effective optical absorption in the UV-visible region. Our study of non-adiabatic molecular dynamics simulation predicts the sufficiently prolonged electron-hole recombination process (6.8 nanoseconds) and the comparatively faster electron (22.48ps) and hole relaxation (0.51ps) dynamics in this two-dimensional aza-COF. According to our theoretical analysis, strong electron-phonon coupling is responsible for the rapid charge relaxation, whereas the electron-hole recombination process is slowed down by relatively weak electron-phonon coupling, relatively lower non-adiabatic coupling, and quick decoherence time. We do hope that our results of NAMD simulation on exciton relaxation dynamics will be helpful for designing photovoltaic devices based on this two dimensional aza-COF.

COF-Topological Quantum Material Nano-heterostructure for CO2 to Syngas Production under Visible Light.

Efficient solar-driven syngas production (CO+H2 mixture) from CO2 and H2O with a suitable photocatalyst and fundamental understanding of the reaction mechanism are the desired approach towards the carbon recycling process. Herein, we report the design and development of an unique COF-topological quantum material nano-heterostructure, COF@TI with a newly synthesized donor-acceptor based COF and two dimensional (2D) nanosheets of strong topological insulator (TI), PbBi2Te4. The intrinsic robust metallic surfaces of the TI act as electron reservoir, minimising the fast electron-hole recombination process, and the presence of 6s2 lone pairs in Pb2+ and Bi3+ in the TI helps for efficient CO2 binding, which are responsible for boosting overall catalytic activity. In variable ratio of acetonitrile-water (MeCN : H2O) solvent mixture COF@TI produces syngas with different ratios of CO and H2. COF@TI nano-heterostructure enables to produce higher amount of syngas with more controllable ratios of CO and H2 compared to pristine COF. The electron transfer route from COF to TI was realized from Kelvin probe force microscopy (KPFM) analysis, charge density difference calculation, excited state lifetime and photoelectrochemical measurements. Finally, a probable mechanistic pathway has been established after identifying the catalytic sites and reaction intermediates by in situ DRIFTS study and DFT calculation.

In situ polymerised polyaniline films over multi-walled carbon nanotubes coatings for enhanced photoelectrochemical performance

Polyaniline (PANI), which is a π-conjugated polymer, has stood out as a promising candidate for dihydrogen generation in photoelectrochemical (PEC) cells owing to its suitable optoelectronic properties and excellent stability. Nevertheless, the PEC performance of this material is still far from adequate for technological applications. Herein, we have focused on improving the PEC performance of PANI films by combining this polymer with multi-walled carbon nanotubes (MWCNTs) layers. Specifically, we have assessed the PEC activity of the in situ polymerised PANI films onto FTO substrates coated with different amounts of MWCTNs for the hydrogen evolution reaction (HER). The FTO/MWCNTs/PANI films with the optimum deposited amount of MWCNTs (i.e., 30 μL) featured a 2.4-fold increase of the cathodic photocurrent density response for the HER compared to that of FTO/PANI film. Moreover, the FTO/(30 μL)-MWCNTs/PANI films exhibited good PEC stability, as observed by the relatively low cathodic photocurrent density decay of up to 7% during 3720 s of stability test. Based on joint analyses of physical and PEC characterisation, the improved PEC performance for the FTO/(30 μL)-MWCNTs/PANI films were assigned to the combined contribution of the following factors: (i) enhancement of light absorption; (ii) possible improvement of excitons dissociation; (iii) minimisation of the electron-hole recombination process; and (iv) facilitation of electrons transfer at the PANI|electrolyte interface for the HER. The enhancement of PEC performance achieved in this work for the fully organic photocathode composed of MWCNTs/PANI paves the way to invest in additional modifications seeking to further improve the dissociation of excitons and the interfacial transfer of charge carriers for the light-driven HER.

Rational Design of Full-Color Fluorescent C3N Quantum Dots.

Carbon-based quantum dots (QDs) exhibit unique photoluminescence due to size-dependent quantum confinement, giving rise to fascinating full-color emission properties. Accurate emission calculations using time-dependent density functional theory are a time-costing and expensive process. Herein, we employed an artificial neural network (ANN) combined with statistical learning to establish the relationship between geometrical/electronic structures of ground states and emission wavelength for C3N QDs. The emission energy of these QDs can be doubly modulated by size and edge effects, which are governed by the number of C4N2 rings and the CH group, respectively. Moreover, these two structural characteristics also determine the phonon vibration mode of C3N QDs to harmonize the emission intensity and lifetime of hot electrons in the electron-hole recombination process, as indicated by nonadiabatic molecular dynamics simulation. These computational results provide a general approach to atomically precise design the full-color fluorescent carbon-based QDs with targeted functions and high performance.

