Se Loss Research Articles

Soil respiration induces co-emission of greenhouse gases and methylated selenium from cold-region Mollisols: Significance for selenium deficiency

Mollisols rich in natural organic matter are a significant sink of carbon (C) and selenium (Se). Climate warming and agricultural expansion to the cold Mollisol regions may enhance soil respiration and biogeochemical cycles, posing a growing risk of soil C and Se loss. Through field-mimicking incubation experiments with uncultivated and cultivated soils from the Mollisol regions of northeastern China, this research shows that soil respiration remained significant even during cold seasons and caused co-emission of greenhouse gases (CO2 and CH4) and methylated Se. Such stimulus effects were generally stronger in the cultivated soils, with maximum emission rates of 7.45 g/m2/d C and 1.42 μg/m2/d Se. For all soil types, the greatest co-emission of CO2 and dimethyl selenide occurred at 25 % soil moisture, whereas measurable CH4 emission was observed at 40 % soil moisture with higher percentages of dimethyl diselenide volatilization. Molecular characterization with three-dimensional fluorescence and ultra-high resolution mass spectrometry suggests that CO2 emission is sensitive to the availability of microbial protein-like substances and free energy from organic carbon biodegradation under variable moisture conditions. Predominant Se binding to biodegradable organic matter resulted in high dependence of Se volatilization on rates of greenhouse gas emissions. These findings together highlight the importance of dynamic organic carbon quality for soil respiration and consequent Mollisol Se loss risk, with implications for science-based management of C and Se resources in agricultural lands to combat with Se deficiency.

RAMAN ANALYSIS OF NANOCRYSTALS BASED ON ZINC SELENIDE

This paper presents the results that were synthesized by nanocrystals based on zinc selenide by thermal synthesis and studied using micro-Raman spectroscopy before and after thermal annealing at 800 ℃ and 1000 ℃. The heat treatment of the synthesized samples was carried out in the AVERON electric vacuum furnace, lasting 60 minutes. The optical properties of the samples – photoluminescence (PL) and raman spectra – have been studied. Photoluminescence spectra were measured at room temperature using a CM2203 spectrofluorimeter. Raman spectra were measured using a Raman spectrometer (NT-MDT). The spectrometer used a solid-state laser with a wavelength of 473 nm. Raman spectra of zinc selenite (ZnSeO3) nanocrystals before annealing showed modes 665, 695, 825 and 973 cm−1. After thermal annealing, a downward shift of peaks was observed. In addition, the Raman spectra showed LO shifts with the duration of the deposition time. The Raman spectra of zinc selenide at room temperature showed the main peaks at 199, 247, 498 and 501 cm−1. During heat treatment of ZnSe at 800 °C and 1000 °C, an expansion of asymmetry was observed for horizontal optical (TO)-phonon and longitudinal optical (LO)-phonon modes with an increase in annealing temperature and redshifts in the shapes of Raman lines. The photoluminescence spectra of zinc selenide, depending on temperature, were represented by wide bands located at wavelengths of 350–650 nm. The PL spectra were recorded at room temperature from 300 to 800 nm in 5 nm increments using a xenon lamp. Zinc selenide before heat treatment showed photoluminescence bands at 1.93, 2.3, 2.56, 2.75 and 2.97 eV. The volume radiation of ZnSe at the boundary of the nearest band corresponded to the band of strong radiation at 2.84 eV. 3.2 eV is associated with the absorption of ZnO nanoparticles through the edge of the band. ZnSeO3 samples before annealing show one wide band of photoluminescence in the blue region of the electromagnetic spectrum about 2.82 eV. After thermal annealing at 1000 °C, a transition to a longer wave region with a wavelength of 2.86 eV is observed. Since thermal annealing is suitable for crystallization, it has led to an increase in luminescent efficiency. 60 minutes of high-temperature firing of the samples resulted in a loss of Se due to the effect of temperature on the zinc selenide content. Thermal combustion of zinc selenide-based nanocrystals was characterized by an increase in FWHM and a decrease in intensity in the photoluminescence spectra with increasing temperature.

