Nanoscale Integration Science

Nanoscale integration science at LLNL focuses on the design, development, and characterization of nanoscale architectures for a wide array of applications ranging from explosive materials to next-generation batteries.

The work supports Laboratory missions, including the National Ignition Facility and Weapons and Complex Integration, as well as external partners such as the US Departments of Energy and Defense.

Learn more about nanoscale integration science at LLNL by exploring our focus areas below.

Focus Areas


Advanced materials characterization

 

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Our group maintains world-class expertise in the advanced characterization of materialsthrough a suite of lab- and synchrotron-based techniques.

The capabilities at LLNLencompass a number of surface characterization methods, including x-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and ultraviolet photoelectron spectroscopy (UPS).

These techniques may be coupled with vacuum thermal treatment. Additionally, samples may be transferred and loaded into diagnostics without air exposure.

Our synchrotron science teamhas a vibrant materials research portfolio that leverages numerous domestic and international synchrotron facilities to address materials characterization challenges within LLNL’s mission. The group has developed expertise in both soft and hard x-ray beamline experimentation.

Techniques routinely used by the group include:

  • X-ray absorption, including extended/near-edge x-ray absorption fine structure spectroscopy (EXAFS/NEXAFS), x-ray emission spectroscopy (XES), x-ray magnetic circular dichroism (XMCD), and scanning transmission x-ray microscopy (STXM)
  • Ultra small-angle x-ray scattering (USAXS/SAXS)
  • X-ray diffraction (XRD)
  • X-ray computed microtomography (CT).

Our team members have extensive experience in planning and conducting synchrotron-based experiments in collaboration with scientists and engineers from a diverse range of fields and have a strong foundation in addressing the challenges associated with in-situ and time-resolved measurements.

I.C. Tran, R.H. Tunuguntla, K. Kim, J.R.I. Lee, T.M. Willey, T.M. Weiss, A. Noy and T. van Buuren, Structure of Carbon Nanotube Porins in Lipid Bilayers: An in Situ Small-Angle X-ray Scattering (SAXS) Study, Nano Lett. 16 (7), 4019 (2016).

T.M. Willey, K. Champley, R. Hodgin, L. Lauderbach, M. Bagge-Hansen, C. May, N. Sanchez, B.J. Jensen, A. Iverson, and T. van Buuren, X-ray imaging and 3D reconstruction of in-flight exploding foil initiator flyers, Journal of Applied Physics 119 (23), 235901 (2016), doi: 10.1063/1.4953681.

M. Bagge-Hansen, L. Lauderbach, R. Hodgin, S. Bastea, L. Fried, A. Jones, T. van Buuren, D. Hansen, J. Benterou, C. May, T. Graber, B. J. Jensen, J. Ilavsky, and T. M. Willey, Measurement of carbon condensates using small-angle x-ray scattering during detonation of the high explosive hexanitrostilbene, Journal of Applied Physics 117 (24), 245902 (2015).

T.M. Willey, L. Lauderbach, F. Gagliardi, T. van Buuren, E.A. Glascoe, J.W. Tringe, J.R.I. Lee, H.K. Springer, and J. Ilavsky, Mesoscale evolution of voids and microstructural changes in HMX-based explosives during heating through the β-δ phase transition, Journal of Applied Physics 118 (5), 055901 (2015).

J.R.I. Lee, M. Bagge-Hansen, R. Tunuguntla, K. Kim, M. Bangar, T.M. Willey, I.C. Tran, D.A. Kilcoyne, A. Noy, and T. van Buuren, Ordering in bio-inorganic hybrid nanomaterials probed by in situ scanning transmission X-ray microscopy, Nanoscale 7 (21), 9477 (2015).

M. Bagge-Hansen, B.C. Wood, T. Ogitsu, T.M. Willey, I.C. Tran, A. Wittstock, M.M. Biener, M.D. Merrill, M.A. Worsley, M. Otani, C.H. Chuang, D. Prendergast, J.H. Guo, T.F. Baumann, T. van Buuren, J. Biener, and J.R.I. Lee, Supercapacitors: Potential‐Induced Electronic Structure Changes in Supercapacitor Electrodes Observed by In Operando Soft X‐Ray Spectroscopy, Adv. Mater. 27 (9), 1512 (2015). [Featured on cover]

M. Bagge-Hansen, A. Wichmann, A. Wittstock, J.R.I. Lee, J.C. Ye, T.M. Willey, J.D. Kuntz, T. van Buuren, J. Biener, M. Baumer, and M.M. Biener, Quantitative Phase Composition of TiO2-Coated Nanoporous Au Monoliths by X-ray Absorption Spectroscopy and Correlations to Catalytic Behavior, J. Phys. Chem. C 118 (8), 4078 (2014).

T.M. Willey, M. Bagge-Hansen, J.R.I. Lee, R. Call, L. Landt, T. van Buuren, C. Colesniuc, C. Monton, I. Valmianski, and I. K. Schuller, Electronic structure differences between H2-, Fe-, Co-, and Cu-phthalocyanine highly oriented thin films observed using NEXAFS spectroscopy, J. Chem. Phys. 139 (3), 034701 (2013), doi: 10.1063/1.4811487.

V. Stepanov, T.M. Willey, J. Ilavsky, J. Gelb, and H.W. Qiu, Structural Characterization of RDX‐Based Explosive Nanocomposites, Propellants, Explosives, Pyrotechnics 38 (3), 386 (2013), doi: 10.1002/Prep.201200151.

Y.M. Wang, R.T. Ott, T. van Buuren, T.M. Willey, M.M. Biener, and A.V. Hamza, Controlling factors in tensile deformation of nanocrystalline cobalt and nickel, Physical Review B 85 (1), 014101 (2012).

