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DOE OSTI2022

Fluid – Fluid Interfacial Area and Its Impact on Relative Permeability - A Pore Network Modeling Study

Abstract Relative permeability (kr) is commonly modeled as an empirical function of phase saturation. Although current empirical models can provide a good match of one or two measured relative permeabilities using saturation alone, they are unable to predict relative permeabilities well when there is hysteresis or when physical properties such as wettability change. Further, current models often result in relative permeability discontinuities that can cause convergence and accuracy problems in simulation. To overcome these problems, recent research has modeled relative permeability as a state function of both saturation (S) and phase connectivity (X). Pore network modeling (PNM) data, however, shows small differences in relative permeability for the same S-X value when approached from a different flow direction. This paper examines the impact of one additional Minkowski parameter (Mecke and Arns, 2005), the fluid-fluid interfacial area, on relative permeability to identify if that satisfactorily explains this discrepancy. We calculate the total fluid-fluid interfacial areas (IA) during two-phase (oil/water) flow in porous media using pore network modeling. The area is calculated from PNM simulations using the areas associated with corners and throats in pore elements of different shapes. The pore network is modeled after a Bentheimer sandstone, using square, triangular, and circular pore shapes. Simulations were conducted for numerous primary drainage and imbibition cycles at a constant contact angle of 0° for the wetting phase. Simultaneous measurements of capillary pressure, relative permeability, saturation, and phase connectivity are made for each displacement. Fluid-fluid interfacial area is calculated from the PNM capillary pressure, the fluid location in the pore elements, and the pore element dimensional data. The results show that differences in the relative permeability at the same (S,X) point is explained well by differences in the fluid-fluid interfacial area (IA). That is, for a larger change in IA at these intersection points, the permeability difference is greater. That difference in relative permeability approaches zero as the difference in IA approaches zero. This confirms that relative permeability can be modeled better as a unique function of S, X, and IA. The results also show that an increase in IA restricts flow decreasing the nonwetting (oil) phase permeability. This decrease is caused by an increase in the throat area fraction compared to the corner area as the total area IA increases. The wetting phase relative permeability, however, shows the inverse trend, in that its relative permeability is greater when IA becomes larger owing to a greater fraction of the total area associated with the corners. The area IA, however, impacts the nonwetting phase relative permeability more than the wetting phase relative permeability. Corner flow improves the wetting phase relative permeability because the wetting phase is continuous there. Finally, a sensitivity analysis shows that relative permeability a is more sensitive to change in S than they are for IA for the case studied implying that if only two parameters are used to model relative permeability it is better to choose S and X.

Engineering↗

NASA NTRS2001

The Role of Remote Sensing Displays in Earth Climate and Planetary Atmospheric Research

The communities of scientists who study the Earth's climate and the atmospheres of the other planets barely overlap, but the types of questions they pose and the resulting implications for the use and interpretation of remote sensing data sets have much in common. Both seek to determine the characteristic behavior of three-dimensional fluids that also evolve in time. Climate researchers want to know how and why the general patterns that define our climate today might be different in the next century. Planetary scientists try to understand why circulation patterns and clouds on Mars, Venus, or Jupiter are different from those on Earth. Both disciplines must aggregate large amounts of data covering long time periods and several altitudes to have a representative picture of the rapidly changing atmosphere they are studying. This emphasis separates climate scientists from weather forecasters, who focus at any one time on a limited number of images. Likewise, it separates planetary atmosphere researchers from planetary geologists, who rely primarily on single images (or mosaics of images covering the globe) to study two-dimensional planetary surfaces that are mostly static over the duration of a spacecraft mission yet reveal dynamic processes acting over thousands to millions of years. Remote sensing displays are usually two-dimensional projections that capture an atmosphere at an instant in time. How scientists manipulate and display such data, how they interpret what they see, and how they thereby understand the physical processes that cause what they see, are the challenges I discuss in this chapter. I begin by discussing differences in how novices and experts in the field relate displays of data to the real world. This leads to a discussion of the use and abuse of image enhancement and color in remote sensing displays. I then show some examples of techniques used by scientists in climate and planetary research to both convey information and design research strategies using remote sensing displays.

