Photoexcited Carriers Research Articles

Precise analyses of photoelectrochemical reactions on particulate Zn0.25Cd0.75Se photoanodes in nonaqueous electrolytes using Ru bipyridyl complexes as a probe.

Recombination of photoexcited carriers at interface states is generally believed to strongly govern the photoelectrochemical (PEC) performance of semiconductors in electrolytes. Sacrificial reagents (e.g., methanol or Na2SO3) are often used to assess the ideal PEC performance of photoanodes in cases of minimised interfacial recombination kinetics as well as accelerated surface reaction kinetics. However, varying the sacrificial reagents in the electrolyte means simultaneously changing the equilibrium potential and the number of electrons required to perform the sacrificial reaction, and thus the thermodynamic and kinetic aspects of the PEC reactions cannot be distinguished. In the present study, we propose an alternative methodology to experimentally evaluate the energy levels of interfacial recombination centres that can reduce PEC performance. We prepare nonaqueous electrolytes containing three different Ru complexes with different bipyridyl ligands; redox reactions of Ru complexes represent one-electron processes with similar charge transfer rates and diffusion coefficients. Therefore, the Ru complexes can serve as a probe to isolate and evaluate only the thermodynamic aspects of PEC reactions. Recombination centres at the interface between a nonaqueous electrolyte and a Zn0.25Cd0.75Se particulate photoanode are elucidated using this method as a model case. The energy level at which photocorrosion proceeds is also determined.

How do the oxygen vacancies affect the photoexcited carriers dynamics in β-Ga2O3？

β-Ga2O3 is a rising star material for solar-blind photoelectronic detectors (PDs) since its excellent properties and lower cost than GaN and SiC. However, the high density of O vacancy (VO) strongly affect the performance of devices. In this work, we investigate the effect of VOs on carrier dynamics in β-Ga2O3 and its meaningful application in solar-blind PDs by the time-dependent density functional theory (TDDFT) and nonadiabatic molecular dynamics (NAMD). We find the three inequivalent VOs (VO1, VO2, and VO3) play different roles in carrier dynamics although they all introduce deep defect states in the bandgap, which significantly shorten the lifetime (τ) of carriers. VO1 and VO3 form nonradiative recombination centers, considerably decreasing the τ from 23.10 ns to 0.12 ns and 0.11 ns, respectively. VO2 forms shallow-level defects, and the τ is 0.47 ns, which weakens the decline of the carrier compared to VO1 and VO3. Our findings provide a different angle to understand the disputation on relationship between point defects and device performance based on β-Ga2O3, and to further improve the device performance by defect engineering.

Plasma-assisted annealing of Pt-doped rutile TiO2 nanoparticles for enhanced decomposition and bacterial inactivation under general lighting

Enhanced photocatalytic activity of rutile-based TiO2 materials under general lighting is practically desired. O2 plasma-assisted annealing (PAA) effects on Pt-doped rutile TiO2 nanoparticles were clarified along with its visible-light-driven photocatalytic activity enhancement. The PAA-treated samples were mainly analyzed using optical spectroscopy and x-ray photoelectron spectroscopy (XPS). The photocatalytic activity was assessed by decomposing methylene blue dye and inactivating Bacillus subtilis under general lighting. The PAA treatment changed the O 1s, Ti 2p, and Pt 4f spectra of XPS from those of the pristine sample. This change indicated that the PAA treatment introduced more oxygen deficiency or oxygen vacancies and more oxygen groups adsorbed on the surface. The introduced oxygen vacancies and adsorbed oxygen groups would change the band structure, which primarily narrowed the bandgap energy or broadened the valence band edge, increased the number of electron-trapping sites from the shallow to midgap levels, and enhanced the upward band-bending at the surface. The PAA-induced change in the band structure enhanced the decomposition and bacterial inactivation because it facilitated the separation and concentration of photoexcited carriers. The findings provide a new perspective on enhancing the photocatalytic activities of rutile-based TiO2 nanoparticles under general lighting.

A strategy for boosting photovoltaic performance based on a two-dimensional ZrSSe/HfSSe van der Waals heterostructure.

