Magnetic alignment experiment of fine graphite-crystals dispersed in He gas oriented to study alignment of crystalline-axes of nano-sized non-magnetic particles

The ensemble of nano-sized crystals is expected to attain additional physical properties when preferential alignments of certain crystal-axes are achieved by a magnetic field. The reduction of temperature T may realize alignment even if the mole number of the particle N and the diamagnetic anisotropy per mole (Deltachi)(DIA) are considerably small for the nano-sized diamagnetic oxides, since alignment proceeds by the balance between the energy of rotational Brownian motion and field-induced anisotropy energy. Alignment of various basic inorganic oxides such as gypsum, quartz, forsterite, KDP or calcite, having a size of 20 nm diameter, is expected to occur by a field intensity of approximately 50 T at T = 10 K; this intensity is presently available at a high magnetic-field laboratory. It is expected that the magnetic alignment of nano-sized particles can be observed by dispersing the particles in He gas, as achieved recently for micron-sized graphite crystals; a cryogenic liquid cannot be used as a dispersing medium. Measured (Deltachi)(DIA) values accumulated for basic inorganic-oxides are explained quantitatively by assuming that individual bonding-orbital composing the material possesses a constant amount of diamagnetic anisotropy; hence the majority of diamagnetic nano-sized insulators are expected to show magnetic alignment at finite field intensity.     

Graphene-Based Heterostructure Composite Sensing Materials for Detection of Nitrogen-Containing Harmful Gases

Graphene-based heterostructure composite is a new type of advanced sensing material that includes composites of graphene with noble metals/metal oxides/metal sulfides/polymers and organic ligands. Exerting the synergistic effect of graphene and noble metals/metal oxides/metal sulfides/polymers and organic ligands is a new way to design advanced gas sensors for nitrogen-containing gas species including NH₃ and NO₂ to solve the problems such as poor stability, high working temperature, poor recovery, and poor selectivity. Different fabrication methods of graphene-based heterostructure composite are extensively studied, enabling massive progress in developing chemiresistive-type sensors for detecting the nitrogen-containing gas species. With the components of noble metals/metal oxides/metal sulfides/polymers and organic ligands which are composited with graphene, each material has its attractive and unique electrical properties. Consequently, the corresponding composite formed with graphene has different sensing characteristics. Furthermore, working ambient gas and response type can affect gas-sensitive characteristic parameters of graphene-based heterostructure composite sensing materials. Moreover, it requires particular attention in studying gas sensing mechanism of graphene-based heterostructure composite sensing materials for nitrogen-containing gas species. This review focuses on related scientific issues such as material synthesis methods, sensing performance, and gas sensing mechanism to discuss the technical challenges and several perspectives.     

Non‐Noble‐Metal‐Based Electrocatalysts toward the Oxygen Evolution Reaction

The development of low‐cost, high‐efficiency, and robust electrocatalysts for the oxygen evolution reaction (OER) is urgently needed to address the energy crisis. In recent years, non‐noble‐metal‐based OER electrocatalysts have attracted tremendous research attention. Beginning with the introduction of some evaluation criteria for the OER, the current OER electrocatalysts are reviewed, with the classification of metals/alloys, oxides, hydroxides, chalcogenides, phosphides, phosphates/borates, and other compounds, along with their advantages and shortcomings. The current knowledge of the reaction mechanisms and practical applications of the OER is also summarized for developing more efficient OER electrocatalysts. Finally, the current states, challenges, and some perspectives for non‐noble‐metal‐based OER electrocatalysts are discussed.     

高角环形暗场成像方法测定负载型纳米贵金属催化剂的粒径

高角环形暗场(HAADF)像的衬度与样品中平均原子序数的平方成正比,并且具有原子尺度的分辨率,因此可以有效地区分贵金属颗粒和催化剂载体,非常适于测量负载型纳米贵金属催化剂中活性中心颗粒的粒径.本文以Pd/ZnO催化剂为例,介绍利用HAADF成像法测定负载型纳米贵金属催化剂中贵金属粒径的方法.     

