Anomalous Structural Transition and Electrical Transport Behaviors in Compressed Zn2SnO4: Effect of Interface.
ABSTRACT: The interface effect is one of the most important factors that strongly affect the structural transformations and the properties of nano-/submicro-crystals under pressure. However, characterization of the granular boundary changes in materials is always challenging. Here, using tetrakaidecahedral Zn2SnO4 microcrystals as an example, we employed alternating current impedance, X-ray diffraction methods and transmission electron microscopy to elucidate the effect of the interface on the structure and electrical transport behavior of the Zn2SnO4 material under pressure. We clearly show that grain refinement of the initial microcrystals into nanocrystals (approximately 5 nm) occurs at above 12.5 GPa and is characterized by an anomalous resistance variation without a structural phase transition. A new phase transition pathway from the cubic to hexagonal structure occurs at approximately 29.8 GPa in Zn2SnO4. The unexpected grain refinement may explain the new structural transition in Zn2SnO4, which is different from the previous theoretical prediction. Our results provide new insights into the link between the structural transition, interface changes and electrical transport properties of Zn2SnO4.
Project description:Many aspects of nanostructured materials at high pressures are still unexplored. We present here, high-pressure structural behavior of two Zn2SnO4 nanomaterials with inverse spinel type, one a particle with size of ?7 nm [zero dimensional (0-D)] and the other with a chain-like [one dimensional (1-D)] morphology. We performed in situ micro-Raman and synchrotron X-ray diffraction measurements and observed that the cation disordering of the 0-D nanoparticle is preserved up to ?40 GPa, suppressing the reported martensitic phase transformation. On the other hand, an irreversible phase transition is observed from the 1-D nanomaterial into a new and dense high-pressure orthorhombic CaFe2O4-type structure at ?40 GPa. The pressure-treated 0-D and 1-D nanomaterials have distinct diffuse reflectance and emission properties. In particular, a heterojunction between the inverse spinel and quenchable orthorhombic phases allows the use of 1-D Zn2SnO4 nanomaterials as efficient photocatalysts as shown by the degradation of the textile pollutant methylene blue.
Project description:Improving the photocatalytic performance of multi-component photocatalysts through structural modulation and band alignment engineering has attracted great interest in the context of solar energy utilization and conversion. In our work, Zn2SnO4/SnO2 hierarchical architectures comprising nanorod building block assemblies were first achieved via a facile solvothermal synthesis route with lysine and ethylenediamine (EDA) as directing agents, and then chemically etched in NaOH solution to enlarge the surface area and augment active sites. The etched Zn2SnO4/SnO2 hierarchical architectures were further decorated by Cu2O nanoparticles though an in situ chemical deposition method based on band alignment engineering. In comparison with unetched Zn2SnO4/SnO2, the specific surface area of Zn2SnO4/SnO2/Cu2O hierarchical architectures became larger, and the responsive region and absorbance intensity became wider and higher in the whole visible-light range. Zn2SnO4/SnO2/Cu2O hybrid photocatalysts presented enormously improved visible-light photocatalytic behaviour for Rhodamine B (RhB) decomposition. The enhancement of photocatalytic behaviour was dominantly attributed to the synergy effect of the larger specific surface area, higher light absorption capacity, and more effective photo-induced charge carrier separation and migration. A proposed mechanism for the enormously promoted photocatalytic behaviour is brought forth on the basis of the energy-band structure combined with experimental results.
Project description:This work presents a method for synthesis of high-yield, uniform and band gap tunable Zn2SnO4 nanocubes. These nanocubes can be further self-assembled into a series of novel nanofilms with tunable optical band gaps from 3.54 to 3.18 eV by simply increasing the heat treatment temperature. The Zn2SnO4 nanocube-nanofilm based device has been successfully fabricated and presents obviously higher photocurrent, larger photocurrent to dark current ratio than the previously reported individual nanostructure-based UV-light photodetectors, and could be used in high performance photodetectors, solar cells, and electrode materials for Li-ion battery.
