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1.
We report an approach for the fabrication of CuIn(S,Se)2‐based photovoltaic devices from hydrazinium precursors in non‐hydrazine solvents, specifically a ethanolamine/dimethyl sulfoxide (EA/DMSO) mixture. For the first time, both Cu hydrazinium precursor and Cu‐In hydrazinium precursor are found with good solubility in non‐hydrazine solvents, producing molecular‐level blending of metal precursors. Sulfur loss in Cu hydrazinium precursor is compensated for by either introduction of excessive S/Se or the formation of S/Se‐bridged Cu‐In compounds. The success of dissolving Cu‐In hydrazinium precursor is ascribed to the coordinated S group and strong intramolecular interaction within non‐hydrazine solvents. X‐ray diffraction (XRD) and Raman characterization indicate the formation of the CuIn(S,Se)2 phase after annealing. Through introducing different amounts of excess S/Se, the ratio between CuInS2 and CuInSe2, as well as the morphology of the resulted CuIn(S,Se)2 film can be controlled. Optimized devices exhibit a power conversion efficiency of 3.8% with a CISS absorber layer of only around 300 nm thickness, which is comparable to N2H4‐based devices of similar thickness.  相似文献   

2.
Here we report a facile one‐pot method for the preparation of high‐quality CdSe nanocrystals (NCs) in aqueous solution under an air atmosphere. Compared with the traditional use of NaHSe or H2Se, the more stable sodium selenite is utilized as the Se source for preparing highly luminescent CdSe nanocrystals. By using mercaptosuccinic acid (MSA) as the capping agent and borate–citrate acid as the buffering solution, CdSe nanocrystals with high quantum yield (up to 70%) have been synthesized conveniently. The influence of different experimental parameters, such as the pH of the precursor solution, the molar ratio of Cd2+ to Na2SeO3 and Cd2+ to MSA on the CdSe nanocrystals, has been systematically investigated. The prepared CdSe NCs were spherical with a size of ~ 5 nm. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

3.
Conformations of disulfide and diselenide were compared in (Boc‐Cys/Sec‐NHMe)2 and (Boc‐Cys/Sec‐OMe)2 using X‐ray crystallography, nuclear magnetic resonance (NMR) spectroscopy, density functional theory (DFT), and circular dichroism (CD) spectroscopy. Conformations of disulfide/diselenide in polypeptides are defined based on the sign of side chain torsion angle χ3 (–CH2–S/Se–S/Se–CH2–); negative indicates left‐handed and positive indicates right‐handed orientation. In the crystals of (Boc‐Cys‐OMe)2 and (Boc‐Sec‐OMe)2, the disulfide exhibits a left‐handed and the diselenide a right‐handed orientation. Characterization of cystine and selenocystine derivatives in solution using 1H‐NMR, natural abundant 77Se NMR, 2D‐ROESY, and chemical shift analysis coupled to DMSO titration has indicated the symmetrical nature and antiparallel orientation of Cys/Sec residues about the disulfide/diselenide bridges. Structural calculations of cystine and selenocystine derivatives using DFT further support the antiparallel orientation of Cys/Sec residues about disulfide/diselenide. The far‐ultraviolet (UV) region CD spectra of cystine and selenocystine derivatives have exhibited the negative Cotton effect (CE) for disulfide and positive for diselenide confirming the difference in the conformational preference of disulfide and diselenide. In the previously reported polymorphic structure of (Boc‐Sec‐OMe)2, the diselenide has right‐handed orientation. In the X‐ray structures of disulfide and diselenide analogues of Escherichia coli protein encoded by curli specific gene C (CgsC) retrieved from Protein Databank (PDB), disulfide has left‐handed and the diselenide right‐handed orientation. The current report provides the evidence for the local conformational difference between a disulfide and a diselenide group under unconstrained conditions, which may be useful for the rational replacement of disulfide by diselenide in polypeptide chains.  相似文献   