Plasmonic Enhancement or Energy Transfer? On the Luminescence of Gold‐, Silver‐, and Lanthanide‐Doped Silicate Glasses and Its Potential for Light‐Emitting Devices

With the technique of synchrotron X‐ray activation, molecule‐like, non‐plasmonic gold and silver particles in soda‐lime silicate glasses can be generated. The luminescence energy transfer between these species and lanthanide(III) ions is studied. As a result, a significant lanthanide luminescence enhancement by a factor of up to 250 under non‐resonant UV excitation is observed. The absence of a distinct gold and silver plasmon resonance absorption, respectively, the missing nanoparticle signals in previous SAXS and TEM experiments, the unaltered luminescence lifetime of the lanthanide ions compared to the non‐enhanced case, and an excitation maximum at 300–350 nm (equivalent to the absorption range of small noble metal particles) indicate unambiguously that the observed enhancement is due to a classical energy transfer between small noble metal particles and lanthanide ions, and not to a plasmonic field enhancement effect. It is proposed that very small, molecule‐like noble metal particles (such as dimers, trimers, and tetramers) first absorb the excitation light, undergo a singlet‐triplet intersystem crossing, and finally transfer the energy to an excited multiplet state of adjacent lanthanide(III) ions. X‐ray lithographic microstructuring and excitation with a commercial UV LED show the potential of the activated glass samples as bright light‐emitting devices with tunable emission colors.     

Effect of Ag particle size on electrical conductivity ofisotropically conductive adhesives

The present work is to introduce nanoparticles in micro-sized metal particles to study particle distribution in polymer matrix. Previous examinations of the silver-filled particles reveal that the micro-sized particle fillers appear as full density silver flakes, while nanoparticle fillers appear as highly porous agglomerates, similar to open-cell foams. Actually little work has been carried out to study the cross-sectional area of a particle-particle-contact in isotropically conductive adhesives (ICA). In this study, transmission electron microscope is chosen as a main measure to analyze the distribution of different-sized particles. The percentage of the nanoparticles varies from 20 wt% and 50 wt% to full percentage within micro-sized particles, and the total metal content in epoxy resin is 70 wt%. So the change of contact area and contact behavior with various volume ratio of nano-sized and micro-sized particles was investigated. At the same time, the electrical resistivity was measured, which is compared with the different level of the filler loading     

Radiation-induced depassivation of latent plasma damage

Plasma treatments are widely used in microelectronic industry but they may leave some residual passivated damage in the gate oxides at the end of the processing. The plasma-induced damage can be amplified by metal interconnects (antenna) attached to the gate during the plasma treatments. Ionising radiation reactivates this latent damage, which produces enhanced oxide charge and Si/SiO₂ interface state density. Two CMOS technologies have been investigated, with 5 and 7 nm gate oxides. Threshold voltage shifts, transconductance decrease, and interface traps build-up are always larger for plasma damaged devices than for reference devices.     

Re-Looking into the Active Moieties of Metal X-ides (X- = Phosph-, Sulf-, Nitr-, and Carb-) Toward Oxygen Evolution Reaction

Non-precious metal-based catalysts for oxygen evolution reaction (OER) have been extensively studied, among which the transition metal X-ides (including phosph-ides, sulf-ides, nitr-ides, and carb-ides) materials are emerging as promising candidates to replace the benchmark Ir/Ru-based materials in alkaline media. However, it is controversial whether the metal Xides host the real active sites since these metal Xides are thermodynamically unstable under a harsh OER environment—it has been reported that the initial metal Xides can be electrochemically oxidized and transformed into corresponding oxides and (oxy)hydroxides. Therefore, the metal Xides are argued as “pre-catalysts”; the electrochemically formed oxides and (oxy)hydroxides are believed as the real active moieties for OER. Herein, the recent advances in understanding the transformation behavior of metal Xides during OER are re-looked; importantly, hypotheses are provided to understand why the electrochemically formed oxides and (oxy)hydroxides catalysts derived from metal Xides are superior for OER to the as-prepared metal oxides and (oxy)hydroxides catalysts.     