Project description:Development of ternary metal oxide (TMO) based electron transporting layer (ETL) for perovskite solar cell open a new approaches toward efficient a unique strategy for solid state dye-sensitized solar cells (ssDSSCs). In the present investigation, highly porous zinc tin oxide (Zn2SnO4) scaffold nanofibers has been synthesized by electrospinning technique and successfully used for methyl ammonium lead halide (CH3NH3PbI3) perovskite sensitized solid state solar cells. The fabricated optimized perovskite solar cell devices exhibited 7.38% power conversion efficiency (PCE) with open circuit voltage (VOC) 0.986 V, current density (JSC) = 12.68 mAcm(-2) and fill factor (FF) 0.59 under AM 1.5 G sunlight (100 mWcm(-2)) which is higher than Zn2SnO4 nanoparticle (η = 2.52%) based perovskite solar cells. This improvement is achieved due to high porosity of Zn2SnO4 nanofibers and high crystallinity of the nanofibers synthesized at 700 °C. These results are remarkably higher than reported perovskite solar cells based on such type of ternary metal oxide ETLs.
Project description:Resistive switching (RS) devices are widely believed as a promising candidate for next generation nonvolatile resistance random access memory. Here, Zn2SnO4-sheathed ZnO core/shell heterostructure nanowires were constructed through a polymeric sol-gel approach followed by post-annealing. The back-to-back bipolar RS properties were observed in the Ohmic contact two-terminal devices based on individual core/shell nanowires. With increasing bias to about 1.5 V, it changes from high-resistance states (HRS) to low-resistance states, and however, it can be restored to HRS by reverse bias. We propose a new mechanism, which is attributed to the injection of electrons into/from interfacial states, arising from the lattice mismatch at ZnO/Zn2SnO4 heterointerface. Upon applying negative/positive voltage at one end of devices, where interfacial states are filled/emptied, barrier will be eliminated/created, resulting into symmetric RS characteristics. The behavior of storage and removal charges demonstrates that the heterostructures have excellent properties for the application in resistance random access memory.
Project description:A 0.4C-2Si-1Cr-1Mo steel with an ultrafine elongated grain (UFEG) structure and an ultrafine equiaxed grain (UFG) structure was fabricated by multipass caliber rolling at 773 K and subsequent annealing at 973 K. A static three-point bending test was conducted at ambient temperature and at 77 K. The strength-toughness balance of the developed steels was markedly better than that of conventionally quenched and tempered steel with a martensitic structure. In particular, the static fracture toughness of the UFEG steel, having a yield strength of 1.86 GPa at ambient temperature, was improved by more than 40 times compared with conventional steel having a yield strength of 1.51 GPa. Furthermore, even at 77 K, the fracture toughness of the UFEG steel was about eight times higher than that of the conventional and UFG steels, despite the high strength of the UFEG steel (2.26 GPa). The UFG steel exhibited brittle fracture behavior at 77 K, as did the conventional steel, and no dimple structure was observed on the fracture surface. Therefore, it is difficult to improve the low-temperature toughness of the UFG steel by grain refinement only. The shape of crystal grains plays an important role in delamination toughening, as do their refinement and orientation.
Project description:High-carbon martensite steels (with C?>?0.5?wt.%) are very hard but at the same time as brittle as glass in as-quenched or low-temperature-tempered state. Such extreme brittleness, originating from a twin microstructure, has rendered these steels almost useless in martensite state. Therefore, for more than a century it has been a common knowledge that high-carbon martensitic steels are intrinsically brittle and thus are not expected to find any application in harsh loading conditions. Here we report that these brittle steels can be transformed into super-strong ones exhibiting a combination of ultrahigh strength and significant toughness, through a simple grain-refinement treatment, which refines the grain size to ~4??m. As a result, an ultra-high tensile strength of 2.4~2.6?GPa, a significant elongation of 4~10% and a good fracture toughness (K1C) of 23.5~29.6?MPa m1/2 were obtained in high-carbon martensitic steels with 0.61-0.65?wt.% C. These properties are comparable with those of "the king of super-high-strength steels"-maraging steels, but achieved at merely 1/30~1/50 of the price. The drastic enhancement in mechanical properties is found to arise from a transition from the conventional twin microstructure to a dislocation one by grain refinement. Our finding may provide a new route to manufacturing super-strong steels in a simple and economic way.
