Atomic Transport Research Articles

Atomic transport properties of water in barium–strontium aluminosilicates: Coupling of reactions and diffusion

AbstractBarium–strontium aluminosilicate (BSAS), with excellent resistance to water vapor corrosion and low water permeability, is considered an ideal environmental barrier coating material. Water vapor plays an important role on the failure of BSAS when it is exposed to service environments. Herein, the atomic transport properties of water in BSAS are investigated using ab initio calculations. The metastable structure of water in BSAS mainly consists of hydroxyl group and H+, where the hydroxyl group mainly exists in the form of Al–OH structure. In BSAS crystals, water first reacts with the aluminosilicate network to form metastable hydroxyl group and H+, and then hydroxyl group and H+ diffuse through the aluminosilicate network. Alkaline earth elements limit the diffusion behavior of water and improve the resistance to water vapor corrosion by maintaining the desired local charge balance of the Al–O4 tetrahedron structure. Furthermore, the ab initio molecular dynamics calculations at service temperature and pressure of BSAS are carried out to verify the above conclusions.

Metal evaporation dynamics in electron cyclotron resonance ion sources: plasma role in the atom diffusion, ionisation, and transport

We present a numerical study of metals dynamics evaporated through resistively heated ovens in electron cyclotron resonance (ECR) plasma traps, used as metal ion beam injectors for accelerators and multi-disciplinary research in plasma physics. We use complementary numerical methods to perform calculations in the framework of the PANDORA trap. The diffusion and deposition of metal vapours at the plasma chamber’s surface are explored under molecular flow regime, with stationary and time-dependent particle fluid calculations via COMSOL Multiphysics®. The ionisation of vapours is then studied in the strongly energised ECR plasma. We have developed a Monte Carlo (MC) code to simulate the in-plasma metal ions’ dynamics, coupled to particle-in-cell simulations of the plasma physics in the trap. The presence of strongly inhomogeneous plasmas leads to charge-exchange and electron-impact ionisations of metals, in turn affecting the deposition rate/pattern of the metal on the walls of the trap. Results show how vapours dynamics depends both on evaporated metals and the plasma target. The 134Cs, 176Lu, and 48Ca isotopes were investigated, the first two being radioisotopes interesting for the PANDORA project, and the third as one of the most required rare isotope by the nuclear physics community. We present an application of the study: MC computing the γ activity due to the deposited radioactive neutral nuclei during the measurement time, we quantitatively estimated the overall γ-detection system’s efficiency using GEANT4, including the poisoning γ-signal from the walls of the trap, relevant for the γ-tagging of short-lived nuclei’s decay rate in the PANDORA experiment. This work can give valuable support both to the evaporation technique and plasma source optimisation, for improving the metal ion beam production, avoiding huge deposit/waste of metals known to affect the long-term source stability, as well as for radio-safety aspects and reducing material waste in case of rare isotopes.

Systematic design of a robust half-W1 photonic crystal waveguide for interfacing slow light and trapped cold atoms

Novel platforms interfacing trapped cold atoms and guided light in nanoscale waveguides are a promising route to achieve a regime of strong coupling between light and atoms in single pass, with applications to quantum non-linear optics and quantum simulation. A strong challenge for the experimental development of this emerging waveguide-QED field of research is to combine facilitated optical access for atom transport, atom trapping via guided modes and robustness to inherent nanofabrication imperfections. In this endeavor, here we propose to interface Rubidium atoms with a photonic-crystal waveguide based on a large-index GaInP slab. With a specifically tailored half-W1 design, we show that a large chiral coupling to the waveguide can be obtained and guided modes can be used to form two-color dipole traps for atoms down to 115 nm from the edge of the structure. This optimized device should greatly improve the level of experimental control and facilitate the atom integration.

Nanoscale Kirkendall shift in thin films studied using x-ray waveguide structures

Kirkendall effect has played an important role in developing the understanding of atomic diffusion and mass transport in solids. In thin films and multilayers, in which the microstructure may be far from thermal equilibrium, behavior of a system can be very different from that of the bulk. Therefore, there is a great need to understand the peculiarities of Kirkendall shift occurring at nanometer or sub-nanometer length scale in such systems. In the present work, Kirkendall shift in thin films has been measured with sub-nanometer accuracy, by making use of x-ray planar waveguide structures. Using this technique, we report an apparently counterintuitive result of Kirkendall shift associated with self-diffusion in nanocrystalline iron. The cavity of the waveguide consists of two layers of iron having different microstructures, separated by a thin marker layer of Ag. Thermal annealing results in shift of the Ag marker towards the Fe layer having a coarser grain structure. The effect is established unambiguously by studying two samples with the order of the two Fe layers reversed, and a third sample with the two Fe layers having the same microstructure. The result can be understood in terms of the difference in the microstructure of the two Fe layers; difference in the grain size and hence different concentration of the grain boundaries in the two layers results in a net mass transfer from one region to the other.