Comprehensive structural and surface investigation of Sb2Se3 thin-films

Earth-abundant antimony selenide (Sb2Se3) is a promising material for the thin-film photovoltaic applications due to its desirable optoelectronic properties and suitable band gap. In this work, we present a comprehensive study on the structural and surface properties of Sb2Se3 thin-films for the potential applications in solar cells. The Sb2Se3 samples were grown on Si (100) substrate and at different substrate temperatures using radio frequency (RF) magnetron sputtering. The XRD diffractogram exhibits that Sb2Se3 is the predominant phase in all the samples, whereas the TEM measurements confirm the nanocrystalline nature of the samples. Raman spectroscopy measurements in the range of 30–500 cm−1 displays the Raman shifts at 148, 190 and 206 cm−1, which confirms the presence of the Sb2Se3 phase. The average surface roughness and grain size were obtained via surface topography with the help of the high-resolution AFM images. The EDS spectra revealed the presence of both Se and Sb as constituent elements in all the samples. The deconvolution of XPS spectra of Se 3p and Sb 3d core level disclose the Sb+3 and Se−2 oxidation state and further confirms the presence of Sb2Se3 phase. The XPS and EDS measurements predict that there is loss of Se during the deposition and it could have adverse effects on the performance of Sb2Se3 solar cell devices.

Loss of Selenium from Mollisol Paddy Wetlands of Cold Regions: Insights from Flow-through Reactor Experiments and Process-Based Modeling

Mollisols are critical agricultural resources for securing global food supply. Due to its health importance, selenium (Se) fate in the Mollisols attracts growing concerns. Land use change from conventional drylands to paddy wetlands impacts Se bioavailability in the vulnerable Mollisol agroecosystems. The underlying processes and mechanisms however remain elusive. Here, results of flow-through reactor experiments with paddy Mollisols from northern cold-region sites indicate that continuous flooding with surface water for 48 d induced redox zonation that facilitated the loss of Mollisol Se by up to 51%. Further process-based biogeochemical modeling suggests largest degradation rates of dissolved organic matter (DOM) in 30 cm deep Mollisols that contained the highest-level labile DOM and organic-bound Se. Electron shunting from degradation of Se-bearing DOM coupled to reductive dissolution of Se-adsorbed Fe oxides accounts mainly for Se(IV) release into the pore water. Consequent changes in DOM molecular composition make the reservoir of organic-bound Se vulnerable to flooding-induced redox zonation and likely enhance Se loss through destruction of thiolated Se and emission of gaseous Se from the Mollisol layer. This study highlights a neglected scenario where the speciation-driven loss of bioavailable Se from the paddy wetlands can be a significant consequence in the cold-region Mollisol agroecosystems.

Selenium Uptake, Translocation, and Metabolization Pattern during Barley Malting: A Comparison of Selenate, Selenite, and Selenomethionine.

Selenium (Se) is an essential trace element for human and animal health. Understanding the uptake and translocation of Se in crops is critical from the perspective of Se biofortification. In this study, barley was malted to investigate the uptake, translocation, and metabolism of exogenous Se including Na2SeO4, Na2SeO3, and selenomethionine (Se-Met). The results showed that the uptake rates of different forms of Se in barley decreased in the following order: Se-Met > Na2SeO3 > Na2SeO4, with the peak uptake occurring at the end of the steeping stages. In the early stages of germination, Se was mainly distributed in the husk and endosperm. Exogenous Se upregulated the transcription levels of Se transport and metabolic enzyme genes in the barley to varying degrees, which promoted Se transformation in various tissues, and improved Se bioeffectiveness. Compared to the Na2SeO3 and Se-Met groups, more Se was transferred from husk and endosperm to acrospire and rootlets in the Na2SeO4 group during the germination stage. Na2SeO4 and Se-Met stimulated the development of rootlets, and accelerated Se metabolism, resulting in a higher Se loss rate. Thus, these comparative findings provide new insights into Se uptake, transformation, and metabolization in barley.