Project description:Nanosized aluminum-doped zinc oxide Zn1-xAlxO (AZO) powders (AZO-NPs) with x = 0.01, 0.03, 0.06, 0.09 and 0.11 were synthesized by chemical precipitation method. The thermogravimetric analysis (TGA) indicated that the precursors were converted to oxides from hydroxides near 250 °C, which were then heated to 500 °C for subsequent thermal processes to obtain preliminary powders. The obtained preliminary powders were then calcined at 500 °C for three hours. The structure and morphology of the products were measured and characterized by angle-dispersive X-ray diffraction (ADXRD) and scanning electron microscopy (SEM). ADXRD results showed that AZO-NPs with Al content less than 11% exhibited würtzite zinc oxide structure and there was no other impurity phase in the AZO-NPs, suggesting substitutional doping of Al on Zn sites. The Zn0.97Al0.03O powders (A₃ZO-NPs) with grain size of about 21.4 nm were used for high-pressure measurements. The in situ ADXRD measurements revealed that, for loading run, the pressure-induced würtzite (B4)-to-rocksalt (B1) structural phase transition began at 9.0(1) GPa. Compared to the predicted phase-transition pressure of ~12.7 GPa for pristine ZnO nanocrystals of similar grain size (~21.4 nm), the transition pressure for the present A₃ZO-NPs exhibited a reduction of ~3.7 GPa. The significant reduction in phase-transition pressure is attributed to the effects of highly selective site occupation, namely Zn2+ and Al3+, were mainly found in tetrahedral and octahedral sites, respectively.
Project description:A facile sol-gel process was used for synthesis of LiFe(MoO4)2 microcrystals. The effects of sintering temperature on the microstructures and electrochemical performances of the as-synthesized samples were systematically investigated through XRD, SEM and electrochemical performance characterization. When sintered at 650°C, the obtained LiFe(MoO4)2 microcrystals show regular shape and uniform size distribution with mean size of 1-2 ?m. At the lower temperature (600°C), the obtained LiFe(MoO4)2 microcrystals possess relative inferior crystallinity, irregular morphology and vague grain boundary. At the higher temperatures (680 and 700°C), the obtained LiFe(MoO4)2 microcrystals are larger and thicker particles. The electrochemical results demonstrate that the optimized LiFe(MoO4)2 microcrystals (650°C) can deliver a high discharge specific capacity of 925 mAh g-1 even at a current rate of 1 C (1,050 mA g-1) after 500 cycles. Our work can provide a good guidance for the controllable synthesis of other transition metal NASICON-type electrode materials.
Project description:We developed a unique strategy for fabricating hierarchically structured (nanoparticles-in-beads) Zn2SnO4 beads (ZTO-Bs), which were then used to produce ternary metal oxide-based dye-sensitized solar cells (DSSCs). DSSCs were fabricated using the ZTO-Bs as the photoelectrodes and highly absorbable organic dyes as the sensitizers. The DSSCs based on the ZTO-Bs and the organic dyes (SJ-E1 and SJ-ET1) exhibited the highest performance ever reported for DSSCs with ternary metal oxide-based photoelectrodes. The optimized DSSCs exhibited a power conversion efficiency of 6.3% (V(OC) of 0.71?V, J(SC) of 12.2?mA cm(-2), FF of 0.72), which was much higher than that for DSSCs with conventional ZTO-NPs-based photoelectrodes or those based on the popular ruthenium-based dye, N719. The unique morphology of the ZTO-Bs allowed for improvements in dye absorption, light scattering, electrolyte penetration, and the charge recombination lifetime, while the organic dyes resulted in high molar absorbability.