MOFs-Derived Strategy and Ternary Alloys Regulation in Flower-Like Magnetic-Carbon Microspheres with Broadband Electromagnetic Wave Absorption.

Broadband electromagnetic (EM) wave absorption materials play an important role in military stealth and health protection. Herein, metal-organic frameworks (MOFs)-derived magnetic-carbon CoNiM@C (M = Cu, Zn, Fe, Mn) microspheres are fabricated, which exhibit flower-like nano-microstructure with tunable EM response capacity. Based on the MOFs-derived CoNi@C microsphere, the adjacent third element is introduced into magnetic CoNi alloy to enhance EM wave absorption performance. In term of broadband absorption, the order of efficient absorption bandwidth (EAB) value is Mn > Fe = Zn > Cu in the CoNiM@C microspheres. Therefore, MOFs-derived flower-like CoNiMn@C microspheres hold outstanding broadband absorption and the EAB can reach up to 5.8 GHz (covering 12.2-18 GHz at 2.0 mm thickness). Besides, off-axis electron holography and computational simulations are applied to elucidate the inherent dielectric dissipation and magnetic loss. Rich heterointerfaces in CoNiMn@C promote the aggregation of the negative/positive charges at the contacting region, forming interfacial polarization. The graphitized carbon layer catalyzed by the magnetic CoNiMn core offered the electron mobility path, boosting the conductive loss. Equally importantly, magnetic coupling is observed in the CoNiMn@C to strengthen the magnetic responding behaviors. This study provides a new guide to build broadband EM absorption by regulating the ternary magnetic alloy.

Extraction-Dominated Temperature Degradation of Population Inversion in Terahertz Quantum Cascade Lasers.

Degraded population inversion (PI) at elevated temperature, regarded as an important temperature degradation factor in terahertz quantum cascade lasers (THz QCL), has hindered the widespread use of these devices. Herein, the mechanism of the temperature degradation of PI is investigated microscopically. It is demonstrated that the limited extraction efficiency of the extraction system dominates the decrease of PI at elevated temperatures. To be specific, the increased temperature brings about intense thermally activated longitudinal optical phonon scattering, leading to large amounts of electrons scattering to lower level state. In this case, the resonant-phonon extraction system is incapable of depleting all the electrons from lower level states. So even though the resonant-tunneling injection seems efficient enough to compensate the electron runoff at the upper state, the electron density at lower level state increases and the overall PI turns out lower. In addition, it is found that strong electron-ionized donor separation at high temperature can induce level misalignment, which can stagger the optimal conditions of injection and extraction. Also, the extraction efficiency gets lower as the extraction system requires accurate coupling between several energy levels.

Insights into Growth-Oriented Interfacial Modulation within Semiconductor Multilayers.

Interfacial engineering plays a crucial role in regulating the quality and property of heterogeneous structures, especially for nanometer-scaled devices. However, traditional methods for interfacial modulation (IFM) generally treat all the interfaces uniformly, neglecting the inherent disparities of interfaces like their growth sequence. Herein, it is found that the growth-oriented characteristic of IFM strongly determines the main regions where the modulation takes effect. Specifically, in a semiconductor quantum well structure, the arsenic atoms modulated at the well-on-barrier (WoB) interface tend to diffuse into and thus affect the next-grown well layer. In contrast, the arsenic atoms introduced at the barrier-on-well (BoW) interface mainly take effect within the next-grown barrier layer. According to theoretical simulations and electron holography (EH) experiments, the depth of quantum wells and the height of potential barriers are extended by introducing arsenic atoms at WoB and BoW interfaces, respectively. Resultantly, while modulating at the BoW interface has little impact on the photoluminescence (PL) spectrum, applying IFM at the WoB interface could dramatically improve the luminescent intensity (about 30%), which demonstrates the impact of the growth-oriented characteristic. Furthermore, in situ bias EH results indicate that IFM at the WoB interface helps to suppress the quantum-confined Stark effect.

Domino Effect of Thickness Fluctuation on Subband Structure and Electron Transport within Semiconductor Cascade Structures.

