Engineering topics

Han, Yong

Publications and source records attributed to Han, Yong.

13 records

DOE OSTI2025

Data for: Subsurface Interface Structure Controlling Local Electronic Properties of Epitaxial Graphene on SiC(0001)

Recently realized high-mobility semiconducting epitaxial graphene on silicon carbide, provided an important step towards integration of the graphene-based system into active components in post-silicon micro- and nano-electronics. However, the exact atomic-scale structure and the complex bonding configurations of the first epitaxial graphene carbon layer remain an open problem. Our recent report has shed new light on understanding this interface, where the external transverse electric field-dependent dynamic switching behavior of the Cbuffer-SiC bonds was observed. Here, using scanning tunneling microscopy and spectroscopy (STM and STS), we present the direct evidence of silicon (Si) vacancies at the interface and provide their distribution at the topmost reconstructed SiC(0001) layer. Experimental STM and density functional theory modeling data were used in the preparation of figures in a published article in the Journal of Physical Chemistry Letters. Files related to the figures and supplementary materials in the article are present in this dataset in .txt format.

Condensed matter imaging↗

DOE OSTI2025

Data for: Subsurface Interface Structure Controlling Local Electronic Properties of Epitaxial Graphene on SiC(0001)

Condensed matter imaging↗

DOE OSTI2024

Strain-modulated intercalated phases of Pb monolayer with dual periodicity in SiC(0001)-graphene interface

Intercalation of metal atoms at the SiC(0001)-graphene (Gr) interface can provide confined 2D metal layers with interesting electronic properties. The intercalated Pb monolayer (ML) has shown the coexistence of the Gr(10 x 10)-moiré and a stripe phase, which still lacks understanding. Using density functional theory calculation and thermal annealing with ab initio molecular dynamics as motivated by experiment, we have studied the formation energy of Gr/Pb/SiC(0001) for different Pb coverages. Near the coverage of a Pb(111)-like ML mimicking the (10 x 10)-moiré, we find a slightly more stable stripe structure, where one half of the structure has compressive strain with Pb occupying the Si-top sites and the other half has tensile strain with Pb off the Si-top sites. This stripe structure along the Gr zigzag direction has a periodicity of 2.3 nm across the [1$\overline{2}$10] direction agreeing with the previous observations using scanning tunneling microscopy. Analysis with electron density difference and density of states show the tensile region has a more metallic character than the compressive region, while both are dominated by charge transfer from Pb ML to SiC(0001). As a result, the small energy difference between the stripe and Pb(111)-like structures means the two phases are almost degenerate and can coexist, which explains the experimental observations.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Formation and coarsening of epitaxially-supported metal nanoclusters

This mini-review describes developments over the last ~30 years in characterizing the nucleation & growth of epitaxially-supported metal nanoclusters (NCs) or islands during vapor deposition, as well as their post-deposition coarsening. A beyond-mean-field treatment for homogeneous nucleation & growth corrects the deficiencies of traditional treatments in describing, e.g., the island size distribution, but also necessitates consideration of the spatial distribution of islands and their capture zones. We discuss advances in modeling capabilities, including those based upon on an ab-initio level treatment of periphery diffusion kinetics, for description of the non-equilibrium growth shapes of these NCs, focusing on 2D NCs. For post-deposition coarsening of arrays of NCs, there is generally a competition between Ostwald Ripening (OR) and Smoluchowski Ripening (SR). SR is also known as Particle Migration & Coalescence. For 2D NCs in homoepitaxial systems, conventional OR is observed on pristine fcc(111) surfaces, dramatically enhanced OR in the presence of even trace amounts of chalcogens for Cu(111) and Ag(111), and anomalous OR on anisotropic fcc(110) surfaces. The unexpected discovery of SR for fcc(100) homoepitaxial systems prompted extensive analysis of the underlying diffusivities of 2D NCs as a function of size, as well as of NC coalescence dynamics. A comprehensive understanding of these processes is now available. Self-assembly of 3D NCs during deposition, issues related to heterogeneous nucleation, directed assembly, NC growth structure selection, and coarsening are addressed. Finally, for SR of 3D epitaxial NCs, recent insights into the size-dependence of diffusivity are described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Versatile stochastic model for predictive KMC simulation of fcc metal nanostructure evolution with realistic kinetics

