Liane G. Benning, University of Leeds
Arda Genc, FEI Company
Dongsheng Li, Pacific Northwest National Laboratory
Jeffrey D. Rimer, University of Houston
Symposium Support Agilent Technologies, Inc.
OO2: In Situ Characterization of Nucleation, Growth and Transformation II
Monday PM, December 01, 2014
Hynes, Level 1, Room 101
2:30 AM - *OO2.01
Solution-Mediated Transformations between Uric Acid Phases
Jennifer Swift 1 Janeth Presores 1
1Georgetown University Washington USAShow Abstract
Uric aicd, a natural product of purine metabolism, can precipitate under physiologic conditions in a variety of anhydrous, hydrated and salt pforms leading to symptoms associated with kidney stones and gout. The evolution of these physiologic deposits is a multi-step process that operates on several different length scales. This talk will describe our efforts to address some of the key steps in the solution-mediated phase transformation of metastable uric acid dihydrate to anhydrous uric acid using a combination of X-ray diffraction, thermal analysis and optical microscopy techniques. The kinetics suggest that the interconversions between uric acid forms is very sensitive to the initial method under which the metastable phase was prepared as well as the composition of the solution in which it transforms.
3:00 AM - OO2.02
ZnO@SiO2 Core-Shell to Hollow Zn2SiO4: An In-Situ TEM Study of Hollow 1-D Nanostructure Formation
Shalini Tripathi 1 Ravishankar N 1
1IISc Bangalore IndiaShow Abstract
Zinc silicate (Zn2SiO4) has gained significant interest as a multifunctional material with several applications. In this study, we demonstrate a method to synthesize Zn2SiO4 nanotubes by exploiting Kirkendall effect at nanoscale. The reaction proceeds through interdiffusion of Zn2+ from ZnO nanorods into the chemically-synthesized Stöber-SiO2shy; shell. Using in-situ heating in the TEM, we have monitored the nucleation and coalescence of the Kirkendall voids in the ongoing process. While heating the samples ex-situ in air leads to microstructural evolution that is similar to the in-situ experiments, there is a significant difference in the samples heated under reducing conditions. Heating the ZnO@SiO2 nanostructures in a reducing atmosphere (95% Ar + 5% H2) leads to the formation of amorphous silica nanotubes owing to etching of ZnO in H2 atmosphere. Moreover, eletron-beam was also found to affect the course of the reaction, by sintering the tubes at higher temperature, thereby damaging the desired tubular morphology. Thus, this ambience-dependent thorough understanding of the relevant diffusion processes for the ZnO-SiO2 diffusion couple at nanoscale presents a general conceptual platform to fabricate different multifunctional one-dimensional hollow nanostructures. These two materials, namely the Zn2SiO4 and SiO2 nanotubes can respectively be used as cathode and anode materials for Li-ion battery.
3:15 AM - OO2.03
High Speed Atomic Force Microscopy Growth Monitoring during Pulsed Laser Deposition
Werner Wessels 1 Tjeerd Bollmann 1 Alexei Ofitserov 2 Gertjan van Baarle 2 Gertjan Koster 1 Guus Rijnders 1
1Mesa+ Institute for nanotechnology University of Twente Enschede Netherlands2Leiden Probe Microscopy Leiden NetherlandsShow Abstract
Pulsed Laser Deposition (PLD) is a physical vapor deposition technique to fabricate a wide range of high quality thin film materials for the next generation devices such as solar-cells, MEMS and OLED&’s. This research is focused on in situ growth front monitoring between subsequent deposition pulses using an high speed Atomic Force Microscope (AFM). A scientific instrument is under development, in which a fast AFM (<10s /frame, 512*512 pixels) is combined with a PLD system, with special attention to a fast and accurate transfer and approach (<1s) mechanism1. Using this instrument, we intend to repeatedly monitor the developing surface during growth (repositioning repeatability +/-60nm) with AFM at typical deposition conditions for complex oxides, nitrides and metals. In the case of PLD, the deposition and growth are separated in time, and therefore the above instrument aims to monitor the decay in adatom density after each laser pulse.
The described technique is an improvement of an earlier instrument, which demonstrated that it is feasible to combine in situ AFM with PLD in above manner2.
This scientific instrument will help to improve the fundamental understanding of the kinetic growth during PLD. In addition, the approach to monitor the same surface area using AFM shortly after a chemical, biological or physical modification on a separated position has the potential to become widely accepted. Here, we present the design and test results of the current setup and our future plans to improve the scan rate and resolution further. This work is supported by NanoNext NL and in strong collaboration with Leiden Probe Microscopy (LPM)
1 W.A. Wessels, J.J. Broekmaat, R.J.L. Beerends, G. Koster & G. Rijnders, Fast and gentle side approach for atomic force microscopy. Rev. Sci. Instru. 84, 123704 (2013)
2 J.J. Broekmaat, In-situ growth monitoring with Scanning Force Microscopy during Pulsed Laser Deposition, PhD Thesis ISBN 978-90-365-2655-5, University of Twente, 2008
3:30 AM - OO2.04
In Situ TEM Studies on Transformations from and to Quasicrystals in Mg-Zn-Y Alloys
Zhiqing Yang 1 Jianfang Liu 1 Hengqiang Ye 1
1Institute of Metal Research, Chinese Academy of Science Shenyang ChinaShow Abstract
Since the discovery of quasicrystals in an Al-Mn alloy, quasiperiodic ordering states have been found in hundreds of intermetallic alloys, soft materials, oxide film, and even dense stacking of hard tetrahedra. Extensive studies have provided explicit knowledge for understanding and modeling the atomic arrangements in intermetallic quasicrystals. Mackay, Bergman or Cd-Yb icosahedral clusters were believed to be building blocks of three-dimensional (3D) icosahedral quasicrystals (IQC). Computer simulations showed that a dodecagonal quasicrystal seed nucleus grew through assimilation of icosahedral clusters in a supercooled liquid. However, the fundamental questions concerning why quasicrystals form, and how they nucleate and grow, are still unclear experimentally on the atomic scale, especially for 3D intermetallic IQCs.
Intermetallic quasicrystals are usually formed in undercooled liquids or frozen supercooled liquids (i.e. metallic glasses) both containing icosahedral atomic clusters that formed in liquids at higher temperature. A hexagonal phase without large icosahedral clusters in a Zn65Mg25Y10 alloy transformed into IQC upon heating at 873 K which is around the melting point of the alloy, consistent with the law of entropy-optimized arrangement of atoms benefiting the stability of quasicrystals at high temperatures. However, it remains a challenge to realize solid-state crystal-to-quasicrystal transformation at relatively low temperatures when entropy doesn&’t predominate the free energy.
We found that Zn6Mg3Y icosahedral quasicrystals started to nucleate and grow epitaxially on Zn3MgY crystals in Mg matrix of a Mg-Zn-Y alloy at about 573 K during in situ heating on a transmission electron microscope (TEM). Interdiffusion resulted in segregation of Y and Zn in Mg at the Mg/Zn3MgY interfaces, which then triggered tetrahedral atomic rearrangement in Mg to form icosahedron pairs with surface distorted icosahedra of Zn3MgY. The icosahedron pairs are tiny embryos of icosahedral quasicrystals. The interfacial icosahedron pairs inherited the same interconnectivity of those in the interior of Zn3MgY, minimizing the nucleation barrier for icosahedral quasicrystal nanoparticles, lattice mismatch and distortion, and interfacial energy. The solid-state icosahedral ordering at lower temperatures sheds new light on understanding the nucleation and growth of quasicrystals.
In addition, In situ TEM observations showed the dynamical processes of eutectic IQC to W and H transformations at 688 K during heating, and the H to W transformation at 623 K on cooling. Quantitative analysis of the in situ transformation process reveals that both of the growth of H and W are diffusion-controlled growths, which agree with Avrami&’s model. These results provide useful information for microstructural optimization in order to improve the mechanical properties of Mg-Zn-Y alloys.
3:45 AM - OO2.05
Surface Step Induced Oscillatory Oxide Growth
Liang Li 1 Langli Luo 1 Jim Ciston 2 3 Wissam A Saidi 4 Eric A Stach 2 Judith C Yang 4 Guangwen Zhou 1
1State University of New York at Binghamton Binghamton USA2Brookhaven National Laboratory Upton USA3Lawrence Berkeley National Laboratory Berkeley USA4University of Pittsburgh Pittsburgh USAShow Abstract
Fundamental understanding of metal oxidation has received extensive interest due to its significant importance in many fields including high temperature corrosion, catalytic reactions, and thin film processing. However, many fundamental questions still remain unresolved concerning the early stages of oxidation, which is inaccessible by the traditional surface science and ‘‘bulk&’&’ materials science techniques. A detailed understanding of the early-stage oxidation is often complicated by surface inhomogeneities caused by the presence of surface defects such as steps. In this work, through the use of in-situ transmission electron microscopy (TEM) we observe that the presence of surface steps leads to the decomposition of the oxide overlayer at the growth front, thereby resulting in oscillatory oxide film growth. Using density-functional theory (DFT) total energy calculations and ab initio molecular dynamics (AIMD) simulations, we show that oxygen adsorption on the lower terrace destabilizes the oxide film formed on the upper terrace that leads to oxide decomposition. Our results reveal the unique role of surface defects in oxide film growth and may have broader implications for understanding the fundamental process governing gas-surface reaction kinetics as modulated by atomic defects on a solid surface.
4:30 AM - *OO2.06
In Situ Study of Uranium(VI) Oxide Colloid Formation and Their Relevance to Geodisposal Relevant Conditions
Sam Shaw 1 Pieter Bots 1 Gareth T.W. Law 2 Katherine Morris 1
1University of Manchester Manchester United Kingdom2University of Manchester Manchester United KingdomShow Abstract
In many countries a significant legacy of radioactive wastes exists. The strategy for radioactive waste management includes, for intermediate level wastes, containment in a Geological Disposal Facility (GDF) in the deep sub-surface which typically will contain cementitious materials. Interaction of groundwater with the cement and wastes will form a plume of hyperalkaline leachate (pH 13 - 10) . Under these conditions, thermodynamic modelling predicts that U(VI) solubility will be limited (ppb or lower) and controlled by equilibrium with alkali and alkaline-earth uranates . In addition to transport in the dissolved phase, colloidal transport of radionuclides may be significant . However, the potential formation of hexavalent uranium (U(VI)) colloids has received little interest despite the observation that U(VI) will be stabilised at elevated pH conditions relative to U(IV) . Here, we focused on the formation and characterisation of such colloidal phases.
Charactersiaterion of colloidal particles using conventional extraction and separation techniques (e.g. filtration) can be challenging for suspended nanoparticles (i.e. <10nm). In this study we have utilised in situ time resolved Small Angle X-ray Scattering (SAXS) to characterise the formation of U(VI) oxide nanoparticles from a synthetic cement leachate (pH asymp; 13) with 10-60 ppm U(VI), and their aging over 2.5 years. Experiments were performed on beam line I22 of the Diamond Light Source. The results show the colloids consisted of 1.5 - 1.8 nm nanoparticles with a proportion of 20 - 60 nm aggregates which form within a few hours. In addition, the colloid remained stable for at least 2.5 years, and in the presence of several mineral phases (e.g. calcite). X-ray absorption spectroscopy in combination with TEM showed that the nanoparticles had a clarkeite (Na/K/Ca-uranate) type structure.
The presented results have clear and hitherto unrecognised implications for the mobility of U(VI) in cementitious environments, in particular those associated with the geological disposal of nuclear waste.