T.M. Willey, J.D. Fabbri, J.R.I. Lee, P.R. Schreiner, A.A. Fokin, B.A. Tkachenko, N.A. Fokina, J.E.P. Dahl, R.M.K. Carlson, A.L. Vance, W.L. Yang, L.J. Terminello, T. van Buuren, and N.A. Melosh, Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold, J. Am. Chem. Soc. 130 (32), 10536 (2008), doi: 10.1021/Ja711131e.

W.L. Yang, J.D. Fabbri, T.M. Willey, J.R.I. Lee, J.E. Dahl, R.M.K. Carlson, P.R. Schreiner, A.A. Fokin, B.A. Tkachenko, N.A. Fokina, W. Meevasana, N. Mannella, K. Tanaka, X.J. Zhou, T. van Buuren, M.A. Kelly, Z. Hussain, N.A. Melosh, and Z. X. Shen, Monochromatic Electron Photoemission from Diamondoid Monolayers, Science 316 (5830), 1460 (2007).

  • Trevor Willey
  • Michael Bagge-Hansen
  • Philip DePond
  • Jean-Baptiste Forien
  • Joshua Hammons
  • Jonathan Lee
  • Aiden Martin

Catalysis and supercapacitors

 

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Microarchitectured hierarchical structures of nanoporous gold created by combining 3D printing with an alloying and dealloying process.

Catalysis

Chemical production, which relies heavily on heterogeneous catalysis, accounts for around 19% of energy usage worldwide.

As part of Harvard’s Energy Research Frontier Center (EFRC) Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), and using our 10+ years in experience in developing novel nanoporous metals, we design new, highly selective and reactive dilute alloy catalyststhat have dual functionality. The principal design feature of our catalyst materials is to combine a minor amount of active metal that facilitates creation of reactive intermediates with a less active majority phase that transforms these intermediates into desirable products with high selectivity. The catalyst design is based on our group’s established work on nanoporous gold (Au) with silver (Ag) as minority species, which shows that even minor amounts of Ag strongly affect reactivity and selectivity by providing reactive sites for oxygen dissociation.

Supercapacitors

LLNL is a center of expertise in developing novel monolithic graphene-based carbon foams with hierarchical 3D architectures and high mass-specific surface area that have many promising applications as electrode materials, ranging from electrical energy storage to desalination and catalysis.

Our work in the field of graphene-based supercapacitorshas generated many groundbreaking discoveries about the fundamental relationships among charge storage behavior, electronic structure, and macroscopic phenomena, such as carbon/electrolyte interface polarization-induced conductivity changes of graphene electrodes (up to 300%) and strain effects (up to 2%). The underlying atomic scale phenomena are explored using a combination of atomistic modeling (DFT and MD) and various in situ characterization techniques, including synchrotron-based in situ electron spectroscopy. Our results open the door to new applications of monolithic nanocarbon foams, including all-carbon bulk actuator and transistor technologies.

J. Biener, M.M. Biener, R.J. Madix, and C.M. Friend, Nanoporous Gold: Understanding the origin of the reactivity of a 21st century catalyst made by pre-Columbian technology, ACS Catalysis 5, 6263 (2015).

S. Dasgupta, et al., Dynamic control over electronic transport in 3D bulk nanographene via interfacial charging, Advanced Functional Materials 24, 3494 (2014).

L.H. Shao, et al., Electrically tunable nanoporous carbon hybrid actuators, Advanced Functional Materials 22, 3029 (2012).

J. Biener, et al., Macroscopic 3D nanographene with dynamically tunable bulk properties, Advanced Materials 24, 5083 (2012).

L.H. Shao, et al., Electrocapillary maximum and potential of zero charge of carbon aerogel, Physical Chemistry Chemical Physics 12, 7580 (2010).

  • Jurgen Biener
  • Zhen Qi

Energy storage materials

Lithium batteries

 

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LLNL scientist Jianchao Ye with an improved lithium ion battery.

State-of-the-art electrode assembly processes typically involve mixing of active materials, carbon black, and binder in a random fashion. The complications resulted from multiple components and uncontrollable porous structure hinder the mechanism understandings. Instead, our lab focuses on monolithic porous electrode designs, which have well-controlled porous structures made without carbon black or binders.

The simplicity and tailorability enable us to exploit new opportunities for improving electrode kinetics and lifetime. The lab has strong capabilities in the synthesis of monolithic porous materials, such as carbon aerogels, graphene aerogels, metal oxide aerogels, ultra-low density foams, and nanoporous metals. Taking graphene aerogels as an example, we found that ion beam bombardment increases coulombic efficiency, hydrogen treatment improves lithium (Li) storage kinetics, and the incorporation of metal oxides synergistically improves the lithium storage capability of graphene. Using atomic layer deposition titanium dioxide (TiO2)-coated nanoporous gold as a model system, we are able to tune the pore size and the thickness of the active material independently and precisely, which allows us to optimize the electrode design for high power applications. The monolithic porous materials are also expected to play a key role in the future design of high-energy/high-power-density lithium-sulfur (Li-S) and lithium-air (Li-O2) batteries.

Li-O2 batteries

With about 10 times higher theoretical specific capacity and specific energy compared with current Li-ion batteries, Li-O2 batteries are considered as transformational energy sources for future electric vehicles. However, current prototype Li-O2 batteries suffer from low power density, low energy efficiency, and poor long-term cycling stability. The main challenge of Li-O2 battery techniques lies in the design of air-breathing cathode materials, which should be specific to their working principles. State-of-the-art Li-O2 batteries simply inherit conventional cathode designs for Li-ion batteries, which results in multiple critical issues that impede technology transfer from lab to industry. We are designing new cathode architectures that can tackle many of these challenges.

Sponsors: Energy-program institutional scientific capability portfolio (ISCP)

Capabilities: Electrochemical characterizations

Graphene-related electrode materials

 

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The morphologies of as-synthesized and He-ion irradiated graphene aerogels.