Commensurate and incommensurate 1D interacting quantum systems

Single-atom imaging resolution of many-body quantum systems in optical lattices is routinely achieved with quantum-gas microscopes. Key to their great versatility as quantum simulators is the ability to use engineered light potentials at the microscopic level. Here, we employ dynamically varying microscopic light potentials in a quantum-gas microscope to study commensurate and incommensurate 1D systems of interacting bosonic Rb atoms. Such incommensurate systems are analogous to doped insulating states that exhibit atom transport and compressibility. Initially, a commensurate system with unit filling and fixed atom number is prepared between two potential barriers. We deterministically create an incommensurate system by dynamically changing the position of the barriers such that the number of available lattice sites is reduced while retaining the atom number. Our systems are characterised by measuring the distribution of particles and holes as a function of the lattice filling, and interaction strength, and we probe the particle mobility by applying a bias potential. Our work provides the foundation for preparation of low-entropy states with controlled filling in optical-lattice experiments.

Hydrogen diffusion in zirconium hydrides from on-the-fly machine learning molecular dynamics

Reactor pressure vessels and fuel cladding tubes have repeatedly failed due to zirconium hydrides. Zirconium hydride precipitation and growth are directly affected by hydrogen atom transport properties, which would make nuclear fuel storage less safe over long periods of time. Herein, we employ first-principles calculations to investigate the hydrogen diffusion mechanism in zirconium hydrides, utilizing on-the-fly machine learning force field molecular dynamics. It is verified that the machine learning force field can accurately describe the hydrogen atomic diffusion properties in zirconium hydrides at several temperatures and compositions. The atomic migration paths of hydrogen in zirconium hydrides as well as their barriers and pre-factors are also calculated. According to our results, the temperature and composition of zirconium hydrides affect the microscopic dynamical behavior of hydrogen.

In Situ Metal-Oxygen-Hydrogen Modified B-Tio2 @Co2 P-X S-Scheme Heterojunction Effectively Enhanced Charge Separation for Photo-assisted Uranium Reduction.

Photo-assisted uranium reduction from uranium mine wastewater is expected to overcome the competition between impurity ions and U(VI) in the traditional process. Here, B-TiO2 @Co2 P-X S-scheme heterojunction with metal-oxygen-hydrogen (M-O-H) is developed insitu modification for photo-assisted U(VI) (hexavalent uranium) reduction. Relying on the DFT calculation and Hard-Soft-Acid-Base (HSAB) theory, the introduction of metal-oxygen-hydrogen (M-O-H, hard base) metallic bonds in the B-TiO2 @Co2 P-X is found to enhance the hydrophilicity and the capture capability for uranyl ion (hard acid). Accordingly, B-TiO2 @Co2 P-500 hybrid nanosheets exhibit excellent U(VI) reduction ability (>98%) in the presence of competing ions. By self-consistent energy band calculations and in-situ KPFM spectral analysis, the formation of the internal electric field between B-TiO2 and Co2 P at the heterojunction is proven, offering a strong driving force and atomic transportation highway for accelerating the S-scheme charge carriers directed migration and promoting the photocatalytic reduction of uranium. This work provides a valuable route to explore the functionally modified photocatalyst with high-efficiency photoelectron separation for U(VI) reduction.

Modeling of CO Oxidation by Diffusion of Oxygen Atoms in Ceria-Zirconia Particulates in a Three-Way Catalyst Particle Membrane Filter

In order to design a microporous membrane filter comprising Three-way Catalyst (TWC) particles with a size distribution of 1 to 2 microns, isothermal CO oxidation experiments and numerical simulations were conducted to investigate the transport of oxygen atoms within primary Ceria-Zirconia (CZ) particulates. These spherical TWC particles were fabricated through the agglomeration of primary CZ and alumina particulates, incorporating Pd and Rh catalysts. By comparing experimental CO2 emissions with simulation results over time, a temperature-dependent diffusion coefficient was determined. The simulation results reveal that the effective distance of oxygen atom transport within CZ particulates, heterogeneously distributed in the spherical TWC particle, is limited to approximately 100 nm from the surface of agglomerated spherical TWC particles within a temperature range of 175 to 225°C.