4.
Thin film solar cells based on co‐evaporated Cu(In,Ga)Se2 absorber films present the highest efficiencies among current polycrystalline thin‐film technologies. Thanks to the development of a novel experimental setup for in situ growth studies, it was possible to follow the formation of the crystalline phases during such deposition processes for the first time. This synchrotron‐based energy‐dispersive X‐ray diffraction and fluorescence setup is suited for real‐time studies of thin film vapor deposition processes. Focusing on the growth of CuInSe2 and CuGaSe2 fabricated by three‐stage processing, we find that the phase transitions in the Cu‐In‐Se system follow the reported pseudo‐binary In2Se3‐Cu2Se phase diagram. This requires a transformation of the Se sublattice during the incorporation of Cu‐Se into the In2Se3 precursor film from the first process stage. In the Cu‐Ga‐Se system, besides an increase in the lattice spacings, we observe no transformation of the Se sublattice. Furthermore, the structural defects of the Ga‐Se precursor film are preserved until the CuGaSe2 stoichiometry is reached. By means of model calculations of the fluorescence signals, we confirm in both systems the segregation of Cu2Se at the surface near a concentration of 25 at.% Cu shortly after the recrystallization of the films. The modeling also reveals that Cu2Se penetrates into the CuInSe2 film, whereas it remains at the surface of the CuGaSe2 film.  相似文献   

5.
Selenium (Se) has been becoming an emerging pollutant causing severe phytotoxicity, which the biochemical mechanism is rarely known. Although hydrogen sulfide (H2S) has been suggested as an important exogenous regulator modulating plant physiological adaptions in response to heavy metal stress, whether and how the endogenous H2S regulates Se-induce phytotoxicity remains unclear. In this work, a self-developed specific fluorescent probe (WSP-1) was applied to track endogenous H2S in situ in the roots of Brassica rapa under Se(IV) stress. Se(IV)-induced root growth stunt was closely correlated with the inhibition of endogenous H2S generation in root tips. Se(IV) stress dampened the expression of most LCD and DCD homologues in the roots of B. rapa. By using various specific fluorescent probes for bio-imaging root tips in situ, we found that the increase in endogenous H2S by the application of H2S donor NaHS could significantly alleviate Se(IV)-induced reactive oxygen species (ROS) over-accumulation, oxidative impairment, and cell death in root tips, which further resulted in the recovery of root growth under Se(IV) stress. However, dampening the endogenous H2S could block the alleviated effect of NaHS on Se(IV)-induced phytotoxicity. Finally, the increase in endogenous H2S resulted in the enhancement of glutathione (GSH) in Se(IV)-treated roots, which may share the similar molecular mechanism for the dominant role of H2S in removing ROS by activating GSH biosynthesis in mammals. Altogether, these data provide the first direct evidences confirming the pivotal role of endogenous H2S in modulating Se(IV)-induced phytotoxicity in roots.  相似文献   

6.
Besides the open circuit voltage (VOC) deficit, fill factor (FF) is the second most significant parameter deficit for earth‐abundant kesterite solar cell technology. Here, various pathways for FF loss are discussed, with focus on the series resistance issue and its various contributing factors. Electrical and physical characterizations of the full range of bandgap (Eg = 1.0–1.5 eV) Cu2ZnSn(SxSe1?x)4 (CZTSSe) devices, as well as bare and exfoliated films with various S/(S + Se) ratios, are performed. High intensity Suns‐VOC measurement indicates a nonohmic junction developing in high bandgap CZTSSe. Grazing incidence X‐ray diffraction, Raman mapping, field emission scanning electron microscopy, and X‐ray photoelectron spectroscopy indicate the formation of Sn(S,Se)2, Mo(S,Se)2, and Zn(S,Se) at the high bandgap CZTSSe/Mo interface, contributing to the increased series resistance (RS) and nonohmic back contact characteristics. This study offers some clues as to why the record‐CZTSSe solar cells occur within a bandgap range centered around 1.15 eV and offers some direction for further optimization.  相似文献   