 Small and Thompson (2009) Scientific Basis for Nuclear Waste Management 1124, 327-332  Gorman-Lewis et al (2008) J. Chem. Thermodyn. 40, 980-990  Silva and Nitsche (1995) Radiochim. Acta. 70-1, 377-396  Gaona et al (2012) Appl. Geochem. 27, 81-95
5:00 AM - OO2.07
Surface Reconstruction Mechanism of Carbon Nanotube Growth on Bulk Stainless Steel
Sebastian William Pattinson 1 Viswanath Balakrishnan 1 Dmitri Zakharov 2 Eric A Stach 2 Anastasios John Hart 1
1Massachusetts Institute of Technology Cambridge USA2Brookhaven National Laboratory Upton USAShow Abstract
The direct growth of carbon nanotubes (CNTs) from bulk stainless steel enables the economical production of corrosion-resistant hierarchical materials with exceptional surface area as well as high thermal and electrical conductivity. Such direct growth has been achieved previously on stainless steel, typically through air annealing or acid treatment prior to synthesis, but often suffers from relatively poor yield, alignment, and lack of control over CNT morphology, preventing the realization of diverse applications ranging from heat exchangers to filtration membranes and capacitors. Previous work has suggested the importance of nanoscale roughness on the stainless steel surface as well as the removal of the steel&’s native chromium oxide outer layer. However, these findings result primarily from ex-situ studies and the exact role that they play, if any, in CNT growth remains unclear. Furthermore, how stainless steel geometry affects CNT growth has not been studied. We present the first direct observations of CNT growth from stainless steel using lattice fringe imaging and electron energy loss spectroscopy in an environmental transmission electron microscope. We will show how the sequential oxidation and reduction of the surface, and associated mechanical forces, lead to the formation of loosely bound, discrete nanoparticles that nucleate and grow CNTs. Among other findings, our in-situ study demonstrates that CNT growth can proceed from Fe-Cr and Fe-Ni alloy particles, and that CNT growth does not require the removal of the chromium surface oxide. We subsequently use the understanding gained from these detailed observations to improve CNT yield and morphological control on diverse stainless steel geometries through sequences of pre-treatments in oxidizing, reducing, and inert atmospheres. In addition to enabling the manufacture of CNT/stainless steel hybrids, these mechanisms are applicable to the general direct growth of CNTs from bulk metal substrates and will help to realize this new class of hierarchical materials.
5:15 AM - OO2.08
In Situ Imaging of Zeolite Surface Growth by Atomic Force Microscopy
Jeffrey Daniel Rimer 1 Manjesh Kumar 1
1University of Houston Houston USAShow Abstract
The exceptional thermal stability, tunable porosity, unique shape-selectivity, and high acidity of zeolites contribute to their frequent use as catalysts and adsorbents. The inability to a priori control crystal growth, however, often yields materials with undesirable physicochemical properties. Approaches capable of selectively tailoring zeolite size, morphology, and/or crystal structure can lead to dramatic improvements in their performance. Given the application of zeolites in areas of biofuels, methane conversion, and CO2 sequestration, there exists a need to expand the fundamental understanding of zeolite growth as well as design synthetic routes to optimize their properties. In this talk, we will discuss a new advancement in atomic force microscopy (AFM) that has enabled us to image zeolite surface growth in situ under realistic synthesis conditions (i.e., high temperature and long duration). AFM offers unparalleled insight of dynamic processes governing zeolite growth at near-molecular resolution . We used in situ AFM to characterize zeolite surface growth over the course of 10 - 30 hours of continuous scanning. A systematic study of silicalite-1 revealed that growth occurs by two concurrent mechanisms: a classical route (i.e., molecule addition) and a non-classical pathway defined by the addition and subsequent rearrangement of amorphous precursor particles. These studies have been expanded to other zeolite crystal structures. We will discuss these findings and place their significance within the broader context of other zeolite crystal structures that are believed to grow by a variety of different pathways.
 A.I. Lupulescu and J.D. Rimer, In Situ Imaging of Silicalite-1 Surface Growth Reveals the Mechanism of Crystallization, Science 344 (2014) 729-732
5:30 AM - OO2.09
Real-Time X-Ray Study of Structural Evolution during Layer-by-Layer Growth of SrTiO3
I-Cheng Tung 1 2 G. Luo 3 Z. L. Luo 4 5 J. H. Lee 2 S. H. Chang 4 D. Morgan 3 H. Hong 2 M. J. Bedzyk 1 J. W. Freeland 2 D. D. Fong 4
1Northwestern University Evanston USA2Argonne National Laboratory Argonne USA3University of Wisconsin-Madison Madison USA4Argonne National Laboratory Argonne USA5University of Science and Technology of China Hefei ChinaShow Abstract
Functional materials based on complex oxides in thin film form offer new and exciting strategies for meeting many of our outstanding energy challenges through systematic control of layer sequencing, strain, etc. However, synthesis of such oxide films can be a major challenge even when utilizing reactive molecular-beam epitaxy (MBE), a powerful deposition technique that is often regarded to allow the construction of materials atomic plane by atomic plane. To understand the fundamental physics of oxide growth by reactive MBE, we present in situ surface x-ray scattering results of the homoepitaxial growth of SrTiO3 thin films on (001)-oriented SrTiO3 substrates. By comparing sequential deposition (alternating Sr and Ti monolayer doses) with that of co-deposition of Sr and Ti, both in a background of oxygen pressure, we find drastically different growth pathways. While the co-deposition is marked by the usual roughening-smoothing transition associated with the completion of each layer, sequential deposition demonstrates strong islanding of the SrO monolayer followed by a smoothing transition during the TiO2 layer deposition. Using in situ x-ray specular reflectivity and surface diffuse x-ray scattering during growth, an area detector simultaneously recorded both the specular x-ray scattering connected to out-of-plane atomic positions and the diffuse x-ray scattering associated with in-plane correlations. During growth of SrTiO3 by co-deposition, where the fluxes of Sr and Ti are roughly equal, the specular intensity at the half-order position is at a minimum while the diffuse intensity is at a maximum. This is consistent with a 2D island growth mode with unit-cell-high SrTiO3 islands that nucleate/grow on the terraces and coalesce before the next layer starts. For the case of sequential deposition, the scattering indicates that the SrO grows as islands and then restructures into SrTiO3 unit cells during the growth of the TiO2 to form an atomically flat layer. Theoretical calculations indicate that the growth of a single monolayer of SrO layer is thermodynamically preferable, so kinetic processes cause the formation of SrO islands. However, smoothing of SrO bilayer islands during the deposition of TiO2 to form perovskite SrTiO3 is energetically favorable. A detail comparison of sequential deposition and co-deposition will be presented, demonstrating the power of quantitative x-ray probes for understanding the process of thin film synthesis.
Work at Argonne, including the Advanced Photon Source, is supported by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
5:45 AM - OO2.10
In-Situ Observations during Graphene and Hexagonal Boron Nitride Growth by Scalable Chemical Vapour Deposition Processes
Piran Ravichandran Kidambi 1 Bernhard C Bayer 2 Raoul Blume 3 Carsten Baehtz 4 Robert S Weatherup 1 Philipp Braeuninger 1 Andrea Cabrero 1 Sabina Caneva 1 Tomasz Cebo 1 Robert Schloegl 3 Stephan Hofmann 1
1University of Cambridge Cambridge United Kingdom2University of Vienna Vienna Austria3Fritz Haber Institute Berlin Germany4Forschungszentrum Dresden-Rossendorf Dresden GermanyShow Abstract
Scalable synthesis of 2D materials such as graphene and hexagonal boron nitride h-BN by chemical vapour deposition (CVD) has generated considerable research interest. However, the growth mechanisms of graphene and h-BN during CVD remain poorly understood. Simplistic models of elemental solubility of the constituent elements (eg: C, B etc.) in metallic catalysts eg: Ni (high solubility - precipitation from bulk) and Cu (low solubility - surface reaction) have so far been speculatively proposed based on ex-situ experiments while critical in-situ experimental evidence remains elusive. [1,2]
Here, using a combination of high-pressure process, time and depth resolved in-situ X-ray photoelectron spectroscopy (XPS) at the BESSY II synchrotron in Berlin [1,2] and in-situ X-ray diffraction (XRD) at the ESRF synchrotron in Grenoble, [1,2] we study the behaviour of polycrystalline transition metal catalyst films and foils during CVD at industrially relevant CVD conditions, i.e. pressure (~0.001 - 0.5 mbar) and extreme temperatures (800-1000oC).
These complementary in-situ XPS and XRD experiments allow us to identify the chemical state/phase of the catalyst and the elemental species at any point of time during CVD. This allows us to observe elemental incorporation into the 2D material structure on the catalyst surface as it happens. The growth mechanisms of these 2D nanostructures is found to be predominantly isothermal along with some precipitation on cooling for both Ni and Cu, i.e. we observe the detailed dynamics of the catalytic behaviour during growth as a complex interplay of isothermal and precipitation based growth mechanisms with kinetic effects playing an important role.
We highlight the use of our in-situ approach as a generic framework to study the growth other 2D and 1D nanostructures during CVD.
1. Kidambi et al. Nano Letters (submitted)
2. Kidambi et al. Nano Letters 13 (10), 4769-4778 (2013).
3. Kidambi et al. J. Phys.Chem. C. 116, 42, 22492-22501 (2012).
4. Kidambi et al. PSS RRL. 5, 9, 341-343 (2011).
OO1: In Situ Characterization of Nucleation, Growth and Transformation I
Monday AM, December 01, 2014
Hynes, Level 1, Room 101
10:00 AM - *OO1.01
An In Situ View of Nucleation
Jim J De Yoreo 1 2
1PNNL Richland USA2University of Washington Seattle USAShow Abstract
Nucleation is the seminal process in the formation of ordered structures ranging from simple inorganic crystals to self-assembled macromolecular matrices. Yet due to its inherent dynamics much of what we know about nucleation comes from observations of the products rather than the processes. Consequently, in situ techniques of imaging and spectroscopy are critical to developing a foundational framework to describe this key step in materials synthesis. Molecular scale observations of structural and morphological evolution provide direct knowledge of nucleation pathways, while measurements of nucleation rates vs. temperature and supersaturation enable one to determine the kinetic and free energy barriers that define these pathways. Optical and force spectroscopic probes then establish the connection between this energy landscape and the underlying molecular interactions. Here we illustrate this approach to understanding nucleation by using in situ methods including AFM, TEM, and optical microscopy combined with FTIR and dynamic force spectroscopy (DFS) to investigate nucleation of ordered states in protein and mineral systems. TEM observations of calcium carbonate reveal the multiple complex pathways available to the system, due to the high driving force required to overcome the large free energy barrier to homogeneous nucleation of the stable phase. AFM and optical measurements of nucleation rates vs. supersaturation demonstrate that organic matrices can direct nucleation of a fixed phase by dramatically reducing these barriers. DFS measurements demonstrate that the underlying source of this control is the matrix-crystal binding energy. AFM studies of self-assembly in both the S-layer protein and collagen systems reveal the key role played by conformational transformations in controlling the pathways and kinetics of matrix assembly. The results demonstrate that the pathway to the final ordered state often passes through transient, less-ordered conformational states. Thus the concept of a folding funnel with kinetic traps used to describe protein folding is also applicable to nucleation of ordered protein matrices. Finally, both AFM and TEM studies of matrix mineralization illustrate the strong control that ion-matrix binding has in defining the location of mineral nucleation. Taken together, these results provide new insights into the mechanisms and pathways controlling nucleation of ordered states in biomolecular and biomineral systems.
10:30 AM - OO1.02
In-Situ Characterization of the Nucleation, Phase Formation, and Chemistry during the Molecular Beam Epitaxy of Oxides
Oliver Bierwagen 1 James S. Speck 2 Patrick Vogt 1 Michael Hanke 1 Andre Proessdorf 1 Vladimir M. Kaganer 1
1Paul-Drude-Institut (PDI) Berlin Germany2University of California Santa Barbara USAShow Abstract
Molecular beam epitaxy (MBE) is a thin film growth method that allows to synthesize high-quality, single-crystalline layers with defined thickness and stoichiometry. During MBE the elements to form the layer are provided as elemental vapor with defined flux in an ultra-high vacuum environment. This setup enables a simple chemistry that is free from incorporation of impurities and free from unwanted reactions and their products.
The MBE growth of oxides is realized by subliming the oxidic source material or evaporating the source metal and providing an oxidizing flux (molecular oxygen or an oxygen plasma).
This contribution demonstrates the in-situ investigation of the MBE of La2O3, In2O3, and Ga2O3 during growth.
In particular, the nucleation and phase formation was analyzed by in-situ reflection-high-energy electron diffraction (RHEED) and x-ray diffraction (XRD) of La2O3 oxide growth. The nucleation of the cubic polymorph on Si(111) substrate was followed by the formation of the bulk-stabile hexagonal phase as determined by XRD, wheras the growth rate could be measured using RHEED oscillations.
In-situ RHEED was also used to investigate the nucleation of In2O3 on ZrO2:Y(001) substrates as function of growth temperature and O/In flux ratio. A regime of fast nucleation was able to realize continuous films whereas the opposite regime of suppressed nucleation could be used to grow isolated islands.
