Probing the Nucleation and Growth Kinetics of Bismuth Nanoparticles via In-situ Transmission Electron Microscopy

The nucleation and growth mechanism of nanoparticles is an important theory,which can guide the preparation of nanomaterials.However,it is still lacking in direct observation on the details of the evolution of intermediate state structure during nucleation and growth.In this work,the evolution process of bismuth nanoparticles induced by electron beam was revealed by in-situ transmission electron microscopy(TEM)at atomic scale.The experimental results demonstrate that the size,stable surface and crystallographic defect have important influences on the growth of Bi nanoparticles.Two non-classical growth paths including single crystal growth and polycrystalline combined growth,as well as,corresponding layer-by-layer growth mechanism along{012}stable crystal plane of Bi nanoparticles with dodecahedron structure were revealed by in-situ TEM directly.These results provide important guidance and a new approach for in-depth understanding of the nucleation and growth kinetics of nanoparticles.

Interface charges boosted ultrafast lithiation in Li_4Ti_5O_12 revealed by in-situ electron holography

It is still a great challenge at present to combine the high rate capability of the electrochemical capacitor with the high electrochemical capacity feature of rechargeable battery in energy storage and transport devices. By studying the lithiation mechanism of Li_4Ti_5O_12 （LTO） using in-situ electron holography, we find that double charge layers are formed at the interface of the insulating Li_4Ti_5O_12 （Li_4） phase and the semiconducting Li_7Ti_5O_12 （Li_7） phase, and can greatly boost the lithiation kinetics. The electron wave phase of the LTO particle is found to gradually shrink with the interface movement, leaving a positive electric field from Li_7 to Li_4 phase. Once the capacitive interface charges are formed, the lithiation of the core/shell particle could be established within 10 s. The ultrafast kinetics is attributed to the built-in interface potential and the mixed Ti3＋/Ti4＋ sites at the interface that could be maximally lowering the thermodynamic barrier for Li ion migration.

Graphene/Rh(111) Structure Studied Using In-Situ Scanning Tunneling Microscopy

Scanning tunnel microscopy （STM） is performed to verify if an Rh ＇nails＇ structure is formed accompanying the graphene growing during chemical vapor deposition. A structure of a graphene island in an Rh vacancy island is used as the start. While the graphene island is removed by oxygenation, the variations of the Rh vacancy island are imaged with an in-situ high-temperature STM. By fitting with our model and calculations, we conclude that the best fit is obtained for 0% Rh, i.e., for the complete absence of nails below graphene on Rh（111）. That is, when graphene is formed on Rh（111）, the substrate remains fiat and does not develop a SUPPorting nail structure.

Improvement of the high-k/Ge interface thermal stability using an in-situ ozone treatment characterized by conductive atomic force microscopy

In this work, an in-situ ozone treatment is carried out to improve the interface thermal stability of HfO_2/Al_2O_3 gate stack on germanium（Ge） substrate. The micrometer scale level of HfO_2/Al_2O_3 gate stack on Ge is studied using conductive atomic force microscopy（AFM） with a conductive tip. The initial results indicate that comparing with a non insitu ozone treated sample, the interface thermal stability of the sample with an in-situ ozone treatment can be substantially improved after annealing. As a result, void-free surface, low conductive spots, low leakage current density, and relative high breakdown voltage high-κ/Ge are obtained. A detailed analysis is performed to confirm the origins of the changes.All results indicate that in-situ ozone treatment is a promising method to improve the interface properties of Ge-based three-dimensional（3D） devices in future technology nodes.

Visualization of atomic scale reaction dynamics of supported nanocatalysts during oxidation and ammonia synthesis using in-situ environmental(scanning) transmission electron microscopy

Reaction dynamics in gases at operating temperatures at the atomic level are the basis of heterogeneous gas-solid catalyst reactions and are crucial to the catalyst function.Supported noble metal nanocatalysts such as platinum are of interest in fuel cells and as diesel oxidation catalysts for pollution control,and practical ruthenium nanocatalysts are explored for ammonia synthesis.Graphite and graphitic carbons are of interest as supports for the nanocatalysts.Despite considerable literature on the catalytic processes on graphite and graphitic supports,reaction dynamics of the nanocatalysts on the supports in different reactive gas environments and operating temperatures at the single atom level are not well understood.Here we present real time in-situ observations and analyses of reaction dynamics of Pt in oxidation,and practical Ru nanocatalysts in ammonia synthesis,on graphite and related supports under controlled reaction environments using a novel in-situ environmental(scanning) transmission electron microscope with single atom resolution.By recording snapshots of the reaction dynamics,the behaviour of the catalysts is imaged.The images reveal single metal atoms,clusters of a few atoms on the graphitic supports and the support function.These all play key roles in the mobility,sintering and growth of the catalysts.The experimental findings provide new structural insights into atomic scale reaction dynamics,morphology and stability of the nanocatalysts.