Effectively restraining random fluctuation of layer thickness (RFT) during the thin-film epitaxy plays an essential part in improving the quality of low-dimensional materials for device application. While it is already challenging to obtain an ideal growth condition for thickness control, the tangle of RFT with interfacial problems makes it even more difficult to guarantee the properties of heterostructures and the performance of devices. In our research, the RFT of potential barriers and wells within a semiconductor multilayer is demonstrated to correlate with the interfacial grading effect (IFG) and to affect the band offset strongly. Then, the synergetic effect of RFT and IFG that serves as the first domino is shown to impact the subband structure and the electron transport successively. On the basis of an investigation of a quantum cascade structure, statistical results indicate a normal distribution of RFT with a standard deviation of about 1 Å and an extreme value of 3 Å (about one monolayer) for all the layers within 38 cascade periods. The "seemingly negligible" RFT could actually reduce the conduction band offset for tens to hundreds of meV and alter the subband gaps at a rate of 40 meV/monolayer at most. Furthermore, the dependence of different subband gaps on the barrier/well thickness differs from one another. In addition, the distribution of wave function could also be regulated dramatically by RFT to change the type of electron transition and thus the carrier lifetime. Further impacts of RFT and the RFT-modulated subband alignment on electron transport result in two different mechanisms (injection-dominant and extraction-dominant) of electron population inversion (PI), which is manifested by comparatively discussing the results of in situ electron holography and macro performances.

Control of electron tunnelling by fine band engineering of semiconductor potential barriers.

Quantum tunnelling (QTN) devices show a promising future for energy saving and ultrafast operation thanks to the unprecedented development of two-dimensional materials. However, the immature techniques for device fabrication hamper severely their further progress and application. To overcome such a challenge, the abundant processing technology used in semiconductor electronics is worth considering. Herein, a device prototype is fabricated based on band engineering to enable flexible control of QTN probability (TP) within a III-V semiconductor multilayer. While the initial heights of all barriers are set to obtain similar TPs under no bias, the conduction band slopes of InGaSb and AlSb barriers are modulated to a state where their TPs vary reversely under electric fields. On this basis, revealed by in situ bias electron holography, a unidirectional accumulation of electrons has been realized inside the multilayer structure. Moreover, the inevitable element segregation/diffusion during device growth plays a key role in band structure optimization, which is confirmed by strain analysis. The feasibility of the above modulation strategy is also confirmed by theoretical simulations. Our findings might provide a new perspective on the innovation of semiconductor devices and the application of QTN effect.

Heterointerface-Driven Band Alignment Engineering and its Impact on Macro-Performance in Semiconductor Multilayer Nanostructures.

Interfaces in semiconductor heterostructures is of continuously greater significance in the trend of scaling materials down to the atomic limit. Since atoms tend to behave more irregularly around interfaces than in internal materials, accurate energy band alignment becomes a major challenge, which determines the ultimate performance of devices. Therefore, a comprehensive understanding of the interplay between heterointerface, energy band, and macro-performance is desiderated. Here, such interplay is explored by investigating asymmetric heterointerfaces with identical fabrication parameters in multiple-quantum-well lasers. The unexpected asymmetry derives from the atomic discrepancy around heterointerfaces, which ultimately improves the optical property through altered valence band offsets. Strain and charge distribution around heterointerfaces are characterized via geometric phase analysis and in situ bias electron holography, respectively. Combining experiments with theories, arsenic-enrichment at one of the interfaces is considered the origin of asymmetry. To reveal actual band alignment, valence band model is modified focusing on the transition around heterojunctions. The enhanced photoluminescence intensity reflects the alleviation of hole confinement insufficiency and the enlargement of valence band offset. The results help to advance the understanding of the general problem of interface in nanostructures and provide guidance applicable to various scenarios for micro-macro correlation.

CoNi@SiO2 @TiO2 and CoNi@Air@TiO2 Microspheres with Strong Wideband Microwave Absorption.

The synthesis of CoNi@SiO2 @TiO2 core-shell and CoNi@Air@TiO2 yolk-shell microspheres is reported for the first time. Owing to the magnetic-dielectric synergistic effect, the obtained CoNi@SiO2 @TiO2 microspheres exhibit outstanding microwave absorption performance with a maximum reflection loss of -58.2 dB and wide bandwidth of 8.1 GHz (8.0-16.1 GHz, < -10 dB).

