Determination of Band Structure of Naturally Occurring Goethite with Al Substitution: A Case Study of Zhushan Iron Zone.

The photocatalytic property of Fe oxide minerals has long been considered to play an important role in shaping modern terrestrial environments. However, due to the complexity of natural settings, a precise determination of the band structure of natural goethite has not been achieved. In this work, the mineralogical characteristics of natural goethite samples obtained from Zhushan, China, were systematically studied through X-ray diffraction, transmission electron microscopy, X-ray energy dispersive spectroscopy, and X-ray fluorescence spectroscopy. Afterward, the band structure for both natural and synthetic goethite samples was determined by synchrotron-based X-ray absorption and emission spectra and photoelectron spectroscopy. The band gap of natural goethite (2.25 eV) was narrower than that of its synthetic counterpart (2.55 eV), and the valence band position of natural goethite was slightly lifted (-5.06 eV) compared to that of synthetic goethite (-5.38 eV). Al doping in natural goethite crystal, as revealed by the mineralogical tests, was the main reason that contributed to this difference. The theoretical calculation showed the narrowed band gap was caused by the contribution of Al-2p orbits at the top of the valence band. Therefore, free electrons can be created under light irradiation with a shorter wavelength. The experiments showed that natural goethite can photo-catalytically degrade methyl orange, and the degradation efficiency was better (47.5%) than that of the synthetic goethite group (31.5%). This study, for the first time, revealed the band structure and confirmed the photocatalytic properties of natural goethite, which should play an important role in surface substance evolution and elemental cycling.

Organochlorine Pesticides in Karst Soil: Levels, Distribution, and Source Diagnosis.

Excessive reclamation and improper use of agrochemicals in karst areas leads to serious non-point source pollution, which is of great concern and needs to be controlled, since contaminants can easily pollute groundwater due to the thin patchy soil and developed karst structures. The occurrences of organochlorine pesticides (OCPs) in karst soil were investigated by analyzing 25 OCPs in the karst soils near the Three Gorges Dam, China. The total concentrations of OCPs ranged 161-43,100 (6410 ± 9620) pg/g, with the most abundant compounds being p,p'-DDT and mirex. The concentration differences between the orchard and vegetable field and between upstream and downstream presented the influences of land-use type and water transport on the OCP spatial distributions. Composition analysis indicated the possible fresh inputs of lindane, technical DDT, aldrin, endrin, mirex, and methoxychlor. Their illegal uses implied an insufficient agrochemical management system in undeveloped karst areas. Principal component analysis with multiple linear regression analysis characterized the dominant sources from current agricultural use and current veterinary use in the study area. OCPs in the soils might not pose significant cancer risk for the residents, but they need to be controlled due to their illegal uses and bioaccumulation effect via the food chain.

Rapid Preparation of MWCNTs/Epoxy Resin Nanocomposites by Photoinduced Frontal Polymerization.

Due to their excellent mechanical and thermal properties and medium resistance, epoxy/carbon nanotubes and nanocomposites have been widely used in many fields. However, the conventional thermosetting process is not only time- and energy-consuming, but also causes the agglomeration of nanofillers, which leads to unsatisfactory properties of the obtained composites. In this study, multi-walled carbon nanotubes (MWCNTs)/epoxy nanocomposites were prepared using UV photoinduced frontal polymerization (PIFP) in a rapid fashion. The addition of MWCNTs modified by a surface carboxylation reaction was found to enhance the impact strength and heat resistance of the epoxy matrix effectively. The experimental results indicate that with 0.4 wt % loading of modified MWCNTs, increases of 462.23% in the impact strength and 57.3 °C in the glass transition temperature Tg were achieved. A high-performance nanocomposite was prepared in only a few minutes using the PIFP approach. Considering its fast, energy-saving, and environmentally friendly production, the PIFP approach displays considerable potential in the field of the fast preparation, repair, and deep curing of nanocomposites and coatings.

Piezoelectricity in Multilayer Black Phosphorus for Piezotronics and Nanogenerators.

Recently, piezoelectric characteristics have been a research focus for 2D materials because of their broad potential applications. Black phosphorus (BP) is a monoelemental 2D material predicted to be piezoelectric because of its highly directional properties and non-centrosymmetric lattice structure. However, piezoelectricity is hardly reported in monoelemental materials owing to their lack of ionic polarization, but piezoelectric generation is consistent with the non-centrosymmetric structure of BP. Theoretical calculations of phosphorene have explained the origin of piezoelectric polarization among P atoms. However, the disappearance of piezoelectricity in multilayer 2D material generally arises from the opposite orientations of adjacent atomic layers, whereas this effect is limited in BP lattices due to their spring-shaped space structure. Here, the existence of in-plane piezoelectricity is experimentally reported for multilayer BP along the armchair direction. Current-voltage measurements demonstrate a piezotronic effect in this orientation, and cyclic compression and release of BP flakes show an intrinsic current output as large as 4 pA under a compressive strain of -0.72%. The discovery of piezoelectricity in multilayer BP can lead to further understanding of this mechanism in monoelemental materials.

Piezo-phototronic Effect Enhanced Efficient Flexible Perovskite Solar Cells.