Photocatalytic activity of dual defect modified graphitic carbon nitride is robust to tautomerism: machine learning assisted ab initio quantum dynamics.

Two-dimensional graphitic carbon nitride (GCN) is a popular metal-free polymer for sustainable energy applications due to its unique structure and semiconductor properties. Dopants and defects are used to tune GCN, and dual defect modified GCN exhibits superior properties and enhanced photocatalytic efficiency in comparison to pristine or single defect GCN. We employ a multistep approach combining time-dependent density functional theory and nonadiabatic molecular dynamics (NAMD) with machine learning (ML) to investigate coupled structural and electronic dynamics in GCN over a nanosecond timescale, comparable to and exceeding the lifetimes of photo-generated charge carriers and photocatalytic events. Although frequent hydrogen hopping transitions occur among four tautomeric structures, the electron-hole separation and recombination processes are only weakly sensitive to the tautomerism. The charge separated state survives for about 10 ps, sufficiently long to enable photocatalysis. The employed ML-NAMD methodology provides insights into rare events that can influence excited state dynamics in the condensed phase and nanoscale materials and extends NAMD simulations from pico- to nanoseconds. The ab initio quantum dynamics simulation provides a detailed atomistic mechanism of photoinduced evolution of charge carriers in GCN and rationalizes how GCN remains photo-catalytically active despite its multiple isomeric and tautomeric forms.

Nonadiabatic molecular dynamics study on effect of Ge/Sn alloy on hot carrier relaxation of CsPbBr<sub>3</sub> perovskite

Perovskite solar cells have been a prominent focus in the field of photovoltaics in recent decades, owing to their exceptional performance: easy synthesis, and cost-effectiveness. The all-inorganic cesium-based perovskite CsPbBr<sub>3</sub>, known for its remarkable thermal stability, has become a star material in the field of optoelectronics due to its outstanding luminescent properties. Despite the high efficiency of lead-based perovskite solar cells, the toxicity associated with lead and the poor long-term stability of these devices remain significant barriers to their large-scale commercialization. As is well known, non-radiative electron-hole recombination significantly shortens the carrier lifetime, acting as a primary pathway for excited state charge to loss energy. This phenomenon directly affects the photovoltaic conversion efficiency and charge transfer performance of perovskite materials. Therefore, maximizing the reduction of non-radiative recombination energy loss in perovskite solar cells has become a crucial research focus. In this study, a systematic exploration is conducted by using a non-adiabatic molecular dynamics approach combined with time-dependent density functional theory to investigate the excited-state carrier dynamics of CsPbBr<sub>3</sub> and its alloyed structures, CsPb<sub>0.75</sub>Ge<sub>0.25</sub>Br<sub>3</sub> and CsPb<sub>0.5</sub>Ge<sub>0.25</sub>Sn<sub>0.25</sub>Br<sub>3</sub>. The study comprehensively analyzes the non-radiative electron-hole recombination scenarios and the mechanisms for reducing charge energy loss based on crystal structure, electronic properties, and excited-state properties. The research findings reveal that alloying with Sn/Ge can reduce the bandgap, increase non-adiabatic coupling, and shorten the decoherence time. The interplay of reduced quantum decoherence, smaller bandgap, and larger non-adiabatic coupling effectively decelerates the electron-hole recombination process. Consequently, the carrier lifetime of the CsPb<sub>0.75</sub>Ge<sub>0.25</sub>Br<sub>3</sub> system extends by 1.6 times. Moreover, under the joint influence of Sn/Ge, the carrier lifetime of the CsPb<sub>0.5</sub>Ge<sub>0.25</sub>Sn<sub>0.25</sub>Br<sub>3</sub> system extends by 4.2 times compared with those of the original system. The overall sequence follows CsPb<sub>0.5</sub>Ge<sub>0.25</sub>Sn<sub>0.25</sub>Br<sub>3</sub> > CsPb<sub>0.75</sub>Ge<sub>0.25</sub>Br<sub>3</sub> > CsPbBr<sub>3</sub>. This study underscores the significant influence of binary alloying of B-site metal cations (in the perovskite structure <i>ABX</i><sub>3</sub>, where B-site refers to the metal cation) on the non-radiative electron-hole recombination of CsPbBr<sub>3</sub>.This research presents an effective alloying scheme that substantially prolongs the carrier lifetime of perovskites, offering a rational approach to optimizing solar cell performance. It lays the groundwork for the future design of perovskite solar cell materials.