The growth of Ga2O3 on Al2O3 was investigated by in-situ laser reflectometry to determine the growth rate and by line-of-sight quadrupole mass spectrometry to identify the desorbing species. Measuring the (positive or negative) growth rate as function of Ga and oxygen flux and the identification of the desorbing species helped identifying the chemical reactions at play. These are: 2Ga+3O->Ga2O3 and 4Ga+Ga2O3 ->3Ga2O.
Being not limited to oxides, these examples demonstrate the suitability of molecular beam epitaxy for many different types of in-situ measurement.
10:45 AM - OO1.03
Nucleation Kinetics of Carbon Nanotube Populations
Mostafa Bedewy 2 1 Viswanath Balakrishnan 2 Sebastian W Pattinson 2 Eric A Stach 3 Dmitri Zakharov 3 Eric R Meshot 4 Erik Polsen 1 Fabrice Laye 1 A. John Hart 2
1University of Michigan Ann Arbor USA2Massachusetts Institute of Technology Cambridge USA3Brookhaven National Laboratory Upton USA4Lawrence Livermore National Laboratory Livermore USAShow Abstract
Understanding the spatiotemporal evolution of populations of carbon nanotubes (CNTs) during the growth of vertically aligned "forests" by chemical vapor deposition (CVD) is key to engineering their morphology and properties. Hence, in situ characterization of the successive stages of the growth process is sought after. Previously, it was shown that Synchrotron X-ray scattering and absorption can provide valuable quantitative information about the morphological evolution and population dynamics of CNTs within a forest. However, the initial stages of nanoparticle formation and CNT nucleation are more elusive and cannot be inferred directly from transmission X-ray measurements. Grazing incidence X-ray scattering was also used to study the dynamics of catalyst film dewetting, but decoupling the scattering signal from catalyst nanoparticles and CNTs becomes challenging upon CNT nucleation. To further elucidate the early nucleation behavior of CNTs, we carry out in situ and operando experimental studies of CNT growth in an environmental transmission electron microscope (TEM). Real-time imaging of particle formation and CNT nucleation shows a characteristic S-shaped kinetics that span a few second, highlighting the non-instantaneous nature of nucleation. Although further studies are needed to identify the differences between active nanoparticles and inactive nanoparticles, results show that inactive nanoparticles that do not bear CNTs are generally encapsulated inside a graphitic coating. In situ TEM images also show the mechanical interactions between neighboring CNTs during the crowding stage that leads to the build-up of alignment in the forest morphology. Moreover, electron energy loss spectroscopy (EELS) is used to infer the kinetics of carbon deposition upon the introduction of the hydrocarbon gas (acetylene) to the reactor. Our findings indicate that tuning the catalyst annealing and growth conditions can modulate the "popping" kinetics of nanoparticles to enable instantaneous nucleation of CNTs and therefore the growth of uniform functional CNT forests.
11:45 AM - *OO1.05
In Situ, Environmental Transmission Electron Microscopy of Material-Gas Reactions
Robert Sinclair 1 Sang Chul Lee 1 Chia-Jung Chung 1 Ai Leen Koh 2
1Stanford University Stanford USA2Stanford University Stanford USAShow Abstract
Our work on in situ studies of the atomic mechanisms of material reactions by high resolution transmission electron microscopy has now been extended to environmental (ETEM) investigations (e.g. ). This technique will be reviewed and recent applications discussed. Our research has focused on simple reactions with a single pure gas and some recent results will be presented.
The oxidation of matter is a basic process with broad implications. Here we demonstrate in situ observations of the oxidation of carbon nanotubes being developed as field emission sources for X-ray medical imaging purposes. The oxidation mechanism is quite different than had been previously proposed but is easily demonstrated by the ETEM .
Likewise, hydrogen storage is promising for possible future energy applications, and so the reaction of hydrogen gas with candidate materials has fundamental importance. Following prior work on hydrogenation of magnesium/palladium thin films , we have extended this investigation to the hydrogenation of magnesium films with palladium nanoparticles. The formation of magnesium hydride in the ETEM is demonstrated, as is the utility of a new vacuum transfer specimen holder.
It is clear from both these studies that the imaging electron beam can influence the observations. Accordingly, protocols have been established whereby any possible influence of the electron beam is avoided, and these procedures will be discussed.
 Sinclair, R., In Situ High-Resolution Transmission Electron Microscopy of Material Reactions, Mats. Res. Bull., 38, 1065-1071, 2013
 Koh, A.L., Gidcumb E., Zhou, O., Sinclair, R, Observations of Carbon Nanotube Oxidation in an Aberration-Corrected Environmental Transmission Electron Microscope, ACS Nano, 7 (3), 2566-2572, 2013
 Chung, C.J., Lee, S.C., Groves, J.R., Brower, E.N., Sinclair, R., Clemens, B.M., Interfacial Alloy Hydride Destabilization in Mg/Pd Thin Films, Phys. Rev. Lett, 108, 106102 1-4, 2012
12:15 PM - OO1.06
In Situ Observation of Graphene Formation on Polycrystalline Cu Substrate
Huafeng Wang 1 Chisato Yamada 1 Shohei Chiashi 2 Shigeo Maruyama 2 Yoshikazu Homma 1
1Tokyo University of Science Tokyo Japan2The University of Tokyo Tokyo JapanShow Abstract
As a stable 2-dimensional material, graphene has been extensively studied. Currently, most of explanations on growth mechanisms are based on the experimental results after graphene formation, and the direct observation on the whole growth process is still lacking. To produce single-crystal graphene as large as possible and finally control its growth, the deep understanding on the growth mechanisms is indispensable. By in situ technique, it is possible to observe the whole process including the morphology change of the substrate surface, formation of graphene crystal and so on during growth. In situ scanning tunneling microscopy (STM) analyses have showed this process at atomic scale . Complementary to in situ STM, in situ scanning electron microscopy (SEM) observation provides a larger field of view, which may help us to better understand the growth mechanisms .
In this study, the whole graphene growth process on polycrystalline Cu substrate is observed by in situ SEM. The morphology changes of Cu surface and graphene structures formed under various conditions are carefully investigated. The influences of experimental parameters including temperature and growth time on the layer number of graphene as well as its quality are also discussed. According to our experimental observations, graphene is not created directly on the surface of Cu substrate but on an adsorbed gas layer over the surface, which is formed during graphene growth. The removal of this gas layer leads to the disappearance of graphene from SEM observation. Therefore, to finally obtain high quality graphene, the adsorbed gas layer on the surface of substrate has to be carefully considered. This result may suggest a possible direction for future research on graphene formation.
 Niu, T.; Zhou, M.; Zhang, J.; Feng, Y.; Chen, W. J. Am. Chem. Soc.135, 8409 (2013).
 Kidambi, P. R. et al. Nano Lett.13, 4769 (2013).
Corresponding Author: Huafeng Wang
Tel: +81-3-5228-8244, Fax: +81-3-5261-1023
12:30 PM - OO1.07
Nanoscale Phase Transformation of Pt-Alloys - Probing Thermally Induced Composition Segregation and Atomic-Ordering via In Situ Single-Nanoparticle Annealing
Sagar Prabhudev 1 Matthieu Bugnet 1 2 Guo-Zhen Zhu 3 Christina Bock 4 Gianluigi A Botton 1 2
1McMaster University Hamilton Canada2McMaster University Hamilton Canada3Shanghai Jiao Tong University Shanghai China4National Research Council Ottawa CanadaShow Abstract
Platinum-alloy nanoparticles are a system of great interest for fuel cell electrocatalysis and magnetic applications. Fine-tuning their structure to enhance catalytic activity and durability is crucial to commercialize fuel cell systems. In an ongoing attempt to reduce the mass loading of platinum (Pt) in proton exchange membrane fuel cells, there has been a tremendous research till date; constantly suggesting that a nanoscale alloying of Pt with 3d transition metals is a more viable option. Pt-Fe nanoalloys, in particular, have gathered much attention in recent years not just as a better catalyst to Pt/C, but also because of its magnetic properties that are deployable in ultra-high density information storage . However, a nanoscale phase transformation of an ensemble of alloy nanoparticles, polydispersed in both their size and composition, results in an assortment of materials with miscellaneous properties . Controlling their collective evolution and probing the interplay between compositional segregation and atomic-ordering is therefore imperative, and demands, full-fledged understanding at the atomic scale. Traditionally, a bulk approach has been followed in this respect, by deriving inference from ex-situ thermal treatments, before and after. Given the inherent dynamicity associated with nanoscale processes, an atomic-perspective is hence so far not been possible. Looking beyond, here we demonstrate an in-situ atomic-resolution imaging and spectroscopy — on single Pt-Fe alloy nanoparticles — over the course of thermal treatment .
Same particle was tracked all through and a combination of atomic-resolution STEM-HAADF imaging and STEM-EEL spectroscopy was performed. While our STEM-HAADF results clearly demonstrate evolution of particle shape, size, ordering and sintering kinetics (ripening and coalescence) over the course of heat treatment, the EELS maps reveal new insights into the segregation process. Additionally, we have stumbled across a new phenomenon that comes to play as a consequence of interaction of nanoparticles with their chemical environment and our results bear witness to its unique role in creating unusual structures (unicore-multishells, as an instance) at the nanoscale. We illustrate through a model as to how these dynamic processes can collectively lead to the formation of various nanoalloy configurations. We believe that a dedicated attempt to understand the nanoscale phase transformation as this, is central to fine-tune the catalytic properties of alloyed-Pt nanoparticles in general, and hence could redefine a new methodology to synthesize next generation fuel cell nanocatalysts.
 Prabhudev, S.; Bugnet, M.; Bock, C.; Botton, G. ACS Nano 7 6103-6110 (2013)
 Prabhudev, S.; Bugnet, M.; Zhu, G-Z.; Bock, C.; Botton, G. (submitted)
12:45 PM - OO1.08
Interrelationship of Growth Stress Evolution and Phase Transformations in Metallic Thin Film Multilayers
Li Wan 1 Xiao-xiang Yu 1 Gregory B. Thompson 1
1University of Alabama Tuscaloosa USAShow Abstract
As materials are reduced to the nanometer length scale, pseudomorphic phases can be stabilized. Thin films provide ideal systems to understand this phase stability because of their near atomic level control of thickness coupled to a high surface area; this creates tailored materials with high surface area-to-volume ratios. Thin films are also susceptible to significant epitaxial strains during growth which can contribute to the effects of interfacial energy reduction for the stabilized these pseudomorphic phases. Using an in situ laser reflectometry technique, the stress evolution of growing thin films was captured in real-time to understand how intrinsic growth stresses relate to phase stability. These associated growth stresses provide insights into adatom mobility during deposition. In the present work, this in situ technique has been utilized to elucidate the pseudomorphic bcc to ‘bulk&’ hcp stability of Ti in either a Ti/Nb or Ti/W multilayer. For Ti/Nb, the bcc phases have near equivalent lattice parameters whereas a significant deviation in bcc lattice parameters exist in the Ti/W system. During the initial growth, the Ti layers grew bcc with a tensile-stress state behavior. Upon reaching a critical thickness, a distinct change in stress occurred. The hcp Ti layer exhibited a relatively neutral stress change upon further growth. The subsequent deposition of either Nb or W resulted in the stress state of the film became very compressive. Atom probe tomography revealed significant intermixing through the Ti/Nb interfaces with segregation of Ti to the Nb grain boundaries. This intermixing resulted in a modification to the thermodynamic energies required for pseudomorphic stabilization. These experimental results have been compared to a hydride Molecular Dynamics + Monte Carlo simulation of the deposition process to clarify the intrinsic role of interfacial energy and strain that contributes to the bcc Ti stabilization. The simulations are compared to both the atom probe characterization and real-time, in situ stress evolution of the multilayer. This work has been supported by NSF-DMR-1207220.
Liane G. Benning, University of Leeds
Arda Genc, FEI Company
Dongsheng Li, Pacific Northwest National Laboratory
Jeffrey D. Rimer, University of Houston
Symposium Support Agilent Technologies, Inc.