Identifying high-efficiency solar photovoltaic systems with two-dimensional (2D) materials is still an urgent challenge to meet modern energy requirements. Very recently, a 2D heterostructure with type-II band alignment has been confirmed to be more favorable for application in photoelectric conversion. However, the staggered band offset of 2D type-II heterostructures cannot always be guaranteed, nor the intrinsic hindrance mechanism of carrier recombination being clear. In this study, taking the emerging ZrSSe/HfSSe van der Waals heterostructure (vdWH) as a generic example, a boosting strategy for improving the photoelectric performances of 2D vdWHs is proposed. Through a series of in-depth systematic research studies based on first-principles, we demonstrate that via applying a vertical strain, an anticipated band alignment transition from type-I to favorable type-II of this ZrSSe/HfSSe vdWH can be induced due to the interfacial charge redistribution, during which a corresponding enlarged photocurrent can be detected from the latter based device compared to the former. Essentially, such enhanced photocurrent at the incident photon energy (Eph) around the band gap is attributed to the suppressed recombination rate of photoexcited carriers. Moreover, when Eph is increased into the visible light region, the photoelectric conversion performances can be further controlled by vertical strain. These generalized findings not only provide an effective manipulation strategy for enhancing the performances of 2D solar photovoltaic systems, but the intrinsic physical mechanism can also be extended to the next practical design and regulation of other 2D photovoltaic devices.

Piezo-photocatalytic reduction of nitrates to N2 over silver dispersed on BaTiO3@TiO2.

This communication first achieved piezo-photocatalytic reduction of nitrates to N2 through designing an Ag2O/BaTiO3@TiO2 core-shell catalyst. The built-in electric field induced by piezoelectric polarization suppresses photoexcited carrier recombination, and simultaneously causes energy band tilting, leading to the generation of electrons with higher reducibility to directly trigger the NO3- reduction to ˙NO32-, even without hole scavengers.

Time-resolved force microscopy using the delay-time modulation method

We developed a time-resolved force microscopy technique by integrating atomic force microscopy using a tuning-fork-type cantilever with the delay time modulation method for optical pump-probe light. We successfully measured the dynamics of surface recombination and diffusion of photoexcited carriers in bulk WSe2, which is challenging owing to the effect of the tunneling current in time-resolved scanning tunneling microscopy. The obtained results were comprehensively explained with the model based on the dipole-dipole interaction induced by photo illumination.

A novel model of nonlocal photoacoustic and plasmaelastic heated by laser pulsed excitation of nanoscale semiconductor medium

The study takes into account the diffusion of photo-excited carriers in the presence of a laser pulse and theoretically investigates photoacoustic wave propagation in the thermoelastic domain. In a nonlocality medium, the phenomena of thermomechanical and acoustic wave interaction are considered. Thermoelasticity, photothermal, and photoacoustic theories provide the controlling formulas. Photoacoustic waves are not dependent on electron–phonon or electron–hole thermalization processes; rather, they are produced by thermoelastic stress resulting from the temperature increase induced by the laser. The optical, elastic, and thermoelastic characteristics of nanoscale semiconductor materials are taken into account and photoacoustic signals are predicted by solving a thermal diffusion issue and a thermoelastic problem in combination. The mathematical model can be solved using the harmonic wave approach. By obtaining numerical solutions, all the physical fields of the physical domain, such as thermal, acoustic, mechanical, and carrier density diffusion, as well as displacements and temperatures, can be derived. The influences of nonlocal parameters, thermal delay, and laser pulse effect are investigated and compared using two- and three-dimensional visual representations, corresponding to two-dimensions and three-dimensions domains, respectively.

Optical Pump-Terahertz Probe Diagnostics of the Carrier Dynamics in Diamonds.