Pyto-Architechture of Ag, Au and Ag–Au bi-metallic nanoparticles using waste orange peel extract for enable carcinogenic Congo red dye degradation

Ecologically inspired to develop silver, gold and silver/gold bimetallic nanoparticles from discarded orange peel extract. The plant-derived compounds included in discarded orange peel extract have been accountable for the development of Ag, Au and Ag–Au bimetallic nanoparticles, that might be used in the biosynthetic process. The qualitative assessment of developed silver, gold and silver/gold bimetallic nanoparticles has been performed by UV–visible, XRD pattern, FT IR analysis, TEM/HRTEM, EDX and BET isotherm analysis. In this investigation, the photocatalytic effect of developed silver, gold and silver/gold bimetallic nanoparticles on Congo red dye breakdown efficiency was achieved at 96%, 94%, and 99.2%, respectively. Due to prolonged electron-hole recombination process was investigated using UV irradiation and reused for up to 5 consecutive runs without significant loss of photocatalytic activity. Moreover, silver, gold, and silver/gold bimetallic nanoparticles manufactured in an environmentally benign manner could potentially contribute to the ecological cleanup.

Advances in modifications of Ag/g-C3N4 for stable and effective photoanode for OER

Silver (Ag) incorporated graphitic carbon nitride (g-C3N4) nano-composites having various ratios of Ag were prepared via a chemical route. The synthesized catalysts were potentially employed in an oxygen evolution reaction (OER) through photoelectrochemical (PEC). An XRD profile of Ag/g-C3N4 nano-composite depicted hexagonal g-C3N4 along with FCC Ag presence. The inhomogeneous distribution of tiny Ag nanospheres on irregularly agglomerated sheets of g-C3N4 was clearly seen in SEM images. The elemental mapping provided distribution of elements in the composite sample. Ag/g-C3N4 nano-composite samples show improvement in absorption edge with a reduction in band gap energy. FTIR studies illustrated strong surface interaction among Ag and g-C3N4 nano-sheets. The prominent reduction in PL peaks intensity for B30 Ag/g-C3N4 nano-composite suggested a long lifetime of photo induced charge carriers. XPS analysis confirmed the existence of metallic Ag on g-C3N4. B30 Ag/g-C3N4 attained better PEC activity results as compared to all other prepared photocatalysts. In OER experiments, B30 Ag/g-C3N4 showed a small onset potential (0.33 V) leading to more production of photo excited electrons and a reduction in photo generated electron-hole recombination process. The improved Jsc and Voc of B30 Ag/g-C3N4 indicated the shorter lifetime of charge carriers across electrode and electrolyte interface through suitable charge separation. Optimized B30 Ag/g-C3N4 is active and steady for efficient PEC water splitting in comparison to other prepared nanosystems.

Interconfigurational d-f luminescence of Pr3+ ions in praseodymium doped Li6Y(BO3)3 single crystals

Luminescence properties of undoped Li6Y(BO3)3 (LYB) crystals grown by the Bridgman method as well as undoped and praseodymium doped LYB crystals grown by the Czochralski method were studied under excitation by ultraviolet light, synchrotron radiation and electron beam in the temperature region of 5–300 K. The emission bands peaking at 4.8, 3.76 and 2.95 eV were found in undoped Czochralski-grown crystals, while the band at 3.34 eV was dominant in the Bridgman-grown crystals. These bands are presumably ascribed to excitons localized at regular and defect-perturbed lattice sites. Intense emission bands peaking at 4.75, 4.50, 4.17 and 3.98 eV were discovered in Pr doped crystals at low temperatures and related to the interconfigurational 4f15d1 → 4f2 radiative transitions in Pr3+ ions. The structure of the emission spectrum is shown to be determined by the 3H4, 3H5, 3H6, 3F2, 3F3, 3F4 terms of the Pr3+ ion. The characteristic decay time of the 4f15d1 → 4f2 emission is τ = 24 ns at low temperatures, however, it shortens to 9 ns by room temperature due to a strong thermal quenching. The study of glow curves and spectra of thermostimulated luminescence in Li6Y(BO3)3:Pr crystal irradiated by 10-keV electron beam shows that Pr3+ ions do not participate in an electron-hole recombination process.

