Increased Lifetime Of Charge Carriers Research Articles

Preparation of Bi2CrO6/CuO heterostructure nanocomposite to increase methylene blue decomposition under visible light irradiation

In this study, the Bi2CrO6/CuO nanocomposite was used for the photocatalytic degradation of methylene blue (MB) under visible light. Nanocomposites with different ratios (1:1, 1:2, 2:1) were synthesized under hydrothermal conditions and investigated for MB removal. Various characterization techniques, including XRD, FT-IR, FE-SEM, BET, DRS, PL, and EDS, were employed to elucidate the physicochemical aspects of the catalysts. The 2:1 nanocomposite ratio was selected as the photocatalyst with the highest removal efficiency (85 %). Four main factors, including initial concentration, solution pH, catalyst dose, and light intensity, were studied using the response surface methodology (RSM) and the Box-Behnken model. Under optimal conditions, the MB removal efficiency reached 90.06 %. Additionally, the effect of oxidizing agents (H2O2) on the enhanced removal of MB was investigated. The improved photocatalytic performance of the Bi2CrO6/CuO (2:1) nanocomposite is attributed to visible light absorption, the formation of a p-n heterostructure, efficient charge separation via the S-scheme mechanism, and increased charge carrier lifetime. Moreover, economic calculations showed that the estimated costs for the photocatalytic removal of MB from wastewater are cost-effective.

Novel Detection Scheme for Temporal and Spectral X-Ray Optical Analysis: Study of Triple-Cation Perovskites

Multimodal x-ray microscopy is key to assessing the property-functionality relationships of semiconductor devices with the utmost sensitivity and spatial resolution. Here, we report on a novel setup—the “Analyzer of X-ray excited Optical Luminescence Offering Temporal and spectraL resolution” (AXOLOTL)—and demonstrate its use by investigating a series of triple-cation mixed-halide perovskite solar cells (PSCs) with varying Cs content. These PSCs exhibit spatially varying performance and are thus ideally probed by multimodal x-ray microscopy to elucidate the origin of the performance variations. Specifically, our nanoscale characterization of the wrinkled perovskite photoabsorber unveils a segregation of I and Br, which is accompanied by a narrowed band gap and an increased charge-carrier lifetime in thick absorber areas. Overall, we demonstrate with this technique the spatial correlation of compositional inhomogeneities, topography, electrical performance, and optical performance, which is of highest interest for identifying loss mechanisms at the nanoscale in high-performance electronic device development, including solar cells. Published by the American Physical Society 2024

Enhanced Photocatalytic and Photovoltaic Performance Arising from Unconventionally Low Donor-Y6 Ratios.

Development of both organic photovoltaics (OPVs) and organic photocatalysts has focused on utilizing the bulk heterojunction (BHJ). The BHJ promotes charge separation and enhances the carrier lifetime, but may give rise to increased charge traps, hindering performance. Here, high photocatalytic and photovoltaic performance is displayed by electron donor-acceptor (D-A) nanoparticles (NPs) and films, using the nonfullerene acceptor Y6 and polymer donor PIDT-T8BT. In contrast to conventional D-A systems, the charge generation in PIDT-T8BT:Y6 NPs is mainly driven by Y6, allowing a high performance even at a low D:A mass ratio of 1:50. The high performance at the low mass ratio is attributed to the amorphous behavior of PIDT-T8BT. Low ratios are generally thought to yield lower efficiency than the more conventional ≈1:1 ratio. However, the OPVs exhibit peak performance at a D:A ratio of 1:5. Similarly the NPs used for photocatalytic hydrogen evolution show peak performance at the 1:6.7 D:A ratio. Interestingly, for the PIDT-T8BT:Y6 system, as the polymer proportion increases, a reduced photocatalytic and photovoltaic performance is observed. The unconventional D:A ratios provide lower recombination losses and increased charge-carrier lifetime with undisrupted ambipolar charge transport in bulk Y6, enabling better performance than conventional ratios. This work reports novel light-harvesting materials in which performance is reduced due to unfavorable morphology as D:A ratios move toward conventional ratios of 1:1.2-1:1.

Passivation of Hematite by a Semiconducting Overlayer Reduces Charge Recombination: An Insight from Nonadiabatic Molecular Dynamics.