DelGenio, Anthony D.↗

DOE OSTI2018

Modeling Mesoscale Processes of Scalable Synthesis Final Scientific/Technical Report

This is the final scientific and technical report for this award. Molecular dynamics (MD) is a powerful tool to study biomolecules at the nanoscale. One of its main limitations however is that such simulations typically require a timestep of 1 femtosecond while reactions and conformational changes typically happen on the time scale of 1 microsecond or more. This discrepancy severely restricts the impact of this method. We have developed a series of algorithms to mitigate this problem and allow predicting long-time scale events using much shorter simulations. The method is based on the concurrent adaptive sampling method. It consists in using probabilistic weights for trajectories and biasing the sampling such that rare but important trajectories, e.g., those that go over energy barriers and lead to relevant conformational changes in the molecule, are observed with much higher frequency that in a standard MD simulation. We will demonstrate below that this approach has been very successful. In collaboration with Jay Grate at PNNL we have applied this novel method to the study the triazine polymers, which can be con gured using different types of side chains in order to adopt different 3-dimensional structures. We have found novel stable con- formations and have analyzed the impact of side chain modifcations on the native folded shape of the polymer. Direct MD simulations would have been untractable for this problem. The method of replica exchange was also used successfully to calculate free energy profiles, in particular for cis-trans torsional angle changes with high energy barriers. Studying molecules at the atomistic scale is essential to design new molecules in chemical engineering, such as the triazine polymers developed by Grate, in material science to study the strength of metals for examples (e.g., dislocation dynamics), or in biochemistry to understand how proteins fold and how they interact with ligands (a key step in designing drugs). Although new hardware makes these simulations increasingly faster (e.g., GPU, Anton from DE Shaw Research), new algorithms are key to making these methods more tractable and increase their impact. At this point, because of limitations in modeling, one of the main techniques for advancing science remains to a large extent numerous and costly experiments. For exam- ple, when designing drug, where multiple variants must be screened, the ability to run tests on a computer rather than experimentally testing with high throughput methods thousands of compounds would represent a signi cant advance with broad benefits for the public at large.

36 MATERIALS SCIENCE↗

NASA NTRS2005

Particle Image Velocimetry Measurements of a Two/Three-dimensional Separating/Reattaching Boundary Layer Downstream of an Axisymmetric Backward-facing Step

Planar Particle Image Velocimetry measurements were obtained in the separating/reattaching flow region downstream of an axisymmetric backward-facing step. Data were acquired for a two-dimensional (2D) separating boundary layer at five different Reynolds numbers based on step height (Re(sub h)), spanning 5900-33000, and for a three-dimensional (3D) separating boundary layer at Re(sub h) = 5980 and 8081. Reynolds number effects were investigated in the 2D cases using mean-velocity field, streamwise and wall-normal turbulent velocity, and Reynolds stress statistics. Results show that both the reattachment length (x(sub r)) and the secondary separation point are Reynolds number dependent. The reattachment length increased with rising Re(sub h) while the secondary recirculation region decreased in size. These and other Re(sub h) effects were interpreted in terms of changes in the separating boundary layer thickness and wall-shear stress. On the other hand, in the 3D case, it was found that the imposed cross-flow component was relatively weak in comparison to the streamwise component. As a result, the primary influences of three dimensionality only affected the near-separation region rather than the entire separation bubble.