Schottky barriers on atomically clean cleaved GaAs

We report here the first systematic study of the electronic properties of Al, Au, Ag and Cu Schottky barrier diodes on n-type GaAs. These diodes were formed on cleaved (110) surfaces in ultra-high vacuum (UHV) using similar conditions and evaporation rates during the initial stages of Schottky barrier formation as in the photoemission spectroscopy (PES) studies. Barrier height determinations using device measuring techniques (current-voltage (I–V), capacitive-voltage (C–-V) and internal photoemission) are compared with the results from the PES studies. Essentially identical barrier heights are found from PES and the electrical measurements for the noble metals. The barrier height of the noble metal: n-GaAs system (0.9 eV) is larger than any simple metal on n-type GaAs previously reported. This is examined in light of recent work by Zur, McGill and Smith [22] and a model is suggested to explain it. Results of this study are found to be consistent with the unified defect model which has hypothesized that the barrier height is established by the energy levels of structural defects formed at the surface during the metal deposition.     

Precious‐Metal‐Free Nanocatalysts for Highly Efficient Hydrogen Production from Hydrous Hydrazine

Hydrous hydrazine (H₂NNH₂·H₂O) has generally been considered a promising hydrogen storage carrier because of inherent advantages such as its high hydrogen content and easy recharging as a liquid. Unfortunately, the decomposition of hydrous hydrazine to H₂ is terribly sluggish and/or not entirely favored—a competing decomposition to ammonia may be preferred. This has been the case using noble‐metal catalysts and using non‐precious‐metal‐based catalysts, even at elevated temperatures. To overcome this challenge, non‐precious‐metal‐based Cu@Fe₅Ni₅ core@shell nanocatalysts are prepared using an in situ seeding‐growth approach. Unexpectedly, the catalyst exerts 100% H₂ selectivity and excellent activity and stability toward the complete decomposition of hydrous hydrazine, which is due to the synergistic effect of the core@shell structure. These promising results will certainly promote the effective application of hydrous hydrazine as a potential hydrogen storage material.     

Carbon Nanotube‐Encapsulated Noble Metal Nanoparticle Hybrid as a Cathode Material for Li‐Oxygen Batteries

Although Li‐oxygen batteries offer extremely high theoretical specific energy, their practical application still faces critical challenges. One of the main obstacles is the high charge overpotential caused by sluggish kinetics of charge transfer that is closely related to the morphology of discharge products and their distribution on the cathode. Here, a series of noble metal nanoparticles (Pd, Pt, Ru and Au) are encapsulated inside end‐opened carbon nanotubes (CNTs) by wet impregnation followed by thermal annealing. The resultant cathode materials exhibit a dramatic reduction of charge overpotentials compared to their counterparts with nanoparticles supported on CNT surface. Notably, the charge overpotential can be as low as 0.3 V when CNT‐encapsulated Pd nanoparticles are used on the cathode. The cathode also shows good stability during discharge–charge cycling. Density functional theory (DFT) calculations reveal that encapsulation of “guest” noble metal nanoparticles in “host” CNTs is able to strengthen the electron density on CNT surfaces, and to avoid the regional enrichment of electron density caused by the direct exposure of nanoparticles on CNT surface. These unique properties ensure the uniform coverage of Li₂O₂ nanocrystals on CNT surfaces instead of localized distribution of Li₂O₂ aggregation, thus providing efficient charge transfer for the decomposition of Li₂O₂.     

Metal Oxide/Polymer Hybrid Nanoparticles with Versatile Functionality Prepared by Controlled Surface Crystallization

Metal oxide/polymer hybrids are prepared from polystyrene nanoparticles functionalized at the surface with phosphonate and phosphate groups. The polymer particles are synthesized with specifically designed surface‐active monomers (surfmers) and used as nucleation surfaces for the controlled in situ crystallization of cerium, iron, and zinc oxide nanocrystals. The formation of the metal oxide is driven by the addition of a base to suspensions of the polymer particles containing the corresponding precursor. The crystal formation at the particle surface is studied for the different hybrid systems by X‐ray diffraction and transmission electron microscopy (TEM). The potential catalytic activity of CeO₂/polymer hybrid particles is proven with the example of the photodegradation of rhodamine B. For the case of magnetic iron oxide‐functionalized latex, a superparamagnetic behavior is found above a blocking temperature of 225 K. ZnO/polymer hybrids present a strong yellow visible photoluminescence. The approach is shown to be versatile not only in terms of the variety in the metal oxides deposited on the surface, but also because the crystallization can take place in both aqueous and alcoholic media.     