Hematite (α-Fe2O3) is a promising photoanode material for photoelectrochemical water splitting. Surface-passivating layers are effective in improving water oxidation kinetics; however, the passivation mechanism is not fully understood due to the complexity of interfacial reactions. Focusing on the Fe-terminated Fe2O3 (0001) surface that exhibits surface states in the band gap, we perform ab initio quantum dynamics simulations to study the effect of an α-Ga2O3 overlayer on charge recombination. The overlayer eliminates surface states and suppresses charge recombination 4-fold. This explains in part the observed cathodic shift in the onset potential for water oxidation. The increased charge carrier lifetime is an outcome of two factors, energy gap and electron-vibrational coupling, with a positive contribution from the former but a negative contribution from the latter. This work presents an advance in the atomistic time-domain understanding of the influence of surface passivation on charge recombination dynamics and provides guidance for designing novel α-Fe2O3 photoanodes.

Synergism between nitrogen vacancies and a unique electrons transfer pathway of Ag modified S-scheme g-C3N4/CdS heterojunction for efficient H2 evolution

Ag modified g-C3N4/CdS (Ag@g-C3N4/CdS) S-scheme heterojunction with a distinctive charge transfer channel was prepared as a photocatalyst for photoreduction of H2O. The effect of nitrogen vacancies and photo-excited charge carriers in the water splitting on the Ag@g-C3N4/CdS was discussed. It was found that the charge carriers transport channel in Ag@g-C3N4/CdS S-scheme heterojunction was instrumental in the enhancement of H2 production. The electrons in Ag nanospheres and in the conduction band (CB) of CdS can recombine with the holes in the valence band (VB) of g-C3N4, which prolonged the lifetime of electrons in the CB of g-C3N4. Meanwhile, a unique charge transfer channel was produced in the Ag@g-C3N4/CdS. Compared with g-C3N4, Ag@g-C3N4/CdS photocatalyst demonstrated an enhanced performance which was assigned to the increased charge carrier lifetime. The supreme Ag@g-C3N4/CdS showed photocatalytic H2 production activity up to 204.19 μmol for 4 h under illuminate (λ ≥ 420 nm), which was 11.74 times than that of g-C3N4.

Heterojunction formation between AgNbO3 and Co3O4 for full solar light utilization with improved charge-carrier separation.

In the present study, the charge-carrier recombination of visible light active perovskite silver niobate (AgNbO3) was reduced by forming heterojunction with Co3O4 through simple impregnation and calcination route. The loading percentage of Co3O4 was varied as 2, 5, and 10 wt.%. The XRD study revealed reduced interlayer spacing in the composite due to the replacement of the bigger Ag+ ions by the smaller Co2+ and Co3+ ions of Co3O4. It was observed that the light harvesting efficiency of the materials was increased with increased loading of Co3O4. The TEM and XPS analysis confirmed the presence of Ag nanoparticles over the perovskite in the composite. The electrochemical analysis revealed enhanced charge-carrier number density and increased charge-carrier lifetime in the composite as a result of the presence of both silver and cobalt ions in the lattice. Further this enhanced charge-carrier separation of the composites was established through photocatalysis of Bisphenol-A under both solar and LED light. Charge-trapping study indicated *O2- and *OH as the major radicals involved and Z-scheme as the predominant charge transfer pathway for generation of these reactive oxygen species.

Sulfur Treatment Passivates Bulk Defects in Sb2Se3 Photocathodes for Water Splitting

AbstractSb2Se3 has emerged as an important photoelectrochemical (PEC) and photovoltaic (PV) material due to its rapid rise in photoconversion efficiencies. However, Sb2Se3 has a complex defect chemistry, which reduces the maximum photovoltage. Thus, it is important to understand these defects and develop defect passivation strategies in Sb2Se3. A comprehensive investigation of the charge carrier dynamics of Sb2Se3 and the influence of sulfur treatment on its optoelectronic properties is performed using time‐resolved microwave conductivity (TRMC), photoluminescence (PL) spectroscopy, and low‐frequency Raman spectroscopy (LFR). The key finding in this work is that upon sulfur treatment of Sb2Se3, the carrier lifetime is increased by the passivation of deep defects in Sb2Se3 in both the surface region and the bulk, which is evidenced by increased charge carrier lifetime of TRMC decay dynamics, increased radiative recombination efficiency, decreased deep defect level emission (PL), and the emergence of new vibration modes by LFR.