OO4: In Situ Characterization of Materials for Energy Applications
Tuesday PM, December 02, 2014
Hynes, Level 1, Room 101
2:30 AM - *OO4.01
In-Operando Soft X-Ray Absorption Spectroscopy for Investigation of Charge Storage and Actuation in Nanostructured Carbon Aerogel Supercapacitors
Jonathan R. I. Lee 1 Michael Bagge-Hansen 1 Brandon Wood 1 Tadashi Ogitsu 1 Trevor Willey 1 Ich Tran 1 Arne Wittstock 1 Monika Biener 1 Matthew Merrill 1 Marcus Worsley 1 Minoru Otani 2 Cheng-Hao Chuang 3 David Prendergast 3 Jinghua Guo 3 Theodore Baumann 1 Tony van Buuren 1 Juergen Biener 1
1Lawrence Livermore National Laboratory Livermore USA2National Institute of Advanced Industrial Science and Technology Tsukuba Japan3Lawrence Berkeley National Laboratory Berkeley USAShow Abstract
Electric double-layer capacitors, or supercapcitors, store charge via polarization of the electrode-electrolyte interface of a very high specific surface area electrode and a suitable electrolyte. Traditionally, the predicted evolution of the electrified interface during the critical stages of charge and discharge almost exclusively considers the active role of the electrolyte: i.e., transport, proximity, and arrangement of ions approaching the electrode surface. Using in situ soft x-ray absorption spectroscopy and complementary ab initio modeling, we demonstrate that the electrode can also undergo complex, reversible, and highly influential structural transformations through the investigation of nanostructured carbon aerogel (CA) electrodes operating in prototypical electric double-layer capacitors. Profound bias- and time-dependent evolution of the electronic structure under applied bias connotes both surface distortion and specific adsorption. Simulations are leveraged to discriminate mechanisms for the observed dynamic structure and bonding of CAs within functioning supercapcitors and provide fundamental insights for charge storage models required for the rational design of electrodes with tailored architecture. This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
3:00 AM - OO4.02
In Situ TEM Study of Thin Coating and Native Oxide Layer on the Structural Evolution of Silicon as Anode for Lithium Ion Battery
Chongmin Wang 3 Yang He 4 3 Meng Gu 3 Chunmei Ban 1 Arda Genc 2 Lee Pullan 2 Scott X Mao 4 Jun Liu 3 Ji-Guang Zhang 3
1National Renewable Energy Laboratory Golden USA2FEI Company Hillsboro USA3Pacific Northwest National Laboratory Richland USA4Department of Mechanical Engineering and Materials Science, University of Pittsburgh Pittsburgh USAShow Abstract
For lithium ion battery, a range of materials has a high theoretical capacity and it is very often that this type of material is prone to cause the fast capacity fading of the battery. To address this problem, a range of microstructural designing concepts has emerged, most notably such as composites based on nanowires, nanotubes, and nanoparticles as well as in combination with surface structural and chemical modifications. For a lot of cases, the nanoscale designing concept is inspired and verified by direct in-situ imaging or spectroscopic analyzing of structural and chemical evolution of the materials under dynamic operating condition. In this presentation, we will explore the behavior of both native oxide layer and aluminum glycerol (ALGL) coating on silicon nanoparticle upon cyclic lithiation/delithation. We discovered that upon initial lithiation, the native oxide layer converts to Li2O, which essentially increases the impedance and exert mechanical confinement on the particle, resulting in incomplete lithiation/delithiation or inactive particle. This study clarifies the role of the native oxide on silicon nanoparticle on cycle performance and provides vivid picture of how coating layer works on preserving capacity.
3:15 AM - OO4.03
In Situ Wide Angle X-Ray Scattering Characterization of Roll to Roll Printed Organic Solar Cell
Xiaodan Gu 1 2 Yan Zhou 1 Ying Diao 1 2 Michael Toney 2 Stefan Mannsfeld 2 Zhenan Bao 1
1Stanford University Stanford USA2SLAC National Accelerator Laboratory Menlo Park USAShow Abstract
The current efforts to improve the OPV device performance almost exclusively employ spin-coating of the active materials in a protected atmosphere, with efficiencies now reaching 12% for small area devices on the order of millimeter squares. The fabrication conditions by which these very high electrical efficiency cells are currently produced generally cannot be simply transferred to a large-scale roll-to-roll industrial production scheme. The efficiency discrepancy between organic solar cells produced in the laboratory and large-scale devices manufactured in a roll-to-roll printing process need to be addressed before the commercialization of large area printed OPV devices. Correlating the process conditions, the morphology and electrical performance of the OPV devices are critical for solving the challenge of mass-producing high efficient large area organic solar cells.
To solve the above mentioned grand challenge, we developed a mini roll-to-roll compatible printing setup for organic solar cells with the capability to follow the film formation during solvent dry in situ with small and wide angle X-ray scattering at Stanford Synchrotron radiation facility. By using this set-up, time resolution down to 10ms was achieved to probe the drying kinetic and crystallization process of the organic semiconductor materials. This set-up also allows to use multiple inks that being delivered to the roll-to-roll printer head with different composition of the active layer between the donor and acceptor materials. We printed a variety of different BHJ OPV materials (both polymer fluorine systems and all polymer systems) on the flexible ITO/PET substrates and characterized the print process using in situ small/wide angle X-ray scattering (SAXS, WAXS). Wide range process parameters were investigated in details during R2R coating process, including solvent quality, drying temperature, shearing speed, blend ratio of donor and acceptor materials, additives, in order to obtain the optimized OPV morphology. By extracting the peak intensity, full widths at half maximum (FWHM) and peak position, rich information about the drying process as well as dried film are obtained. Finally the morphology of the OPV devices are correlated to electrical performance of the device (e.g. VOC , Jsc , FF, PCE), thus shed light on the best protocol for drying process to obtain the highest possible efficiency for the R2R coating of OPV materials on flexible substrates.
3:30 AM - OO4.04
Li Electrodeposition Dynamics Visualized In-Situ via a TEM Liquid Cell
Andrew Jay Leenheer 1 Katherine L Jungjohann 1 Kevin R Zavadil 1 Charles Thomas Harris 1
1Sandia National Laboratories Albuquerque USAShow Abstract
Understanding the nanoscale changes that occur in battery materials and interfaces is critical to improve battery reliability, safety, and efficiency. Direct visualization of the material dynamics during cycling is now possible with miniature cells in a transmission electron microscope (TEM), and here we describe the development of a custom hermetically-sealed TEM liquid cell that allows electrochemical control in realistic aprotic electrolyte environments relevant to Li-ion and other high voltage battery chemistries. In particular, imaging phenomena related to the electrode/electrolyte interface such as solid-electrolyte interphase (SEI) formation from electrolyte decomposition requires a sealed liquid cell. Here we demonstrate the liquid cell operation with lithium electrodeposition and stripping with precise electrochemical control and awareness of the TEM electron beam effects.
The liquid cell design consists of a thin, electron-transparent liquid cavity confined between two silicon nitride membranes microfabricated on silicon chips. Multiple current collector electrodes (W or Al) on the bottom chip allow a variety of experiments on the same platform as well as facile assembly of nanoparticles via dielectrophoresis. Sealable fluid fill ports on the top chip enable a variety of electrolytes, and the stand-alone design permits electrochemical testing independent of the TEM holder.
To demonstrate Li electrodeposition, the cell was filled with 1:1 ethylene carbonate:dimethyl carbonate with 1 M LiPF6 electrolyte and sealed with epoxy. The electrodes were nanopatterned Ti patches on W electrodes masked with Al2O3 such that a small, controlled working electrode area was fully viewable in the TEM. Applying a pA-level galvanostatic current resulted in clear, reversible Li electrodeposition on the Ti electrode, and features in the well-defined chronopotentiometry corresponded to specific events seen in the micrographs.
The electron beam damage was minimized in scanning (STEM) imaging mode with a low pA-level beam current, but some beam-induced effects were still evident. The Li deposition morphology grown while irradiated in-operando always formed circular/spherical deposits, while more crystalline/dendritic deposits were seen with the beam off during deposition and subsequent in-situ imaging. Additionally, growth of a beam-induced SEI was clearly visible with prolonged exposure. Knowledge of the deposition morphology and beam effects gives a deeper understanding of Li electrodeposition and progress towards suppression of detrimental dendrite formation.
3:45 AM - OO4.05
Bouncing Alkaline Batteries: A Basic Solution
Shoham Bhadra 2 Benjamin Joseph Hertzberg 3 Peter James Gjeltema 3 Barry James Van Tassell 4 Joshua Gallaway 5 Mylad Chamoun 1 Can Erdonmez 1 Frances Ross 6 Daniel Steingart 3
1Brookhaven National Laboratory Upton USA2Princeton University Princeton USA3Princeton University Princeton USA4City College of New York New York USA5City College of New York New York USA6IBM Yorktown Heights USAShow Abstract
Understanding the evolution of the electrochemical constituents of a battery during discharge can offer detailed information about state of charge as well as failure mechanisms. However, typical methods of characterizing the internal components of batteries are often only applicable post mortem. Previous work has used energy-dispersive x-ray diffraction (EDXRD) spectroscopy to image discrete volumes within Zn-MnO2 “alkaline” batteries, and has shown the evolution of the internal components during discharge. Most notably, the oxidation of the anode from Zn to ZnO has been quantified as a function of state of charge. Recently, there has been popular interest in the tendency of an alkaline AA battery to bounce after being dropped on its end when discharged to full capacity, compared to a flat landing with minimal bounce when the battery is as-received. This bounce test presents a non-destructive method of assessing the material properties of the battery, and thus the state of the electrochemical constituents.
In this work, we present an explanation for this bouncing, and quantify it by measuring the coefficient of restitution (COR) of alkaline AA batteries as a function of depth of discharge (DOD). The COR is shown to be constant at low DOD, but then begins to rise rapidly at 20% DOD, finally saturating at a value of 0.63 +/- 0.05 at 50% DOD. We have found this rise and saturation to correlate strongly to EDXRD spectra, showing that increase in COR corresponds to the formation within the anode of a contiguous pathway of ZnO particles from the separator to the current collector. The saturation is best explained due to densification of the anode core to a porous ZnO solid. SEM microscopy of as-received and fully-discharged batteries has confirmed this process. Of note is the sensitivity of the COR to the amount of ZnO formation, which rivals the sensitivity of in situ energy-dispersive x-ray diffraction spectroscopy.
Building from these results, we present a method similar to the Split Hopkinson Pressure Bar experiment, in which a compressive impulse is applied to a metal bar and the resulting strain wave is measured before and after transmittance through a sample. We show that the speed of the strain wave within an alkaline cell varies with state of charge, and therefore that acoustic determination of state of charge is possible. We also present 1-D wave simulations to support the results from the Split Hopkinson Pressure Bar experiment. Based on these results, we suggest future methods that can incorporate a transducer/detector system in which the state of charge of a cell can be measured in situ without interruption of the battery system operation.
4:30 AM - OO4.06
Tracking Liquid-Solid Interactions in Batteries Using In-Situ Liquid-Cell TEM
Khim Karki 1 Peng Gao 1 Wei Zhang 1 Daan Hein Alsem 2 Norman Salmon 2 Feng Wang 1
1Brookhaven National Laboratory Upton USA2Hummingbird Scientific Lacey USAShow Abstract
A mechanistic understanding of the electrochemical reactions that occur at battery electrodes is needed to provide a scientific underpinning for the design of new electrode materials. The development of the in-situ open-cell transmission electron microscopy (TEM) technique - using either an ionic liquid or Li2O electrolytes - has made it possible to track dynamic structural and morphological changes that occur within individual nanostructures at high tempo-spatial resolutions [1,2]. However, the direct use of conventional liquid electrolytes, which have high vapor pressure, is inconducive for the high vacuum environment of TEM. We will demonstrate the utility of the liquid-cell technique to observe charge/discharge processes at electrodes in real time. This has the advantage of being flexible enough to utilize any standard liquid electrolyte, thereby allowing the direct exploration of both electrode-electrolyte interfacial reactions as well as structural and morphological changes. We have studied conversion-based iron fluorides, such as FeF2 as a model system. Iron fluorides are promising candidates to replace current intercalation-based cathode materials (e.g. LiCoO2 and LiFePO4; capacities <160 mAh/g), because of their ability to accommodate more than one electron per transition metal, thus resulting in higher specific capacities (>500 mAh/g) [2, 3]. We performed in-situ TEM studies of lithium reactions within individual crystalline FeF2 nanorods, directly visualizing such conversion process in the bulk as phase nucleation and transformation, as well as related interfacial phenomena. In contrast to rapid lithium diffusion on the FeF2 rod surface , lithium diffusion into the bulk was severely impeded. Moreover, there was a preferential orientation-dependent diffusion of lithium, accompanied by an anisotropic volume expansion during lithiation. A detailed understanding of the orientation dependence of the lithium transport across electrolyte-solid interface and through the bulk of FeF2 nanorods will be discussed.
 Huang et al., Science330 (2010) 1515.
 Wang et al., Nat. Commun.3 (2012) 1201.