Foliar selenium biofortification of broccolini: effects on plant growth and mineral accumulation

ABSTRACT Foliar biofortification is one effective way to alleviate the inadequate intake of selenium (Se) of millions of people worldwide. To evaluate the efficacy of foliar Se application in broccolini (a new hybrid crop variety derived from a cross between kalian cabbage and broccoli), three treatments were tested: 0, 0.05% or 0.10% (w/v) sodium selenate, applied at the early flowering stage. Florets were harvested in four sequential harvests, showing that both yield and nutritional composition were better in the early harvests, producing fewer but heavier and nutrient-richer florets. Although no overall effects on biomass were observed, the increase in total Se concentrations was more than 80- and 170-folds in both root and shoot of 0.05% and 0.10% Se, respectively, and by 270- and 600-fold in the florets. Although boiling resulted in > 50% loss of Se, an intake of 100 g of fresh weight boiled broccolini biofortified with 0.05% Se treatment will provide ~590 μg Se day−1. This amount is in excess of the tolerable upper limit for Se intake. Therefore, whilst broccolini is clearly a good Se accumulator with the potential to be biofortified with Se, lower application rates would need to be determined to be used for human food purposes.

Direct solid sampling of biological species for the rapid determination of selenium by high-resolution continuum source graphite furnace atomic absorption spectrometry

A direct solid sampling method based on high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GFAAS) for the determination of selenium (Se) in biological tissues was optimized. The main analytical line of Se at 196.0267 nm was used to carry out all HR-CS AAS measurements. Different chemical modifiers were evaluated to prevent the loss of Se during the application of the GFAAS temperature program and avoid the interferences due to the presence of phosphorus compounds in sample matrix. The best results were achieved using ruthenium coated platforms and a palladium nanoparticle suspension (Pd NP) as co-injected modifier. Calibration was performed using aqueous standard solutions of Se(IV). For solid sampling, the optimal range of sample mass was between 0.2 and 0.8 mg. The limit of detection (LOD) was 0.06 ng (0.075 μg g−1 using a sample mass of 0.8 mg). The developed solid sampling HR-CS GFAAS method was used for Se determination in two certified reference materials of dogfish tissues and lyophilized and powdered real samples of fish tissues and chicken liver. The precision obtained in these analyses, expressed as relative standard deviation (RSD), was between 5.5 and 8.6% (n = 6). For validation purposes, the results obtained by the solid sampling HR-CS GFAAS method were compared with those found performing the analysis by HR-CS hydride generation AAS (HR-CS HGAAS) after microwave acid digestion of the samples. The Se concentrations obtained for both methods agreed at a 95% confidence level (Student's t-test), indicating the suitability of the proposed solid sampling HR-CS GFAAS method to determine Se in biological samples.

Effect of Processing on Some Quality Parameters of Flour and Bread Made from Wheat Grain Biofortified with Zn and Se

Millions of people have inadequate Se and Zn intakes, but agronomic biofortification could prevent this. This study evaluated the effect of the combined Zn and Se biofortification on the quality parameters of grain, and on the composition of minerals (Zn, Se, Mg, Ca and Fe) and their availability in bread-making wheat (Triticum aestivum L.) products, white flour, wholemeal bread and white bread were evaluated. The studied treatments were soil Zn (no Zn, and 50 kg Zn ha−1) and foliar applications (0, 10 g Se ha−1, 8 kg Zn ha−1, and 10 g Se ha−1 + 8 kg Zn ha−1) and were tested in a two-year field experiment (2017–2018, 2018–2019). The foliar combined biofortification increased the concentration of both minerals in white flour, wholemeal bread and white bread by about 33%, 24% and 51%, respectively for Zn, and 3.3-fold, 3.4-fold and 2.7-fold for Se, showing a synergistic effect on Se concentration with the Se and Zn combination. While the loss of Zn and Se during the milling process was41% and 18%, respectively, baking caused a loss of 15% and 19%, respectively, for wholemeal bread, and up to 61% and 29% for Zn and Se for white bread. Hence, although the consumption of wholemeal bread instead of white bread may enhance Zn and Se intake more than biofortification, until consumption habits change, the biofortification of wheat can help to mitigate inadequate Zn and Se intakes in the general population.