Thioacetamide Additive Homogenizing Zn Deposition Revealed by In Situ Digital Holography for Advanced Zn Ion Batteries

Zinc ion batteries are considered as potential energy storage devices due to their advantages of low-cost,high-safety,and high theoretical capacity.However,dendrite growth and chemical corrosion occurring on Zn anode limit their commercialization.These problems can be tackled through the optimization of the electrolyte.However,the screening of electrolyte additives using normal electrochemical methods is time-consuming and labor-intensive.Herein,a fast and simple method based on the digital holography is developed.It can realize the in situ monitoring of electrode/electrolyte interface and provide direct information concerning ion concentration evolution of the diffusion layer.It is effective and time-saving in estimating the homogeneity of the deposition layer and predicting the tendency of dendrite growth,thus able to value the applicability of electrolyte additives.The feasibility of this method is further validated by the forecast and evaluation of thioacetamide additive.Based on systematic characterization,it is proved that the introduction of thioacetamide can not only regulate the interficial ion flux to induce dendrite-free Zn deposition,but also construct adsorption molecule layers to inhibit side reactions of Zn anode.Being easy to operate,capable of in situ observation,and able to endure harsh conditions,digital holography method will be a promising approach for the interfacial investigation of other battery systems.

In-situ formation of Al-CaB_6 composites with low resistivity

In this work, in-situ CaB6 reinforced aluminum matrix composites were fabricated, and the microstructure, resistivity, microhardness and coefficient of thermal expansion (CTE) of Al-CaB6 composites were studied. It is found that CaB6 compounds can be formed by reducing reaction occurred in the Al melt: . CaB6 exhibits a hexahedron morphology and distributes uniformly in the Al alloy matrix. The resistivity of Al-CaB6 composites is 3.02*10-8 Ω·m, which is close to that of pure Al and lower than that of 6063Al/Ga composites. The average microhardness of Al-CaB6 composites can reach 1270 MPa, 259.8% higher than that of pure Al. Compared to pure Al, the CTE of Al-CaB6 composites is much lower.

High-resolution electron microscopy for heterogeneous catalysis research

Heterogeneous catalysts are the most important catalysts in industrial reactions. Nanocatalysts, with size ranging from hundreds of nanometers to the atomic scale, possess activities that are closely connected to their structural characteristics such as particle size, surface morphology, and three-dimensional topography. Recently, the development of advanced analytical transmission electron microscopy（TEM） techniques, especially quantitative high-angle annular darkfield（HAADF） imaging and high-energy resolution spectroscopy analysis in scanning transmission electron microscopy（STEM） at the atomic scale, strengthens the power of（S）TEM in analyzing the structural/chemical information of heterogeneous catalysts. Three-dimensional reconstruction from two-dimensional projected images and the real-time recording of structural evolution during catalytic reactions using in-situ（S）TEM methods further broaden the scope of（S）TEM observation. The atomic-scale structural information obtained from high-resolution（S）TEM has proven to be of significance for better understanding and designing of new catalysts with enhanced performance.

面向微光学元件表面形貌测量的涡旋相移数字全息技术

非接触、无损害的相移数字全息技术对微光学元件检测具有独特优势。因传统的相移数字全息技术需要对相移器进行精细控制和繁琐校准,同时其光路易受到机械振动干扰,导致全息再现像的质量降低。本文借助涡旋光特殊的相位分布,提出了一种基于涡旋相移数字全息的微光学元件表面形貌测量方法。该方法利用螺旋相位板调制涡旋相位,引入高精度相移。基于构建的涡旋相移数字全息显微实验装置,采用干涉极值法确定了相移干涉图之间的真实相移量,并对螺旋相位板的旋转角度与相移量的关系进行标定,实验验证了涡旋相移的可行性;对微透镜阵列进行了重复测量实验,将测试结果与ZYGO白光干涉仪的测试结果进行比较。结果表明:测量得到单个微透镜的平均纵向矢高为12.897μm,平均相对误差为0.155%。所提方法可以实现对被测微光学元件表面形貌的高精度测量,具有易操作、稳定可靠、准确性高等优点。

A novel random phase-shifting digital holographic microscopy method

This paper proposes a new method that reconstructs the information of specimen by using random phase shift step in digital holographic microscopy (DHM). The principles of the method are described and discussed in detail. In practical experiment, because the phase shifter is neither perfectly linear nor calibrated, digital holograms with inaccurate phase shift step are recorded by the charge-coupled device (CCD). The phase could be accurately reconstructed from the recorded digital holograms by using the random phase-shifting algorithm, which makes up for reconstructed phase error caused by ordinary phase-shifting algorithm. The phase aberration compensation is also discussed. In order to verify the flexibility of the proposed method, numerical simulation of random phase-shifting DHM was carried out. The simulation results illustrated that the presented method is effective when the phase shift step is unknown or random in DHM.