High energy light-ion bombardment is used to introduce lattice defects in a 3D interconnected network of graphene aerogels (GAs). When these materials are used as anodes for lithium ion batteries, we observe improved percentage reversible capacity and cycle stability compared to those without ion-beam treatment. Furthermore, all ion-beam treated 3D graphene samples exhibit substantially higher Coulombic efficiencies, suggesting a beneficial role of vacancy-type defects in stabilizing solid-electrolyte interphases. Although 3D graphene exhibits initial reversible capacities that are 2–3 times higher than that of graphite, fast capacity fading is observed but becomes more stable after ion-beam treatment.

Our experimental results demonstrate that ion-beam treatment is an effective route to tune and produce good-performance graphene electrodes and that vacancy-type defects help to promote reversible lithium storage capacity in graphene. 3D GAs irradiated to the highest dose studied (1016 cm-2) fail rapidly upon electrochemical cycling, likely caused by the excessive ion-beam damage and graphene restacking. Raman I(D)/I(D0) signature is considered linked to defect type in graphene and thus is proposed, for the first time, as an indicator of the reversible capacity for GAs.

Atomic hydrogen exists ubiquitously in graphene materials made by chemical methods. Yet determining the effect of hydrogen on the electrochemical performance of graphene remains a significant challenge. We have reported the experimental observations of high rate capacity in hydrogen-treated 3D graphene nanofoam electrodes for lithium ion batteries. Structural and electronic characterization suggests that defect sites and hydrogen play synergistic roles in disrupting sp2 graphene to facilitate fast lithium transport and reversible surface binding, as evidenced by the fast charge-transfer kinetics and increased capacitive contribution in hydrogen-treated 3D graphene.

In concert with experiments, multiscale calculations reveal that defect complexes in graphene are prerequisite for low-temperature hydrogenation, and that the hydrogenation of defective or functionalized sites at strained domain boundaries plays a beneficial role in improving rate capacity by opening gaps to facilitate easier Li penetration. Additional reversible capacity is provided by enhanced lithium binding near hydrogen-terminated edge sites. These findings provide qualitative insights in helping the design of graphene-based materials for high-power electrodes.

Graphene/metal oxide (GMO) nanocomposites promise a broad range of utilities for lithium ion batteries, pseudocapacitors, catalysts, and sensors. When applied as anodes for lithium ion batteries, GMOs often exhibit high capacity, improved rate capability, and cycling performance. Numerous studies have attributed these favorable properties to a passive role played by the exceptional electronic and mechanical properties of graphene in enabling metal oxides (MOs) to achieve near-theoretical capacities. In contrast, the effects of MOs on the active lithium storage mechanisms of graphene remain enigmatic.

Via a unique two-step solvent-directed sol-gel process, we have synthesized and directly compared the electrochemical performance of several representative GMOs, namely Fe2O3/graphene, SnO2/graphene, and TiO2/graphene. We observe that MOs can play an equally important role in empowering graphene to achieve large reversible lithium storage capacity. The magnitude of capacity improvement is found to scale roughly with the surface coverage of MOs, and depend sensitively on the type of MOs. We define a synergistic factor based on the capacity contributions.

Our quantitative assessments indicate that the synergistic effect is most achievable in conversion-reaction GMOs (Fe2O3/graphene and SnO2/graphene) but not in intercalation-based TiO2/graphene. However, a long cycle stability up to 2000 cycles was observed in TiO2/graphene nanocomposites. We propose a surface coverage model to qualitatively rationalize the beneficial roles of MOs to graphene. Our first-principles calculations further suggest that the extra lithium storage sites could result from the formation of Li2O at the interface with graphene during the conversion-reaction. These results suggest an effective pathway for reversible lithium storage in graphene and shift design paradigms for graphene-based electrodes.

Sponsors: Laboratory Directed Research and Development

Capabilities:

  • Electrochemical characterizations
  • Supercomputing
  • Nanomaterial synthesis
  • Io-beam irradiation
  • Near edge X-ray absorption fine structure (NEXAFS)
  • Small-angle x-ray scattering (SAXS)

Porous electrode designs

 

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Much progress has recently been made in the development of active materials, electrode morphologies and electrolytes for lithium ion batteries. Well-defined studies on size effects of the 3D electrode architecture, however, remain rare due to lack of suitable material platforms where the critical length scales (such as pore size and thickness of the active material) can be freely and deterministically adjusted over a wide range without affecting the overall 3D morphology of the electrode.

Our group completed a systematic study on length scale effects on the electrochemical performance of model 3D np-Au/TiO2 core/shell electrodes. Bulk nanoporous gold provides deterministic control over the pore size and is used as a monolithic metallic scaffold and current collector. Extremely uniform and conformal TiO2 films of controlled thickness were deposited on the current collector by employing atomic layer deposition (ALD).

Our experiments demonstrate profound performance improvements by matching the Li(+) diffusivity in the electrolyte and the solid state through adjusting pore size and thickness of the active coating which, for 200 micrometer thick porous electrodes, requires the presence of 100 nanometer pores. Decreasing the thickness of the TiO2 coating generally improves the power performance of the electrode by reducing the Li(+) diffusion pathway, enhancing the Li(+) solid solubility, and minimizing the voltage drop across the electrode/electrolyte interface. With the use of the optimized electrode morphology, supercapacitor-like power performance with lithium-ion-battery energy densities was realized. Our results provide the much-needed fundamental insight for the rational design of the 3D architecture of lithium ion battery electrodes with improved power performance.

Sponsors: Laboratory Directed Research and Development

Capabilities:

  • Atomic layer deposition (ALD)
  • Dealloying
  • Electrochemical characterizations
  • Transmission electron microscopy (TEM)

Fracture behaviors of silicon micropillars

 

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Cross-sectional morphology evolutions during the progressive lithiation for four types of silicon pillars: (a) bare-Circular-Si, (b) Al2O3-ALD-Circular-Si, (c) TiO2-ALD-Circular-Si, and (d) TiO2-ALD-Square-Si.