Stochastic lattice-gas models provide the natural framework for analysis of the surface diffusion-mediated evolution of crystalline metal nanostructures on the appropriate time scale (often 10 1 –10 4 s) and length scale. Model behavior can be precisely assessed by kinetic Monte Carlo simulation, typically incorporating a rejection-free algorithm to efficiently handle the broad range of Arrhenius rates for hopping of surface atoms. The model should realistically prescribe these rates, or the associated barriers, for a diversity of local surface environments. However, commonly used generic choices for barriers fail, even qualitatively, to simultaneously describe diffusion for different low-index facets, for terrace vs step edge diffusion, etc. We introduce an alternative Unconventional Interaction–Conventional Interaction formalism to prescribe these barriers, which, even with few parameters, can realistically capture most aspects of behavior. Here, the model is illustrated for single-component fcc metal systems, mainly for the case of Ag. It is quite versatile and can be applied to describe both the post-deposition evolution of 2D nanostructures in homoepitaxial thin films (e.g., reshaping and coalescence of 2D islands) and the post-synthesis evolution of 3D nanocrystals (e.g., reshaping of nanocrystals synthesized with various faceted non-equilibrium shapes back to 3D equilibrium Wulff shapes).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Real-Time KMC Simulation of Vacancy-Mediated Intermixing in Au@Ag Octahedral Core–Cubic Shell Nanocrystals with Ab Initio-Guided Kinetics

Utilization of core–shell rather than monometallic nanocrystals (NCs) facilitates fine-tuning of NC properties for applications. However, compositional evolution via intermixing can degrade these properties prompting recent experimental studies. We develop an atomistic-level stochastic model for vacancy-mediated intermixing exploiting a formalism which allows incorporation at an ab initio density functional theory level of not just the thermodynamics of vacancy formation, but also relevant diffusion barriers for a vast number of possible local environments (in the core and in the shell, at the interface, and in the intermixed phase). This facilitates a predictive treatment and comprehensive understanding of intermixing on the relevant time scale (e.g., 10 1 –10 3 s). In contrast, previous modeling at the atomistic level utilized only unrealistic generic prescriptions of barriers or employed simplified continuum treatments. For Au@Ag octahedral core–cubic shell NCs, our modeling not only captures the experimentally observed rate or time scale for intermixing of ~100 s at 450 °C for 60 nm NCs, but also elucidates the underlying rate controlling processes and the effective intermixing barrier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Crystal structure and shape selection in the growth of 3D metallic crystallites on layered materials: Fe on MoS 2

Nucleation and growth of supported 3D metal clusters or crystallites during deposition on MoS 2 , or on other weakly-adhering layered materials, can potentially produce diverse growth shapes, and even crystal structures differing from the bulk metal. For Fe deposition on MoS 2 , SEM and AFM observations reveal three distinct crystallite shapes. By comparison with atomistic structure models incorporating realistic Fe-MoS 2 interface structures, here we conclude that these are: triangular fcc(111) pyramids with sloped {100} side facets; bcc(110) A-frame tents with sloped {100} side facets; and bcc(110) mesas with vertical {100} and {110} side facets. The following picture is proposed for the competitive formation of clusters and crystallites with different structures: (i) small nanoclusters formed at the onset of deposition exhibit facile fluxional dynamics allowing sampling of different crystal structures and shapes; (ii) sufficient fluxionality implies a Boltzmann distribution of sampled structures, and thus coexistence of different structures follows from the demonstrated similar energies for those structures; (iii) growing clusters reach a threshold size above which the characteristic time scale for restructuring exceeds that for cluster growth. Thereafter, clusters are locked-in to a specific crystal structure and shape as revealed by imaging of larger crystallites. Despite a penalty for fcc(111) over bcc(111) pyramids based on bulk energetics, favorable surface and interface energies makes them preferable for smaller sizes.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Thermal Shape Stability of fcc Metal Nanocrystals Synthesized with Faceted Nonequilibrium Shapes