Hudy, Laura M.↗

DOE OSTI2020

Deposit geometry and oxygen concentration spatial variations due to composition change in printed functionally graded components

Functionally graded materials (FGMs) with site specific chemical composition are commonly manufactured by directed energy deposition (DED). Although previous work fabricated an FGM with a compositional variation between a ferritic and austenitic alloy, difficulties arose due to variations in deposit shape with composition change. This problem also occurs for FGMs in literature; however, unlike other cases, the thermophysical properties of these two alloys were similar throughout the build. Here, we investigate the role of chemical composition and surface-active elements on deposit geometry during the manufacture of FGMs by laser DED. Single-track experiments for the relevant FGM compositions are analyzed with results from a well-tested, three-dimensional, transient numerical heat transfer and fluid flow model and thermodynamic calculations. Experiments showed deposit shape varied as a function of composition for constant laser power and scan speed. Thermodynamic analysis indicated that the oxygen solubility in the fusion zone varied significantly for each composition used for the FGM. Numerical modeling revealed that the change in fluid flow caused by Marangoni convection due to dissolved oxygen in the fusion zone were mainly responsible for the changes in deposit shape observed in experiments. Finally, because oxygen can be introduced into the fusion zone through the feedstock as well as the surrounding atmosphere, these findings elucidate a previously unconsidered aspect of process control during DED fabrication of FGMs.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Quickest Detection for Changes in Maximal kNN Coherence of Random Matrices

This paper addresses the problem of quickest detection of a change in the maximal coherence between columns of a n p random matrix based on a sequence of matrix observations having a single unknown change point. The random matrix is assumed to have identically distributed rows and the maximal coherence is defined as the largest of the ( 2 p) correlation coefficients associated with any row. Likewise the κ nearest neighbor (kNN) coherence is defined as the κ-th largest of these correlation coefficients. The forms of the preand postchange distributions of the observed matrices are assumed to belong to the family of elliptically contoured densities with sparse dispersion matrices but are otherwise unknown. A nonparametric stopping rule is proposed that is based on the maximal kNN sample coherence between columns of each observed random matrix. This is a summary statistic that is related to a test of existence of a hub vertex in a sample correlation graph having degree at least κ. Performance bounds on the delay and false alarm performance of the proposed stopping rule are obtained in the purely high-dimensional regime where p → ∞ and n is fixed. When the prechange dispersion matrix is diagonal it is shown that, among all functions of the proposed summary statistic, the proposed stopping rule is asymptotically optimal under a minimax quickest change detection model as the stopping threshold approaches infinity. Furthermore, the theory developed also applies to sequential hypothesis testing and fixed sample size tests.

96 KNOWLEDGE MANAGEMENT AND PRESERVATION↗

NASA NTRS2007

Bifurcation and Hysteresis of the Magnetospheric Structure with a varying Southward IMF: Field Topology and Global Three-dimensional Full Particle Simulations

Using a three-dimensional full electromagnetic particle model (EMPM), we have performed global simulations of the interaction between the solar wind and the terrestrial magnetosphere, and have investigated its asymptotic stability. The distance between the dayside magnetopause subsolar point and the Earth center, R(sub mp) is measured, as the intensity of southward IMF |B(sub z)| is slowly varying. Based on the field topology theory, one analyzes the variation of R(sub mp) as a reference index of the dynamics of this interaction, when IMF |B(sub z)| successively increases and decreases to its original value. Two striking results are observed. First, as the IMF |B(sub z)| increases above a critical value, the variation of R(sub mp) suddenly changes (so called 'bifurcation' process in field topology). Above this critical value, the overall magnetic field topology changes drastically and is identified as being the signature of magnetic reconnection at the subsolar point on the magnetopause. Second, this subsolar point recovers its original location R(sub mp) by following different paths as the IMF |B(sub z)| value increases (from zero to a maximum fixed value) and decreases (from this maximum to zero) passing through some critical values. These different paths are the signature of 'hysteresis' effect, and are characteristic of the so-called 'subcritical-type' bifurcation. This hysteresis signature indicates that dissipation processes take place via an energy transfer from the solar wind to the magnetosphere by some irreversible way, which leads to a drastic change in the magnetospheric field topology. This hysteresis is interpreted herein as a consequence of the magnetic reconnection taking place at the dayside magnetopause. The field topology reveals to be a very powerful tool to analyze the signatures of three-dimensional magnetic reconnection without the obligation for determining the mechanisms responsible for, and the consequences of the reconnection on the overall magnetospheric dynamics.