Crystalline silicon nanostructures are commonly known to exhibit anisotropic expansion behavior during the lithiation that leads to grooving and fracture. Experiments have shown surprisingly relatively uniform volume expansion behavior of large aspect-ratio, well-patterned, n-type (100) silicon micropillars during the initial lithiation. The comparison results with and without atomic layer metal oxides (Al2O3 and TiO2) coatings reveal drastically enhanced solid electrolyte interphase (SEI) formation, higher volume expansion, and increased anisotropy. Square pillars are found to exhibit nearly twice volume expansion without fracture compared to circular pillars. Models are invoked to qualitatively address these beneficial or detrimental properties of silicon for lithium ion battery.

Our experiments and computer simulations point at the critical relevance of SEI and pristine geometry in regulating volume expansion and failure. ALD-coated ultrathin metal oxides can act as an ion channel gate that helps promote fast Li(+) transport into the bulk by changing the surface kinetics, suggesting new ways of designing electrodes for high-performance lithium ion battery applications.

Sponsors: Laboratory Directed Research and Development

Capabilities:

  • Microfabrication
  • Atomic layer deposition
  • Electrochemical characterizations

J.C. Ye, Y. An, E. Montalvo, P.G. Campbell, M.A. Worsley, I.C. Tran, Y. Liu, B.C. Wood, J. Biener, H. Jiang, M. Tang, and Y.M. Wang, Solvent-directed sol-gel assembly of 3-dimensional graphene-tented metal oxides and strong synergistic disparities in lithium storage, J Mater Chem A 4, 4032 (2016). [Featured on cover].

J.C. Ye, S. Charnvanichborikarn, M.A. Worsley, S.O. Kucheyev, B.C. Wood, and Y.M. Wang, Ion beam-induced defects in 3D graphene aerogels and their beneficial roles in lithium storage capability, Carbon 85, 269 (2015).

J.C. Ye, A.C. Baumgaertel, Y.M. Wang, J. Biener, and M.M. Biener, Structural optimization of 3D porous electrodes for high-rate performance lithium ion batteries, ACS Nano 9, 2194 (2015).

J.C. Ye, M.T. Ong, T.W. Heo, P.G. Campbell, M.A. Worsley, S. Shan, Y.Y. Liu, S. Charnvanichborikarn, M.J. Matthews, J. Lewicki, M. Bagge-Hansen, J.R.I. Lee, B.C. Wood, and Y.M. Wang, Universal roles of hydrogen in electrochemical performance of graphene: high rate capacity and atomistic origins, Scientific Reports 5, 16190 (2015).

J.C. Ye, Y.H. An, T.W. Heo, M.M. Biener, R.J. Nikolic, M. Tang, H. Jiang, and Y.M. Wang, Enhanced lithiation and fracture behavior of silicon mesoscale pillars via atomic layer coatings and geometry design, J Power Sources 248, 447 (2014).

  • Yonghao An
  • Juergen Biener
  • Monika Biener
  • Tom Braun
  • Michael Bagge-Hansen
  • Patrick Campbell
  • Tae Wook Heo
  • Sergei Kucheyev
  • Jon Lee
  • Siwei Liang
  • Manyalibo J. Matthews
  • Rebecca Nikolic
  • Mitchell T. Ong
  • Zhen Qi
  • Ming Tang
  • Morris Wang
  • Brandon Wood
  • Marcus Worsley
  • Jianchao Ye

Fundamental condensed matter physics

From fundamental condensed matter physics to innovative devices

In the device world, understanding and controlling the quantum dynamics of electrons holds the key to solving challenges associated with shrinking dimensions and increased versatility in electronic and photonic components.

This calls for a transition in paradigm from up-to-date development of condensed matter physics to ground-shaking engineering breakthroughs. Our research not only adopts interdisciplinary approaches that integrate engineering methods and chemical synthesis, but also investigates the fundamental limit of electron/photon transport at nanometer-scale to most effectively produce innovative devices with improved or new capabilities. Current research interests focus on understanding and manipulating spin at the interface of a topological insulator and a non-magnetic material. This work aims at the electrical control of spin in non-magnetic materials without applying a magnetic field.

Optical & electrical methods

To enable the development of new materials and devices, a variety of optical and electrical methods have been implemented.

 

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Near-infrared scanning photocurrent microscopy

 

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Superconducting magnet system

 

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He3 cryostat
 

 

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Ultraviolet photoluminescence system

 

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Terahertz time-domain spectroscopy

D.-X. Qu, X. Che, X. Kou, L. Pan, J. Crowhurst, M. Armstrong, J. Dubois, K.L. Wang, and G.F. Chapline, Spin manipulation at the interface of a topological insulator and a non-magnetic semiconductor (2017).

  • Dongxia Qu
  • George Chapline

Nanoscale and mesoscale properties of high explosives

 

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Three-dimensional rendering of cracks and voids in LX-10 and PBX-9501 before and after heating.

The nanoscale integration science group leads small-scale detonation experiments primarily at the Dynamic Compression Sector beam line at the Advanced Photon Source.

We at LLNL have commissioned an end station for performing research on small-scale detonations using the intense, pulsed x-rays available at synchrotrons. We research excess carbon behind detonation fronts condensing into various carbon nanomaterials, including detonation nanodiamond. We also perform various imaging experiments to investigate detonator performance, void collapse, front curvature, and other detonation properties.

Specifications:

  • 3 g detonations, in vacuum
  • 4 x PiMax 1024i detection system; collects up to eight frames per event
  • APS 24-bunch mode (one frame from a 100-ps pulse every 153.4 ns)
  • Small-angle scattering from ~0.005 to 0.5 1/Angstrom; 14.5 keV or 24 keV
  • 5 mm x 1.5 mm white-beam imaging
  • We are also developing methods for imaging up to about 20-mm field of view.

