New insights into the mechanism of reactive adsorption desulfurization on Ni/ZnO catalysts:Theoretical evidence showing the existence of interfacial sulfur transfer pathway and the essential role of hydrogen

As well known in the petroleum industry and academia,Ni/ZnO catalysts have excellent desulfurization performance.However,the sulfur transfer mechanism of reactive adsorption desulfurization(RADS)that occurs on Ni/ZnO catalysts remains controversial.Herein,a periodic Ni nanorod supported on ZnO slab was built to represent the Ni/ZnO system,and density functional theory calculations were performed to study the sulfur transfer process and the role of H_(2)within the process.The results elucidate that the direct solid-state diffusion of S from Ni to interfacial oxygen vacancies(Ov)is more favorable than the hydrogenation of S to SH/H_(2)S on Ni and the subsequent H_(2)S desorption,and accordingly,H_(2)O is produced on Ni rather than on ZnO.Ab initio thermodynamics analysis shows that the hydrogen atmosphere applied in preparing Ni/ZnO catalysts greatly promotes the O_(v)formation on ZnO surface,which accounts for the presence of interfacial O_(v)in freshly prepared catalysts.Under RADS condition,hydrogenation of interfacial O atoms to form O-H groups facilitates the reverse spillover of these lattice O atoms from ZnO to Ni,accompanied with the interfacial O_(v)generation.In contrast to the classic S transfer mechanism via H_(2)S,the present work clearly demonstrates that the interfacial S transfer is a feasible reaction pathway in the RADS mechanism.More importantly,the existence of interfacial O_(v)is an essential prerequisite for this interfacial S diffusion,and H_(2)plays a key role in facilitating the O_(v)formation.

Nano silica aerogel-induced formation of an organic/alloy biphasic interfacial layer enables construction of stable high-energy lithium metal batteries

Lithium metal batteries represent promising candidates for high-energy-density batteries, however, many challenges must still be overcome,e.g., interface instability and dendrite growth. In this work, nano silica aerogel was employed to generate a hybrid film with high lithium ion conductivity(0.6 mS cm^(-1)at room temperature) via an in situ crosslinking reaction. TOF-SIMS profile analysis has revealed conversion mechanism of hybrid film to Li–Si alloy/Li F biphasic interface layer, suggesting that the Li–Si alloy and Li F-rich interface layer promoted rapid Li+transport and shielded the Li anodes from corrosive reactions with electrolyte-derived products. When coupled with nickel-cobalt-manganese-based cathodes, the batteries achieve outstanding capacity retention over 1000 cycles at 1 C. Additionally the developed film coated on Li enabled high coulombic efficiency(99.5%) after long-term cycling when coupled with S cathodes. Overall, the results presented herein confirm an effective strategy for the development of high-energy batteries.

Optimizing the Performance of CsPbI3-Based Perovskite Solar Cells via Doping a ZnO Electron Transport Layer Coupled with Interface Engineering

Interface engineering has been regarded as an effective and noninvasive means to optimize the performance of perovskite solar cells(PSCs).Here,doping engineering of a ZnO electron transport layer(ETL)and CsPbI3/ZnO interface engineering via introduction of an interfacial layer are employed to improve the performances of CsPbI3-based PSCs.The results show that when introducing a TiO2 buffer layer while increasing the ZnO layer doping concentration,the open-circuit voltage,power conversion efficiency,and fill factor of the CsPbI3-based PSCs can be improved to 1.31 V,21.06%,and 74.07%,respectively,which are superior to those of PSCs only modified by the TiO2 buffer layer or high-concentration doping of ZnO layer.On the one hand,the buffer layer relieves the band bending and structural disorder of CsPbI3.On the other hand,the increased doping concentration of the ZnO layer improves the conductivity of the TiO2/ZnO bilayer ETL because of the strong interaction between the TiO2 and ZnO layers.However,such phenomena are not observed for those of a PCBM/ZnO bilayer ETL because of the weak interlayer interaction of the PCBM/ZnO interface.These results provide a comprehensive understanding of the CsPbI3/ZnO interface and suggest a guideline to design high-performance PSCs.