Inheritance of Crystallographic Orientation during Lithiation/Delithiation Processes of Single-Crystal α-Fe2O3 Nanocubes in Lithium-Ion Batteries.

Iron oxides are very promising anode materials based on conversion reactions for lithium-ion batteries (LIBs). During conversion processes, the crystal structure and composition of the electrode material are drastically changed. Surprisingly, in our study, inheritance of a crystallographic orientation was found during lithiation/delithiation processes of single-crystal α-Fe2O3 nanocubes by ex situ transmission electron microscopy. Single-crystal α-Fe2O3 was first transformed into numerous Fe nanograins embedded in a Li2O matrix, and then the conversion between Fe and FeO nanograins became the main reversible electrochemical reaction for energy storage. Interestingly, these Fe/FeO nanograins had almost the same crystallographic orientation, indicating that the lithiated/delithiated products can inherit the crystallographic orientation of single-crystal α-Fe2O3. This finding is important for understanding the detailed electrochemical conversion processes of iron oxides, and this feature may also exist during lithiation/delithiation processes of other transition-metal oxides.

Porous Au-Ag Alloy Particles Inlaid AgCl Membranes As Versatile Plasmonic Catalytic Interfaces with Simultaneous, in Situ SERS Monitoring.

We present a novel porous Au-Ag alloy particles inlaid AgCl membrane as plasmonic catalytic interfaces with real-time, in situ surface-enhanced Raman spectroscopy (SERS) monitoring. The Au-Ag alloy particles inlaid AgCl membranes were obtained via a facile two-step, air-exposed, and room-temperature immersion reaction with appropriate annealing process. Owing to the designed integration of semiconductor component AgCl and noble metal Au-Ag particles, both the catalytic reduction and visible-light-driven photocatalytic activities toward organic contaminants were attained. Specifically, the efficiencies of about 94% of 4-nitrophenol (4-NP, 5 × 10(-5) M) reduction after 8 min of reaction, and degradation of rhodamine 6G (R6G, 10(-5) M) after 12 min of visible light irradiation were demonstrated. Moreover, efficiencies of above 85% of conversion of 4-NP to 4-aminophenol (4-AP) and 90% of R6G degradation were achieved as well after 6 cycles of reactions, by which robust recyclability was confirmed. Further, with distinct SERS signals generated simultaneously from the surfaces of Au-Ag particles under laser excitation, in situ SERS monitoring of the process of catalytic reactions with superior sensitivity and linearity has been realized. Overall, the capability of the Au-Ag particles inlaid AgCl membranes to provide SERS monitored catalytic and visible-light-driven photocatalytic conversion of organic pollutants, along with their mild and cost-effective fabrication method, would make sense for in-depth understanding of the mechanisms of (photo)catalytic reactions, and also future development of potable, multifunctional and integrated catalytic and sensing devices.

Ultrathin ß-Ni(OH)2 nanoplates vertically grown on nickel-coated carbon nanotubes as high-performance pseudocapacitor electrode materials.

Various metal hydroxides/oxides grown on conductive substrates such as nickel foam have been reported and studied as supercapacitor electrode materials. However, the capacitances of these electrodes are extremely limited because of the low content of active materials grown on the limited surface of nickel foam. To achieve high capacitance, we use nickel-coated carbon nanotubes (Ni-CNTs) as the conductive substrate for the growth of ß-Ni(OH)2. By a facile chemical method, ultrathin ß-Ni(OH)2 nanoplates are vertically grown on the surface of Ni-CNTs. The density, thickness, and content of ß-Ni(OH)2 can be easily controlled by modulating the ratio of NiCl2·6H2O to Ni-CNTs. This hierarchical nanostructure can provide remarkable synergistic effects: facilitate electron and ion transport and accelerate the reversible redox reactions. As-prepared Ni-CNTs@ß-Ni(OH)2 composites exhibit high specific capacitances (∼1807 F g(-1) at 2 A g(-1), based on the mass of ß-Ni(OH)2; ∼1283 F g(-1) at 2 A g(-1), based on the mass of composite), good rate capabilities, and excellent cycling stabilities. This strategy has potential for large-scale production and can be applied to the preparation of other hierarchical nanostructured metal hydroxide/oxide composites.