We perform USAXS and CT imaging of various explosives and their formulations to determine nano-, meso-, and microstructural features of high explosives under temperature cycling.

T.M. Willey, K. Champley, R. Hodgin, L. Lauderbach, M. Bagge-Hansen, C. May, N. Sanchez, B.J. Jensen, A. Iverson, and T. van Buuren, X-ray imaging and 3D reconstruction of in-flight exploding foil initiator flyers, J. Appl. Phys. 119 (23) 235901 (2016).

M. Bagge-Hansen, L. Lauderbach, R. Hodgin, S. Bastea, L. Fried, A. Jones, T. van Buuren, D. Hansen, J. Benterou, C. May, T. Graber, B. J. Jensen, J. Ilavsky, and T.M. Willey, Measurement of carbon condensates using small-angle x-ray scattering during detonation of the high explosive hexanitrostilbene, J. Appl. Phys. 117 (24) 245902 (2015).

T.M. Willey, L. Lauderbach, F. Gagliardi, T. van Buuren, E.A. Glascoe, J.W. Tringe, J.R.I. Lee, H.K. Springer, and J. Ilavsky, Mesoscale evolution of voids and microstructural changes in HMX-based explosives during heating through the β-δ phase transition, J. Appl. Phys. 118 (5) 055901 (2015).

V. Stepanov, T.M. Willey, J. Ilavsky, J. Gelb, and H.W. Qiu, Structural Characterization of RDX‐Based Explosive Nanocomposites, Propell., Explos., Pyrot. 38 (3), 386 (2013), doi: 10.1002/Prep.201200151.

T.M. Willey, D.M. Hoffman, T. van Buuren, L. Lauderbach, R.H. Gee, A. Maiti, G.E. Overturf, L.E. Fried, and J. Ilavsky, The Microstructure of TATB‐Based Explosive Formulations During Temperature Cycling Using Ultra‐Small‐Angle X‐Ray Scattering, Propell., Explos., Pyrot. 34 (5), 406 (2009).

  • Trevor Willey
  • Michael Bagge-Hansen
  • Joshua Hammons
  • Michael Nielsen
  • Lisa Lauderbach
  • Ralph Hodgin

Interfacial dynamics and assembly

The Nanomaterials Assembly Laboratory explores molecular processes at interfaces and uses quantitative measurements to address how these processes modify the way materials assemble and disassemble.

We use in situ methods to track dynamic phenomena, with a current focus on systems that evolve in fluid environments. We are particularly interested in nanocrystal assembly, nanocrystal shape control, catalysis, biomimetic approaches to material assembly, biomineralization, corrosion, and the fundamental physics and chemistry of growth and dissolution underlying these phenomena. We currently study growth dynamics at electrified interfaces, with applications in batteries, catalysis, and mesocrystal materials such as exchange-spring magnets. A few examples include battery interfaces, mesocrystal materials, and catalysis, which are outlined in further detail below.

Battery Interfaces

To study battery interfaces, we couple in situ electrochemical atomic-force microscopy with in situ scattering techniques such as ultra- small-angle x-ray scattering and wide-angle x-ray scattering. Current studies investigate the propensity for detrimental growths (such as oxide passivation and dendrite formation) as a function of electrolyte and additive chemistry. In collaboration with colleagues at the University of California, Berkeley, we have found that certain ionic liquids suppress roughening and hence lessen the probability of dendrite formation.

Similar approaches are used to track the effect of surfactants during nanocrystal growth or understand how additives alter biomineral formation.

 

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An example of four in situ Atomic Force Microscopy images of electrodeposited zinc formed in an ionic liquid electrolyte during a recharging cycle.

Mesocrystal Materials

Three-dimensional nanocrystal assemblies represent a new form of solid material that, if well-coupled, can have properties derived from both their individual building blocks and emergent cooperative interactions. One of the stumbling blocks for developing these novel materials is the need to control the crystalline quality of the assemblies via a fast and scalable process. Current projects address this gap by developing new additive-manufacturing techniques to control the ordering of nanocrystal assemblies.

 

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An example of ordered nanocrystal films and colloidal crystals created using electrophoretic deposition. The images at top show a film composed of 15-nm nickel nanocrystals; the bottom images illustrate faceted superlattices composed of 7-nm silver nanocrystals.

Catalysis

Recent work has focused on developing high-surface-area electroactive-catalyst materials and understanding the catalyst-degradation mechanism in solution environments. We use a suite of in situ tools to:

  • Measure activity
  • Monitor changes in surface morphology induced by relevant factors such as potential, pH, light
  • Identify active sites
  • Identify corrosion mechanisms
  • Assist in corrosion mitigation

 

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An example of in situ imaging of etch-pit formation and dissolution of MoS2 in chelating acids and oxidizing conditions.

M.A. Worsley, J.D. Kuntz, and C.A. Orme, High surface area graphene-supported metal chalcogenide assembly, US Patent 9314777 B2 (2016).

J.S. Keist, C.A. Orme, P.K. Wright, and J.W. Evans, An in situ AFM Study of the Evolution of Surface Roughness for Zinc Electrodeposition within an Imidazolium Based Ionic Liquid Electrolyte, Electrochimica Acta 152, 161 (2015), doi: 10.1016/j.electacta.2014.11.091.

M.A. Worsley, S.J. Shin, M.D. Merrill, J. Lenhardt, A.J. Nelson, L.Y. Woo, and C.A. Orme, Ultralow Density, Monolithic WS 2, MoS 2, and MoS 2/Graphene Aerogels, ACS Nano 9 (5), 4698 (2015), doi:10.1021/acsnano.5b00087.

T. Olson, C. Orme, T. Han, et al, Shape control synthesis of fluorapatite structures based on supersaturation: prismatic nanowires, ellipsoids, star and aggregate formation, CrystEngChem 20, 6384 (2012).