 Wang et al., J. Am. Chem. Soc. 133 ( 2011) 18828.
This work is financially supported by Northeastern Center for Chemical Energy Storage, an Energy Frontier Research Center funded by the U.S. DOE, BES under award number DE-SC0001294, and the LDRD at Brookhaven National Laboratory. Research carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, under Contract No. DE-AC02-98CH10886.
4:45 AM - OO4.07
High-Temperature Evaporation Behavior of LiFePO4 Crystals in a Geometrically Confined Environment
Sung-Yoon Chung 1
1KAIST Daejeon Korea (the Republic of)Show Abstract
When polycrystals are dispersed in the matrix, such as a solution or vapor, it is readily observed that particles larger than those of average size grow, accompanying the dissolution of smaller particles into the matrix at the same time. This particle coarsening process has generally been referred to as Ostwald ripening. As the entire microstructure of polycrystalline materials consists of both growing and shrinking crystals, scrutiny of shrinking (or evaporating) characteristics is essential for a complete understanding of the kinetic evolution of microstructure. Recent advances in transmission electron microscopy (TEM) enable atomic-scale imaging for direct visualization of lattice defects, phase transition, and structural evolution. In particular, a variety of techniques have been utilized for real-time observations in TEM, providing unexpected and new experimental findings in LiFePO4 (S.-Y. Chung et al., Nature Phys.5, 68 (2009); Nano Lett.12, 3068 (2012); J. Am. Chem. Soc.135, 7811 (2013)). By capturing real-time in situ high-resolution electron micrographs at high temperatures, in this presentation we demonstrate the evaporation behavior of LiFePO4 crystals embedded in a solid crystalline matrix, instead of crystals in a vapor, during recrystallization. Low-energy grain boundaries between an embedded nanocrystal and a matrix are clearly observed transitioning into comparatively high-energy surfaces before substantial evaporation begins, creating unavoidable free energy instability at the early stage of evaporation. Additionally, post-transition evaporation behavior is discussed in terms of the local strain field distribution inside the crystal and the anisotropic grain-boundary energy. This study suggests that the initial energy instability induced by the boundary transition strongly influences the overall evaporation rate of crystals that are geometrically confined by a solid phase.
5:00 AM - OO4.08
In Situ Potential Cycling of Pt-Alloy/C Nanoparticles in a TEM
Sagar Prabhudev 1 Guo-Zhen Zhu 2 Jie Yang 3 Christine Gabardo 3 Gianluigi Botton 1 Leyla Soleymani 4
1McMaster University Hamilton Canada2Shanghai Jiao Tong University Shanghai China3McMaster University Hamilton Canada4McMaster University Hamilton CanadaShow Abstract
Controllability over the size, shape, composition and surface properties of nanoparticles is imperative to achieve enhanced catalysis in energy conversion and storage systems. Equally important is to gain insights into the native chemical environment and various dynamic mechanisms that come into play during the actual catalyst reaction processes. Particularly in the case of proton exchange membrane (PEM) fuel cells, the nanocatalyst degradation is a serious limiting factor for commercialization. Although structural degradation of nanoparticles has been extensively studied in the past through various ex-situ electrochemical methods, employing an in-situ technique can greatly improve our understanding of the mechanisms involved during electrochemical cycles. In-situ imaging through liquids is certainly a promising approach for exploring biological and materials processes in their native operating environment . This report describes our recent findings on simultaneous investigation of both, the structural evolution and electrochemical responses of platinum-iron (Pt-Fe) nanoalloy catalyst particles, using an in-situ liquid cell inside a TEM. In-situ studies were conducted using a Protochips flow cell with 50 nm thick silicon nitride viewing windows spaced about 250 nm apart. Through identical location imaging over the course of several potential cycles, we illustrate how the coarsening mechanisms, including nucleation and the growth, are not uniform, both in space and in time scale. The growth rate was, interestingly, found to be both site- and potential-dependent. Further, these particles were found to exhibit considerably different behaviors when attached to an electrode as opposed to when isolated in the bulk of the electrolyte. In addition to experimental characterization results, we demonstrate this with a numerical model studying the distribution of current density, which relates to the rate of electrode reactions in the electrochemical cell. An increased current density was observed near the working electrode that was found to be decreasing as we moved towards the counter electrode. In addition, we observe current density hot spots between particle aggregates. We expect higher electrochemical reaction rates to occur at areas with increased current density. However due to the highly localized nature of this effect, we do not expect it to influence the electrochemical reaction rates in regions beyond a few microns away from the particles. In summary, with Pt-Fe nanoalloy system as a candidate material, we demonstrate that the in-situ structural characterization of nanocatalysts under electrochemical bias and inside the native electrolyte environment provides much deeper insights into the catalyst degradation mechanisms compared to the routine ex-situ electrochemical studies .
 N. de Jonge and F. Ross, Nature Nanotechnology 6 (2011) 695.
 Prabhudev. S, et.al. ACS Nano 2013, 7, 6103-6110
5:15 AM - OO4.09
In-Situ Scanning Electron Microscope Observations of Strain-Confined Lithium Nucleation at Electrode/Electrolyte Interfaces in All-Solid-State-Lithium Battery
Munekazu Motoyama 1 2 Makoto Ejiri 1 Yasutoshi Iriyama 1 2
1Nagoya University Nagoya Japan2JST-ALCA Chiyoda-ku JapanShow Abstract
We will present in-situ scanning electron microscope (SEM) observations of the growth and dissolution of Li islands/whiskers through solid electrolyte interfaces coated with a metal current collector as a function of current density during charge-discharge processes.
A great deal of attention has been paid to the development of next-generation-rechargeable batteries that may store several times more energy than commercial Li-ion batteries. The research on all-solid-state-lithium batteries (SSLB) has been significantly propelled by advancements in techniques to decrease solid/solid interface resistivity and new discoveries of solid Li+ ionic electrolytes.
Inorganic solid electrolyte blocks Li dendrite growth if Li metal is used as the negative electrode. This is certainly attractive because the theoretical energy density of Li metal (2060 Ah L-1) is much greater than those of presently commercialized negative electrodes (< 1000 Ah L-1). Moreover, there are also other advantages of using ceramic electrolyte: (1) non-flammability; (2) simplified battery pack design due to no risk of electrolyte leakage; (3) longer cycle and calendar life compared to organic liquid electrolyte.
Amorphous electrolyte plays a key role in blocking Li growth from the anode for using Li metal as the negative electrode in SSLB. It is thus important to study how Li metal grows and dissolves through amorphous solid electrolyte interfaces during charging and discharging. Extensive studies of electrochemical Li deposition and dissolution have not sufficiently been devoted to solid electrolyte systems.
Since solid electrolytes are not volatile, conventional electron microscope techniques can be applied for observations of in-situ electrochemical experiments using this class of electrolytes.
We have studied the electrochemical Li deposition and dissolution under galvanostatic condition (50 mu;A cm-2 to 1.0 mA cm-3) using an amorphous electrolyte of lithium phosphorous oxynitride (LiPON)1. Li deposition invokes non-uniform nucleation that leads to whisker-like growths on a LiPON layer. Consequently, analyzing every step of Li growth trajectories at fixed sites during charge-discharge processes is an important step toward understanding the mechanisms of non-uniform Li growth. We will discuss the mechanism of Li nucleation at solid/solid interfaces under significant strain-confinements due to a rigid electrolyte, which are different from liquid/solid interfaces.
The authors thank the Advanced Low Carbon Technology Research and Development Program (ALCA) of the Japan Science and Technology Agency (JST) for the financial support.
1. M. Motoyama, M. Ejiri, and Y. Iriyama, Electrochemistry,82, 364 (2014).
5:30 AM - *OO4.10
Dynamics of Heterogeneous Catalysts
Robert Schloegl 1 2
1Fritz Haber Institute of the Max Planck Society Berlin Germany2Max Planck Institute for Chemical Energy Conversion Mamp;#252;lheim a. d. Ruhr GermanyShow Abstract
It is widely assumed about heterogeneous catalysts, that they are rigid and neither lost nor deactivated (ideally) during operation. They can be pre-determined in their function by a rational synthesis based on crystal structures.
Although this conjecture is true for the bulk phases of such catalysts we have now learned that the functional surface of heterogeneous catalysts is not rigid and not pre-determined directly by synthesis. Performance catalysts activate in contact with their feeds and respond to temporal changes of the local chemical potential.
The contribution exemplifies this new concept in catalysis and gives examples of how in-situ controlled synthesis can be used to optimize the response of a performance catalyst to its desired activation.
 a B. Frank, T. P. Cotter, M. E. Schuster, R. Schlögl, A. Trunschke, Chem. Eur. J. 2013, 19, 16938-16945; b M. Sanchez Sanchez, F. Girgsdies, M. Jastak, P. Kube, R. Schlögl, A. Trunschke, Angew. Chem. Int. Ed. 2012, 51, 7194-7197; c M. Eichelbaum, M. Hävecker, C. Heine, A. Karpov, C.-K. Dobner, F. Rosowski, A. Trunschke, R. Schlögl, Angew. Chem. Int. Ed. 2012, 51, 6246-6250.
OO3: In Situ Characterization of Nucleation, Growth and Transformation III
Tuesday AM, December 02, 2014
Hynes, Level 1, Room 101
9:15 AM - *OO3.01
Real Time Imaging through Liquids Using Transmission Electron Microscopy
Haimei Zheng 1
1Lawrence Berkeley National Laboratory Berkeley USAShow Abstract
Liquid cell Transmission Electron Microscopy (TEM) allows imaging through liquids with high spatial and temporal resolution has attracted significant interest in recent a few years. Many different areas have been explored including nanoparticle growth, materials corrosion, electrode-electrolyte interfaces, diffusion in liquids, etc. In this talk, I will first present our study on nanoparticle shape evolution during solution synthesis. Both growth by monomer attachment and nanoparticle coalesce have been observed. The growth mechanisms and shape controlling factors have been identified with the assistance of theoretical calculation. Second, I will show our progress in the study of electrochemical processes by the development of electrochemical liquid cells. At the end, the electron beam effects in the liquid cell study will be discussed.
9:45 AM - OO3.02
Atomic Scale Studies of Vo Ordering Mechanism in Epitaxial LaCoO3-X Thin Films by Real-Time Observation
Jae Hyuck Jang 1 Rohan Mishra 2 Liang Qiao 1 Dongwon Shin 1 Michael Biegalski 1 Albina Borisevich 1
1Oak Ridge National Lab Oak Ridge USA2Vanderbilt University Nashville USAShow Abstract
Transition metal oxides (TMOs) have attracted attention for solid oxide fuel cell, gas sensor and catalytic applications. The energetics of the oxygen reduction reaction at the cathode is the key determinant for solid oxide fuel cell functionality. Although oxygen diffusion in cathode materials, including the path oxygen ion takes through the lattice, has been studied by DFT , it is still difficult to investigate diffusion mechanism experimentally, especially at atomic resolution. Recently, it became possible to characterize oxygen vacancy distribution and vacancy ordering at an atomic scale in the static case using quantitative aberration-corrected STEM.  In this study, we take this approach to the next level by observing lattice dynamics of phase transition from perovskite LaCoO3 to brownmillerite LaCoO2.5 with atomic resolution. We also perform DFT calculations to confirm the energetically favorable ion trajectories in LaCoO3 based on the local atomic structure which is obtained by in-situ experiments.
We find that while before electron beam exposure films do not show any signs of vacancy ordering, they nevertheless contain a substantial amount of vacancies; the ordering is quickly induced by electron beam exposure. In the case of LCO film, beam exposure leads to a sequence of different phases, starting from disordered perovskite LaCoO3-x to eventually brownmillerite La2Co2O5-x, which is similar to the phase evolution observed in the bulk . Specifically, we directly observe the evolution of the sequence of octahedral (O) and tetrahedral (T) layers from 4:1 (OOOOT) to 2:1 (OOT) and finally 1:1(OTOT), which shows the oxygen vacancy motion along lateral direction as well as vertical direction during the transition from 4:1 to 2:1. When oxygen vacancies travel from one adjacent layer to another in the out-of-plane direction for a film, metastable configurations are sometimes observed. Motion of oxygen ions induced a cascade of changes in the positions of nearby La and Co atoms, as well asin the tilt patterns of the adjacent CoO6 octahedra. Kinetics of the Vo ordering as well as pathways to uncovering the exact atomic mechanism of oxygen vacancy ordering in LaCoO3-x at an atomic scale will be discussed.