Zn and N Codoped TiO2 Thin Films: Photocatalytic and Bactericidal Activity.

We explore a series of Zn and N codoped TiO2 thin films grown using chemical vapor deposition. Films were prepared with various concentrations of Zn (0.4-2.9 at. % Zn vs Ti), and their impact on superoxide formation, photocatalytic activity, and bactericidal properties were determined. Superoxide (O2•-) formation was assessed using a 2,3-bis(2-methoxy-4-nitro-5-sulfophenyl)-5-[(phenylamino)carbonyl]-2H-tetrazolium sodium salt (XTT) as an indicator, photocatalytic activity was determined from the degradation of stearic acid under UVA light, and bactericidal activity was assessed using a Gram-negative bacterium E. coli under both UVA and fluorescent light (similar to what is found in a clinical environment). The 0.4% Zn,N:TiO2 thin film demonstrated the highest formal quantum efficiency in degrading stearic acid (3.3 × 10-5 molecules·photon-1), while the 1.0% Zn,N:TiO2 film showed the highest bactericidal activity under both UVA and fluorescent light conditions (>3 log kill). The enhanced efficiency of the films was correlated with increased charge carrier lifetime, supported by transient absorption spectroscopy (TAS) measurements.

Enhanced Light Absorption and Charge Carrier Management in Core‐Shell Fe2O3@Nickel Nanocone Photoanodes for Photoelectrochemical Water Splitting

AbstractSolar driven photoelectrochemical (PEC) water splitting is a clean and sustainable approach to generate green fuel, Hydrogen. Hematite (Fe2O3) is considered as potential photoanode because of its abundance, chemical stability and suitable band gap, though its short carrier diffusion length puts a limit on the film thickness and subsequent light absorption capability. In this regard, here we have designed and constructed a unique photoanode by depositing ultrathin films of Fe2O3 on purpose‐built three‐dimensional (3D) nickel nanocone arrays. In this design, 3D nanostructures not only provide ameliorated surface area for PEC reactions but also enhance light absorption capability in ultrathin Fe2O3 films, while ultrathin films promote charge carrier separation and effective transfer to the electrolyte. The 3D electrodes exhibit a substantial improvement in light absorption capability within the entire visible region of solar spectrum, as well as enhanced photocurrent density as compared to the planar Fe2O3 photoelectrode. Detailed investigation of reaction kinetics suggests an optimum Fe2O3 film thickness on 3D nanocone arrays obtained after 6 deposition cycles in achieving maximum charge carrier separation and transfer efficiencies (82 % and 88 %, respectively), mainly ascribable to the increased charge carrier lifetime overcoming recombination losses.

Effects of Interfacial Layers on the Open Circuit Voltage of Polymer/Fullerene Bulk Heterojunction Devices Studied by Charge Extraction Techniques.

Interfacial layers are frequently used in organic solar cells performing various functions, including blocking surface recombination, improving selectivity of charge carrier extraction, modification of the work function of the contact materials, and enhancing light absorption within the photoactive layer through an optical cavity effect. The aim of this work is to investigate the origin of performance enhancement of bulk heterojunction solar cells using various electron and hole interfacial layers, with a particular focus on separating the contributions of work function modification and reduced recombination to the improvement of the open circuit voltage ( Voc). Solar cells using poly[ N-9'-hepta-decanyl-2,7-carbazole- alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]:[6,6]-phenyl C70-butyric acid methyl ester (1:4) active layers were prepared with a combination of polymeric, metal oxide, and polyelectrolyte electron and/or hole interfacial layers. Four device structures with (i) no interfacial layers (reference); (ii) only hole; (iii) only electron; (iv) both electron and hole interfacial layers were fabricated and compared using current-voltage, transient photovoltage, and charge extraction measurements. The voltage gains (Δ Voc) at matched charge density attributed to work function modification (Δ Voch or Δ Voce) are distinguished from the increase in Voc arising from increased charge carrier density. At the hole contact, Δ Voch was 0.21 V by using a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) hole interfacial layer, whereas Δ Voce was 0.29 V on the electron contact using a polyethoxylate imine-TiO x interfacial layer compared to reference devices. The electron lifetime also improved by orders of magnitude with the use of either electron or hole contact layers, contributing to a further 0.35-0.38 V increase in the open circuit voltage (Δ Vocrec) because of increased charge density. The increased charge carrier lifetime is proposed to originate from the larger spatial separation of the electrons and holes in the device because of the increased internal field. Using both an electron and a hole interfacial layer did not significantly increase the charge carrier lifetime compared to single interfacial layer devices; therefore, the Voc did not increase significantly. The findings presented clarify the role of interfacial layers in organic solar cells and provide new insights into using time-resolved charge extraction techniques to understand the influence of interfacial layers on the open circuit voltage.