Cai, DongSheng↗

DOE OSTI2023

Rashba spin-orbit coupling enhanced magnetoresistance in junctions with one ferromagnet

We explain how Rashba spin-orbit coupling (SOC) in a two-dimensional electron gas (2DEG), or in a conventional s-wave superconductor, can lead to a large magnetoresistance even with one ferromagnet. However, such enhanced magnetoresistance is not generic and can be nonmonotonic and change its sign with Rashba SOC. For an in-plane rotation of magnetization, it is typically negligibly small for a 2DEG and depends on the perfect transmission which emerges from a spin-parity-time symmetry of the scattering states, while this symmetry is generally absent from the Hamiltonian of the system. The key difference from considering the normal-state magnetoresistance is the presence of the spin-dependent Andreev reflection at superconducting interfaces. In the fabricated junctions of quasi-2D van der Waals ferromagnets with conventional s-wave superconductors (Fe 0.29 ⁢TaS 2 /NbN) we find another example of enhanced magnetoresistance where the presence of Rashba SOC reduces the effective interfacial strength and is responsible for an equal-spin Andreev reflection. The observed nonmonotonic trend in the out-of-plane magnetoresistance with the interfacial barrier is an evidence for the proximity-induced equal-spin-triplet superconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2018

Dimensional reduction and ionic gating induced enhancement of superconductivity in atomically thin crystals of 2H-TaSe 2

The effects of dimensional reduction and ion intercalation on superconductivity (SC) in the presence of charge density waves (CDWs) in two-dimensional crystals of 2H-TaSe 2 were characterized. We prepared atomically thin crystals by mechanical exfoliation and performed electrical transport measurements on devices made by photolithography. The superconducting transition temperature ($T$ $^{SC}_{c}$) was found to increase monotonically as the thickness decreased, changing from 0.14 K in the bulk to higher than 1.4 K for a 3-nm-thick crystal. Here, the temperature dependence of upper critical field was found to be anomalous. The CDW transition temperature ($T$ $^{CDW}_{c}$) was found to decrease, but to a less extent than $T$ $^{SC}_{c}$, from 120 K in the bulk to around 113 K for the 3-nm-thick crystal. In addition, ion intercalation was found to increase $T$ $^{SC}_{c}$ and suppress $T$ $^{CDW}_{c}$ in an atomically thin crystal of 2H-TaSe 2 . The implications of these findings are discussed. We suggest that dimensional reduction and ion intercalation are potentially effective ways to engineer material properties for layered transition metal chalcogenides.

2D material↗

DOE OSTI2021

A Pore‐Scale Investigation of Mineral Precipitation Driven Diffusivity Change at the Column‐Scale

Abstract Mineral precipitation affects the pore structure and thus transport properties of porous media. In this study, we investigated the pore‐scale dynamics of precipitation in diffusion controlled systems and the resulting impacts on the effective diffusivity, using a micro‐continuum reactive transport model. Forty two‐dimensional pore structures representing both idealized and realistic geometries were simulated with consideration of different precipitation scenarios and rates. A homogeneous nucleation scenario reproduced patterns observed in previous experimental study showing mixing‐induced precipitation, and a surface growth scenario captured the pattern for mineral precipitation on a substrate with the same or similar mineral structures. In all cases, local precipitation resulted in the reduction in the average porosity of the domain ( Φ ) until the cessation of diffusive transport and the termination of precipitation. The minimum porosity reached was referred to as the critical porosity ( Φ c ). The effective diffusivity ( D eff ) decreased with Φ and dropped sharply to effectively zero, that is, the critical effective diffusivity ( D eff c ), as Φ c was reached. These pore‐scale dynamics can be captured by a revised relationship that explicitly considers the critical porosity and the corresponding effective diffusivity, and the pre‐exponential coefficient and the exponent of the relationship varied with initial pore structure and the precipitation kinetics. Overall, the homogeneous nucleation scenario results in systematically larger Φ c and coefficients that give rise to a sharper decrease in diffusivity as Φ c is approached, compared to the surface growth scenario. The revised relationship was also implemented at continuum scale and used to examine column scale diffusivity change and reactions.