Multi-prior physics-enhanced neural network enables pixel super-resolution and twin-imagefree phase retrieval from single-shot hologram

Digital in-line holographic microscopy(DIHM)is a widely used interference technique for real-time reconstruction of living cells’morphological information with large space-bandwidth product and compact setup.However,the need for a larger pixel size of detector to improve imaging photosensitivity,field-of-view,and signal-to-noise ratio often leads to the loss of sub-pixel information and limited pixel resolution.Additionally,the twin-image appearing in the reconstruction severely degrades the quality of the reconstructed image.The deep learning(DL)approach has emerged as a powerful tool for phase retrieval in DIHM,effectively addressing these challenges.However,most DL-based strategies are datadriven or end-to-end net approaches,suffering from excessive data dependency and limited generalization ability.Herein,a novel multi-prior physics-enhanced neural network with pixel super-resolution(MPPN-PSR)for phase retrieval of DIHM is proposed.It encapsulates the physical model prior,sparsity prior and deep image prior in an untrained deep neural network.The effectiveness and feasibility of MPPN-PSR are demonstrated by comparing it with other traditional and learning-based phase retrieval methods.With the capabilities of pixel super-resolution,twin-image elimination and high-throughput jointly from a single-shot intensity measurement,the proposed DIHM approach is expected to be widely adopted in biomedical workflow and industrial measurement.

Resolution enhancement of digital holographic microscopy via synthetic aperture:a review

Digital holographic microscopy(DHM),which combines digital holography with optical microscopy,is a wide field,minimally invasive quantitative phase microscopy(QPM)approach for measuring the 3D shape or the inner structure of transparent and translucent samples.However,limited by diffraction,the spatial resolution of conventional DHM is relatively low and incompatible with a wide field of view(FOV)owing to the spatial bandwidth product(SBP)limit of the imaging systems.During the past decades,many efforts have been made to enhance the spatial resolution of DHM while preserving a large FOV by trading with unused degrees of freedom.Illumination modulation techniques,such as oblique illumination,structured illumination,and speckle illumination,can enhance the resolution by adding more high-frequency information to the recording system.Resolution enhancement is also achieved by extrapolation of a hologram or by synthesizing a larger hologram by scanning the sample,the camera,or inserting a diffraction grating between the sample and the camera.For on-chip DHM,spatial resolution is achieved using pixel super-resolution techniques.In this paper,we review various resolution enhancement approaches in DHM and discuss the advantages and disadvantages of these approaches.It is our hope that this review will contribute to advancements in DHM and its practical applications in many fields.

Antifouling mechanism of natural product-based coatings investigated by digital holographic microscopy

Using natural product-based antifouling coatings has proven to be an effective strategy to combat biofouling.However,their antifouling mechanisms are still unclear.In this study,the antifouling mechanism of natural product-based coatings consisting of bio-sourced poly(lactic acid)-based polyurethane and ecofriendly antifoulant(butenolide)derived from marine bacteria was revealed by observing 3D bacterial motions utilizing a 3D tracking technique-digital holographic microscopy(DHM).As butenolide content increases,the density of planktonic marine bacteria(Pseudomonas sp.)near the surface decreases and thus leads to a reduced adhesion,indicating that butenolide elicits the adaptive response of Pseudomonas sp.to escape from the surface.Meanwhile,among these remained cells,an increased percentage is found to undergo subdiffusive motions compared with the case of smaller dose of butenolide.Further experiments show that butenolide can accelerate their swimming velocity and reduce flick frequency.Antibacterial assay confirms that butenolide-based coating shows high efficacy of antifouling performance against Pseudomonas sp.but without killing them like 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one(DCOIT).

The multi-functional aspect of scanning holographic microscopy: a review(Invited Paper)

Recent developments in scanning holographic microscopy that offer the prospects of new quantitative tools and imaging modalities in bio, micro, and nano sciences are reviewed. The versatility of the method is emphasized. Scanning holography can operate in an incoherent mode for fluorescence imaging, in a coherent mode for quantitative phase imaging, or in a tomographic mode for axial sectioning and rejection of the out-of-focus haze. Possible applications are illustrated with examples, and future prospects are discussed.