Diamond is a promising material for terahertz applications. In this work, we use a non-invasive optical pump-terahertz probe method to experimentally study the photoinduced carrier dynamics in doped diamond monocrystals and a new diamond-silicon composite. The chemical vapor deposited diamond substrate with embedded silicon microparticles showed two photoinduced carrier lifetimes (short lifetime on the order of 4 ps and long lifetime on the order of 200 ps). The short lifetime is several times less than in boron-doped diamonds and nitrogen-doped diamonds which were grown using a high temperature-high pressure technique. The observed phenomenon is explained by the transport of photoexcited carriers across the silicon-diamond interface, resulting in dual relaxation dynamics. The observed phenomenon could be used for ultrafast flexible terahertz modulation.

Eco-benign synthesis of α-Fe2O3 mediated Trachyspermum ammi: A new insight to photocatalytic and bio-medical applications

Environmental contaminants are a golabl concern, and even at very low quantities, they can be extremely harmful to the aquatic ecosystem. Microbial resistance and photocatalysis are popular strategies for removing hazardous substances from the environment. The present study developed the green synthesis of α-Fe2O3 nanoparticles from Trachyspermum ammi plant leaf extract. The crystalline and structural stability of green synthesized α-Fe2O3 nanoparticles were studied by XRD. The surface morphology was investigated by TEM and FESEM equipped with EDX analysis. Metal, oxygen bond (Fe-O) and their interaction on the surfaces and their valency were explored from FTIR and XPS spectra. Optical orientations and electron movements were revealed from UV-DRS analysis. Visible light photocatalytic methylene blue degradation confirmed the largest surface area, rate of recombination, photo-excited charge carriers, photo-sensitivity range and radical generations of α-Fe2O3 nanoparticles. The green synthesized α-Fe2O3 nanoparticles bacterial susceptibility was examined by the well diffusion method using (10, 20, 50, 100) µg/L concentration of nanoparticles. The antibacterial activity enhanced with the higher concentration of α-Fe2O3 (100 µg/L). The gram-negative bacteria of E.coli has high bacterial susceptibility on α-Fe2O3 nanoparticles. The reactive oxygen species and OH radicals of α-Fe2O3 nanoparticles are demonstrated better resistivity against bacterial strains. The present study, therefore, suggested that the green synthesis would be an appropriate approach to synthesize the nanomaterials and confirming their suitability for use in industrial wastewater treatment and biomedical applications.

Cu2O/BiVO4 heterostructure controllably triggers radical and non-radical persulfate activation via light “on-off” for efficient organic contaminants degradation

The regulation of peroxydisulfate (PDS) activation pathway is crucial for its practical application in complicated water matrix. In this work, we have developed a Cu2O/BiVO4 (Cu-BVO) heterostructure to achieve controlled triggering of both radical and non-radical PDS activation by dexterously utilizing light “on-off” for highly efficient degradation of organic contaminants. In dark condition, Cu-BVO serves as an electron donor to facilitate the cleavage of O-O bond in PDS via a radical pathway to generate •OH and •O2-. Upon light irradiation, Cu-BVO unexpectedly acts as an electron acceptor in the reversed electron flow to generate a metastable surface complex (Cu-BVO-PDS*) via non-radical pathway. Analysis of the kinetic behavior of the excited electrons and holes suggests that the directional migration of photo-excited charge carriers in Cu-BVO results in the electron-deficient region on the Cu2O surface, which provides an ideal platform for the generation of Cu-BVO-PDS*.

SnS2/MoS2 van der Waals Heterostructure Photodetector with Ultrahigh Responsivity Realized by a Photogating Effect.

Photoresponsivity is a fundamental parameter used to quantify the ability of photoelectric conversion of a photodetector device. High-responsivity photodetectors are essential for numerous optoelectronic applications. Due to the strong light-matter interactions and the high carrier mobility, two-dimensional (2D) materials are promising candidates for the next-generation photodetectors. However, poor light absorption, lack of photoconductive gain, and the interfacial recombination lead to the relatively low responsivity of 2D photodetectors. The photogating effect, which extends the lifetime of photoexcited carriers, provides a simple approach to enhance responsivity in photodetector devices. Here, the O2 plasma treatment introduced surface traps on the SnS2 surface, leading to a gate-tunable photogating effect in SnS2/MoS2 heterojunctions. The heterojunction device exhibits an ultrahigh responsibility of up to 28 A/W. Moreover, the photodetector possesses a wide spectral photoresponse spanning from 300 to 1100 nm and a high specific detectivity (D*) of 4 × 1011 Jones under a 532 nm laser at VDS = 1 V. These results demonstrate that O2 plasma treatment is an efficient and simple avenue to achieve photogating effects, which can be employed to enhance the performance of van der Waals heterostructure photodetector devices and make them suitable for future integration into advanced electronic and optoelectronic systems.