Synthesis of QDs self-modified Bi2MoO6/Bi4Ti3O12 photocatalysts via controlling charge unidirectional flow for effective degradation of organic pollutants

Reinforcing separation of charge carriers and increasing electron density played a leading role in improving photocatalytic performance. In this work, incorporating homojunction and heterojunction in quantum dots (QDs) self-modified Bi2MoO6/Bi4Ti3O12 (BMO(Q)/BTO) composites had been rationally designed, and a newfangled photocatalyst had been acquired which could realize the fine manipulation of charge carriers flow direction. Among multitudinous samples, the 15-BMO(Q)/BTO composite exhibited the optimal photocatalytic properties and pervasive applicability for removing the various pollutants (dye, mercaptan and heavy metal) under visible light. We utilized the three-dimensional excitation-emission matrix fluorescence spectroscopy (3D EEMs) to fully grasp the degradation behaviors of RhB. The encouraging increase in photocatalytic activity was mainly attributed to the unified transfer of electrons generated by BMO QDs and BTO to the conduction band of BMO, which effectively increased charge carrier lifetime and improved the conduction band electron density. Furthermore, the photocatalytic degradation mechanism over 15-BMO(Q)/BTO composite was systematically investigated by the calculation, trapping experimental and ESR. The ·OH undertook the active constituent in the process of degradation pollutants. The result suggested that the construction of homojunction/heterojunction photocatalysts to enhance electrons density was a reliable design idea.

Nanoarchitecture of TiO2 microspheres with expanded lattice interlayers and its heterojunction to the laser modified black TiO2 using pulsed laser ablation in liquid with improved photocatalytic performance under visible light irradiation

Different morphologies and crystal phases of black titanium dioxide (TiO2) were synthesized using Pulsed Laser Ablation in Liquid (PLAL). The synthesized laser modified black TiO2 (LMB-TiO2) structures included hydrogenated anatase TiO2 nanoparticles, as the core shell structures, and TiO2 microspheres. TiO2 core-shell nanoparticles, which had crystalline-disordered structures, demonstrated the laser ablation pulse duration-dependence growth of amorphous shells and hence formation of disordered TiO2 nanoparticles with different thickness of hydrogen-doped amorphous shells were shown. TiO2 microspheres with the yolk–shell like structures (YSHL-TiO2 microspheres), on the other hand, showed the formation of rutile phases in the shell which encapsulate Lattice Expanded Planes (LEPs) in the core. The microspheres demonstrated phase transitions from anatase to rutile and size-dependent lattice interlayers expansion from 0.35 nm to 0.94 nm. The maximum particle size growth occurred when the samples were subjected to the laser ablation for 120 min. The crystal phase transition, consequently, led to the formation of heterostructured photocatalysts through construction of hydrogenated anatase TiO2 nanoparticles junctions with rutile TiO2 microspheres. The photocatalytic degradation of methylene blue (MB) using LMB-TiO2 heterostructure was tested under visible light irradiation Results showed approximately 99% of MB was degraded after 60 min. Enhanced visible light absorption and increased charge carrier lifetime due to formation of different types of heterojunctions may explain the higher photocatalytic performance of LM-TiO2 samples. Moreover, the Photoluminescence analysis indicated that hydroxyl radicals were the main active species involved in the photocatalytic degradation tests and therefore the photocatalysis mechanism was accordingly suggested.