* Research supported by the U.S. Department of Energy (DOE), Basic Energy Sciences (BES), Division of Materials Sciences and Engineering, and through a user project supported by ORNL&’s Center for Nanophase Materials Sciences (CNMS), which is sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. DOE.
 A. Chroneos, Energy Environ. Sci. 4, 2774 (2011)
 Young-Min et al., Nat. Mater. 11 888 (2012)
 Ole H. Hansten et al., J. Mater. Chem. 8(9) 2081 (1998)
10:00 AM - OO3.03
In Situ Monitoring of the Growth of Organic and Metallic Thin Films Prepared by Pulsed Laser Deposition
Michal Novotny 1 Jiri Bulir 1 Amina Bensalah-Ledoux 2 Premysl Fitl 3 Petr Hruska 1 Marek Skeren 4 Stephan Guy 2 Martin Vrnata 3 Jan Lancok 1
1Institute of Physics ASCR Prague Czech Republic2Institut Lumiamp;#232;re Matiamp;#232;re Lyon France3Institute of Chemical Technology, Prague Prague Czech Republic4Czech Technical University in Prague Prague Czech RepublicShow Abstract
Pulsed laser deposition (PLD) is a well-established technique in fabrication of thin film of inorganic materials, eg. metals. Moreover PLD was also shown as successful technique in preparation of some organic materials, eg. molecular materials for optolectronics. PLD profits from its simplicity, modesty, versatility and flexibility. Varying deposition conditions, ie. fluence, laser repetition rate, ambient pressure, substrate and its temperature, one can easily influence nucleation and the growth of thin film and consequently its properties. The in-situ monitoring of optical or electrical properties allows sophistically control such processes. We chose zinc phthalocyanine (ZnPc) and silver as organic and inorganic material examples, respectively, to demonstrate benefits obtained of the implementation of the in-situ monitoring. These materials possess a great potential for application in optoelectronic devices, eg. OLEDs and solar cells.
We investigated, using in-situ monitoring of absorbance measurement in UV-VIS spectral range, the growth of ZnPc in vacuum on suprasil quartz substrates at room temperature. The effect of laser fluence (in the region from 10 mJ.cm-2 to 100 mJ.cm-2) and laser repetition rate of 50 Hz and 200 Hz on ZnPc film growth and properties was evaluated. In-situ monitoring revealed the growth rate and β-polymorph of ZnPc film.
The growth of silver ultra thin film on fused silica and ZnPc substrates was characterized using in-situ monitoring of electrical properties. Electrical conductivity and I-V curve were measured by four-wire technique. We demonstrated that we could estimate the point of coalescence and influence the growth mode in the real-time as well as the subsequent evolution of the surface roughness and control.
The optical properties of the films were ex-situ characterized by spectral ellipsometry and morphology was examined by SEM and AFM.
10:15 AM - OO3.04
Application of K-Kit for TEM Imaging of Nanomaterials in Liquid State
Lin-Ai Tai 3 Chih-Jung Sun 1 Yufeng Ko 2 Pradeep Sharma 2 Tri-Rung yew 4 Chung-Shi Yang 3 CH Chu 2 YF Hsieh 2
1Bio Materials Analysis Technology Inc. Hsinchu Taiwan2Materials Analysis Technology Hsinchu Taiwan3Institute of Biotechnology and Pharmaceutical Research, National Health Research Institutes Miaoli Taiwan4Department of Materials Science and Engineering, National Tsing-Hua University Hsinchu TaiwanShow Abstract
Electron microscopy of nanomaterials in liquid state is essential for providing precise information about dispersibility, aggregation and agglomeration of nanomaterials in their native environment (solvents, or buffers). Moreover, to determine exact shape and size of nanomaterials in liquid is very important and useful. Drying/freezing of the samples is the traditional way to do the electron microscopy of the colloidal nanoparticles and bio-nanomaterials in liquid. However, this approach of sample preparation, sometimes, induces structural damages, and changes the aggregation and agglomeration of the nanomaterials. In this work, we report the application of K-kit for liquid state TEM characterization of gold nanoparticles/polystyrene nanobeads, and CMP slurry nanoparticles in liquid. Resolution and image quality of these nanoparticles in liquid are found to be comparable with those in dry state. Furthermore, K-kit was demonstrated as a high resolution solution for investigating liquid state dynamic processes in TEM. Examples of the dynamic changes of polystyrene nanobeads in PBS buffer solution and wet chemical growth of gold nanoparticles are presented in this work.
10:30 AM - OO3.05
In-Situ TEM Study of the Reduction of Nanostructured Iron Oxides
Wenhui Zhu 1 Qiyue Yin 1 Lu Yuan 1 Guangwen Zhou 1
1State University of New York at Binghamton Vestal USAShow Abstract
The chemical and physical properties of oxides depend sensitively on the phase, microstructure, atomic termination, stoichiometry and defects, all of which can be modified by oxide reduction. A fundamental understanding of the microscopic processes of the reduction of metal oxides is indispensable to obtain controllable functionalities of the oxide. Hematite (α-Fe2O3) exhibits a wide range of functionalities and has been demonstrated as catalysis, gas sensing, water splitting, dye solar cells, etc. However, the variable oxidation states of iron results in a fairly complicated phase diagram of iron oxides with several easily interchangeable phases, which makes it a challenge in understanding the reduction mechanism of hematite. We have obtained three different kinds of nanostructures of hematite, i.e., one-dimensional nanowires, two-dimensional nanoblades and nanobelts. By employing in-situ transmission electron microscopy, we studied the microscopic processes of the reduction of nanostructured hematite, i.e., one-dimensional nanowires, two-dimensional nanoblades and nanobelt,s, by hydrogen gas at elevated temperatures. Our results reveal that the reduction proceeds via heterogeneous, topotactic nucleation of lower oxides of iron, which results in various hybrid nanostructures of iron oxides. We showed that α-Fe2O3 nanowires can be reduced to γ- Fe2O3 nanowires, followed by transformation to Fe3O4, i.e., α-Fe2O3 --> γ- Fe2O3 --> Fe3O4. The comparative study of the reduction of Al2O3-coated α-Fe2O3 is also performed to understand the effect of surface confinement on the oxide reduction processes.
10:45 AM - OO3.06
2D Electron Transparent Windows for Ambient Pressure Imaging and Spectroscopy of Interfacial Processes
Andrei Kolmakov 1
1NIST Gathersburg USAShow Abstract
We have tested graphene as electron transparent window material for environmental cells dedicated for ambient pressure XPS spectroscopy and electron microscopy of interfaces under atmospheric pressure liquid and gaseous samples. These windows have thicknesses comparable or smalle compared to the effective attenuation length of 200-1000 eV electrons what allow to conduct interfacial spectroscopy of fully hydrated or gaseous samples . Based on this unique combination of properties and on recent developments in graphene fabrication and transfer protocols we demonstrate the capability to perform in situ electron microscopy and XPS spectroscopy studies of the dynamic electrochemical processes taking place at liquid electrolyte-solid interface.
11:30 AM - *OO3.07
Visualizing Electrochemical Deposition Using Liquid Cell Electron Microscopy
Frances M. Ross 1
1IBM T. J. Watson Research Center Yorktown Heights USAShow Abstract
Liquid cell transmission electron microscopy enables observation of processes in liquids with good spatial and temporal resolution, yielding information that is complementary to that available from light microscopy, scanning probe microscopy and scattering techniques. Here we discuss its application to electrochemical deposition, measuring local structure and growth rate during the formation of metal films from aqueous electrolytes. Control of the morphology of electrochemically deposited films is critical for creating high quality coatings and high performance structures for interconnects, sensors, magnetic storage devices and batteries. Liquid cell electron microscopy can give detailed information on morphology evolution as a function of electrolyte composition, electrode geometry and current/voltage parameters. We will show in movies the progression of the growth front during deposition in different materials systems, and quantify the onset of growth instabilities such as dendrites. Parameters of the growth front such as roughness, local velocity and curvature allow us to test models for growth instabilities and examine the effect of surfactants, electrode geometry and modulation of the applied voltage. We will consider some experimental issues, including electron beam artifacts and the effect of the thin liquid layer on diffusion, and discuss the extent to which microscopy can help to guide the fabrication of specific morphologies by electrochemical deposition.
12:00 PM - OO3.08
In Situ and Ex Situ Characterization of Phase Transitions and Electrochromic Processes in WO3 Thin Films during Electrochemical Ion Insertion
Sabrina Darmawi 2 Sebastian Wenzel 1 Christian Schneider 1 Matthias T. Elm 1 2 Juergen Janek 1 Peter J. Klar 2
1Justus-Liebig Universitaet Giessen Germany2Justus-Liebig Universitaet Giessen GermanyShow Abstract
Tungsten trioxide (WO3), the most commonly used chromogenic material, has been investigated since the 1960s. In an electrochemical cell arrangement the transmission characteristics of WO3 thin films can be reversibly changed by application of an external electric field. For this reason it is widely used for electrochromic (EC) devices, such as "smart windows", which can be employed for efficient fenestration for buildings due to the ability of switching the transmittance of light and solar energy. WO3 is a cathodic EC material, meaning that it changes its color upon ion insertion, e.g. H+ or Li+ ions. Although WO3 has been extensively studied since its EC properties were discovered, the mechanism responsible for the coloration/bleaching effect is still unclear and part of recent scientific discussion. In this work we provide some new insights into the coloration mechanism by studying nanocrystalline tungsten thin films combining electrochemical and analytical techniques such as UV-Vis, Raman, x-ray photoelectron spectroscopy as well as x-ray diffraction.
By employing in situ transmission spectroscopy at a fixed spectral band pass during electrochemical experiments, such as cyclic voltammetry, we identified a two-step insertion process for both protons and lithium ions, of which one step exhibits significantly lower coloration efficiency than the other. To obtain a better understanding of the insertion process we analyzed inserted WO3 thin films at different stages using UV-Vis and x-ray photoelectron spectroscopy. Our analyses show that the first step denotes the reduction from initial WVI+ to WV+ and the second step the reduction of WV+ to WIV+. We found that the blue coloration in tungsten oxide is not present for all oxidation states of tungsten but rather mainly for WIV+. That is, crystalline WO3 only shows a significant transmission change when it is reduced to the WIV+ state.
Furthermore, we present an experimental setup for spectrally and spatially resolved in situ intercalation/diffusion experiments. A compact three-electrode cell with the WO3 film as working electrode is attached to a microscope system, a subtractive double spectrometer and a CCD. Patterning the thin film with a translucent electrochemically inactive layer separates certain areas of the WO3 film from the liquid electrolyte. Upon application of an external electric field ions from the electrolyte are inserted into the uncovered WO3 parts and diffuse into the covered areas. Due to time controlled CCD data acquisition diffusion/migration processes can be studied with a high spatial and time resolution.
12:15 PM - OO3.09
Effects of Superimposed Thermal and Electric Fields on the Densification Behavior of 8% Y2O3 Doped ZrO2: An In Situ EDXRD Study with a 200 keV Synchrotron Probe
Ilyas Savkliyildiz 1 Koray Akdogan 1 Hulya Bicer 1 Tevfik Ertugrul Ozdemir 1 William Paxton 1 Zhong Zhong 2 Thomas Tsakalakos 1
1Rutgers University Piscataway USA2Brookhaven National Laboratory Upton USAShow Abstract
Effects of superimposed thermal and electric fields on the densification behavior of 8% yttria doped zirconia (8YSZ) of 200 nm particle size was studied as a function of applied electric field strength in the range 143-320 V/cm and 20 oC/min heating rate using time-resolved in situ high temperature EDXRD with a polychromatic 200 keV synchrotron probe where spectra were collected with 2 second intervals. The isothermal densification occurred in the 790-930 oC range, which resulted in 95-98 % of the theoretical density with discontinues current draw up to 3 A through samples. No local melting at particle-particle contacts was observed in scanning electron micrographs, implying densification was due to solid state mass transport processes. It was found that the higher the applied electric field on sample, the temperature at which densification and the current draw occur, decreases. During current draw, anomalous elastic volume expansion of unit cell by 1% to 3% range is observed. It was found that time dependence of (211) and (112) peak widths depict a decrease at these a singularities at 790 oC-930 oC , which is not related to a phase transformation. We attribute the reduction in densification temperature and time to ultrafast ambipolar diffusion of species arising from the superposition of mass fluxes due to Fickian diffusion, thermodiffusion (Soret effect), and electromigration, which in turn are a consequence of a superposition of chemical, temperature, and electrical potential gradients. On the other hand, we propose defect pile-up at particle-particle contacts and subsequent tunneling as a mechanism creating the “burst-mode” discontinuous densification at the singularities observed at 790 oC and 930 oC.