Non-isoplanatic lens aberration correction in dark-field digital holographic microscopy for semiconductor metrology

In the semiconductor industry,the demand for more precise and accurate overlay metrology tools has increased because of the continued shrinking of feature sizes in integrated circuits.To achieve the required sub-nanometre precision,the current technology for overlay metrology has become complex and is reaching its limits.Herein,we present a dark-field digital holographic microscope using a simple two-element imaging lens with a high numerical aperture capable of imaging from the visible to near-infrared regions.This combination of high resolution and wavelength coverage was achieved by combining a simple imaging lens with a fast and accurate correction of non-isoplanatic aberrations.We present experimental results for overlay targets that demonstrate the capability of our computational aberration correction in the visible and near-infrared wavelength regimes.This wide-ranged-wavelength imaging system can advance semiconductor metrology.

Multiframe full-field heterodyne digital holographic microscopy

Digital holographic microscopy using multiframe full-field heterodyne technology is discussed in which two acousto-optic modulators are applied to generate low-frequency heterodyne interference and a high-speed cam- era is applied to acquire multiframe full-field holograms. We use a temporal frequency spectrum analysis algo- rithm to extract the object＇s information. The twin-image problem can be solved and the random noise can be significantly suppressed. The relationship between the frame number and the reconstruction accuracy is dis- cussed. The typical objects of microlenses and biology cells are reconstructed well with lO0-frame holograms for illustration.

数字全息显微术对细胞的研究

通过数字全息显微的方法分析研究了新鲜洋葱表皮细胞的形貌结构.根据全息理论、光的衍射理论和透镜的相位变换性质,从理论上分析了数字全息显微原理,并依据四步相移和最小二乘去包裹技术,研究了重构细胞相位的方法.分析比较了不同参考光对数字全息显微分辨率的影响,设计了用球面光波作为参考光记录数字全息显微的装置.以新鲜洋葱表皮细胞为样本完成了实验检测和相位重构,得到了细胞的相位和三维信息,并粗略估计了细胞宽度和厚度.系统分辨率达到了1 .3μm.

数字全息显微系统结构参量对再现像质的影响

为了获取高质量的数字全息显微再现像,分析了同轴相移数字全息显微系统结构参量对再现像质的影响.首先经过计算得出理想成像时,像空间物光波频率完全由物体面形结构频率和系统放大倍率决定.然后基于显微成像时物光波的所有频率分量都应该被有效记录的分析,得出在同轴相移系统中放大倍率必须使物光波的空间频率缩小到满足采样要求;并得出在相同的放大倍率下记录距离会影响有效记录的物体尺寸,记录器件离开像平面的距离越小,有效记录的物体尺寸越大,在像平面上时有效记录的物体尺寸最大.计算机仿真和光学实验都证明了上述结论的正确性.

无透镜片上显微成像技术:理论、发展与应用

同时实现大视场、高分辨率成像是光学显微技术发展至今不断追求的永恒目标。传统光学显微镜由于其光学设计原理限制,空间带宽积一般总是限制在百万像素量级,从而无法同时兼顾高分辨率与大视场。另一方面,复杂的光学系统也使显微镜变得日趋昂贵、笨重、复杂且难以维护,极大地限制了其推广和应用。无透镜片上显微成像技术是近年来发展出的一种新概念计算成像技术:其不利用成像透镜聚焦,而直接将所观测的样本紧贴于成像器件光敏面上方记录图像,并结合相应的图像恢复算法实现清晰物像的反演与重构。由于具有视野大、分辨率高、无需标记、成本低、便携性好和可实现三维(3D)成像等优点,无透镜片上显微镜有望拓展传统显微成像技术的疆界,成为一种新型的快捷、便携的就地检验(POCT)工具。文中从无透镜成像基本原理、实验系统、重构方法及其典型应用进行了综述。最后,讨论了无透镜显微成像现存的一些关键问题以及今后可能的发展方向。

数字全息术用于光学元件表面缺陷形貌测量

利用像面数字全息显微术对光学元件表面缺陷的三维形貌测量进行了理论及实验研究。设计并搭建了相应光路系统记录全息图,采用角谱算法数值重建物光场,通过相位修正消除了系统误差引入的波前畸变,获得了经过待测光学元件表面缺陷调制的物光相位分布,并根据建立的相位分布与表面缺陷面形的关系模型计算得到缺陷三维形貌。实验以多个划痕和麻点等常见表面缺陷作为测量对象,分别获得了它们的三维形貌,以其中一条实际宽度为35μm、深度为270nm的划痕为例,测量得到该划痕的宽度为35.21μm,平均深度为267.6nm,与真实值相比,横向测量误差为0.6%,纵向测量误差为0.9%。实验结果证实该测量方法是有效、可靠的,能够准确测量光学元件表面缺陷的三维形貌,因而有助于判断光学元件损伤程度以及分析缺陷对系统波前的影响,对保障高功率激光装置的安全正常运行有重要意义。