SiCp/Al-Si基复合材料界面结构调控及强化机制的研究进展

SiCp/Al-Si基复合材料具有高的比强度、比刚度、比模量,良好的导热、导电、耐磨性及尺寸稳定性等优点,作为结构功能性材料应用于空间工程、电子封装、交通运输和精密仪器等领域。其研究热点主要集中在界面结构调控、强化机制及性能调控等方面。在SiCp/Al-Si复合材料中存在着增强体与基体界面、析出相与基体界面、析出相与增强体界面,这些界面受各种因素影响,会出现多种界面反应和界面产物,界面结构和结合状态复杂而多样。基于此,本文综述了制备工艺、基体合金成分和SiCp表面改性等方面对SiCp/Al-Si基复合材料界面结构的影响及调控,并总结了影响其力学性能的因素及强化机制的研究现状,最后对复合材料未来的发展及研究方向进行了展望。

Theoretical Studies on the Si(001)-SiO_2 Interface Structure

Novel models （2× 1） of Si（001）-SiO2 interface structure have been established. The method of the first-principle General Gradient Approximation （GGA） is employed to structurally optimize the established theoretical models under the K-point space of periodic boundary condition. The structures after optimization have been analyzed, and the results show that the interfaces present in disordered state and both Si-O-Si and Si=O structures exist. Meanwhile, the bonding of surface structure is analyzed via the graphics of electron localization function（ELF）.

Improved efficiency and stability of perovskite solar cells with molecular ameliorating of ZnO nanorod/perovskite interface and Mg-doping ZnO

Despite the advanced efficiency of perovskite solar cells(PSCs),electron transportation is still a pending issue.Here the polymer polyvinylpyrrolidone(PVP)is used to enhance the electron injection,which is thanks to the passivation of the defects at the interface between the ZnO electron transporting layer(ETL)and the perovskite.The application of the PVP layer inhibits the device degradation,and 80%of the primary efficiency is kept after 30 d storage in air condition.Additionally,the efficiency of the device is further enhanced by improving the conductivity and crystallinity of the ZnO ETL via Magnesium(Mg)doping in the ZnO nanorods(ZnO NRs).Moreover,the preparation parameters of the ZnO NRs are optimized.By employing the high-crystallinity ZnO ETL and the PVP layer,the power conversion efficiency(PCE)of the champion device is increased from 16.29%to 19.63%.These results demonstrate the advantages of combining mesoscale manipulation with interface modification and doping together.

Primary Mg_(2)Si phase and Mg_(2)Si/α-Mg interface modified by Sn and Sb elements in a Mg-5Sn-2Si-1.5Al-1Zn-0.8Sb alloy

The microstructure of primary Mg_(2)Si and the interface of Mg_(2)Si/α-Mg modified by Sn and Sb elements in an as-cast Mg-5Sn-2Si-1.5Al-1Zn-0.8Sb(wt.%) alloy were investigated.In the primary Mg_(2)Si phase not only the Si atoms but also the Mg atoms could be substituted by Sn and Sb atoms,resulting in the slightly reduced lattice constant a of 0.627 nm.An OR of Mg_(2)Si phase and α-Mg in the form of[001]Mg_(2)Si‖[01■1]α,(220)Mg_(2)Si‖(0■12)αwas discovered.Between primary Mg_(2)Si phase and α-Mg matrix two transitional nano-particle layers were formed.In the rim region of primary Mg_(2)Si particle,Mg_(2)Sn precipitates sizing from 5 nm to 50 nm were observed.Adjacent to the boundary of primary Mg_(2)Si particle,luxuriant columnar crystals of primary Mg_(2)Sn phase with width of about 25 nm and length of about100 nm were distributed on the α-Mg matrix.The lattice constant of the Mg_(2)Sn precipitate in primary Mg_(2)Si particle was about 0.756 nm.Three ORs between Mg_(2)Sn and Mg_(2)Si were found,in which the Mg_(2)Sn precipitates had strong bonding interfaces with Mg_(2)Si phase.Three new minor ORs between Mg_(2)Sn phase and α-Mg were found.The lattice constant of primary Mg_(2)Sn phase was enlarged to 0.813 nm owing to the solution of Sn and Sb atoms.Primary Mg_(2)Sn had edge-to-edge interfaces with α-Mg.Therefore,the primary Mg_(2)Si particle and α-Mg were united and the interfacial adhesion was improved by the two nano-particles layers of Mg_(2)Sn phase.