7.
The hydrazine‐based deposition of Cu(In,Ga)(S,Se)2 (CIGS) thin films has attracted considerable attention in recent years due to its potential for the high‐throughput production of photovoltaic devices based on this absorber material. This article provides an introduction as well as presenting a complete picture of the current status of hydrazine‐based CIGS solar‐cell fabrication, including the three major steps of this deposition process: dissolution of the precursor materials in hydrazine, deposition of a film from the resulting precursor solution, and the completion and characterization of a photovoltaic device following absorber deposition. Recent discoveries are then discussed, regarding the dissolution chemistry of the relevant precursor complexes in hydrazine, which together represent the true foundation of this processing method. Recent studies on CIGS film formation are then summarized, including the control and analysis of the crystalline phase, electronic bandgap, and film morphology. Finally, the latest progress in high‐performance device fabrication is highlighted, with a focus on optoelectronic characterization including current–voltage, junction capacitance, and minority carrier lifetime measurements. Finally, a discussion and future outlook is provided.  相似文献   

8.
9.
Disposal of saline irrigation wastewater in hydrologically closed sinks in the semi-arid western U.S. has concentrated selenium-rich salts to hazardous levels and phytoextraction, along with plant-enhanced volatilization of methyl-selenides, is an active area of research. Here, we provide an overview of our ongoing studies of Stanleya pinnata (Brassicaceae), a previously unstudied candidate that is a primary accumulator (hyperaccumulator) of Se that is widespread and broadly adapted in the western U.S. When grown in sand culture under uniform greenhouse conditions, 16 populations representing S. pinnata's broad biogeographical range differed in shoot Se concentration by 1.4- to 3.6-fold, and the shoot concentrations were positively correlated with the indigenous soil Se levels at the collection sites. Thus, S. pinnata exhibits significant ecotypic variation in Se accumulation. All populations accumulated SeO4 2- preferentially over SO4 2- consistent with S. pinnata's classification as a primary Se accumulator, while hydroponically-grown Brassica juncea consistently accumulated sulfate preferentially over selenate. The Se in S. pinnata shoots was predominately in the soluble amino-acid pool, which may serve as direct precursor to volatile forms such as dimethyldiselenide; inorganic forms (e.g. selenate) dominated in B. juncea. Preliminary results suggest that S. pinnata may volatilize unusually large quantities of Se when grown at high sulfate concentrations, an unexpected result not heretofore reported in any species. In a sand–culture experiment, S. pinnata exhibited excellent tolerance of excess boron, but only moderate tolerance of salinity, and superior genotypes will likely be needed for phytoremediation of highly salinized soils and sediments. Stanleya pinnata is a perennial that responded favorably to repeated cuffing in the greenhouse, a trait that could prove valuable in field-scale phytoremediation. Environmental concerns about Se are common in the western USA, and S. pinnata is a potentially useful species for phytoremediation due to its broad adaptation to western soils and environments, and its uptake, metabolism and volatilization of Se.  相似文献   

10.

Microbial volatilization of selenium (Se) may be an effective bioremediation technique to remove Se from dewatered sediments. In this laboratory study, soil management parameters (wetting and drying cycles, aeration, mixing, aggregate size, and water quality) were assessed for their influence upon Se volatilization. Selenium volatilization rates were higher under continuously moist conditions (—33 kPa) compared with wetting and drying cycles. After 6 months of incubation, a continuously moist seleniferous soil had lost approximately 21% of the Se inventory, whereas the same soil incubated under wetting and drying cycles had dissipated 7% of the total Se. Incubation under anoxia (N2 atmosphere) increased evolution of dimethyl selenide (DMSe) 1.4‐fold compared with aerated conditions. When soil samples were incubated under static versus continuously mixed conditions, the latter treatment enhanced volatilization 1.8‐fold. This was attributed to increased availability of the Se to the methylating soil microbiota. The optimum aggregate size to promote volatilization of Se was 0.53 mm when compared to 0.15, 1, and 2 mm. The application of saline well water (7.5 dS m‐1) over 6 months, compared with deionized water, had little effect on volatilization rates of Se from a highly saline (22 dS mr‐1) seleniferous dewatered sediment. Each of these parameters should be considered in promoting volatilization of Se as a bioremediation approach in the cleanup of seleniferous sediments.  相似文献   