Polarization enhancement of microwave absorption by increasing aspect ratio of ellipsoidal nanorattles with Fe3O4 cores and hierarchical CuSiO3 shells.

The shape anisotropy of the nanostructured nanorattles is one of the key factors that affect their microwave absorption performance. In the present study, the microwave absorption performance of ellipsoidal Fe3O4@CuSiO3 nanorattles with different aspect ratios was investigated. Results demonstrated that the ellipsoidal nanorattles with the aspect ratio of 3-4 exhibited about 20% enhancement of microwave absorption intensity compared with spherical Fe3O4@CuSiO3. Generally, as the aspect ratio increased from 2.0 to 3.5, the microwave absorption peak was enhanced monotonously from -20 dB to -30 dB. It was found that the ellipsoidal nanorattles with larger aspect ratio exhibited higher coercivity and double resonance peaks of the real part of complex permittivity, resulting in the improvement of microwave absorption performance. Our research gives insights into the understanding of the anisotropic effect of nanorattles on microwave absorption performance.

Ultrathin BaTiO3 nanowires with high aspect ratio: a simple one-step hydrothermal synthesis and their strong microwave absorption.

In this paper, we report the facile synthesis of ultrathin barium titanate (BaTiO3) nanowires with gram-level yield via a simple one-step hydrothermal treatment. Our BaTiO3 nanowires have unique features: single crystalline, uniform size distribution and ultra high aspect ratio. The synergistic effects including both Ostwald ripening and cation exchange reaction are responsible for the growth of the ultrathin BaTiO3 nanowires. The microwave absorption capability of the ultrathin BaTiO3 nanowires is improved compared to that of BaTiO3 nanotorus,1 with a maximum reflection loss as high as -24.6 dB at 9.04 GHz and an absorption bandwidth of 2.4 GHz (<-10 dB). Our method has some novel advantages: simple, facile, low cost and high synthesis yield, which might be developed to prepare other ferroelectric nanostructures. The strong microwave absorption property of the ultrathin BaTiO3 nanowires indicates that these nanowires could be used as promising materials for microwave-absorption and stealth camouflage techniques.

Microwave absorption enhancement, magnetic coupling and ab initio electronic structure of monodispersed (Mn(1-x)Co(x))3O4 nanoparticles.

Monodispersed manganese oxide (Mn1-xCox)3O4 (0 ≤ x ≤ 0.5) nanoparticles, less than 10 nm size, are respectively synthesized via a facile thermolysis method at a rather low temperature, ranging from 90 to 100 °C, without any inertia gas for protection. The influences of the Co dopant content on the critical reaction temperature required for the nanoparticle formation, electronic band structures, magnetic properties, and the microwave absorption capability of (Mn1-xCox)3O4 are comprehensively investigated by means of both experimental and theoretical approaches including powder X-ray diffraction (XRD), electron energy loss spectroscopy (EELS), super conductivity quantum interference device (SQUID) examination, and first-principle simulations. Co is successfully doped into the Mn atomic sites of the (Mn1-xCox)3O4 lattice, which is further confirmed by EELS data acquired from one individual nanoparticle. Therefore, continuous solid solutions of well-crystallized (Mn1-xCox)3O4 products are achieved without any impurity phase or phase separation. With increases in the Co dopant concentration x from 0 to 0.5, the lattice parameters change systemically, where the overall saturation magnetization at 30 K increases due to the more intense coupling of the 3d electrons between Mn and Co, as revealed by simulations. The microwave absorption properties of the (Mn1-xCox)3O4 nanoparticles are examined between 2 and 18 GHz. The maximum absorption peak -11.0 dB of the x = 0 sample is enhanced to -11.5 dB for x = 0.2, -12.7 dB for x = 0.25, -15.6 dB for x = 0.33, and -24.0 dB for x = 0.5 respectively, suggesting the Co doping effects. Our results might provide novel insights into the understanding of the influences of metallic ion doping on the electromagnetic properties of metallic oxide nanomaterials.