T.C. Monson, C. Hollars, C. Orme, and T. Huser, Improving Nanoparticle Dispersion and Charge Transfer in Cadmium Telluride Tetrapod and Conjugated Polymer Blends, ACS Applied Materials & Interfaces 3 (4), 1077 (2011).

A. Orme , B. Sadigh, M. Surh, J. Vandersall, P. Bedrossian, W.D. Wilson, T.W. Barbee Jr., and P.T. Beernink, Inducing order using nanolaminate templates, J. Materials Research, special issue on self-assembly 26, 194 (2011).

J.L. Giocondi, B.S. El-Dasher, G.H. Nancollas, and C.A. Orme, Molecular mechanism of crystallization impacting calcium phosphate cements, Trans. R. Soc. A 368, 1937 (2010). [Invited review]

L.Y. Woo, R.S. Glass, R. Gorte, C.A. Orme, A. Nelson, Dynamic Changes in LSM Nanoparticles on YSZ: A Model System for Non-Stationary SOFC Cathode Behavior, Journal of the Electrochemical Society 156 (5), B602 (2009).

S.R. Qiu and C.A. Orme, Dynamics of Biomineral Formation at the Near-Molecular Scale, Chemical Reviews, focus issue on biomineralization 108 (11), 4784 (2008). [Invited]

J. Gray and C.A. Orme, Electrochemical Impedance Spectroscopy Study of the Passive Films of Alloy 22 in Low pH Nitrate and Chloride Environments, Electrochimica Acta 52, 2370 (2007).

J.J. Gray, B.S. El Dasher, C.A. Orme, Competitive effects of metal dissolution and passivation modulated by surface structure: An AFM and EBSD study of the corrosion of alloy 22, Surface Science 600, 2488 (2006).

R. Hayes, J.J. Gray, A. Szmodis, and C.A. Orme, Influence of Chromium and Molybdenum on the Corrosion of Nickel Based Alloy Systems, Corrosion 62, 491 (2006).

J.P. Bearinger, C.A. Orme, and J.L. Gilbert, Effect of hydrogen peroxide on titanium surfaces: In situ imaging and step-polarization impedance spectroscopy of commercially pure titanium and titanium, 6-aluminum, 4-vanadium, Journal of Biomedical Materials Research Part A 67A, 702 (2003).

C.A. Orme, A. Noy, A. Wierzbicki, M.T. McBride, M. Grantham, H.H. Teng, P.M. Dove, and J.J. DeYoreo, Formation of chiral morphologies through selective binding of amino acids to calcite surface steps, Nature 411, 775 (2001).

H.H. Teng, P.M. Dove, C.A. Orme, and J.J. De Yoreo, Thermodynamics of calcite growth: Baseline for understanding biomineral formation, Science 282, 724 (1998).

  • Christine Orme

Materials research for laser targets

 

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X-ray radiography image of a Cu-metal-loaded carbon foam target for experiments at the Omega laser facility.

Several nanoscale integration science group members are collaborating in materials research for the laser target-fabrication program at LLNL.

Target-related work is underway for the inertial-confinement fusion (ICF) and high-energy density (HED) programs. We work in the following areas of materials research:

  • Condensed hydrogens
  • Nanoporous materials
  • Fusion fuel-capsule fabrication
  • Fusion fuel-capsule support
  • Ion-beam-induced processing
  • Metal bonding
  • Synchrotron-based material characterization

Our work on condensed hydrogens involves the nucleation and growth of hydrogen crystals, including crystallization and melting in confined geometries.

Research on nanoporous materials includes ice templating and sol-gel-based synthesis methods and advanced characterization of aerogels.

Our fusion fuel-capsule fabrication effort is currently focused on the development of unconventional sputter and chemical-vapor deposition methods.

Our work on the fusion-capsule support involves superconducting levitation and the development of freestanding thin films with improved mechanical properties.

Our ion-beam-induced processing effort includes ion implantation doping, modification of porous materials, and reactive-ion etching.

Metal-bonding research is currently focused on thermocompression and roll bonding of various metal foils.

For most of this research, we use synchrotron-based characterization, such as x-ray scattering, absorption, and emission.

A.M. Engwall, S.J. Shin, J. Bae, Y.M. Wang, Enhanced properties of tungsten films by high-power impulse magnetron sputtering, Surface and Coatings Technology 363, 191 (2019).

F. Fornasiero, M. LeBlanc, S. Charnvanichborikarn, S.O. Kucheyev, S.J. Shin, K.P. Gong, L.J. Ci, J. Park, and R. Miles, Hierarchical reinforcement of randomly-oriented carbon nanotube mats by ion irradiation, Carbon 99, 491 (2016).

O. Kucheyev, E. Van Cleve, L.T. Johnston, S.A. Gammon, and M.A. Worsley, Hydrogen crystallization in low-density aerogels, Langmuir 31, 3854 (2015).

T. Johnston, M.M. Biener, J.C. Ye, T.F. Baumann, and S.O. Kucheyev, Pore architecture of nanoporous gold and titania by hydrogen thermoporometry, Journal of Applied Physics 118, 025303 (2015).

F. Perez, J.R. Patterson, M. May, J.D. Colvin, M.M. Biener, A. Wittstock, S.O. Kucheyev, S. Charnvanichborikarn, J.H. Satcher Jr., S.A. Gammon, J.F. Poco, S. Fujioka, Z. Zhang, K. Ishihara, N. Tanaka, T. Ikenouchi, H. Nishimura, and K.B. Fournier, Bright x-ray sources from laser irradiation of foams with high concentration of Ti, Physics of Plasmas 21, 023102 (2014).

S. Charnvanichborikarn, M.A. Worsley, M. Bagge-Hansen, J.D. Colvin, T.E. Felter, and S.O. Kucheyev, Ice templating synthesis of low-density porous Cu-C nanocomposites, Journal of Materials Chemistry A 2, 18600 (2014).