Full-Duplex Cell-Free Massive MIMO With Low-Resolution ADCs

This paper studies the sum spectral/energy efficiency (SE/EE) of a full-duplex (FD) cell-free (CF) massive multiple-input multiple-output (MIMO) system with low-resolution analog-to-digital converters (ADCs) at the access points (APs) and the downlink (DL) users. We characterize the joint impact of the residual self-interference, inter-AP interference, uplink (UL)-to-DL interference, pilot contamination and quantization noise (QN) by deriving closed-form solutions for the UL/DL SE. It is shown that the UL SE loss due to the QN can be compensated by increasing the receiving antenna arrays. By contrast, in the DL, increasing the transmit antennas is ineffective in compensating for the DL SE loss. Furthermore, the analysis shows that the operating region of the FD CF massive MIMO is reduced as the ADCs’ resolution declines. We investigate the EE/SE trade-offs.

Selenium and tellurium in Reykjanes Ridge and Icelandic basalts: Evidence for degassing-induced Se isotope fractionation

Selenium behaves as a chalcophile and moderately volatile element during planetary accretion and magmatic processes on Earth. Together with the geochemically similar S and Te, Se is more volatile than most other moderately volatile elements and thus potentially becomes a new tracer to constrain the mechanism of volatile depletion in the Earth’s mantle and other planetary bodies. As previously observed for several volatile elements, stable isotopes of Se are expected to fractionate upon eruptive outgassing of magmas. To understand the degassing behavior of Se and associated isotope fractionation, we report on Se and Te contents and Se isotope compositions (δ82Se) of submarine glasses across a range of distant ridge depth intervals along the Reykjanes Ridge and subglacial/subaerial basalts on Iceland (51–65°N; N = 22). Selenium (150–399 ng/g) and Te (2.61–14.5 ng/g) contents of the submarine glasses display progressive enrichment along the Reykjanes Ridge towards Iceland. This can be explained either by enhanced mantle melting towards Iceland or by enrichment of Se–Te contents in the mantle source due to the Icelandic plume–Reykjanes Ridge interaction. Both scenarios are equally plausible. The δ82Se values of submarine Reykjanes Ridge glasses range between −0.20 ± 0.08‰ and −0.08 ± 0.08‰ (on average −0.15 ± 0.07‰; 2SD, N = 15), which are unaffected by the Icelandic plume contribution and remain strictly within the previously reported average for depleted MORBs. These new data combined with literature δ82Se for depleted MORBs define a highly homogeneous depleted mantle composition δ82Se = −0.15 ± 0.11‰ (2SD, N = 44). On the other hand, we observed degassing of Se and Te to a variable extent (~40–95%) in submarine Reykjanes glasses at depths shallower than ~250 m and in subaerial/subglacial basalts on Iceland. Degassing-induced Se isotope fractionation shifted δ82Se of subaerial lavas towards heavier values (by up to ~0.44‰) well outside the range of submarine MORBs. However, when Se outgassing is associated with subglacial eruption, the outer glass rim of basalt preserves the primary/undegassed Se isotopic signature; whereas the pillow interior experiencing further Se loss (~50%) is enriched in heavier isotopes (−0.01 ± 0.12‰) relative to the outer glass rim (−0.22 ± 0.08‰). These observations are complemented by measurements of BHVO-2G from high-temperature heating experiments of the natural Hawaiian basalt BHVO-2, which show evaporation of 40% Se and 85% Te and resulting shift in δ82Se by ~+0.74‰. Degassing-induced Se isotope fractionation during volcanic eruption may be well explained by a simple Rayleigh distillation model with an empirical fractionation factor α of ~0.9998 (between volcanic gas and silicate melt). The results presented here show that Se isotope and Se–Te systematics can potentially contribute further constraints on degassing of chalcophile and volatile elements during terrestrial volcanism and large-scale planetary processes.