Great Influence of Pressure and Isotope Effects on Nonradiative Charge Loss in Hybrid Organic-Inorganic Perovskites.

The intrinsic softness of hybrid organic-inorganic perovskites (HOIPs) allows their lattice and optoelectronic performance to be tunable to external pressure. Using nonadiabatic (NA) molecular dynamics, we demonstrate that a mild pressure accelerates hot electron relaxation and suppresses nonradiative electron-hole recombination in CH3NH3PbI3. Both processes are governed by NA coupling, which is enhanced between the electronic states of the quasi-continuous bands while is decreased between the band-edge states by reducing the electron-hole wave function overlap. Hydrogen/deuterium isotope exchange alleviates the pressure-induced NA coupling by increasing lattice rigidity and decreasing wave function overlap, slowing down both the hot electron relaxation and electron-hole recombination processes. The simulated time scales of sub-3 ps for hot electron relaxation and half nanoseconds for recombination agree well with the experiments. The study suggests that the isotope exchange can mitigate the pressure-caused fast losses of hot electrons and further prolong the charge carrier lifetime in HOIPs.

Synthesis of optically enriched cobalt-doped zinc oxide nanocomposites: Reduction of methylene blue dye

This study reports the synthesis of highly pure nanosized composite materials using a sol-gel self-combustion synthesis (SCS) approach. The complex generated within the polyvinyl alcohol and precursor(s) induces combustion once the ignition temperature is reached, resulting in a porous nanocatalyst as the gaseous by-products are removed. The XRD and TEM morphological analyses confirmed the crystalline nature, interstitial inclusion of cobalt into the ZnO lattice, and the nanoscale size range (20–50 nm) of the synthesized materials. The photoluminescence spectra of the doped nanocomposites showed a significant decrease in intensity as well as a high percentage of visible light absorption potential over pure ZnO NPs. This confirms the presence of better charge transfer and its significance in preventing electron-hole recombination processes. The UV–vis-DRS and Mot-Schottky investigations showed better optoelectronic properties for the cobalt-doped ZnO composites (CZ-Cs) compared to that of the pure ZnO NPs. The indirect bandgap reduction (redshift) from 3.22 to 2.70 eV shows the perfect inclusion of cobalt in the ZnO lattice. It was revealed that the CZ-Cs showed better catalytic reduction potential for methylene blue dye within 12 min than ZnO. Thus, the solution combustion synthesis approach effectively synthesizes optoelectrically improved nanocomposite materials, which have promising prospects for catalysis, sensors, and biomedical applications.

Engineering interfacial band hole extraction on chemical-vapor-deposited MoS2/CdS core-shell heterojunction photoanode: The junction thickness effects on photoelectrochemical performance

Heterojunction fabrication is a promising strategy that can greatly boost the charge carrier separation and improve the solar-to-hydrogen conversion efficiency of photoelectrochemical (PEC) cells. However, such technology still suffers from limited contact interfaces. In this study, the chemical vapor deposition (CVD) technique was for the first time used to construct the CdS/MoS2 heterojunction photoanode with a unique core-shell nanoarchitecture, in which a continuous crystalline MoS2 nanosheet layer was grown directly on one-dimensional (1D) oriented CdS nanorods (NRs) in a plane-to-plane stacking fashion. The optimization of junction thickness with adjustable MoS2 loading from mono to a few layers was achieved by experimental parameters variation. Systematic characterizations show that the MoS2 shell plays a dual role as an optical absorption booster for more photo-exciton generation and a surface passivator of trap states. Meanwhile, the formed heterojunction helps regulate the unidirectional charge migration for a significantly suppressed electron-hole recombination process, which synergistically contributes to higher quantum yield and efficiency. As a result, the optimized CdS/MoS2 heterojunction photoanode with 3-layered MoS2 wrapping exhibits the highest photocurrent density and photoconversion efficiency, over a two-fold increase, compared to those of pristine CdS and the previously reported CdS/MoS2 heterojunctions. Moreover, due to the rapid hole extraction from CdS and transferred surface oxidation sites, the present CdS/MoS2 heterostructure demonstrates better corrosion resistance and higher photostability. The present work is expected to provide a versatile platform for exploiting the CVD technique to develop other MoS2-based heterojunction photoelectrodes with extensive PEC applications.