S. Charnvanichborikarn, S.J. Shin, M. A. Worsley, I.C. Tran, T.M. Willey, T. van Buuren, T.E. Felter, J.D. Colvin, and S.O. Kucheyev, Nanoporous Cu-C composites based on carbon-nanotube aerogels, Journal of Materials Chemistry A 2, 962 (2014).

J. Shin, I.C. Tran, T.M. Willey, T. van Buuren, J. Ilavsky, M.M. Biener, M.A. Worsley, A.V. Hamza, and S.O. Kucheyev, Robust nanoporous alumina monoliths by atomic layer deposition on low-density carbon-nanotube scaffolds, Carbon 73, 443 (2014).

Y. Zheng, H. Lee, T.H. Weisgraber, M. Shusteff, J. DeOtte, E.B. Duoss, J.D. Kuntz, M.M. Biener, Q. Ge, J.A. Jackson, S.O. Kucheyev, N.X. Fang, and C.M. Spadaccini, Ultralight, ultrastiff mechanical metamaterials, Science 344, 1373 (2014).

H. Kim, S.J. Shin, J.M. Lenhardt, T. Braun, J.D. Sain, C.A. Valdez, R.N. Leif, S.O. Kucheyev, K.J.J. Wu, J. Biener, J.H. Satcher Jr, and A.V. Hamza, Deterministic control over high-Z doping of polydicyclopentadiene-based aerogel coatings, ACS Applied Materials and Interfaces 5, 8111 (2013).

O. Kucheyev, M. Stadermann, S.J. Shin, J.H. Satcher Jr, S.A. Gammon, S.A. Letts, T. van Buuren, and A.V. Hamza, Super-compressibility of ultralow-density nanoporous silica, Advanced Materials 24, 776 (2012).

S.O. Kucheyev and A.V. Hamza, Condensed hydrogen for thermonuclear fusion, Journal of Applied Physics 108 (9) 091101 (2010). [Featured on cover]

  • Sergei Kucheyev
  • Swanee Shin
  • Tyler Fears
  • Leonardus Bimo Bayu Aji
  • Joseph Wallace
  • Juergen Biener
  • Morris Wang
  • Michael Bagge-Hansen
  • Alison Engwall

Radiation effects in materials

 

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LLNL’s 4-mega-electronvolt (MV) accelerator facility

Work at the 4-mega-electronvolt (MV) accelerator laboratory provides multi-programmatic support to several key laboratory missions. The two major components of our work are ion-beam modification (IBM) of materials and ion-beam analysis (IBA) of materials.

Ion-beam modification

Our ion-beam modification work investigates the following areas:

  • Ion implantation of radiochemical dopants
  • Radiation effects in nanomaterials
  • Defect-interaction dynamics
  • Radiation damage at interfaces

Our recent ion-implantation effort has focused on material doping with specific isotopes for neutron capture (radiochemical) experiments at the National Ignition Facility (NIF).

We are working on radiation processing and ion-beam analysis of nanoporous materials such as aerogels.

We also are developing a novel experimental method to access the dynamic regime of radiation damage formation in nuclear and electronic materials. Our approach is based on using pulsed ion beams to measure defect lifetimes, interaction rates, and diffusion lengths. In accelerator-based experiments, ion-energy, mass, and beam-flux available could mimic all materials phenomena associated with nuclear energy—namely, alpha emission, heavy-ion recoil, and fission fragments—all without the hazard of handling or creating radioactive materials.

Ion-beam analysis

High- and medium-energy ion scattering is routinely used for measuring depth profiles of the elemental composition and lattice disorder in materials. We particularly specialize in non-routine, challenging cases of ion-beam analysis of samples that are, for example, non-flat, too small or large for a routine analysis, highly porous (and hence, fragile) difficult to handle, electrically insulating, toxic, radioactive, or unstable under the ion beam. Specific techniques used in the 4-MV accelerator laboratory include the following:

  1. Rutherford backscattering spectrometry (RBS) with light ions (1H, 2H, 3He, 4He, 12C, 15N, and 16O) with a wide range of ion energies (< 4 MeV for H, < 8 MeV for He, and < 12 MeV for C, N, and O). A beam-filtering unit specially designed for producing a high-energy He++ beam uncontaminated with H2+ species is available. RBS with variable scattering angles, including transmission RBS and 180-degree-scattering angle detection, is also available.
  2. Elastic-recoil detection analysis (ERDA) with MeV He ions for studying depth profiles of hydrogen isotopes
  3. Ion channeling
  4. Resonant non-Rutherford and nuclear-reaction analysis (NRA)
  5. Particle-induced x-ray emission (PIXE) and particle-induced gamma-ray emission (PIGE).
  6. Ion-beam-induced luminescence (IBIL).

Capabilities

The 4 MV accelerator laboratory at LLNL provides unique capabilities for IBA and radiation processing of materials.

LLNL researchers have access to the capabilities of the 4-MV accelerator laboratory for IBA and ion irradiation. For experimental requests, contact Sergei Kucheyev at 925-422-5866 or kucheyev [at] llnl.gov.

The 4-MV accelerator

 

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LLNL’s 4-mega-electronvolt (MV) accelerator terminal.

The 4-MV accelerator is a so-called single-ended ion accelerator with an axial-extraction cold-cathode Penning ion source, which produces isotopically pure beams of ions from 1 atomic mass unit (protons) to 136 atomic mass unit (xenon) at high and stable currents. The accelerator tube and the beamlines are bakeable, all metal-ceramic, designed to maintain ultra-high-vacuum (UHV) conditions. The major beam focusing is achieved by magnetic and electrostatic quadrupole lenses. The ion source is capable of producing high-current beams. Typical ion currents for singly-charged ions are limited to about 20 micro-Amperes on the target. Inert gas ions are the workhorse of the ion-beam analysis and are ideal for research projects that focus on the relatively high-dose regime, inherent to most nuclear-energy materials, without the notorious chemical effects of implanted species.