11.
Selenium (Se) is essential for health of humans, animals, and plants. Especially wheat is a major source of Se in the terrestrial food chain. In this study, an element analysis was optimized and the content of Ca, Mg, K, S, P, Fe, Se, Mn, Cu, Zn, and Mo in leaves, roots, and seeds were measured during growth of wheat (Triticum aestivum L. cv. Manu) in Hoagland nutrient solution with 5 and 15 μM Na2SeO4. Se was transported to all investigated tissues and accumulated in the seeds in proportion to used amounts. The supplementation of Se, independently of concentration, weakly modified the micro- and macro-elements content in the seedlings. In the flag-leaf stage, an increase of the Mo and S content in the shoots and the S and Cu content in the roots was found. Moreover, in the generative phase, a decrease in Ca and Fe in the roots was registered. Increased Se in the nutrient solution strongly stimulated the Se accumulation in the seeds.  相似文献   

12.
Photovoltaic thin film solar cells based on kesterite Cu2ZnSn(Sx,Se1–x)4 compounds (CZTSSe) have reached >12% sunlight‐to‐electricity conversion efficiency. This is still far from the >20% record devices known in Cu(In1–y,Gay)Se2 and CdTe parent technologies. A selection of >9% CZTSSe devices reported in the literature is examined to review the progress achieved over the past few years. These devices suffer from a low open‐circuit voltage (Voc) never better than 60% of the Voc max, which is expected from the Shockley‐Queisser radiative limit (S‐Q limit). The possible role of anionic (S/Se) distribution and of cationic (Cu/Zn) disorder on the Voc deficit and on the ultimate photovoltaic performance of kesterite devices, are clarified here. While the S/Se anionic distribution is expected to be homogeneous for any ratio x, some grain‐to‐grain and other non‐uniformity over larger area can be found, as quantified on our CZTSSe films. Nevertheless, these anionic distributions can be considered to have a negligible impact on the Voc deficit. On the Cu/Zn order side, even though significant bandgap changes (>10%) can be observed, a similar conclusion is brought from experimental devices and from calculations, still within the radiative S‐Q limit. The implications and future ways for improvement are discussed.  相似文献   

13.
Prostaglandin E2 (PGE2) mediates immune responses of the beet armyworm, Spodoptera exigua, including oenocytoid cell lysis (a class of lepidopteran hemocytes: OCL) via its specific membrane receptor to release inactive prophenoloxidase (PPO) into hemolymph. PPO is activated into phenoloxidase in the plasma to play crucial roles in the immune responses of S. exigua. The mechanism of OCL has not been elucidated, however we posed the hypothesis that a rapid accumulation of sodium ions within the oenocytoids allows a massive influx of water by the ion gradient, which leads to the cell lysis. It remains unclear which sodium channel is responsible for the OCL in response to PGE2. This study identified a specific sodium channel called sodium‐potassium‐chloride cotransporter 1 (Se‐NKCC1) expressed in hemocytes of S. exigua and analyzed its function in the OCL in response to PGE2. Se‐NKCC1 encodes a basic membrane protein (pI value = 8.445) of 1,066 amino acid residues, which contains 12 putative transmembrane domains. Se‐NKCC1 was expressed in all developmental stages and tissues. qPCR showed that bacterial challenge significantly induced its expression. A specific inhibitor of NKCC, bumetanide, prevented the OCL in a dose‐dependent manner. When RNA interference (RNAi) using double‐stranded RNA specific to Se‐NKCC1 suppressed its expression, the OCL and PPO activation were significantly inhibited in response to PGE2. The RNAi treatment also reduced nodule formation to bacterial challenge. These results suggest that Se‐NKCC1 is associated with OCL by facilitating inward transport of ions in response to PGE2.  相似文献   