ZnO和铪锆氧化物(Hf_(0.5)Zr_(0.5)O_(2))堆栈能带对准研究

铪锆氧化物(HZO)克服了传统铁电材料的缺陷,能够与CMOS工艺兼容,并且可以微缩,在高端芯片领域有很大的发展潜力。而其瓶颈在于循环寿命低,主流研究试图通过界面工程、介质掺杂等工艺改善其铁电性能并提高其寿命。本工作提出了以ZnO作为HZO与上电极的过渡层,制备HZO/ZnO堆栈,并通过X射线光电子能谱研究了ZnO过渡层与HZO的基本物理问题,即二者的能带结构和退火对能带对准的影响。结果表明,退火过程中界面处发生了元素扩散和偶极子的改变,使HZO/ZnO的能带偏移发生变化,异质结由type-Ⅱ型变为type-Ⅰ型。本工作将为HZO存储器的改善寿命的ZnO过渡层提供基础物理学依据。

Forward and reverse electron transport properties across a CdS/Si multi-interface nanoheterojunction

The electron transport behavior across the interface plays an important role in determining the performance of op- toelectronic devices based on heterojunctions. Here through growing CdS thin film on silicon nanoporous pillar array, an untraditional, nonplanar, and multi-interface CdS/Si nanoheterojunction is prepared. The current density versus voltage curve is measured and an obvious rectification effect is observed. Based on the fitting results and model analyses on the forward and reverse conduction characteristics, the electron transport mechanism under low forward bias, high forward bias, and reverse bias are attributed to the Ohmic regime, space-charge-limited current regime, and modified Poole-Frenkel regime respectively. The forward and reverse electrical behaviors are found to be highly related to the distribution of inter- facial trap states and the existence of localized electric field respectively. These results might be helpful for optimizing the preparing procedures to realize high-performance silicon-based CdS optoelectronic devices.

Electronic relaxation of deep bulk trap and interface state in ZnO ceramics

This paper investigates the electronic relaxation of deep bulk trap and interface state in ZnO ceramics based on dielectric spectra measured in a wide range of temperature, frequency and bias, in addition to the steady state response. It discusses the nature of net current flowing over the barrier affected by interface state, and then obtains temperature-dependent barrier height by approximate calculation from steady I-V （current-voltage） characteristics. Additional conductance and capacitance arising from deep bulk trap relaxation are calculated based on the displacement of the cross point between deep bulk trap and Fermi level under small AC signal. From the resonances due to deep bulk trap relaxation on dielectric spectra, the activation energies are obtained as 0.22 eV and 0.35 eV, which are consistent with the electronic levels of the main defect interstitial Zn and vacancy oxygen in the depletion layer. Under moderate bias, another resonance due to interface relaxation is shown on the dielectric spectra. The DC-like conductance is also observed in high temperature region on dielectric spectra, and the activation energy is much smaller than the barrier height in steady state condition, which is attributed to the displacement current coming from the shallow bulk trap relaxation or other factors.