Growth and structural characterization of Sb2Se3 solar cells with vertical Sb4Se6 ribbon alignment by RF magnetron sputtering

Sb2Se3, (ASe) thin-films were deposited as the absorber layers in photovoltaic solar cells using the radio frequency magnetron sputtering deposition technique. Starting from a binary target, high quality crystallization and good vertical alignment of Sb4Se6 ribbons were attained at growth temperatures below 300 °C, and use of an additional selenization process was unnecessary for compensating Se loss. By the structural characterization of films grown on different substrates, a strong dependence of the ribbon orientation on the substrate type was verified. This study clearly confirms that the ribbon alignment is the key factor for enhancing the performance of Sb2Se3 solar cells, in particular the short circuit current density (J sc). A photovoltaic efficiency of 0.24% and a J sc of 5 mA cm−2 were obtained by depositing ASe on Mo, in a CuInGaSe2-like solar cell structure (Al:ZnO/ZnO/CdS/ASe/Mo/Glass), while the J sc was boosted up to 27 mA cm−2 when the ASe solar cells were fabricated in superstrate configuration with an Au/ASe/CdS/FTO architecture, leading to an efficiency of 2.36%.

Defect Engineering in Ultrathin SnSe Nanosheets for High-Performance Optoelectronic Applications.

Ultrathin lamellar SnSe is highly attractive for applications in areas such as photonics, photodetectors, photovoltaic devices, and photocatalysis, owing to its suitable band gap, exceptional light absorption capabilities, and considerable carrier mobility. On the other hand, SnSe nanosheets (NSs) still face challenges of being difficult to prepare and their devices having low photoelectric conversion efficiencies. Herein, ultrathin SnSe NSs with controlled Se defects were synthesized with high yield by a facial Li intercalation-assisted liquid exfoliation method. The loss of Se, a narrowing of the band gap, and an increase in lattice disorders involving vacancies, distortions, and phase transition were observed in SnSe NSs prepared with a long lithiation process. Comparing between the 24 and 72 h lithiation samples, the ones processed for a longer time displayed a faster recombination time due to more defect-induced mid-states. Inspiringly, enhancements of 4-10 times were observed for photodetector device parameters such as photocurrent, photoresponsivity, photoresponse speed, and specific detectivity of the 72 h lithiation SnSe NSs. Additionally, these devices show good stability and a broad detection range, from ultraviolet to the near infrared region. Our results provide a promising avenue for the mass production of SnSe NSs with high photoelectric performance and open up opportunities for applications in photonics, optoelectronics, and photocatalysis.

Understanding the Reactions Between Fe and Se Binary Diffusion Couples

Spurred by recent discoveries of high-temperature superconductivity in Fe–Se-based materials, the magnetic, electronic, and catalytic properties of iron chalcogenides have drawn significant attention. However, much remains to be understood about the sequence of phase formation in these systems. Here, we shed light on this issue by preparing a series of binary Fe–Se ultrathin diffusion couples via designed thin-film precursors and investigating their structural evolution as a function of composition and annealing temperature. Two previously unreported Fe–Se phases crystallized during the deposition process on a nominally room-temperature Si substrate in the 27–33 and 37–47% Fe (atomic percent) composition regimes. Both phases completely decompose after annealing to 200 °C in a nitrogen glovebox. At higher temperatures, the sequence of phase formation is governed by Se loss in the annealing process, consistent with what would be expected from the phase diagram. Films rich in Fe (53–59% Fe) crystalized during deposition as β-FeSe (P4/nmm) with preferred c-axis orientation to the amorphous SiO2 substrate surface, providing a means to nonepitaxial self-assembly of crystallographically aligned, iron-rich β-FeSe for future research. Our findings suggest that the crystallization of binary Fe–Se compounds at room temperature via near diffusionless transformations should be a significant consideration in future attempts to prepare metastable ternary and higher-order compounds containing Fe and Se.

Effect of Rice Grain (Oryza sativa L.) Enrichment with Selenium on Foliar Leaf Gas Exchanges and Accumulation of Nutrients.