Mass transport and thermal properties of liquid (melting to boiling point) tungsten: a molecular dynamics simulations

We present molecular dynamics simulation to obtain melting point, structural and atomic transport properties of liquid tungsten. We considered the second-neighbor extended Finnis-Sinclair (EFS) potential as an effective interaction. We find melting temperature (T M) and density in agreement with the reported values. EFS potential gives accurate information for structure factor S(q), pair correlation function g(r), and transport coefficients like self-diffusion coefficient and viscosity upto ∼1.5T M. Large viscosity proposes the rheological nature of liquid W. The self-diffusion coefficient follows the Arrhenius law giving the activation energy 1.22 eV. We find ’shoulder’ in the second peak of S(q), which disappears with temperatures. This characteristic is attributed to the high density and clustering of W-atoms at the near-neighbor distance. The asymmetric first peak in g(r) and shoulder in S(q) proposes that the liquid W exhibits non-normal metallic behaviour. Discrepancy observed in caloric properties for temperature >6000 K is also discussed. We propose that the ’softness’ and broad dip in EFS potential are responsible for these discrepancies, and necessitate the inclusion of angular forces. The single particle correlation is discussed in terms of the velocity autocorrelation function and the long-wavelength limit of S(q) is utilized to derive adiabatic sound velocity in confirmation with reported results.

Atomistic modeling of helium bubble network formation in copper

The helium (He) bubble network formation process in bulk copper (Cu) is investigated using atomistic simulations. Self-interstitial atoms (SIAs) emitted by trap mutation during the growth process of a single He bubble change surrounding lattices and stress fields and affect the transport of nearby He atoms. Interstitial He atoms or dimers can become trapped by deformed lattices and become nucleation sites for new He bubbles. The interaction of He with SIAs mutually hinders their movements. Finally, a distributed network of He bubbles, which are mostly formed along stacking fault edges, is generated. System temperature and He insertion rate have significant influences on this network.

Strong Metal-Support Interaction Facilitated Multicomponent Alloy Formation on Metal Oxide Support.

Multicomponent alloy (MA) contains a nearly infinite number of unprecedented active sites through entropy stabilization, which is a desired platform for exploring high-performance catalysts. However, MA catalysts are usually synthesized under severe conditions, which induce support structure collapse and further deteriorate the synergy between MA and support. We propose that a strong metal-support interaction (SMSI) could facilitate the formation of MA by establishing a tunnel of oxygen vacancy for metal atom transport under low reduction temperature (400-600 °C), which exemplifies the holistic design of MA catalysts without deactivating supports. PtPdCoFe MA is readily synthesized on anatase TiO2 with the help of SMSI, which exhibits good catalytic activity and stability for methane combustion. This strategy demonstrates excellent universality on various supports and multicomponent alloy compositions. Our work not only reports a holistic synthesis strategy for MA synthesis by synergizing unique properties of reducible oxides and the mixing entropy of alloy but also offers a new insight that SMSI plays a vigorous role in the formation of alloy NPs on reducible oxides.

Atomic order, magnetic and transport phenomena in half-Heusler CoMnSb0.9Z0.1 alloys (Z = Si, Al, Sn, and Bi)

In this study, we investigate the effects of doping with ∼10 at% of Si, Al, Sn, and Bi on the atomic order, microstructure, and magnetic properties of CoMnSb samples prepared using the arc-melting method. X-ray diffraction, scanning electron microscopy, and magnetometry techniques were employed to derive the structural and magnetic parameters. The samples demonstrate a superstructure with an Fm-3m space group. They exhibit a saturation moment of 3.71–4.71 μB per formula unit at 5 K and a Curie temperature ranging from 474 to 507 K. Rietveld refinement performed on the XRD data revealed a possible occupation of magnetic atoms in the vacant 32f (x’, x’, x’) sites and atomic swapping, both of which may affect the magnitudes of the magnetic moment and Curie temperature. The electrical measurement results show that the grain boundaries and voids govern the conductivity of the samples. The spin polarization of the Si-doped sample was determined based on the grain-boundary magnetoresistance effect, which showed that this sample has a high degree of atomic order, consistent with the low magnetic moment, Curie temperature, and lattice constant.