Boosting the performance of crossed ZnO microwire UV photodetector by mechanical contact homo-interface barrier

One-dimensional(1D)micro/nanowires of wide band gap semiconductors have become one of the most promising blocks of high-performance photodetectors.However,in the axial direction of micro/nanowires,the carriers can transport freely driven by an external electric field,which usually produces large dark current and low detectivity.Here,an UV photodetector built from three cross-intersecting ZnO microwires with double homo-interfaces is demonstrated by the chemical vapor deposition and physical transfer techniques.Compared with the reference device without interface,the dark current of this ZnO double-interface photodetector is significantly reduced by nearly 5 orders of magnitude,while the responsivity decreases slightly,thereby greatly improving the normalized photocurrent-to-dark current ratio.In addition,ZnO double-interface photodetector exhibits a much faster response speed(~0.65 s)than the no-interface device(~95 s).The improved performance is attributed to the potential barriers at the microwire-microwire homo-interfaces,which can regulate the carrier transport.Our findings in this work provide a promising approach for the design and development of high-performance photodetectors.

First-principles calculations of the hole-induced depassivation of SiO2/Si interface defects

The holes induced by ionizing radiation or carrier injection can depassivate saturated interface defects.The depassivation of these defects suggests that the deep levels associated with the defects are reactivated,affecting the performance of devices.This work simulates the depassivation reactions between holes and passivated amorphous-SiO_(2)/Si interface defects(HP_(b)+h→P_(b)+H^(+)).The climbing image nudged elastic band method is used to calculate the reaction curves and the barriers.In addition,the atomic charges of the initial and final structures are analyzed by the Bader charge method.It is shown that more than one hole is trapped by the defects,which is implied by the reduction in the total number of valence electrons on the active atoms.The results indicate that the depassivation of the defects by the holes actually occurs in three steps.In the first step,a hole is captured by the passivated defect,resulting in the stretching of the Si-H bond.In the second step,the defect captures one more hole,which may contribute to the breaking of the Si-H bond.The H atom is released as a proton and the Si atom is three-coordinated and positively charged.In the third step,an electron is captured by the Si atom,and the Si atom becomes neutral.In this step,a Pb-type defect is reactivated.

Passivation and dissociation of P_(b)-type defects at a-SiO_(2)/Si interface

It is well known that in the process of thermal oxidation of silicon,there are P_(b)-type defects at amorphous silicon dioxide/silicon(a-SiO_(2)/Si)interface due to strain.These defects have a very important impact on the performance and reliability of semiconductor devices.In the process of passivation,hydrogen is usually used to inactivate P_(b)-type defects by the reaction P_(b)+H_(2)→P_(b)H+H.At the same time,P_(b)H centers dissociate according to the chemical reaction P_(b)H→P_(b)+H.Therefore,it is of great significance to study the balance of the passivation and dissociation.In this work,the reaction mechanisms of passivation and dissociation of the P_(b)-type defects are investigated by first-principles calculations.The reaction rates of the passivation and dissociation are calculated by the climbing image-nudged elastic band(CI-NEB)method and harmonic transition state theory(HTST).By coupling the rate equations of the passivation and dissociation reactions,the equilibrium density ratio of the saturated interfacial dangling bonds and interfacial defects(P_(b),P_(b)0,and P_(b)1)at different temperatures is calculated.

Effect of Metallurgical Behaviour at the Interface between Ceramic and Interlayer on the Si_3N_4/1.25Cr-0.5Mo Steel Joint Strength

By using newly developed CuNi5~25Ti16~28 B rapldly solidifled brazing filler the joining of Si3 N4/1.25Cr-0.5Mo steel has been carried out with interlayer method. If employing the interlayer structure of steel (0.2 mm)/W (2.0 mm)/Ni(0.2 mm), the joint strength can be increased greatly compared with employing that of Ni/W/Ni, and the three point bend strength of the Joint shows the value of 261 MPa. The metallurgical behaviour at the interface between Si3N4 and the interlayer has been studied. It is found that Fe participated in the interfacial reactions between Si3N4 and the brazing filler at the Si3N4/steel (0.2 mm) interface and the compound Fe5Si3 was produced. However, since the reactions of Fe with the active Ti are weaker than those of Ni with Ti, the normal inter facial reactions were still assured at the interface of Si3N4/steel (0.2 mm) instead of Si3N4/Ni (0.2 mm), resulting in the improvement of the joint strength. The mechanism of the formation of Fe5Si3 is also discussed. Finally, some ideas to further ameliorate and simplify the interlayer structure are put forward.