An agronomic itinerary for Se biofortification of two rice cultivars (Ariete and Ceres) through foliar fertilization with sodium selenate and sodium selenite with different concentrations (25, 50, 75 and 100 g Se.ha−1), was implemented in experimental fields. The selenium toxicity threshold was not exceeded, as shown by the eco-physiological data obtained through leaf gas exchanges. The highest Se enrichment in paddy grains was obtained with selenite for both cultivars, especially at the highest doses, i.e., 75 and 100 g Se.ha−1, with approximately a 5.0-fold increase compared with control values. In paddy grains, Zn was the most affected element by the treatments with Se with decreases up to 54%. When comparing the losses between rough and polished grains regardless of the cultivars, Se species and concentrations, it was observed that only Cu, Mg and Zn exhibited losses <50%. The remaining elements generally had losses >70%. The loss of Se is more pronounced in Ceres cultivar than in Ariete but rarely exceeds 50%. The analysis by µ-EDXRF showed that, in Ariete cultivar, Se is mostly homogeneously distributed in the grain regardless of any treatments, while in Ceres cultivar, the Se distribution seems to favor accumulation in the periphery, perhaps in the bran.

Magnetic phases in superconducting, polycrystalline bulk FeSe samples

The FeSe compound is the simplest high-temperature superconductor (HTSc) possible, and relatively cheap, not containing any rare-earth material. Although the transition temperature, Tc, is just below 10 K, the upper critical fields are comparable with other HTSc. Preparing FeSe using solid-state sintering yields samples exhibiting strong ferromagnetic hysteresis loops (MHLs), and the superconducting contribution is only visible after subtracting MHLs from above Tc. Due to the complicated phase diagram, the samples are a mixture of several phases, the superconducting β-FeSe, and the non-superconducting δ-FeSe and γ-FeSe. Furthermore, antiferromagnetic Fe7Se8 and ferromagnetic α-Fe may be contained, depending directly on the Se loss during the sintering process. Here, we show MHLs measured up to ±7 T and determine the magnetic characteristics, together with the amount of superconductivity determined from M(T) measurements. We also performed a thorough analysis of the microstructures in order to establish a relation between microstructure and the resulting sample properties.

How Oxygen Exposure Improves the Back Contact and Performance of Antimony Selenide Solar Cells.

The improvement of antimony selenide solar cells by short-term air exposure is explained using complementary cell and material studies. We demonstrate that exposure to air yields a relative efficiency improvement of n-type Sb2Se3 solar cells of ca. 10% by oxidation of the back surface and a reduction in the back contact barrier height (measured by J-V-T) from 320 to 280 meV. X-ray photoelectron spectroscopy (XPS) measurements of the back surface reveal that during 5 days in air, Sb2O3 content at the sample surface increased by 27%, leaving a more Se-rich Sb2Se3 film along with a 4% increase in elemental Se. Conversely, exposure to 5 days of vacuum resulted in a loss of Se from the Sb2Se3 film, which increased the back contact barrier height to 370 meV. Inclusion of a thermally evaporated thin film of Sb2O3 and Se at the back of the Sb2Se3 absorber achieved a peak solar cell efficiency of 5.87%. These results demonstrate the importance of a Se-rich back surface for high-efficiency devices and the positive effects of an ultrathin antimony oxide layer. This study reveals a possible role of back contact etching in exposing a beneficial back surface and provides a route to increasing device efficiency.

Growth and optical properties of nanocrystalline Sb2Se3 thin-films for the application in solar-cells

Antimony selenide (Sb2Se3) is a promising material for thin-film solar-cells due to its attractive optoelectronic properties with the desirable band gap. In the present work, four different Sb2Se3 films were grown on Si/SiO2 (100) substrates at ambient temperature using ultra-high vacuum molecular beam evaporation technique and different evaporation temperatures. The compositional analysis with the help of wavelength-dispersive X-ray spectroscopy measurements demonstrate that there is a loss of Se in the as-deposited samples. However, the X-ray diffraction study indicates that the as-deposited films are nanocrystalline in nature, with average crystallite size slightly increasing with the evaporation temperature. The blue shift of Raman peaks with the increase of evaporation temperature indicates the possibility of the presence of small amount of compressive strain in the crystal lattice and it appears because of the anion vacancy (VSe) due to the loss of Se. The obtained band gap value ranges from 1.075 eV to 1.21 eV, which indicate that the as-deposited nanocrystalline Sb2Se3 films are suitable for application in thin-film photovoltaic solar-cells. The tuning of the band-gap with the evaporation temperature opens a new road to optimize the device efficiency for the low-cost thin-film photovoltaics.