Atomic Diffusion Mechanism in BF2+ Implanted and Annealed n-Fz Si junction using Analytical Approach: Comparison with 2-D TCAD Process Simulation Result

Ion implantation controls the diffusion of the dopants inside the n-Fz Si bulk of the p+n Si microstrip detector. In order to understand about the diffusion mechanism of BF2 + molecules/dopants into the n-Fz Si bulk of Double Sided Silicon Strip Detector (back side) for the R3B Silicon Tracker, it is essential to know the precise information about the microscopic defect introduces inside the Si lattice of the detector for the next phase upgrade of the R3B experiment. The purpose of this paper is to present the atomic transport and electrical activation behavior of implanted BF2+ molecules/dopants at an energy of 80 KeV and a dose of 1015 ion/cm2 into the n-Fz Double Sided Silicon Strip Detector for the R3B Silicon Tracker after annealing at 400 °C - 1350 °C.The result shows the amorphous-crystalline interface position and recrystallization temperature using the results revealed from the 2-D TCAD process simulation of the Si microstrip detector.

Determination of the Thermomigration Force on Adatoms.

Thermal gradients in nanomaterials can cause surface mass transport phenomena. However, the atomic fluxes are challenging to quantify and the underlying atomic mechanisms are complex. Using low energy electron microscopy we have examined in operando, under a thermal gradient of 10^{4} K/m, the thermomigration of supercooled Si(111)-1×1 advacancy islands. The islands move in the direction of the thermal gradient at 0.26±0.06 nm/s. This reveals that the adatoms move toward the cold region and the effective force exerted on Si adatoms is 1.4±0.4×10^{-8} eV/nm. We quantify the heat of transport of Si atoms Q^{*}=1.2±0.4 eV and show that it corresponds to the combined effects of adatom creation at step edges and adatom diffusion on atomically flat terraces.

Dynamic heterogeneity of atomic transport in a body-centered cubic WTaVCr non-equiatomic high-entropy alloy

Compared to face-centered cubic (fcc) high-entropy alloys (HEAs), body-centered cubic (bcc) HEAs generally possess larger lattice distortion, resulting in distinct point defect properties. In this work, molecular dynamics (MD) simulations and molecular statics (MS) calculations were performed to study the dynamic heterogeneity in a bcc W40Ta35V10Cr15 non-equiatomic HEA with large lattice distortion. Defect energies in W40Ta35V10Cr15 HEA show a strong preference for a specific element and possess large energy spreads, resulting in dynamic heterogeneity of atomic transport in the process of defect diffusion and evolution. V and Cr interstitials exhibit higher occurrence probability and faster diffusion compared to W and Ta interstitials. Such diffusion heterogeneity brings about high recombination probabilities of W and Ta interstitials and large fractions of V and Cr in surviving interstitials during displacement cascades. The binding ability of interstitials correlates with the magnitude of interstitial formation energies. The smaller the interstitial formation energies, the weaker the binding abilities. A large number of surviving V and Cr interstitials with smaller interstitial formation energies exhibit weak binding abilities and discrete distribution. Our findings suggest that the dynamic heterogeneity in W40Ta35V10Cr15 HEA with large lattice distortion may be the underlying mechanism of outstanding irradiation resistance.

Diffusion, atomic transport, and ordering in Al-Zr alloys: FCC and liquid phases

Additive manufacturing of materials with controlled microstructure demands knowledge of atomic scale properties near the solid-liquid transition state. Many of these properties are not affordable by experimental techniques and computer modeling is the possible solution to the problem. In this paper, we present the results of an extended atomistic study of intrinsic atomic transport due to vacancy diffusion in FCC and L12 solid phases and diffusion in the liquid phase of Al-Zr alloys. A deceleration of the overall self-diffusion was observed when Zr was added to Al. The effect was stronger in the solid and weaker in the liquid. Additionally, the effect was strongly temperature dependent in the solid phases, but not in the liquid. Atomic transport was chemically biased: transport of Zr atoms was significantly slower than that of Al atoms, and this bias effect was stronger in the solid phases. The overall diffusion and chemical ordering processes in the liquid state were five to six orders in magnitude faster than in the solid. Chemical short-range order parameters in the liquid saturated at values close to those in the ordered L12 structure of Al3Zr. Chemical and structural ordering in the solid phases was negligible over the modeled microsecond time scale. The results are discussed in view of optimizing additive manufacturing parameters for the controlled formation of metastable L12 precipitates.