Fabrication of Nanocomposite Thermoelectric Materials by a Pulsed Laser Deposition Method

We applied a pulsed laser deposition (PLD) technique to fabricate nanocomposite half-Heusler thermoelectrics by employing two different methods: a dry process and a wet process. First, we tried to obtain nanosized thermoelectric particles by using PLD in a liquid solvent. Nanosized (<100 nm) spherical and crystalline half-Heusler particles containing Ti, Zr, Hf, Ni, and Sn elements were obtained by this method, showing good controllability of stoichiometry. The key is to select a solvent that prevents oxidation. Second, the dry PLD process was employed to coat the thermoelectric powder with metal oxides. To this end, we developed a PLD coating apparatus. After sintering the coated powder using the spark plasma sintering (SPS) technique, we confirmed that a nanosized layer of the metal oxides was uniformly formed at the grain boundaries of the half-Heusler matrix. With these two examples, the capability of the PLD techniques to fabricate well-controlled nanocomposite thermoelectric materials is demonstrated.     

Over 1.1 eV Workfunction Tuning of Cesium Intercalated Metal Oxides for Functioning as Both Electron and Hole Transport Layers in Organic Optoelectronic Devices

In this paper, over 1.1 eV continuous tuning of metal oxides workfunction is realized by cesium intercalation, making the metal oxide function as both electron transport layer and hole transport layer in organic optoelectronic devices. The demonstrated metal oxides are commonly used molybdenum oxide and vanadium oxide. The proposed approach of synthesizing cesium intercalated metal oxides has interesting properties of room‐temperature, ambient atmosphere, water free and solution process, favoring the formation of metal oxides as carrier transport layers at different regions in multilayered devices and large scale fabrication of organic optoelectronics at low cost. Besides the wide range of controllable workfunction adjustment, band structures, and electrical properties are investigated in detail, to understand the effects of cesium intercalation on metal oxides. The device results show that, using the proposed cesium intercalation approach, each of the two investigated metal oxides can function as both ETL and HTL in organic solar cells and organic light emitting diodes with very good device performances. Consequently, with the interesting properties in film synthesis, the proposed cesium intercalated metal oxides can achieve continuously workfunction tuning over a large range and contribute to evolution of the simple route for fabricating high performance organic optoelectronic devices.     

金属粒子-介质复合薄膜中非平衡态电子瞬态弛豫的研究

利用飞秒脉冲激光和泵浦－探测技术测量了贵金属－介质复合薄膜（Ｃｕ－Ｂａ－Ｏ、Ａｕ－Ｂａ－Ｏ）的瞬态光学透过率随延迟时间的变化曲线，观察到了薄地光的吸收迅速增大并在皮秒时间内的状的现象，该现象是薄膜中超微粒子内费米能级附近电子被飞秒激光脉冲激光，产生非平衡态电子而经历瞬态弛豫造成的，本文从理论上给出了复合薄膜中Ａｕ超微粒子的电子声子相互作用常数ｇ的数值。     

Large‐Scale Fabrication of Three‐Dimensional Surface Patterns Using Template‐Defined Electrochemical Deposition

A new strategy to achieve large‐scale, three‐dimensional (3D) micro‐ and nanostructured surface patterns through selective electrochemical growth on monolayer colloidal crystal (MCC) templates is reported. This method can effectively create large‐area (>1 cm²), 3D surface patterns with well‐defined structures in a cost‐effective and time‐saving manner (<30 min). A variety of 3D surface patterns, including semishells, Janus particles, microcups, and mushroom‐like clusters, is generated. Most importantly, our method can be used to prepare surface patterns with prescribed compositions, such as metals, metal oxides, organic materials, or composites (e.g., metal/metal oxide, metal/polymer). The 3D surface patterns produced by our method can be valuable in a wide range of applications, such as biosensing, data storage, and plasmonics. In a proof‐of‐concept study, we investigated, both experimentally and theoretically, the surface‐enhanced Raman scattering (SERS) performance of the fabricated silver 3D semishell arrays.     