14.
Biosynthesis of metal nanoparticles represents a clean, eco‐friendly and sustainable “green chemistry” engineering. Lately, a number of metal selenides were successfully synthesized by biological methods. Here, cuprous selenide (Cu2Se) nanospheres were prepared under mild conditions by a novel biological‐chemical coupling reduction process. The simple process takes place between EDTA‐Cu and Na2SeO3 in presence of an alkaline solution containing NaBH4 and a selenite‐reducing bacteria, Pantoea agglomerans. It is noteworthy that the isolated Pantoea agglomerans and Cu+ ions, where the latter are obtained from reducing Cu2+ ions by NaBH4, play a key role, and Cu+ ions not only can promote the generation of Se2? ions as a catalyst, but also can react with Se2? ions to form Cu2Se. XRD pattern, SEM, and TEM images indicated that Cu2Se nanoparticles were tetragonal crystal structure and the nanospheres diameter were about 100 nm. EDX, UV–vis, and FTIR spectra show that the biosynthesized Cu2Se nanospheres are wrapped by protein and have a better stability. This work first proposes a new biosynthesis mechanism, and has important reference value for biological preparation of metal selenide nanomaterials. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1264–1270, 2016  相似文献   

15.
The present study involved two pot experiments to investigate the response of mung bean to the individual or combined SO42− and selenate application under drought stress. A marked increment in biomass and NPK accumulation was recorded in mung bean seedlings fertilized with various SO42− sources, except for CuSO4. Compared to other SO42− fertilizers, ZnSO4 application resulted in the highest increase in growth attributes and shoot nutrient content. Further, the combined S and Se application (S + Se) significantly enhanced relative water content (16%), SPAD value (72%), photosynthetic rate (80%) and activities of catalase (79%), guaiacol peroxidase (53%) and superoxide dismutase (58%) in the leaves of water-stressed mung bean plants. Consequently, the grain yield of mung bean was markedly increased by 105% under water stress conditions. Furthermore, S + Se application considerably increased the concentrations of P (47%), K (75%), S (80%), Zn (160%), and Fe (15%) in mung bean seeds under drought stress conditions. These findings indicate that S + Se application potentially increases the nutritional quality of grain legumes by stimulating photosynthetic apparatus and antioxidative machinery under water deficit conditions. Our results could provide the basis for further experiments on cross-talk between S and Se regulatory pathways to improve the nutritional quality of food crops.Supplementary InformationThe online version contains supplementary material available at 10.1007/s12298-021-00992-6.  相似文献   

16.
The kesterite material Cu2ZnSn(S,Se)4 (CZTSSe) is an attractive earth‐abundant semiconductor for photovoltaics. However, the power conversion efficiency is limited by a large density of I–II antisite defects, which cause severe band tailing and open‐circuit voltage loss. Ag2ZnSnSe4 (AZTSe) is a promising alternative to CZTSSe with a substantially lower I–II antisite defect density and smaller band tailing. AZTSe is weakly n‐type, and this study reports for the first time on how the carrier density is impacted by stoichiometry. This study presents the first‐ever photovoltaic device based on AZTSe, which exhibits an efficiency of 5.2%, which is the highest value reported for an n‐type thin‐film absorber. Due to the weakly n‐type nature of the absorber, a new architecture is employed (SnO:F/AZTSe/MoO3/ITO) to replace conventional contacts and buffer materials. Using this platform, it is shown that the band tailing parameter in AZTSe more closely resembles that of CIGSe than CZTSSe, underscoring the strong promise of this absorber. In demonstrating the ability to collect photogenerated carriers from AZTSe, this study paves the way for novel thin‐film heterojunction architectures where light absorption in the n‐type device layer can supplement absorption in the p‐type layer as opposed to producing a net optical loss.  相似文献   