Tremendous work has been made recently to improve the power conversion efficiencies (PCEs) of perovskite solar cells (PSCs); the best reported value is now over 23%. However, further improving the PCEs of PSCs is challenged by material properties, device stability, and packaging technologies. Here, we report a new approach to increase the PCEs of flexible PSCs via introducing the piezo-phototronic effect in the PSCs by growing an array of ZnO nanowires on flexible plastic substrates, which act as the electron-transport layer for PSCs. From the piezo-phototronic effect, the absolute PCE was improved from 9.3 to 12.8% for flexible perovskite solar cells under a static mechanical strain of 1.88%, with a ∼40% enhancement but no change in the components of materials and device structure. A corresponding working model was proposed to elucidate the strategy to boost the performance of the PSCs. These findings present a general approach to improve PCEs of flexible PSCs without changing their fundamental materials.

Controllable Growth of Aligned Monocrystalline CsPbBr3 Microwire Arrays for Piezoelectric-Induced Dynamic Modulation of Single-Mode Lasing.

CsPbBr3 shows great potential in laser applications due to its superior optoelectronic characteristics. The growth of CsPbBr3 wire arrays with well-controlled sizes and locations is beneficial for cost-effective and largely scalable integration into on-chip devices. Besides, dynamic modulation of perovskite lasers is vital for practical applications. Here, monocrystalline CsPbBr3 microwire (MW) arrays with tunable widths, lengths, and locations are successfully synthesized. These MWs could serve as high-quality whispering-gallery-mode lasers with high quality factors (>1500), low thresholds (<3 µJ cm-2 ), and long stability (>2 h). An increase of the width results in an increase of the laser quality and the resonant mode number. The dynamic modulation of lasing modes is achieved by a piezoelectric polarization-induced refractive index change. Single-mode lasing can be obtained by applying strain to CsPbBr3 MWs with widths between 2.3 and 3.5 µm, and the mode positions can be modulated dynamically up to ≈9 nm by changing the applied strain. Piezoelectric-induced dynamic modulation of single-mode lasing is convenient and repeatable. This method opens new horizons in understanding and utilizing the piezoelectric properties of lead halide perovskites in lasing applications and shows potential in other applications, such as on-chip strain sensing.

Large and Ultrastable All-Inorganic CsPbBr3 Monocrystalline Films: Low-Temperature Growth and Application for High-Performance Photodetectors.

Stability is a key problem that hinders the practical application of lead halide perovskite. Therefore, all-inorganic perovskite CsPbX3 monocrystalline films are urgently needed to fabricate photoelectric devices. Herein, a low-temperature and substrate-independent growth method is demonstrated to grow millimeter-level inorganic perovskite monocrystalline thin films. These films present good optical and electrical properties comparable to bulk ones. What is more, they exhibit excellent long-term stability toward humidity and thermal treatment. The as-grown CsPbBr3 monocrystalline films are then fabricated into photodetectors with high photodetection performance. These results demonstrate that the CsPbBr3 monocrystalline films have potential in fabricating high-performance optoelectronic devices.

In2O3 Nanowire Field-Effect Transistors with Sub-60 mV/dec Subthreshold Swing Stemming from Negative Capacitance and Their Logic Applications.

Heat dissipation is a key issue for scaling metal-oxide-semiconductor field-effect transistors (MOSFETs). The Boltzmann distribution of electrons imposes a physical limit on the subthreshold swing (SS), which impedes both the reduction of the switching energy and the further increase of the device density. The negative capacitance effect is proposed to rescue MOSFETs from this phenomenon called "Boltzmann tyranny". Herein, we report In2O3 nanowire (NW) transistors with SS values in the sub-60 mV/dec region, which utilize the ferroelectric P(VDF-TrFE) as the dielectric layer. An ultralow SS down to ∼10 mV/dec is observed and spans over 5 orders of magnitude in the drain current. Meanwhile, a high on/off ratio of more than 108 and a transconductance ( gm) of 2.3 µS are obtained simultaneously at Vd = 0.1 V. The results can be understood by the "voltage amplification" effect induced from the negative capacitance effect. Moreover, the steep slope FET-based inverters indicate a high voltage gain of 41.6. In addition to the NOR and NAND gates, the Schmitt trigger inverters containing only one steep slope FET are demonstrated. This work demonstrates an avenue for low-power circuit design with a steep SS.

Progress in piezo-phototronic effect modulated photovoltaics.

Wurtzite structured materials, like ZnO, GaN, CdS, and InN, simultaneously possess semiconductor and piezoelectric properties. The inner-crystal piezopotential induced by external strain can effectively tune/control the carrier generation, transport and separation/combination processes at the metal-semiconductor contact or p-n junction, which is called the piezo-phototronic effect. This effect can efficiently enhance the performance of photovoltaic devices based on piezoelectric semiconductor materials by utilizing the piezo-polarization charges at the junction induced by straining, which can modulate the energy band of the piezoelectric material and then accelerate or prevent the separation process of the photon-generated electrons and vacancies. This paper introduces the fundamental physics principles of the piezo-phototronic effect, and reviews recent progress in piezo-phototronic effect enhanced solar cells, including solar cells based on semiconductor nanowire, organic/inorganic materials, quantum dots, and perovskite. The piezo-phototronic effect is suggested as a suitable basis for the development of an innovative method to enhance the performance of solar cells based on piezoelectric semiconductors by applied extrinsic strains, which might be appropriate for fundamental research and potential applications in various areas of optoelectronics.