Microstructure of interaction interface between Al-Si,Zn-Al alloys and Al_2O_(3p)/6061Al composite

Interaction behaviors between Al-Si, Zn-Al alloys and Al2O)3p)/6061Al composite at different heating temperatures were investigated. It is found that Al2O)3p)/6061Al composite can be wetted well by AlSi-1, AlSi-4 and Zn-Al alloys and an interaction layer forms between the alloy and composite during interaction. Little Al-Si alloys remain on the surface when they fully wet the composite and Si element in Al-Si alloy diffuses into composite entirely and assembles in the composite near the interface of Al-Si alloy/composite to form a Si-rich zone. The microstructure in interaction layer with Si penetration is still dense. Much more residual Zn-Al alloy exists on the surface of composite when it wets the composite, and porosities appear at the interface of Zn-Al alloy/composite. The penetration of elements Zn, Cu of Zn-Al alloy into composite leads to the generation of shrinkage cavities in the interaction layer and makes the microstructure of Al2O)3p)/6061Al composite loose.

ZnO/SiC/Si(111)异质外延

使用 Si C作为过渡层 ,采用自行设计建造的连通式双反应室高温 MOCVD系统很好地克服了 Zn O和 Si C生长时的交叉污染问题 ,在 Si基片上外延出高质量的 Zn O薄膜 .测量了样品的 XRD和摇摆曲线 ,以及室温下的 PL谱 .实验结果表明 ,Si C过渡层的引入大大提高了 Zn O薄膜的质量和发光性能 ,并有望实现在 Si上制备 Zn O单晶薄膜 .

氧离子束辅助激光淀积生长ZnO/Si的XPS研究

利用X射线光电子能谱深度剖析方法对ZnO/Si异质结构进行了分析 .用该法可生长出正化学比的ZnO ,不过生长的ZnO薄膜存在孔隙 ,工艺还有待进一步改进 .

MOCVD方法在Ni/Si(111)模板上生长ZnO薄膜

用常压金属有机化学气相外延方法在Ni／Si（111）模板上生长ZnO薄膜，研究了ZnO低温缓冲层的厚度（50h，300h）对薄膜性能的影响。采用原子力显微镜，X射线衍射和光致发光光谱仪对这些样品进行分析。结果表明：缓冲层的厚度对zno外延薄膜的表面形貌、晶体结构及发光性能都有较大影响。在50h～100A低温缓冲层上生长的ZnO外延膜，晶粒尺寸大小均匀，发光和结晶性能良好。

SiC缓冲层对Si表面生长的ZnO薄膜结构和光电性能的改善

用脉冲激光沉积(PLD)技术制备了ZnO/SiC/Si和ZnO/Si薄膜并制成了紫外探测器。利用X射线衍射(XRD),光致发光(PL)谱,I-V曲线和光电响应谱对薄膜的结构和光电性能进行了研究。实验结果表明:SiC缓冲层改善了ZnO薄膜的结晶质量和光电性能,其原因可能是SiC作为柔性衬底能够减少ZnO与Si之间大的晶格失配和热失配导致的界面缺陷和界面态。

SiO_2/Si衬底制备ZnO薄膜及表征

本文报道了利用脉冲激光沉积技术在热氧化p型硅衬底上生长ZnO外延薄膜。引入高阻非晶SiO2缓冲层,有效地降低了检测过程中单晶衬底对ZnO薄膜的电学性能影响。利用XRD,SEM,Hall和PL对其进行研究。结果表明,在衬底温度为500℃时,生长的ZnO薄膜具有优良的晶体质量,电学性能和发光性能。