17.
Alloy CdTe1‐xSex quantum dots (QDs) have been fabricated by an organic route using Cd, Te and Se precursors in a mixture of trioctylamine and octadecylphosphonic acid at 280 °C. The variation of photoluminescence (PL) peak wavelength of the CdTe1‐xSex QDs compared with CdTe QDs confirmed the formation of an alloy structure. The Se component drastically affected the stability of CdTe1‐xSex QDs. A Cd0.5Zn0.5S shell coating on CdTe1‐xSex cores was carried out using oleic acid as a capping agent. CdTe1‐xSex/Cd0.5Zn0.5S core/shell QDs revealed dark red PL while a yellow PL peak was observed for the CdTe1‐xSex cores. The PL efficiency of the core/shell QDs was drastically increased (less than 1% for the cores and up to 65% for the core/shell QDs). The stability of QDs in various buffer solutions was investigated. Core/shell QDs can be used for biological applications because of their high stability, tunable PL and high PL efficiency. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

18.
A simple, low‐cost and convenient method was developed for the synthesis of highly luminescent CdSe quantum dots (QDs) in an aqueous medium. Compared with previous methods, this synthesis was carried out in one pot using ascorbic acid (C6H8O6) to replace NaBH4 or N2H4 · H2O as a reductant, and selenium dioxide to replace selenium or its other hazardous, expensive and unstable compounds as a precursor. The mechanism of CdSe QDs formation was elucidated. The influence of various experimental variables, including refluxing time, Cd/MSA and Cd/Se molar ratios, on the luminescent properties of the QDs were systematically investigated. X‐Ray powder diffraction and transmission electron microscopy characterization indicated that the QDs had a pure cubic zinc‐blended structure with a spherical shape. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

19.
The metal sulfide or selenides have attracted increasing attention for high‐energy lithium‐ion batteries due to their unique layer structure flexibility, higher conductivity, and lower voltage polarization than metal oxides. However, low initial coulomb efficiency (ICE), serious structure destruction, and irreversible bonding chemistry are still big challenges for their practical application. Herein, layer GeSe2 and its carbon composite are synthesized by high‐energy ball milling and it is surprisingly found that crystalline c‐GeSe2 possesses higher reversible capacity and better rate performances than their amorphous counterparts. More specially, the broken Ge? Se bondings upon lithiation are also observed to regenerate after delithiation. These unusual phenomena are investigated by both experimental tools and theoretical calculations. Compared to other typical MX2 (M = Mo, W, X = S, Se), the electronegativity of Ge is more close to selenium and the formation energy of Ge? Se bonding is much smaller. Thus, a mild driven force such as thermoheating at low temperature can recover the ordered layer structure, helping to heal the high conductivity and unimpeded Li diffusion pathways for crystalline GeSe2. Similarly, electrochemical delithium force also triggers the rebuilding of Ge? Se bonding upon Li‐extraction, boosting GeSe2/C with large capacity (1050 mA h g?1), ultrahigh ICE (94%), and cycling stability.  相似文献   

20.
Nanocrystals of Li4Ti5O12 (LTO) have been prepared by processing an ethanol‐toluene solution of LiOEt and Ti(OiPr)4 using a carbon black template. The mechanism of crystal growth has been tracked by SEM and TEM microscopies. The resulting nanocrystals grown using the carbon template (C‐LTO) show less aggregation than materials prepared from solution without the template (S‐LTO), which is reflected in higher surface area (27 m2/g) and concomitantly smaller particle size (58 nm) for C‐LTO compared to 20 m2/g and 201 nm for S‐LTO. Electrochemically, thin‐film electrodes composed of C‐LTO demonstrate reversible cycling, storing ~160 mAh/g at both 1 C (175 mA/g) and 10 C current. Important is that resistance to charge transfer between the C‐LTO nanocrystals and added conducting carbon is 3 times smaller than that for S‐LTO. Accordingly, C‐LTO shows excellent rate capability, maintaining an energy‐storage capacity >150 mAh/g even at 100 C current. These characteristics solidify C‐LTO a suitable replacement for carbon as a Li‐ion battery anode.  相似文献   

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