Highly refined capabilities of the shape-controlled solution-phase synthesis of metal nanocrystals (NCs) allow the generation of NCs with faceted nonequilibrium shapes, which optimize properties for target applications such as catalysis and plasmonics. Often, for such applications and also for TEM analysis, the NCs are removed from the solution-phase environment. We explore the postsynthesis evolution of these metastable NCs in a high-vacuum TEM environment. Specifically, here we analyze their reshaping toward the equilibrium Wulff shapes mediated by surface diffusion, where such reshaping degrades the above-mentioned optimized properties. Typical sizes for these NCs range from 5 to 30 nm or 10 3 –10 6 atoms, and reshaping often occurs on the time scale of minutes for temperatures around, say, 400 °C. We discuss the development of predictive stochastic atomistic-level models for NC evolution with a realistic description of surface diffusion. These models, in contrast to Molecular Dynamics, can naturally address the relevant time and length scales for these systems. KMC simulation results for the stochastic models are described, focusing on the reshaping of slightly elongated nanorods and of mildly truncated octahedra and nanocubes. In addition, we review appropriate theoretical formulations for reshaping, which involves the nucleation and growth on 2D islands or layers on outer facets of the NC. We note the limitations of classical nucleation theory in some scenarios and demonstrate the successes of a more fundamental and general master equation-based analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

DFT Analysis of the Binding of Rare Earth Nitrates at Internal and External Surfaces of MCM-22

MCM-22-type zeolites constitute a well-characterized tunable class of aluminosilicates suitable for elucidating the fundamental aspects of the binding of rare earth elements (REEs) in layered materials. Starting from the pure silica version ITQ-1 with a unit cell of Si 72 O 144 , a model for periodic bulk crystalline MCM-22 with a finite Al concentration is provided by replacing a Si atom with an Al atom in the unit cell at suitable tetrahedral sites near an internal pore surface. Then, a H atom is added to an O atom bridging Si and Al atoms to create a Brønsted acid site (BAS). There are no internal silanol groups in this bulk model. To generate a model for an external surface, we adopt the fully hydroxylated surface structure of a layer within the ITQ-1 precursor with two silanols per lateral unit cell. A BAS on the external surface can be generated by replacing a near-surface Si atom with an Al atom and adding a H atom, as above. The strength of binding at a BAS of REE, X, taken to be present in the solution phase as nitrates, is determined from the energy change in the reaction X(NO 3 ) 3 + ≡Si–{OH}–Al≡ → ≡Si–{OX(NO 3 ) 2 }–Al≡+ HNO 3 . The strength of binding at the silanols is determined similarly. Binding energies are determined from two approaches. The first performs periodic plane-wave density functional theory (DFT) total energy analysis for an entire unit cell of MCM-22. The second utilizes cluster models capturing the local environment of REE binding sites and performs DFT analysis with localized basis sets. The two approaches yield consistent results for Nd, revealing similarly strong binding at either an external or internal BAS, but much weaker binding at a silanol site. This is consistent with the picture deduced from recent experiments. Here, we also comment on binding at Al-bridged siloxane sites, which have been suggested as alternative binding sites to BAS.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Imaging flow cytometry using linear array spot excitation

Not Available

Han, Yong↗

NASA NTRS2003

Measurement of Low Amounts of Precipitable Water Vapor Using Ground-Based Millimeterwave Radiometry