SnO_2-ZnO的乙醇气敏特性研究

为了解决乙醇传感器灵敏度不够高和选择性较差的问题,使用稀土金属氧化物代替贵金属及其化合物作为催化剂和添加剂制成了以SnO2-ZnO为主体的气敏材料,并对其气敏性能进行了研究。结果表明,此方法可有效提高SnO2-ZnO气敏材料对乙醇气体的灵敏度及选择性;利用制成的SnO2-ZnO气敏材料,可以生产出高灵敏度、高选择性的乙醇传感器。     

Effect of Bath Life of Ni(P) on the Brittle-Fracture Behavior of Sn-3.0Ag-0.5Cu/ENIG

The effect of bath life of Ni(P) on the brittle-fracture behavior of Sn-3.0 wt.%Ag-0.5 wt.%Cu (SAC)/electroless nickel immersion gold (ENIG) was evaluated in this study. The bath lives of Ni(P) for the ENIG surface finish in this study were varied from 0 to 3 metal turnover (MTO), which were indirectly indicative of Ni(P) bath life, with “0 MTO” denoting the as-make-up state and “3 MTO” denoting almost waste plating solution. The SAC/ENIG sample when Ni(P) was plated in the 3 MTO bath (3 MTO sample) had thicker (Cu,Ni)₆Sn₅ and P-rich layers than when Ni(P) was plated in the 0 MTO bath (0 MTO sample). The brittle-fracture behavior of the 0 and 3 MTO samples was evaluated by use of a igh-speed shear (HSS) test with a strain rate of 0.1–2.0 m/s. The shear strength of the 0 MTO sample was higher than that of the 3 MTO sample. The incidence of brittle fracture increased as the bath life of Ni(P) of ENIG (= MTO of Ni(P)) increased. Observation by transmission electron microscopy (TEM) revealed nano-sized voids (or particles) in the Ni-Sn-P layer. As the MTO of the Ni(P) increased, the number of nano-sized voids in the Ni-Sn-P layer of the SAC/ENIG interface increased. The poor brittle-fracture behavior of the 3 MTO sample originated from the weak interface at the thick P-rich layer and from the large nano-sized voids.     

Encapsulation of Perchlorate Salts within Metal Oxides for Application as Nanoenergetic Oxidizers

In this work, high‐oxygen‐content strong oxidizer perchlorate salts were successfully incorporated into current nanothermite composite formulations. The perchlorates were encapsulated within mild oxidizer particles through a series of thermal decomposition, melting, phase segregation, and recrystallization processes, which occurred within confined aerosol droplets. This approach enables the use of hygroscopic materials by stabilizing them within a matrix. Several samples, including Fe₂O₃/KClO₄, CuO/KClO₄ and Fe₂O₃/NH₄ClO₄ composite oxidizer particles, have been created. The results show that these composite systems significantly outperform the single metal oxide system in both pressurization rate and peak pressure. The ignition temperatures for these mixtures are significantly lower than those of the metal oxides alone, and time‐resolved mass spectrometry shows that O₂ release from the oxidizer also occurs at a lower temperature and with high flux. The results are consistent with O₂ release being the controlling factor in determining the ignition temperature. High‐speed imaging clearly shows a much more violent reaction. The results suggest that a strategy of encapsulating a very strong oxidizer, which may not be environmentally compatible, within a more stable weak oxidizer offers the opportunity to both tune reactivity and employ materials that previously could not be considered.     

Plasma-induced charging damage in ultrathin (3-nm) gate oxides

Plasma-induced damage in various 3-nm-thick gate oxides (i.e., pure oxides and N₂O-nitrided oxides) was investigated by subjecting both nMOS and pMOS antenna devices to a photoresist ashing step after metal pad definition. Both charge-to-breakdown and gate leakage current measurements indicated that large leakage current occurs at the wafer center as well as the wafer edge for pMOS devices, while only at the wafer center for nMOS devices. These interesting observations could be explained by the strong polarity dependence of ultra thin oxides in charge-to-breakdown measurements of nMOS devices. In addition, pMOS devices were found to be more susceptible to charging damage, which can be attributed to the intrinsic polarity dependence in tunneling current between nand p-MOSFETs. More importantly, our experimental results demonstrated that stress-induced leakage current (SILC) caused by plasma damage can be significantly suppressed in N₂O-nitrided oxides, compared to pure oxides, especially for pMOS devices. Finally, nitrided oxides were also found to be more robust when subjected to high temperature stressing. Therefore, nitrided oxides appear to be very promising for reducing plasma charging damage in future ULSI technologies employing ultrathin gate oxides