Microstructure evolution at the interface between Cu and eutectic Sn–Bi alloy with the addition of Ag or Ni

The study investigated the growth kinetics and rate-controlling processes of intermetallic layers formed at the interface between Cu and eutectic Sn–Bi alloys with Ag or Ni addition at solid-state temperatures. Isothermal sections of the equilibrium phase diagram were calculated to understand phase stability at the interface. The thicknesses of the intermetallic layers were plotted against annealing time, and a power function equation with an exponent slightly smaller than 0.25 described their relationship, indicating boundary diffusion with grain growth as the predominant control mechanism. The relationship between the exponent and annealing temperature suggested that the grain growth in the intermetallic layer followed an approximate parabolic law. The eutectic microstructure in Sn–57Bi–1Ag and Sn–57Bi–1Ni alloys changed with annealing, with differences in the Bi region width. However, the contact surface area between the Bi region and Cu6Sn5 compound was similar in both alloys. Activation enthalpies for the rate-controlling process of intermetallic layer growth were evaluated, providing insights into the energy barrier for atomic diffusion or transport across the interface.

Extreme Ultraviolet Radiation Sources from Dense Plasmas

The concept of dense and hot plasmas can be used to build up powerful and brilliant radiation sources in the soft X-ray and extreme ultraviolet spectral range. Such sources are used for nanoscale imaging and structuring applications, such as EUV lithography in the semiconductor industry. An understanding of light-generating atomic processes and radiation transport within the plasma is mandatory for optimization. The basic principles and technical concepts using either a pulsed laser or a gas discharge for plasma generation are presented, and critical aspects in the ionization dynamics are outlined within the framework of a simplified atomic physics model.

Activation of atomic transport via vibrational coupling-induced force fluctuations

Vibrational coupling, although well-explored in many fields, has seldom been investigated in the context of mass transport. In this Letter, we examine the impact of vibrational coupling on atomic transport using simple molecular dynamics simulations. Our study shows that the atomic transport can be activated when the natural frequency of the atomic slit is close to the natural frequency of the atom being transported. We uncover the presence of fluctuating forces induced by vibrational coupling with higher amplitudes observed when the coupling is strong. We show that the transport activation mechanism is due to the high force fluctuations that arise during strong vibrational coupling allowing the atom to temporarily surpass the transport barrier of the slit. Our findings will serve as a foundation for the continued examination of vibrational coupling in the realm of mass transport.

(Invited) Graphene Ion Blocking Layers for Robust Metal-Halide Perovskite Heterostructures

Despite being only one atomic layer thick, a continuous monolayer of graphene should be completely impermeable to atoms and ions. As such, graphene monolayers could potentially be employed as ion blocking layers in numerous technologies where charge and/or energy transport across a key interface is desirable, but ionic or atomic transport is not. As a key example, the development of metal-halide perovskite/perovskite heterostructures is hindered by rapid interfacial halide diffusion leading to mixed alloys rather than sharp interfaces. This halide diffusion hinders the creation of tailored interfaces that funnel energy or charge in specified directions within energy technologies such as photovoltaic solar cells or light-emitting diodes. To circumvent this issue, we developed an ion-blocking layer consisting of single layer graphene (SLG) deposited between the metal-halide perovskite layers and demonstrate that it effectively blocks anion diffusion in perovskite/perovskite heterostructures. We study these interfaces with a suite of spectroscopy and elemental analysis tools to demonstrate that halides do not diffuse across the graphene-modified interface, whereas control samples without the SLG show rapid homogenization of the halides and loss of the sharp interface. The SLG has little electronic impact on the band alignment and optical properties of the individual semiconductors, as supported by density functional theory calculations, facilitating photoinduced energy transfer across the abrupt heterointerface and light-emitting diodes with no evidence of ion-diffusion during operation. Our results demonstrate that monolayer graphene can be used as an ion blocking layer in a variety of different heterostructures for advanced opto-electronic and electrochemical applications. Further, it establishes a route towards robust perovskite/perovskite heterostructures that are difficult to achieve by other means.