Extremely dry conditions characterized by amounts of precipitable water vapor (PWV) as as 1-2 mm commonly occur in high-latitude regions during the winter months. While such atmospheres carry only a few percent of the latent heat energy compared to tropical atmospheres, the effects of low vapor amounts on the polar radiation budget - both directly through modulation of longwave radiation and indirectly through the formation of clouds - are considerable. Accurate measurements of precipitable water vapor (PWV) during such dry conditions are needed to improve polar radiation models for use in understanding and predicting change in the climatically sensitive polar regions. To this end, the strong water vapor absorption at 183.310 GHz provides a unique means of measuring low amounts of PWV. Weighting function analysis, forward model calculations based upon a 7-year radiosonde dataset, and retrieval simulations consistently predict that radiometric measurements made using several millimeter-wavelength (MMW) channels near the 183 GHz line, together with established microwave (MW) measurements at the 22.235 GHz water vapor line and -3 1 GHz atmospheric absorption window can be used to determine within 5% uncertainty the full range of PWV expected in the Arctic. This unique collective capability stands in spite of accuracy limitations stemming from uncertainties due to the sensitivity of the vertical distribution of temperature and water vapor at MMW channels. In this study the potential of MMW radiometry using the 183 GHz line for measuring low amounts of PWV is demonstrated both theoretically and experimentally. The study uses data obtained during March 1999 as part of an experiment conducted at the Department of Energy s Cloud and Radiation Testbed (CART) near Barrow, Alaska. Several radiometers from both NOAA and NASA were deployed during the experiment to provide the first combined MMW and MW ground-based data set during dry arctic conditions. Single-channel retrievals of PWV were performed using the MW and MMW data. Discrepancies in the retrieved values were found to be consistent with differences observed between measured brightness temperatures (TBs) and forward-modeled TBs based on concurrent radiosonde profiles. These discrepancies are greater than can be explained by measurement error alone and are attributed to absorption model uncertainty. We discuss here the measurements, retrieval technique, and line model discrepancies along with difficulties and potential of MMW/MW PWV measurement.

Racette, Paul E.↗

NASA NTRS2000

MM-Wave Radiometric Measurements of Low Amounts of Precipitable Water Vapor

An experiment was conducted during March, 1999 to study ways in which to improve techniques for measuring low amounts of total-column precipitable water vapor (PWV). The experiment was conducted at the DOE's ARM program's North Slope of Alaska/Adjacent Arctic Ocean Cloud and Radiation Testbed site (DoE ARM NSA/AAO CaRT) located just outside Barrow, Alaska. NASA and NOAA deployed a suite of radiometers covering 25 channels in the frequency range of 20 GHz up to 340 GHz including 8 channels around the 183 GHz water vapor absorption line. In addition to the usual CaRT site instrumentation the NOAA Depolarization and Backscatter Unattended Lidar (DABUL), the SUNY Rotating Shadowband Spectroradiometer (RSS) and other surface based meteorological instrumentation were deployed during the intensive observation period. Vaisala RS80 radiosondes were launched daily as well as nearby National Weather Service VIZ sondes. Atmospheric conditions ranged from clear calm skies to blowing snow and heavy multi-layer cloud coverage. Measurements made by the radiosondes indicate the PWV varied from approx. 1 to approx. 5 mm during the experiment. The near-surface temperature varied between about -40 C to - 15 C. In this presentation, an overview of the experiment with examples of data collected will be presented. Application of the data for assessing the potential and limitations of millimeter-wave radiometry for retrieving very low amounts of PWV will be discussed.

Racette, P.↗

NASA NTRS1994

Observations of water vapor by ground-based microwave radiometers and Raman lidar

In November to December 1991, a substantial number of remote sensors and in situ instruments were operated together in Coffeyville, Kansas, during the climate experiment First ISCCP Regional Experiment Phase 2 (FIRE 2). Includede in the suite of instruments were (1) the NOAA Environmental Technology Laboratory (ETL) three-channel microwave radiometer, (2) the NASA GSFC Raman lidar, (3) ETL radio acoustic sounding system (RASS), and (4) frequent, research-quality radiosondes. The Raman lidar operated only at night and the focus of this portion of the experiment concentrated on clear conditions. The lidar data, together with frequent radiosondes and measurements of temperature profiles (every 15 min) by RASS allowed profiles of temperature and absolute humidity to be estimated every minute. We compared 20 min measurements of brightness temperature (T(sub b) with calculations of T(sub b) that were based on the Liebe and Layton (1987) and Liebe et al. (1993) microwave propagation models, as well as the Waters (1976) model. The comparisons showed the best agreement at 20.6 GHz with the Waters model, with the Liebe et al. (1993) model being best at 31.65 GHz. The results at 90 GHz gave about equal success with the Liebe and Layton (1987) and Liebe et al. (1993) models. Comparisons of precipitable water vapor derived independently from the two instruments also showed excellent agreement, even for averages as short as 2 min. The rms difference between Raman and radiometric determinations of precipitable water vapor was 0.03 cm which is roughly 2%. The experiments clearly demonstrate the potential of simultaneous operation of radiometers and Raman lidars for fundamental physical studies of water vapor.

Han, Yong↗