Surface Plasmon Resonance Induced Photocatalysis in 2D/2D Graphene/g-C3N4 Heterostructure for Enhanced Degradation of Amine-Based Pharmaceuticals under Solar Light Illumination

Pharmaceuticals, especially amine-based pharmaceuticals, such as nizatidine and ranitidine, contaminate water and resist water treatment. Here, different amounts of graphene sheets are coupled with g-C3N4 nanosheets (wt% ratio of 0.5, 1, 3 and 5 wt% of graphene) to verify the effect of surface plasmon resonance introduced to the g-C3N4 material. The synthesized materials were systematically examined by advanced analytical techniques. The prepared photocatalysts were used for the degradation of amine-based pharmaceuticals (nizatidine and ranitidine). The results show that by introducing only 3 wt% graphene to g-C3N4, the absorption ability in the visible and near-infrared regions dramatically enhanced. The absorption in the visible range was 50 times higher when compared to the pure sample. These absorption features suggest that the surfaces of the carbon nitride sheet are covered by the graphene nanosheet, which would effectively apply the LSPR properties for catalytic determinations. The enhancement in visible light absorption in the composite was confirmed by PL analysis, which showed greater inhibition of the electron-hole recombination process. The XRD showed a decrease in the (002) plan due to the presence of graphene, which prevents further stacking of carbon nitride layers. Accordingly, the Gr/g-C3N4 composite samples exhibited an enhancement in the photocatalytic performance, specifically for the 5% Gr/g-C3N4 sample, and close to 85% degradation was achieved within 20 min under solar irradiation. Therefore, applying the Gr/g-C3N4 for the degradation of a pharmaceutical can be taken into consideration as an alternative method for the removal of such pollutants during the water treatment process. This enhancement can be attributed to surface plasmon resonance-induced photocatalysis in a 2D/2D graphene/g-C3N4 heterostructure.

Defect-Induced Ultrafast Nonadiabatic Electron-Hole Recombination Process in PtSe2 Monolayer.

Defects are inevitable in two-dimensional materials due to the growth condition, which results in many unexpected changes in materials' properties. Here, we have mainly discussed the nonradiative recombination dynamics of PtSe2 monolayer without/with native point defects. Based on first-principles calculations, a shallow p-type defect state is introduced by a Se antisite, and three n-type defect states with a double-degenerate shallow defect state and a deep defect state are introduced by a Se vacancy. Significantly, these defect states couple strongly to the pristine valence band maximum and lead to the enhancement of the in-plane vibrational Eg mode. Both factors appreciably increase the nonadiabatic coupling, accelerating the electron-hole recombination process. An explanation of PtSe2-based photodetectors with the slow response, compared to conventional devices, is provided by studying this nonradiative transitions process.

Development of novel TiN–LiAlSiO4/SnS/AuPd multilayer films for H2 generation by photocatalysis

TiN–LiAlSiO4/SnS/AuPd multilayer films were deposited on glass substrates using screen-printing and SILAR (successive ionic layer adsorption reaction) methods. The films were used as photocatalysts for H2 generation using a solar simulator source. The incorporation of the SnS provokes the presence of particles of different morphology and size, allowing a better light absorption on the surface of the films. In addition, AuPd nanoparticles were deposited on the multilayer films to improve photocatalytic activity. XRD and TEM analysis revealed that whatever the proportion, the main phase is TiN. The SEM images showed that the electrostatic attraction between TiN and SnS is a key factor that influences the morphology of the films. The optical band-gap values for the films were similar (∼3.86 eV). According to profilometry measurements, the thickness of films varies from 218 to 887 nm, and PL results showed that when the thickness decreases the electron-hole pair recombination processes decrease too. The highest H2 generation was reached by T20:L80/SnS/AuPd, around 99 μmol/m2 after 3 h of irradiation, while T80:L20/SnS/AuPd produces only 33 μmol/m2, and coincidentally, showed lower and higher thickness, respectively. Moreover, the presence of AuPd nanoparticles did not provoke any structural and optical modification on the films. However, it caused the existence of active sites for H2 generation and diminish the electron-hole pair recombination, evidenced by PL analysis. Finally, these results corroborate that the film with a low thickness and higher LiAlSiO4 showed better photocatalytic activity because of the inhibition of the electro-hole pair recombination.