58 GEOSCIENCES↗

DOE OSTI2022

Twisted bilayers of thin film magnetic topological insulators

Twisted bilayer graphene (TBG) near "magic angles" has emerged as a rich platform for strongly correlated states of two-dimensional (2D) Dirac semimetals. Here we show that twisted bilayers of thin film magnetic topological insulators (MTIs) with large in-plane magnetization can realize flat bands near 2D Dirac nodes. Using a simple model for thin films of MTIs, we derive a continuum model for two such MTIs, twisted by a small angle with respect to each other. When the magnetization is in plane, we show that interlayer tunneling terms act as effective SU (2) vector potentials, which are known to lead to flat bands in TBG. We show that by changing the in-plane magnetization, it is possible to tune the twisted bilayer MTI band dispersion to quadratic band touching or to flat bands, similar to the TBG. If realized, this system can be a highly tunable platform for strongly correlated phases of two-dimensional Dirac semimetals.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2022

Gate-Tunable Transport in Quasi-One-Dimensional α-Bi 4 I 4 Field Effect Transistors

Bi 4 I 4 belongs to a novel family of quasi-one-dimensional (1D) topological insulators (TIs). While its β phase was demonstrated to be a prototypical weak TI, the α phase, long thought to be a trivial insulator, was recently predicted to be a rare higher order TI. Here, we report the first gate tunable transport together with evidence for unconventional band topology in exfoliated α-Bi 4 I 4 field effect transistors. We observe a Dirac-like longitudinal resistance peak and a sign change in the Hall resistance; their temperature dependences suggest competing transport mechanisms: a hole-doped insulating bulk and one or more gate-tunable ambipolar boundary channels. Our combined transport, photoemission, and theoretical results indicate that the gate-tunable channels likely arise from novel gapped side surface states, two-dimensional (2D) TI in the bottommost layer, and/or helical hinge states of the upper layers. Markedly, a gate-tunable supercurrent is observed in an α-Bi 4 I 4 Josephson junction, underscoring the potential of these boundary channels to mediate topological superconductivity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2018

Uncertainty Quantification and Global Sensitivity Analysis of Subsurface Flow Parameters to Gravimetric Variations During Pumping Tests in Unconfined Aquifers

We study the contribution of typically uncertain subsurface flow parameters to gravity changes that can be recorded during pumping tests in unconfined aquifers. We do so in the framework of a Global Sensitivity Analysis and quantify the effects of uncertainty of such parameters on the first four statistical moments of the probability distribution of gravimetric variations induced by the operation of the well. System parameters are grouped into two main categories, respectively, governing groundwater flow in the unsaturated and saturated portions of the domain. We ground our work on the three-dimensional analytical model proposed by Mishra and Neuman (2011), which fully takes into account the richness of the physical process taking place across the unsaturated and saturated zones and storage effects in a finite radius pumping well. The relative influence of model parameter uncertainties on drawdown, moisture content, and gravity changes are quantified through (a) the Sobol' indices, derived from a classical decomposition of variance and (b) recently developed indices quantifying the relative contribution of each uncertain model parameter to the (ensemble) mean, skewness, and kurtosis of the model output. Our results document (i) the importance of the effects of the parameters governing the unsaturated flow dynamics on the mean and variance of local drawdown and gravity changes; (ii) the marked sensitivity (as expressed in terms of the statistical moments analyzed) of gravity changes to the employed water retention curve model parameter, specific yield, and storage, and (iii) the influential role of hydraulic conductivity of the unsaturated and saturated zones to the skewness and kurtosis of gravimetric variation distributions. The observed temporal dynamics of the strength of the relative contribution of system parameters to gravimetric variations suggest that gravity data have a clear potential to provide useful information for estimating the key hydraulic parameters of the system.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Effect of topology changes on the breakup of a periodic liquid jet