PH-Dependent photocatalytic performance of faceted BiOBr semiconductor particles in degradation of dyes

Bismuth oxyhalides, such as bismuth-oxy-bromide (BiOBr), show high performance in photocatalytic oxidation of water pollutants. Process conditions, and in particular the pH of the solution, largely affect the photocatalytic efficacy, which is fundamentally poorly understood. We prepared {001} faceted bismuth-oxy-bromide (BiOBr), and determined by advanced AFM analysis that the surface charge of the {001} facet of BiOBr is slightly positive at acidic pH (pH 3) and significantly negative and increasing in negative surface charge in the order pH 6 < pH 9. Decomposition of MB or RhB by illumination of BiOBr is strongly favored by basic conditions (pH 9-10), as evident from discoloration experiments, and determination of the TOC as a function of time of illumination. Reference experiments show the pH dependent degradation profiles cannot be explained by differences in quantities of adsorption of the dye, but rather by the lifetime and/or quantity of BiOBr related photoexcited (surface) charge carriers (holes and electrons) – correlating with surface charge. Using MeOH and other scavengers, we show oxidation of MB or RhB is mainly induced by superoxide anions (•O2− radicals) at low pH and by holes or hydroxyl radicals at high pH – in agreement with surface charge induced band bending. This study provides novel understanding of the pH dependence of the rates of photocatalytic degradation of dyes using BiOBr photocatalysts.

S-induced Phase Change Forming In2 O3 /In2 S3 Heterostructure for Photoelectrochemical Glucose Sensor.

In the past several decades, Photoelectrochemical (PEC) sensing still remains a great challenge to design highly-efficient semiconductor photocatalysts via a facile method. It is of much importance to design and synthesize various novel nanostructured sensing materials for further improving the response performance. Herein, we present an In2 O3 /In2 S3 heterostructure obtained by combining microwave assisted hydrothermal method with S-induced phase change, whose energy band and electronic structure could be adjusted by changing the S content. Combining theoretical calculation and spectroscopic techniques, the introduction of sulfur was proved to produce multifunctional interfaces, inducing the change of phase, oxygen vacancies and band gap, which accelerates the separation of photoexcited carriers and reduces their recombination, improving the electronic injection efficiency around the interface of In2 O3 /In2 S3 . As anticipated, an enhanced glucose response performance with a photocurrent of 0.6 mA cm-2 , a linear range of 0.1-1 mM and a detection limit as low as 14.5 μM has been achieved based on the In2 O3 /In2 S3 heterostructure, which is significant superior over its pure In2 O3 and S-doped In2 O3 counterparts. This efficient interfacial strategy may open a new route to manipulate the electrical structure, and energy band structure regulation of sensing material to improve the performance of photoelectrodes for PEC.

Halogen-Site Regulation in Cs3Bi2X9 Quantum Dots for Efficient and Selective Oxidation of Benzyl Alcohol Driven by Solar Light.