Single atom Cu(I) promoted mesoporous titanias for photocatalytic Methyl Orange depollution and H2 production

Tailoring the physicochemical properties and hence reactivity of semiconductor photocatalysts in a predictable fashion, remains a challenge to their industrial application. Here we demonstrate the striking promotional effect of incorporating single Cu(I) atoms, on aqueous phase photocatalytic dye degradation and H2 production over surfactant-templated mesoporous TiO2. X-ray absorption spectroscopy reveals that ultra-low concentrations of copper (0.02–0.1 wt%) introduced into the mesoporous TiO2 surface create isolated Cu (I) species which suppress charge recombination, and confer a six-fold photocatalytic promotion of Methyl Orange degradation and four-fold enhancement of H2 evolution. The impact of mesopore structure and photophysical properties on photocatalytic activity is also quantified for the first time: calcination increases mesopore size and nanocrystalline order, and induces an anatase to rutile phase transition that is accompanied by a decrease in the optical band gap, increased charge carrier lifetime, and a concomitant significant activity enhancement.

Improved a-B10C2+xHy/Si p-n heterojunction performance after neutron irradiation

The impact of neutron irradiation, in the energy range of ∼0.025 eV, on amorphous semiconducting partially dehydrogenated boron carbide (a-B10C2+xHy) on silicon p-n heterojunction diodes was investigated. The heterojunction devices were created by synthesizing a-B10C2+xHy via plasma enhanced chemical vapor deposition on n-type silicon. Unlike many electronic devices, the performance of the a-B10C2+xHy heterojunction diode improved with neutron irradiation, in spite of the large neutron cross section of 10B. There is also increased charge carrier lifetime of more than 200% with modest neutron irradiation of approximately 2.7 × 108 to 1.08 × 109 neutrons/cm2.

Improving charge transport and suppressing charge recombination in small molecule ternary solar cells via incorporating Bis-PC71BM as a cascade material

The development of small molecule organic solar cells (SMOSCs) has attracted considerable attention and achieved comparable power conversion efficiency (PCE) with polymer solar cells. Here, we demonstrate a bulk heterojunction (BHJ) small molecular solar cell with PCE of 5.31% by incorporating Bisadduct of phenyl-C71-butyric acid methyl ester (Bis-PC71BM) as an additional acceptor material into the host binary blend of 2-[4-(N-butyl-N-phenylamino)-2,6-dihydroxyphenyl]-4-[(4-(N-butyl-N-phenylamino)-2,6-dihydroxyphenyl)-2,5-dien-1-ylidene]-3-oxocyclobut-1-en-1-olate (SQ-BP): [6,6]-phenyl C71 butyric acid methyl ester (PC71BM). The short circuit current (JSC) and the fill factor (FF) of ternary SMOSCs are improved by decreasing the carrier recombination loss, increasing exciton dissociation and enhancing the carrier transport. The transient photovoltage (TPV) measurement indicates that the gradient HOMO energy alignment suppresses the charge recombination and leads to the increased charge carrier lifetime in ternary SMOSCs. As a result, the PCE of ternary devices with 5 wt% Bis-PC71BM is about 20% greater than that of SQ-BP: PC71BM based binary SMOSCs.

Carrier‐Selectivity‐Dependent Charge Recombination Dynamics in Organic Photovoltaic Cells with a Ferroelectric Blend Interlayer

Interfacial energetics determines the performance of organic photovoltaic (OPV) cells based on a thin film of organic semiconductor blends. Here, an approach to modulating the “carrier selectivity” at the charge collecting interfaces and the consequent variations in the nongeminate charge carrier recombination dynamics in OPV devices are demonstrated. A ferroelectric blend interfacial layer composed of a solution‐processable ferroelectric poly­mer and a wide bandgap semiconductor is introduced as a tunable electron selective layer in inverted OPV devices with non‐Ohmic contact electrodes. The direct rendering of dipole alignment within the ferroelectric blend layer is found to increase the carrier selectivity of the charge collecting interfaces up to two orders of magnitude. Transient photovoltaic analyses reveal that the increase of carrier selectivity significantly reduces the diffusion and recombination among minority carriers in the vicinity of the electrodes, giving rise to the 85% increased charge carrier lifetime. Furthermore, the carrier‐selective charge extraction leads to the constitution of the internal potential within the devices, even with energetically identical cathodes and anodes. With these carrier‐selectivity‐controlled interlayers, the devices based on various photoactive materials commonly display significant increments in the device performances, especially with the high fill factor of up to 0.76 under optimized conditions.