Adaptation of Fish Metabolism to Thermal Pollution of Subarctic Lake Imandra

Kola nuclear power plant, which discharges warm water into one of the bays of sub-arctic Lake Imandra, significantly changes the fish habitat, creating temperature gradient from 2 to 8°C compared to water temperature in the other part of the lake. The permeation, metabolism and bioaccumulation of elements in the stenothermal cold-water species (Coregonus lavaretus L.) in warm water impact zone are characterized. One of the main adaptation mechanisms of ionic regulation is the intense metabolism of Na due to the high respiratory activity of whitefish in warmer water. This feature is associated with elevated accumulation of Rb and loss of Se, Mo, and Si. At elevated temperatures, the main metabolic need is caused by Se deficiency. An extensive metabolism of selenoproteins involves risks of toxic effects and bioaccumulation of Hg, As and Cu with an increase of existing stressor or appearance of new ones.

Investigating the Formation of MoSe2 and TiSe2 Films from Artificially Layered Precursors.

The reaction of ultrathin layers of Mo and Ti with Se was investigated, and significantly different reaction pathways were found. However, in both systems postdeposition annealing results in smooth dichalcogenide films with specific thicknesses determined by the precursor. X-ray diffraction (XRD) patterns of as-deposited Mo|Se films around a 1:2 ratio of Mo to Se contain weak, broad reflections from small and isolated MoSe2 crystallites that nucleated during deposition and a sharper intensity maximum resulting from the composition modulation created from the alternating deposition of Mo and Se layers. In contrast, as-deposited Ti|Se films around a 1:2 ratio of Ti to Se contain narrow and intense 00l reflections from TiSe2 crystallites and do not contain a Bragg reflection from the sequence of deposited Ti|Se layers. The as-deposited TiSe2 crystallites have a larger c-axis lattice parameter than was previously reported for TiSe2, however, which suggests a poor vertical interlayer registry and/or high defect densities including interstitial atoms. In-plane XRD patterns show the nucleation of both TiSe2 and Ti2Se during deposition, with the Ti2Se at the substrate. For both systems, annealing the precursors decreases the peak width and increases the intensity of reflections from crystalline TiSe2 and MoSe2. Optimized films consist of a single phase after the annealing and show clear Laue oscillations in the specular XRD patterns, which can only occur if a majority of the diffracting crystallites in the film consist of the same number of unit cells. The highest quality films was obtained when an excess of ∼10% Se was deposited in the precursor, which presumably acts as a flux to facilitate diffusion of metal atoms to crystallite growth fronts and compensates for Se loss to the open system during annealing.

Atomic Structure and Dynamics of Defects and Grain Boundaries in 2D Pd2Se3 Monolayers

AbstractStructural imperfections of 2D crystals such as point vacancies and grain boundaries (GBs) have considerable impacts on their chemical-physical properties. Here we study the atomic structure and dynamics of defects and GBs in monolayer Pd2Se3 using annular dark field scanning transmission electron microscopy (ADF-STEM). The Pd2Se3 monolayers are reproducibly created by thermally induced phase transformation of few-layered PdSe2 films in an in-situ heating holder in the TEM to promote Se loss. Diverse point vacancies, one-dimensional (1D) defects, GBs and defect ring complexes are directly observed in monolayer Pd2Se3, which show a series of dynamics triggered by electron beam. High mobility of vacancies leads to self-healing of point vacancies by migration to the edge and subsequent edge etching under the beam. Specific defects are stabilized by Se–Se bonds, which shift in a staggered way to buffer strain, forming a wave-like 1D defect. Bond rotations are also observed and play an important role in defect and GB dynamics in Pd2Se3 during vacancy production. The GBs form in a meandering pathway and migrate by a sequence of Se–Se bond rotations without large scale vacancy formation. In the GB corners and tilted GBs, other highly symmetric vacancy defects also occur to adapt to the orientation change. These results give atomic level insights into the defects and GBs in Pd2Se3 2D monolayers.