Here, the breakup of a periodic jet is examined computationally, using a front-tracking/finite-volume method, where the interface is represented by connected marker points moving with the fluid, while the governing equations are solved on a fixed grid. Tracking the interface allows control of whether topology changes take place or not. The Reynolds and Capillary numbers are kept relatively low ($Re = 150$ and $Ca = 2$) so most of the flow is well resolved. The effect of topology changes is examined by following the jet until it has mostly disintegrated, for different “coalescence criterion,” based on the thickness of thin films and threads. The evolution of both two-dimensional and fully three-dimensional flows is examined. It is found that although there is a significant difference between the evolution when no breakup takes place and when it does, once breakup takes place the evolution is relatively insensitive to exactly how it is triggered for a range of coalescence criterion, and any differences are mostly confined to the smallest scales.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2018

Geodetic measurements and numerical models of transient deformation at Raft River geothermal field, Idaho, USA

Here, we perform synthetic aperture radar interferometry using data acquired between 2004 and 2016 by the Envisat, and ALOS-2 satellite missions to measure transient deformation at the Raft River geothermal field in Cassia County in Southern Idaho where geothermal production began in late 2007. Time-series analysis of multiple interferometric pairs indicates uplift at an exponentially decaying rate, over an ~8 km-by-5 km area centered near three injection wells that recycle produced brine. Similarly, subsidence at an exponentially decaying rate is observed in a 4 km-by-4 km area west of the production wells. These two signatures stay in the same location in all of the well-correlated Envisat interferometric pairs spanning the time interval between 2007 and 2010. The boundary separating the uplifting and subsiding areas is associated with the steeply dipping Bridge fault zone. Using two-dimensional numerical models, we explore first-order, bi-directional coupling between hydrological and mechanical processes. Our results suggest that: (i) most of the deformation occurs due to pore pressure changes following the start of geothermal production, (ii) the rate of deformation decays to zero over a time scale on the order of ~5 years as the system reaches steady state, and (iii) a reservoir-scale permeability of the order of ~1E–14 m 2 is required to explain the transient deformation.

15 GEOTHERMAL ENERGY↗

DOE OSTI2019

Numerical study of groundwater flow cycling controlled by seawater/freshwater interaction in Woodville Karst Plain

Seawater intrusion due to sea level rise and climate change could significantly contaminate coastal groundwater resources, particularly in Florida, the flat low-land state in the United States. Based on the field investigation and hydrological measurements, a three-dimensional SEAWAT model is developed to evaluate the groundwater flow cycling and seawater intrusion to freshwater system in the Woodville Karst Plain (WKP), a typical karst groundwater system in the Floridan aquifer. The karst conduit network in the aquifer acts as fast flow pathway for groundwater flow and solute transport, so seawater could deeply intrude into the aquifer. Wakulla Spring, an inland spring 17 km from the coast and a coastal submarine spring, Spring Creek Spring Complex are connected through the conduit network. The flow direction between the two springs switches under various rainfall conditions in this region, thus the discharges at two karst springs are used to estimate the location of seawater/freshwater mixing interface. The SEAWAT modeling results indicate that the mixing interface, defined as 2 PSU (Practical Salinity Unit), intrudes 3 to 5 km through the subsurface karst conduit during the dry season and severely contaminates nearly 1 km width of groundwater around the conduit. The salinity distribution and the distance of seawater intrusion through the conduit system are very sensitive to precipitation variation and the sea level boundary condition. Furthermore, predictions are made for seawater intrusion to the aquifer under various sea level rise, precipitation scenarios and water pumping. The results show that the seawater intrusion could reach and contaminate inland freshwater systems if sea level rises 1.0 m or during a long-term no-precipitation season. Finally, this study provides insights for modeling and predicting the vulnerability of a coastal karst aquifer through the simulation of variable-density flow.