TiO2 nanofiber solid-state dye sensitized solar cells with thin TiO2 hole blocking layer prepared by atomic layer deposition

We incorporated a thin but structurally dense TiO2 layer prepared by atomic layer deposition (ALD) as an efficient hole blocking layer in the TiO2 nanofiber based solid-state dye sensitized solar cell (ss-DSSC). The nanofiber ss-DSSCs having ALD TiO2 layers displayed increased open circuit voltage, short circuit current density, and power conversion efficiency compared to control devices with blocking layers prepared by spin-coating liquid TiO2 precursor. We attribute the improved photovoltaic device performance to the structural integrity of ALD-coated TiO2 layer and consequently enhanced hole blocking effect that results in reduced dark leakage current and increased charge carrier lifetime.

Interface-engineering additives of poly(oxyethylene tridecyl ether) for low-band gap polymer solar cells consisting of PCDTBT:PCBM_70 bulk-heterojunction layers

We herein report on the improved photovoltaic (PV) effects of using a polymer bulk-heterojunction (BHJ) layer that consists of a low-band gap electron donor polymer of poly(N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)) (PCDTBT) and an acceptor of [6,6]-phenyl C₇₁ butyric acid methyl ester (PCBM₇₀), doped with an interface-engineering surfactant additive of poly(oxyethylene tridecyl ether) (PTE). The presence of an interface-engineering additive in the PV layer results in excellent performance; the addition of PTE to a PCDTBT:PCBM₇₀ system produces a power conversion efficiency (PCE) of 6.0%, which is much higher than that of a reference device without the additive (4.9%). We attribute this improvement to an increased charge carrier lifetime, which is likely to be the result of the presence of PTE molecules oriented at the interfaces between the BHJ PV layer and the anode and cathode, as well as at the interfaces between the phase-separated BHJ domains. Our results suggest that the incorporation of the PTE interface-engineering additive in the PCDTBT:PCBM₇₀ PV layer results in a functional composite system that shows considerable promise for use in efficient polymer BHJ PV cells.

Time of flight study of high performance CVD diamond detector devices

AbstractIn comparison with polycrystalline diamond, single crystal diamond (SC CVD) offers important advantages for applications to electronics and detection. This is because SC CVD diamond exhibits improved charge transport characteristics, specifically a high drift mobility and an increased charge carrier lifetime. So far, only limited studies have dealt with the measurements of electrical transport parameters in SC diamond and majority of these studies were based on industrial material only. In our study we have investigated the electrical transport properties of PE CVD SC diamond grown using relatively high pressure growth conditions and high deposition growth rates (typically 20 μm/hour) by two independent methods: the laser Time‐of‐Flight (TOF) and the alpha particle TOF techniques. Raman spectroscopy, defect spectroscopy were used to characterize the quality of the samples prepared. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Photoelectrochemical studies on the n-MoS2–Cysteine interaction

The amino acid Cysteine, which plays a significant role as a charge transfer bridge, e.g. in redox proteins like Ferredoxin or Mo-Nitrogenase and in artificial systems like Self Assembled Monolayers (SAM’s) on gold, was adsorbed on both, natural and synthetic molybdenum disulfide and the changes were studied with combined photoelectrochemical and microwave conductivity techniques. In contrast to pyrite (FeS2), where modification with cysteine enhances the electrochemical corrosion, with molybdenum disulfide this is not the case. It was found that cysteine chemically interacts with both dangling bonds of molybdenum on edge sites as well as with dz2 orbitals of molybdenum that protrude through the van der Waals surface. The interaction with the edge sites leads to a decrease in dark current and hydrogen evolution activity. In inert electrolyte the interaction with the van der Waals surface leads to a decrease in decomposition-photocurrents due to the action of cysteine as a recombination centre for charge carriers. If, however, a reducing agent such as hydroquinone/quinone or hexacyanoferrate is added, photocurrents increase because the adsorbed cysteine now acts as charge transfer bridge and no longer as a recombination centre. This is supported by a significantly increased microwave conductivity indicating increased charge carrier lifetime.