Sluggish charge kinetics and low selectivity limit the solar-driven selective organic transformations under mild conditions. Herein, an efficient strategy of halogen-site regulation, based on the precise control of charge transfer and molecule activation by rational design of Cs3Bi2X9 quantum dots photocatalysts, is proposed to achieve both high selectivity and yield of benzyl-alcohol oxidation. In situ PL spectroscopy study reveals that the Bi─Br bonds formed in the form of Br-associated coordination can enhance the separation and transfer of photoexcited carriers during the practical reaction. As the active center, the exclusive Bi─Br covalence can benefit the benzyl-alcohol activation for producing carbon-centered radicals. As a result, the Cs3Bi2Br9 with this atomic coordination achieves a conversion ratio of 97.9% for benzyl alcohol and selectivity of 99.6% for aldehydes, which are 56.9- and 1.54-fold higher than that of Cs3Bi2Cl9. Combined with quasi-in situ EPR, in situ ATR-FTIR spectra, and DFT calculation, the conversion of C6H5-CH2OH to C6H5-CH2* at Br-related coordination is revealed to be a determining step, which can be accelerated via halogen-site regulation for enhancing selectivity and photocatalytic efficiency. The mechanistic insights of this research elucidate how halogen-site regulation in favor of charge transfer and molecule activation toward efficient and selective oxidation of benzyl alcohol.

Comparison of Modification Methods of Photocatalyst G-C3N4 in Hydrogen Production Performance

Non-metallic polymer semiconductor graphite phase carbon nitride (g-C3N4) is a low-cost, environmentally friendly raw material with suitable bandgap width and stable chemical properties. However, there are still problems such as lower surface area, higher recombination rate of photo-excited charge carriers, and lower utilization rate of visible light. This paper introduces the structure, physicochemical properties, preparation methods, and modification ideas of graphite phase carbon nitride, focusing on several popular modification achievements in recent years, as well as a horizontal comparison of their respective production methods, mechanisms, and hydrogen production efficiency. Finally, the challenges and prospects in the modification of carbon nitride are discussed.

Charge Separation to Facilitate The Conversion of Copper‐Phenylacetylide from Aggregation‐Induced Emission to Efficient Photocatalysis

AbstractAggregation‐induced emission (AIE) materials are considered promising photocatalyst candidates due to their robust light‐harvesting and efficient photoexcitation, if their photoexcited carriers can be separated effectively. Herein, by skillfully selecting multi‐alkynyl ligands instead of phenylacetylene to construct multi‐channel charge separation, copper‐phenylacetylide (CP‐1) with AIE properties is successfully transformed into efficient photocatalysts CP‐2P (copper‐1,4‐diethynylbenzene) and CP‐2M (copper‐1,3‐diethylnylbenzene). In these structures, the multi‐alkynyl ligands connects the copper‐ladder into multi‐dimensional metal‐organic frameworks with greatly reduced bandgap, enhances charge transfer and separation, and facilitated oxygen adsorption and activation. As a representative, CP‐2P has the best photocatalytic activity and stability for photocatalytic aerobic oxidation, such as thioanisole oxidation (conv. &gt; 99%, methyl phenyl sulfoxide sel. ≧ 94%), benzyl alcohol oxidation (conv. &gt; 99%, benzaldehyde sel. &gt; 99%) and benzylamine oxidation (conv. &gt; 99%, N‐benzylidene benzylamine sel. &gt; 99%), which can be used for large‐scale sunlight‐driven organic photosynthesis. This work confirms the feasibility of controlled conversion of the conventional copper‐alkynyl from AIE material to efficient photocatalyst using charge separation strategy, which provides an important guidance for the rational design of new high‐efficiency photocatalyst.

Efficient charge separation and improved photoelectric properties of GaN/WS2/MoS2 heterojunction: A molecular dynamics simulations

Utilizing the stacking of two-dimensional (2D) materials to fabricate heterojunction represents an exceedingly effective approach for designing high-performance optoelectronic devices. In this paper, the GaN/WS2/MoS2 heterojunction was systematically studied using DFT calculations. The interface effect caused the effective separation of photo-excited carriers in the GaN/WS2/MoS2 heterojunction by inducing a stepwise transfer of the carriers, forming a build-in electric field. Due to the decrease in bandgap, the heterojunction exhibited enhanced light absorption ability across the entire spectral region. Especially, the carrier recombination time reached the microsecond level, greatly extending the lifetime of photo-excited carriers and effectively improving the energy conversion performance of photodetectors. Moreover, the augmentation of tensile strain enhances both the self-powering capacity and the near-infrared light detection capability of the GaN/WS2/MoS2 heterojunction. The exceptional performances exhibited by the GaN/WS2/MoS2 heterojunction make it a highly up-and-coming candidate for optoelectronics application.