Beamlines and end stations

 

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The ion-beam modification end station.

The 4 MV-accelerator currently has two main beamlines geared for IBM and IBA, respectively. These two beamlines have three target chambers.

The IBM beamline and target chamber are used exclusively for ion-beam modification of materials. During irradiation, samples can be cooled by liquid nitrogen to 77 K or heated to 1500 K. The ion dose (fluence) can be accurately controlled over a very wide range of 1e8 to 1e18 ions/cm2. Samples up to four inches in diameter can be irradiated. The sample chamber that allowed irradiation of 12-inch wafers was recently decommissioned and is no longer available. In the IBM chamber, implantation can be performed with rastered, defocused, or pulsed ion beams, with exquisite control of the beam flux.

The IBA beamline has two sample chambers. The first chamber is used mostly for IBA and occasionally IBM experiments requiring tightly focused beams or the special diagnostics available in this chamber. It has a precision goniometer and detectors for the following:

  • Rutherford backscattering spectrometry (RBS)
  • Elastic-recoil detection analysis (ERDA)
  • Particle-induced x-ray emission (PIXE)
  • Particle-induced gamma-ray emission (PIGI)
  • Ion-beam-induced luminescence (IBIL)
  • A mass spectrometer for ion-induced desorption experiments

A low-energy electron gun is used for neutralizing insulating samples during the analysis. The IBA beamline has an electrostatic microprobe installed. Samples up to four inches in diameter can be analyzed in the IBA chamber, which can be used for experiments with radioactive targets and beryllium and high-explosive samples.

The second IBA chamber hosts an array of surface-preparation and surface-science analytical tools and detectors for RBS, ERDA, and NRA, and a medium-energy ion scattering (MEIS) detector for an RBS analysis with enhanced energy and depth resolution.

F. Fornasiero, M. LeBlanc, S. Charnvanichborikarn, S.O. Kucheyev, S.J. Shin, K.P. Gong, L.J. Ci, J. Park, and R. Miles, Hierarchical reinforcement of randomly-oriented carbon nanotube mats by ion irradiation, Carbon 99, 491 (2016).

L.B. Bayu Aji, J.B. Wallace, L. Shao, and S.O. Kucheyev, Non-monotonic temperature dependence of radiation defect dynamics in silicon carbide, Scientific Reports 6, 30931 (2016).

B. Wallace, L.B. Bayu Aji, T.T. Li, L. Shao, and S.O. Kucheyev, Damage buildup in Ar-ion-irradiated 3C-SiC at elevated temperatures, Journal of Applied Physics 118, 105705 (2015).

C. Ye, S. Charnvanichborikarn, M.A. Worsley, S.O. Kucheyev, B.C. Wood, and Y.M. Wang, Enhanced electrochemical performance of ion-beam-treated 3D graphene aerogels for lithium ion batteries, Carbon 85, 269 (2015).

B. Wallace, S. Charnvanichborikarn, L.B. Bayu Aji, M.T. Myers, L. Shao, and S.O. Kucheyev, Radiation defect dynamics in Si at room temperature studied by pulsed ion beams, Journal of Applied Physics 118, 135709 (2015).

B. Wallace, L.B. Bayu Aji, L. Shao, and S.O. Kucheyev, Time constant of defect relaxation in ion-irradiated 3C-SiC, Applied Physics Letters 106, 202102 (2015).

S. Charnvanichborikarn, M.A. Worsley, S.J. Shin, and S.O. Kucheyev, Heavy-ion-induced modification of structural and mechanical properties of carbon-nanotube aerogels, Carbon 57, 310 (2013).

T. Myers, S. Charnvanichborikarn, L. Shao, and S.O. Kucheyev, Pulsed ion beam measurement of the time constant of dynamic annealing in Si, Physical Review Letters 109, 095502 (2012).

M. Stadermann, S.O. Kucheyev, J. Lewicki, and S.A. Letts, Radiation tolerance of ultra-thin Formvar films, Applied Physics Letters 101, 071908 (2012).

S. Charnvanichborikarkn, S.J. Shin, M.A. Worsley, and S.O. Kucheyev, Tailoring properties of carbon-nanotube-based foams by ion bombardment, Applied Physics Letters 101, 103114 (2012).

  • Sergei Kucheyev
  • Swanee Shin
  • Leonardus Bimo Bayu Aji

Publications


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J. Ye, Y. An, E. Montalvo, P.G. Campbell, M.A. Worsley, I.C. Tran, Y. Liu, B.C. Wood, J. Biener, H. Jiang, M. Tang, and Y.M. Wang, Solvent-directed sol-gel assembly of 3-dimensional graphene-tented metal oxides and strong synergistic disparities in lithium storage, J. Mater. Chem. A 4, 4032 (2016), doi: 10.1039/C5TA10730J.

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M. Bagge-Hansen, B.C. Wood, T. Ogitsu, T.M. Willey, I.C. Tran, A. Wittstock, M.M. Biener, M.D. Merrill, M.A. Worsley, M. Otani, C.H. Chuang, D. Prendergast, J.H. Guo, T.F. Baumann, T. van Buuren, J. Biener, and J.R.I. Lee, Supercapacitors: Potential‐Induced Electronic Structure Changes in Supercapacitor Electrodes Observed by In Operando Soft X‐Ray Spectroscopy, Adv. Mater. 27 (9), 1512 (2015), doi: 10.1002/adma.201570057.

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S.O. Kucheyev and A.V. Hamza, Condensed hydrogen for thermonuclear fusion, Journal of Applied Physics 108 (9) 091101 (2010), doi: 10.1063/1.3489943.

People


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