12:30 PM - *OO3.10
Anomalous lattice expansion and defect phenomena in 8% Y2O3 doped ZrO2 due to superimposed thermal and electric fields: An in situ EDXRD study with a 200 keV synchrotron probe
Enver Koray Akdogan 1 2 Ilyas Savkliyildiz 1 Hulya Bicer 1 William Paxton 1 Tevfik E Ozdemir 1 Zhong Zhong 2 Thomas Tsakalakos 1
1Rutgers University Piscataway USA2Brookhaven National Laboratory Upton USAShow Abstract
We report on the discovery of anomalous lattice expansion and related defect phenomena in 8% yttria doped zirconia (8YSZ) particulate matter of 250 nm median particle size under superimposed thermal and electric fields. We carried out in situ high temperature EDXRD with a polychromatic 200 keV synchrotron probe. Densification occurred in the 876-905thinsp;°C range, which resulted in 97% of the theoretical density. No local melting at particle-particle contacts was observed in scanning electron micrographs, implying densification was due to solid state mass transport processes. The maximum current draw at 905thinsp;°C was 3 A, corresponding to instantaneous absorbed power density of 570thinsp;W/cm3. Densification of 8YSZ was accompanied by anomalous elastic volume expansions of the unit cell by 0.45% and 2.80% at 847thinsp;°C and 905thinsp;°C, respectively. The anomalous expansion at 905thinsp;°C at which maximum densification was observed is characterized by three stages: (I) linear stage, (II) anomalous stage, and (III) anelastic recovery stage. The densification in stage I (184thinsp;s) and II (15thinsp;s) was completed in 199thinsp;s, while anelastic relaxation in stage III lasted 130thinsp;s. The residual strains (ε) at room temperature, as computed from tetragonal (112) and (211) reflections, are ε(112)thinsp;=thinsp;0.05% and ε(211)thinsp;=thinsp;0.13%, respectively. Time dependence of (211) and (112) peak widths (β) show a decrease with both exhibiting a singularity at 905thinsp;°C. Moreover, parameterized Warren-Averbach analysis revealed an anisotropic and abrupt increase in (101) and (110) coherently diffracting domain size from 32 and 21 nm to 88 and 128 nm, and a decrease in d-spacing variation (DSV) from 0.72% and 0.64% to 0.44% and 0.52%, respectively, while burst-mode densification occurred. The CCDS and DSV exhibit time-dependent recovery to their initial state upon cool down from 905 oC to RT under zero E-field. Through thermokinetic computations we show that the observed anomalous lattice expansion and the accompanying changes in coherently diffracting domain size is not a consequence of thermal expansion due to Joule heating. The results provide direct proof of a new oxygen vacancy transport modality under the action of the simultaneous fields in particulate matter which we call the burst mode transport leading to burst mode densification.
Liane G. Benning, University of Leeds
Arda Genc, FEI Company
Dongsheng Li, Pacific Northwest National Laboratory
Jeffrey D. Rimer, University of Houston
Symposium Support Agilent Technologies, Inc.
OO6: Dynamics of Catalytic Materials and In Situ TEM Characterization of Chemistry
Wednesday PM, December 03, 2014
Hynes, Level 1, Room 101
2:30 AM - *OO6.01
Atomic Level Investigation of Catalytic Nanoparticles under Reactive Environment with Environmental TEM
Libor Kovarik 1 Zhehao Wei 1 Arda Genc 2 JaHun Kwak 3 Janos Szanyi 1 Charles Peden 1
1Pacific Northwest National Lab Richland USA2FEI Hillsboro USA3UNIST Ulsan Korea (the Republic of)Show Abstract
Supported transition metal nanoparticles are important class of materials used extensively in catalytic applications due to their high surface to volume ratio and high concentration of low coordinated atomic sites. When exposed to high temperatures and gas environment, there is a range of thermally activated processes that can lead to morphological, structural and surface transformation, and the ability to characterize the catalytic nanoparticles under in-situ conditions is critical for rationalization of structure-property relationship, and thus essential for future advancement of catalytic technologies. In the current work, we will present atomic level in-situ TEM observations of Pd nanoparticles during exposure to elevated temperature and oxidizing environment. The in-situ observations were performed with environmental FEI Titan 80-300 equipped with a CEOS Cs -image corrector operated at 80kV and 300kV. In particular, the work will focus on the characterization of oxide nucleation and growth, and identifying the crystallographic features of Pd metal-oxide transformation. We will also show how coherency strains from the substrate play role in inhibiting phase transformation, and show that a distinct chemical interaction with the substrate can lead to significant changes in the initial stages of oxide formation. The obtained observations will be placed in the context of classical theory of oxidations. As a part of this presentation, we will also describe a gas control unit that enabled us to carry out switching between well-controlled mixtures of gasses, and demonstrate the use of this system to study gas-induced transformations at the atomic scale. This research is part of the Chemical Imaging Initiative at Pacific Northwest National Laboratory. The work was conducted in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by DOE&’s Office of Biological and Environmental Research and located at PNNL.
3:00 AM - OO6.02
Imaging the Reconstruction and the Catalytic Activity of Catalystsrsquo; Single Particles: In-Situ Studies by Field Emission Techniques
Cedric Barroo 1 Yannick De Decker 1 Norbert Kruse 1 2 Thierry Visart de Bocarme 1
1Universitamp;#233; Libre de Bruxelles Bruxelles Belgium2Washington State University Pullman USAShow Abstract
In order to improve the understanding of catalytic processes, information about the surface structure and the catalytic behavior of the active materials has to be gleaned. In particular, synergistic effects between the local structure and composition have to be considered and are, in fact, frequently observed.
A thorough description of such effects at the atomic scale remains challenging. Field emission techniques, including field ion microscopy (FIM) and field emission microscopy (FEM), are especially suited for studying these effects: the nanosized metal tip used as a sample represents a good model for a single catalytic nanoparticle. Furthermore, such high-field studies can be performed during an ongoing catalytic reaction by real-time imaging and in direct space. Nanoscale lateral resolution is achieved and provides information about the local surface composition in a time-resolved manner. Reaction-induced structural changes of the surface of the catalyst can also be assessed with step-site resolution in FIM mode. FEM is based on the emission of electrons from the sample, which can be locally affected by the presence of adsorbates. Local variations of the work function are detected in the form of a brightness pattern and the surface composition of the sample can be qualitatively investigated during the ongoing catalytic process, allowing for the determination of the elementary processes.
In this work, we study the morphological and structural changes occurring over platinum samples after oxygen exposure. The effects of reconstruction on the local catalytic activity of the NO2 hydrogenation reaction are also investigated. For this purpose, the microscope is run as an open nanoreactor. Accordingly, the chemical system is kept far from its thermodynamic equilibrium, a necessary condition to observe nonlinear spatiotemporal behaviors. Aperiodic and highly periodic oscillations of various complexity have been reported for the NO2+H2 reaction on platinum, as well as the propagation of chemical waves on a single facet of the nanocrystal. This proves the robustness of dissipative, nonlinear behaviors down to the nanoscale. The velocity of the observed waves is of the order of a few mu;m/s, which is in good agreement with previous studies of catalytic reactions at the mesoscale.
As a conclusion, we show that nanoparticle dynamics must be accounted for in models describing the nonlinear features of catalytic reactions and, more generally, included in the description of catalytic properties of nanosized particles.
3:15 AM - OO6.03
In Situ Studies for the Rational Engineering of Catalytic Graphene Growth
Robert Weatherup 1 Andrea Cabrero-Vilatela 1 Bernhard Bayer 1 Piran Kidambi 1 Sabina Caneva 1 Raoul Blume 2 Carsten Baehtz 3 Robert Schloegl 4 Stephan Hofmann 1
1University of Cambridge Cambridge United Kingdom2Helmholtz-Zentrum Berlin famp;#252;r Materialien und Energie Berlin Germany3Helmholtz-Zentrum Dresden-Rossendorf Dresden Germany4Fritz Haber Institute Berlin GermanyShow Abstract
A key requirement for future applications of graphene is the development of scalable, economic production methods. Catalytic growth techniques are highly promising for achieving this, however the underlying mechanisms have yet to be fully understood, and control over the material structure and quality thus remains rudimentary.
Here, we apply complementary in situ techniques to develop a detailed, multi-scale understanding of catalytic graphene growth on polycrystalline Ni catalysts. We focus on technologically relevant low temperature (le;600°C) exposures to gaseous hydrocarbons,[1,2] and vacuum annealing (le;600°C) of Ni/solid-carbon stacks We combine time- and depth- resolved X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction/Reflectivity (XRD/XRR), and Scanning Tunnelling Microscopy (STM) to probe the structural and chemical properties of graphene and the catalyst during growth.[1,2,3,4] We show that graphene forms directly during isothermal hydrocarbon exposures, whilst the contribution of precipitation upon cooling is minor. Similarly, for Ni/tetrahedral amorphous carbon (ta-C) stacks, graphene growth is found to occur predominantly during ramping up and annealing by C dissolution and diffusion through the catalyst. A detailed growth rationale is established from these measurements, and we relate this to the understanding of the growth kinetics we have previously developed. Further systematic growth studies on other polycrystalline transition metal catalyst foils (Co, Cu, Pt) demonstrate that the growth behaviour broadly resembles that on Ni, highlighting the generality of our model.
Based on this, we introduce several approaches to control the structural properties of the graphene produced. Catalyst alloying is demonstrated as a means of improving graphene growth by tuning reactivity and selectivity. We show that alloying Au with Ni results in an order of magnitude increase in graphene domain sizes,[1,5] enabling monolayer graphene growth at 600°C of comparable uniformity and quality to that reported for Cu-based growth at >900°C. For the catalytic transformation of solid C sources, we introduce C diffusion barriers as a general and simple method to prevent premature C dissolution during temperature ramping, significantly improving the graphene produced. A thin Al2O3(1-3 nm) barrier inserted into a Ni/ta-C stack enables growth of uniform monolayer graphene at 600°C, with domain sizes >100 mu;m, and a Raman D/G ratio of <0.07.
The understanding of the growth process developed is broadly relevant to catalytic graphene growth on a wide range of catalysts, and the ability to rationally engineer the growth process highlights the importance of our approach.
(1) Weatherup et al. Nano Lett. 2011, 11, 4154-4160
(2) Weatherup et al. ChemPhysChem 2012, 13, 2544-2549
(3) Weatherup et al. Nano Lett. 2013, 13, 4624-4631
(4) Patera et al. ACS Nano 2013, 7, 7901-7912
(5) Weatherup et al. ACS Nano 2012, 6, 9996-10003
4:30 AM - OO6.04
Thermal Stability of Silica-Coated and Uncoated Gold Nanorods in Different Environments
Wei-Chen Wu 1 Joseph B. Tracy 1
1North Carolina State University Raleigh USAShow Abstract
SiO2-coated gold nanorods (SiO2-GNRs) are of broad of interest because they have better thermal stability than uncoated GNRs. Thermal stability of GNRs is a key issue for photothermal heating and other applications that involve exposure of GNRs to high intensity light because uncoated GNRs will revert into spherical shapes, usually at temperatures below 250 °C, in both air and in solution. As the GNR aspect ratio decreases, the optical properties change, and the redshift in the longitudinal surface plasmon resonance (LSPR) vanishes. Here, we report the thermal stability of SiO2-GNRs under different environments and compare with uncoated GNRs. When we measuere by in situ TEM (pressure of ~10-5 Pa), SiO2-GNRs maintain their rod shape within the SiO2 shells at temperatures up to 1200 °C, which exceeds the bulk melting temperature of Au. Uncoated GNRs maintain their shape but sublime into the vacuum at ~900 °C. For comparison, during heating on TEM substrates in a furnace under ambient atmosphere, SiO2-GNRs become spherical at ~700 °C, while uncoated GNRs become spherical at temperatures below 400 °C. The environment in which the samples are heated critically affects their stability.