58 GEOSCIENCES↗

DOE OSTI2023

Quantification of the Impact of Acidified Brine on Fracture-Matrix Transport in a Naturally Fractured Shale Using in Situ Imaging and Modeling

Understanding flow, transport, chemical reactions, and hydromechanical processes in fractured geologic materials is key for optimizing a range of subsurface processes including carbon dioxide and hydrogen storage, unconventional energy resource extraction, and geothermal energy recovery. Flow and transport processes in naturally fractured shale rocks have been challenging to characterize due to experimental complexity and the multiscale nature of quantifying continuum scale descriptions of mass exchange between micrometer-scale fractures and nanometer-scale pores. In this study, we use positron emission tomography (PET) to image the transport of a conservative tracer in a naturally fractured Wolfcamp shale core before and after the core was exposed to low pH brine conditions. Image-based experimental observations are interpreted by fitting an analytical transport model to fracture-containing voxels in the core. Results of this analysis indicate subtle increases in matrix diffusivity and a slightly more uniform fracture velocity distribution following exposure to low pH conditions. These observations are compared with a multicomponent one-dimensional reactive transport model that indicates the capacity for a 10% increase in porosity at the fracture-matrix interface as a result of the low pH brine exposure. This porosity change is the result of the dissolution of carbonate minerals in the shale matrix to low pH conditions. Further, this image-based workflow represents a new approach for quantifying spatially resolved fracture-matrix transport processes and provides a foundation for future work to better understand the role of coupled transport, reaction, and mechanical processes in naturally fractured rocks.

58 GEOSCIENCES↗

DOE OSTI2024

Unraveling sources of emission heterogeneity in Silicon Vacancy color centers with cryo-cathodoluminescence microscopy

Diamond color centers have proven to be versatile quantum emitters and exquisite sensors of stress, temperature, electric and magnetic fields, and biochemical processes. Among color centers, the silicon-vacancy (SiV - ) defect exhibits high brightness, minimal phonon coupling, narrow optical linewidths, and high degrees of photon indistinguishability. Yet the creation of reliable and scalable SiV - -based color centers has been hampered by heterogeneous emission, theorized to originate from surface imperfections, crystal lattice strain, defect symmetry, or other lattice impurities. Here, we advance high-resolution cryo-electron microscopy combined with cathodolumines cence spectroscopy and 4D scanning transmission electron microscopy (STEM) to elucidate the structural sources of heterogeneity in SiV - emission from nanodiamond with sub-nanometer-scale resolution. Our diamond nanoparticles are grown directly on TEM membranes from molecular-level seedings, representing the natural formation conditions of color centers in diamond. We show that individual subcrystallites within a single nanodiamond exhibit distinct zero-phonon line (ZPL) energies and differences in brightness that can vary by 0.1 meV in energy and over 70% in brightness. These changes are correlated with the atomic-scale lattice structure. We find that ZPL blue shifts result from tensile strain, while ZPL red shifts are due to compressive strain. We also find that distinct crystallites host distinct densities of SiV - emitters and that grain boundaries impact SiV - emission significantly. Finally, we interrogate nanodiamonds as small as 40 nm in diameter and show that these diamonds exhibit no spatial change to their ZPL energy. Our work provides a foundation for atomic-scale structure-emission correlation, e.g., of single atomic defects in a range of quantum and two-dimensional materials.

36 MATERIALS SCIENCE↗