Construction of co-zeolitic imidazolate framework/Bi2WO6 heterojunction photocatalyst with improved adsorption and photodegradation of ciprofloxacin

Refractory pharmaceutical pollutants have become a serious and formidable threat to both human health and the ecosystem. Photocatalysis presents an intriguing approach of using visible light to break down these environmental contaminants directly. Nevertheless, this technique is plagued by a fast combination of the photogenerated charges, which results in poor efficiency and instability. In this work, a novel ZIF-67/Bi2WO6 heterojunction photocatalyst has been developed as an efficient photocatalyst for ciprofloxacin (CIP) degradation under visible-light irradiation. The obtained ZIF-67/Bi2WO6 Z-type heterojunction exhibit dramatically improved visible-light-driven photocatalytic performance compared to pure ZIF-67 and Bi2WO6. Particularly, ZIF-67/Bi2WO6 shows the highest photocatalytic efficiency for the decomposition of CIP, achieving 91.5 %, at 10 mg/L in 90 min. The enhanced photocatalytic performance is attributed to the Z-type heterostructure with strong visible light absorption and effective separation of photoexcited carriers. The scavengers' studies showed that •O2– and •OH radicals have the most effect on the decomposition process. Besides, ZIF-67/Bi2WO6 is endowed excellent durability and stability. Thus, this work shows that ZIF-67/Bi2WO6 may reveal a promising potential for the degradation of several refractory pharmaceutical contaminants.

A New Metal-Free Molecular Perovskite-Related Single Crystal with Quantum Wire Structure for High-Performance X-Ray Detection.

The family of metal-free molecular perovskites, an emerging novel class of eco-friendly semiconductor, welcomes a new member with a unique 1D hexagonal perovskite structure. Lowering dimensionality at molecular level is a facile strategy for crystal structure conversion, optoelectronic property regulation, and device performance optimization. Herein, the study reports the design, synthesis, packing structure, and photophysical properties of the 1D metal-free molecular perovskite-related single crystal, rac-3APD-NH4I3(rac-3APD= racemic-3-Aminopiperidinium), that features a quantum wire structure formed by infinite chains of face-sharing NH4I6 octahedra, enabling strong quantum confinement with strongly self-trapped excited (STE) states to give efficient warm orange emission with a photoluminescence quantum yield (PLQY) as high as ≈41.6%. The study accordingly unveils its photoexcited carrier dynamics: rac-3APD-NH4I3 relaxes to STE state with a short lifetime of 10ps but decays to ground state by emitting photons with a relatively longer lifetime of 560ps. Additionally, strong quantum confinement effect is conducive to charge transport along the octahedral channels that enables the co-planar single-crystal X-ray detectors to achieve a sensitivity as high as 1556 µC Gyair -1 cm-2. This work demonstrates the first case of photoluminescence mechanism and photophysical dynamics of 1D metal-free perovskite-related semiconductor, as well as the promise for high-performance X-ray detector.

Physics of photovoltaic signal modifications in p–n photodiodes

The photovoltaic signal is an important characteristic of photodetectors, including but not limited to those that are based on p–n or p–i–n photodiodes. In an open-circuit configuration, pulsed excitation of the detector with ultrafast (femto or nanosecond) pulses leads to a photovoltaic signal that decays slowly (micro-second time scale). If the physics in the detector is dominated by the recombination of the photo-excited charge carriers, one expects the signal to decay without changing its sign. However, some experiments using short-pulse excitation have found that photovoltaic signals can undergo a sign change as a function of time following excitation, with positive signals immediately following the excitation, turning to negative signals several microseconds later. Here, we study various physical effects (density, temperature, electrostriction, pressure, photostriction, and bandgap renormalization) and determine their effect on photovoltaic signals. If, following ultrafast excitation, the carrier density and temperature are increased, and during relaxation the system reaches a state sufficiently close to the quasi-thermal equilibrium in which the carrier density is still elevated, but smaller than the intrinsic thermal equilibrium density at the elevated temperature, then the signal can become negative.