4:45 AM - OO6.05
In Situ High Resolution TEM on Zinc-Blende Phase Precipitation at Liquid/Solid Interface in InAs Nanowires
Scott X. Mao 2 He Zheng 2 3 Jian Yu Huang 1 Jeffrey G. Cederberg 4 Jesper Wallentin 5 Jian Wang 6 Jianbo Wang 3
1 Albuquerque USA2University of Pittsburgh Pittsburgh USA3Wuhan University Wuhan China4Sandia National Laboratories Albuquerque USA5Lund University Lund Sweden6Los Alamos National Laboratory Los Alamos USAShow Abstract
The mass transport at liquid catalyst and nanowire (NW) interface is critical in understanding the vapor-liquid-solid growth mechanism in III-V semiconductor nanowires. Here, through in-situ high resolution transmission electron microscope observation, we show the oscillatory dissolution and precipitation process at the liquid catalyst/NW interface in InAs NW coated by amorphous carbon during heating. The NW morphology during precipitation indicates that nucleation occurs at the liquid/solid interface or liquid/solid/amorphous carbon triple point, under which condition the formation of zinc blende nuclei is preferred. The precipitation process observed at atomic resolution advances the basic understanding of mass transport between the liquid and solid phases.
5:00 AM - OO6.06
In Situ TEM Study of Electrical Wind Force-Driven Amorphization in Phase-Change Materials
Sung-Wook Nam 1 2
1University of Pennsylvania Philadelphia USA2IBM T.J. Watson Research Center Yorktown Heights USAShow Abstract
Electrical wind force is an important element in electrical switching behaviors of phase-change materials. It has been reported that the electrical wind force influences the motions of dislocations, which determines the degree of order-disorder states existing in phase-change materials . In this presentation, we discuss electrical wind force-driven behaviors occurring in phase-change materials. At first, we report atomic mass-transport behaviors as DC voltage biases are applied in line-shape Ge2Sb2Te5 (GST) devices. As the electrical current density reached 3-4 MA/cm2 by DC voltage bias, a directional mass transport was identified by forming asymmetric surface morphology on the line-shape GST devices. By electric current, Joule-heating raised the temperature up to ~300 oC, implying that the mass transport of GST occurs in hexagonal phase (solid state) regime. In second, we extend the roles of electrical wind force to electrical switching behaviors of GST. We studied the effects of electrical voltage pulses on crystalline-to-amorphous phase transition of GST by in situ transmission electron microscopy (TEM). Electrical voltage pulse plays a critical role by creating dislocations through heat shock process: Rising edge of the pulse produces vacancies by heating, whereas during rapid cooling, atomic vacancies are condensed into dislocation loops. As the dislocations feel the electrical wind force, they become mobile and glide in the direction of hole-carrier motion. Continuous increase in the density of dislocations moving unidirectionally leads to dislocation jamming, which eventually induces the crystalline-to-amorphous phase transition. We interpret it through one-dimensional traffic model in which the increase of dislocation density exceeding a certain threshold point induces a catastrophic jamming of dislocations. Density functional theory (DFT) calculations of generalized-stacking-fault (GSF) energy show that basal plane of GST hexagonal phase provides favorable pathways of dislocation motions. Our understanding about dislocation-templated amorphization suggests that the transition from crystalline to amorphous states in phase-change materials may not require a melting process.
 S.W. Nam et al, Science, 336, 1561-1566 (2012)
5:15 AM - OO6.07
Writing Silica Structures in Liquid with Scanning Transmission Electron Microscopy
Marcel Van de Put 1 Paul Bomans 1 Heiner Friedrich 1 Niels De Jonge 2 Nico Sommerdijk 1
1Eindhoven University of Technology Eindhoven Netherlands2Institute for New Materials Saarbrucken GermanyShow Abstract
Conventional and cryogenic transmission electron microscopy (TEM) are key techniques for the real-space imaging of soft matter at the nanometer scale.1 Still, these techniques can only produce snapshots, and not reveal the true dynamics of a system that will give insight in the dynamic interactions between the different components. In contrast, the application of liquid phase TEM (LP-TEM), using 200-500 nm thick cells with electron transparent (generally SixNy) windows allows the dynamic monitoring of events in liquid samples, thus avoiding the need for specimen preparation at every time point.2
Currently LP-TEM still has some limitations, e.g. the interaction of the electron beam with the fluid is a matter of concern as it may induce free electrons in the liquid by and also gradients in temperature and pH (due to water decomposition), and beam induced deposition of nanoparticles is also often observed. Indeed, many of the reported experiments so far have either a) used the electron beam to drive the processes under investigation, b) have imaged objects rather than processes, or c) reported on the effects of the electron beam on the events observed.
Here, we exploit these beam-sample interactions to write silica nanostructures in aqueous medium. By applying a focused electron beam in STEM mode we can control the localized deposition of fused silica nanostructures with defined thickness from a solution of monodisperse silica nanoparticles. The thickness of the deposits is linear with the applied electron dose. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) demonstrate that the deposited patches are a result of the merging of the original 20 nm-diameter nanoparticles, and that the related surface roughness depends on the electron dose rate used. Using this approach, sub-micrometer scale structures are written on the SiN in liquid by controlling the electron exposure as function of the lateral position. The observed process could be useful in future work for the direct writing of three dimensional nanoscale silica structures in liquid.
5:30 AM - OO6.08
The Effect of Hydrogen Peroxide on Beam-Induced Radiolysis in Liquid Cell Electron Microscopy
Nicholas M Schneider 1 Michael M Norton 1 Frances M Ross 2 Haim H Bau 1
1University of Pennsylvania Philadelphia USA2IBM T. J. Watson Research Center Yorktown Heights USAShow Abstract
Liquid cell electron microscopy is a powerful tool to study nanoscale phenomena in liquids in situ. However, energy transferred from the fast-moving electrons to the irradiated medium generates radical and molecular species; for water these include hydrogen, oxygen, hydrated electrons and hydrogen peroxide. These species may influence phenomena under study in liquid cell electron microscopy. In particular, the formation of bubbles composed of radiolytic gaseous species can strongly affect imaging. Additives to the initial solution are known to alter radiolysis product formation. Here we examine the effect of hydrogen peroxide, an important additive in oxidation and reduction reactions, on the production of radiolytic species in liquid cell electron microscopy. We computed the concentrations of radiolysis products as functions of initial hydrogen peroxide concentration, beam current, beam size, time, and position relative to the beam center. These calculations predict that the concentration of hydrogen increases as the concentration of hydrogen peroxide increases. Bubble nucleation is a function of the saturation concentration, which is fixed by the pressure within the device during observation. The pressure inside the device was controlled during the filling of our closed cell, the nanoaquarium, and then estimated in situ by considering the deflection of the silicon nitride windows based on transmitted beam intensity. The predictions are consistent with experimental observations in a liquid cell indicating that the presence of hydrogen peroxide lowers the critical dose rate required to nucleate bubbles as a result of the higher radiolytic production of hydrogen.
Acknowledgements: The study was supported, in part, by the National Science Foundation through grants 1129722 and 1066573. Device fabrication was carried out at the Cornell NanoScale Facility (NSF Grant ECS-0335765), a member of the National Nanotechnology Infrastructure Network.
OO7: Poster Session I: In Situ Characterization of Dynamic Processes during Materials Synthesis and Transformation I
Wednesday PM, December 03, 2014
Hynes, Level 1, Hall B
9:00 AM - OO7.01
Observations of Magnetic Domain Structure Change in Nd2Fe14B Magnets at Elevated Temperature with External Magnetic Field by Lorentz Microscopy
Toshimasa Suzuki 1 Koichi Kawahara 1 Haruka Tanaka 1 Kimihiro Osaki 2
1Japan Fine Ceramics Center Nagoya Japan2AIST Nagoya JapanShow Abstract
The Nd2Fe14B magnets with excellent properties have extended the applications in the field of motors for Hybrid Electric and Electric Vehicles. It is well known that the Nd2Fe14B magnets without doping dysprosium (Dy) show decrease of coercivity at elevated temperatures. Development of the Nd2Fe14B magnets which can use at elevated temperature is expected. Therefore, in order to reduce deterioration of coercivity of Nd2Fe14B magnets at elevated temperatures, it is important to observe the generating site of reverse magnetic domains in Nd2Fe14B magnets. In this study, we observed thermal and magnetic field demagnetization process in polycrystalline Nd2Fe14B magnets by transmission electron microscopy (TEM) / Lorentz microscopy.
Nd2Fe14B polycrystalline samples with average grain size of below 800 nm were prepared by HDDR process. Thin foils suitable for TEM observations were#12288;prepared by a focused ion beam (FIB) thinning method#12288;(Hitachi FB-2100). TEM observations were carried out in a HF-3300EH at the temperature range from room temperature to 523K.
After magnetization by external magnetic field of 2.0 T, the magnetic domain walls were observed by the Fresnel mode with in situ heating. At 498K, reverse magnetic domains were observed in thin foil sample. The observed reverse magnetic domain would indicate the beginning of thermal demagnetization.
Similar observations were repeatedly conducted without (condition 1) and with applying an external reverse magnetic field of 25 mT (condition 2) using the same thin foil. As the results, the reverse domains were revealed to be generated at lower temperature under the condition 2 than under the condition 1. Moreover, in the case of condition 2, the reverse domains were found to be generated nearly the same region.
Acknowledgement: This work has been supported by Future Pioneering Projects /Development of magnetic material technology for high-efficiency motors from Japanese Ministry of Economy, Trade and Industry
9:00 AM - OO7.02
Correlating Molecular Architecture of Polyethylene with Deformation Behavior
Abhiram S Kannan 1 Aaron Eberle 2 David Fiscus 3 David G Bucknall 1
1Georgia Institute of Technology Atlanta USA2ExxonMobil Research and Engineering Annandale USA3ExxonMobil Chemical Company Baytown USAShow Abstract
We are utilizing synchrotron based in situ small- and wide-angle X-ray scattering (SAXS and WAXS respectively) to study the structural variation during continuous tensile mechanical testing of melt blown Linear Low Density Polyethylene (LLDPE) films. These experiments allow us to link the true macro-scale mechanical response of the films with the continuously evolving film morphology. Clear differences in the morphological evolution are observed between samples strained along the processing machine direction (MD) or the transverse direction (TD) of the films.
At large macroscopic strains, the growth of a new lamellae-amorphous morphology occurs, the dimensions of which are independent of strain. When strained in the TD direction, this characteristic dimension is shown to be independent of the choice of processing conditions under which the films were melt blown. This behavior however is absent in the samples strained along the MD where the processing conditions affect the dimensions of the structural feature at high strains. The large strain TD characteristic dimension therefore reflects an inherent behavior of the specific polyethylene. Exploiting correlation analysis of the SAXS data, the length scale contributions of the crystalline and amorphous factions to the characteristic dimension can be extracted. Coupling these results with the average branch distribution along the backbone we observe a relationship between the characteristic dimension at high strain and the distribution of low molecular weight branches and the resulting branch spacing along the backbone of the LLDPE. These structural insights will potentially allow correlations of mechanical performance parameters to the polymer molecular architecture in these polyethylenes.
9:00 AM - OO7.03
Optical Fiber-Based Approach to In-Situ Monitoring of Group 11 Metal-Organic Chemical Vapor Deposition: Generation of Isotropic and Anisotropic Ultrathin Films
David J. Mandia 1 Wenjun Zhou 2 Jacques Albert 2 Sean T. Barry 1
1Carleton University Ottawa Canada2Carleton University Ottawa CanadaShow Abstract
Use of a tilted fiber Bragg grating (TFBG) as a sensing device for the monitoring of metal-organic chemical vapor deposition (MOCVD) for a variety of group 11 ultrathin films has been employed. Mechanistically, a TFBG-polarized transmission amplitude spectrum in the near-infrared (NIR) range works as a real-time film sensing platform by undergoing attenuation under finite changes to the surrounding refractive index (SRI) as a film nucleates and grows. Moreover, the polarization mode (S or P) of core-guided light interrogating the growing film provides accurate real-time information about the growth profile of metal thin films deposited from single-source precursors developed in our lab. Use of MOCVD affords many advantages over other line-of-sight techniques such as physical vapor deposition (PVD) due to its ability to uniformly coat complex surfaces such as optical fibers. The MOCVD of anisotropic (polarization-dependent) and isotropic (polarization-independent) ultrathin gold films from gold (I) guanidinate ([Au(NiPr)2CNMe2]2) and gold (I) iminopyrrolidinate ([Au(Me2-tBu-ip]2) compounds, respectively, has been explored extensively. Atomic force and scanning electron microscopies as well as an ensemble of both soft and hard (synchrotron radiation) x-ray spectroscopies were employed to corroborate a variety of the TFBG-extracted thin film metrics (e.g. thickness and g