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DOE OSTI2025

Unveiling the nature of Ga-based chalcogenides for electrical switching selectors

Three-dimensional phase-change memory with stackable crossbar architecture is a promising technology to meet the urgent demands for high-density storage and rapid information processing in the era of explosive data growth. The performance depends strongly on the properties of ovonic threshold switching (OTS) selectors, which control the on/off states of memory units. Amorphous GaS serves as an outstanding OTS material, distinguished by its sizable mobility gap and high crystallization temperature, while the underlying mechanism continues to be inadequately comprehended. Here, in this work, we systematically studied the structural and electronic properties of amorphous Ga-X (X = S/Se/Te) using first-principles calculations. The results show that Ga atoms adopt tetrahedral motifs, while S/Se/Te atoms predominantly exhibit the structure of a distorted triangular pyramid. This structural arrangement is ascribed to the substantial dative bonds formed by the lone-pair electrons of the anions and the vacant sp3 orbitals around Ga atoms. Large mobility gaps (e.g., GaS: 2.43 eV, GaSe: 1.76 eV, GaTe: 1.26 eV) and distinct mid-gap states (e.g., ∼0.66 eV above valence band tail) ensure that these three chalcogenide glasses can be switched on under an external electric field while effectively suppressing leakage current without a bias, and the defect electronic states originate from short, robust Ga-Ga bonds due to the formation of distorted chain-like local structures. Our research elucidates the mechanisms of amorphous Ga-X as OTS materials, enriching the spectrum of electrical switching selectors by incorporating III-VI chalcogenides. This inclusion offers novel opportunities for the refinement and optimization of high-density integrated memory systems.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Aromatic Amide Foldamers Show Conformation‐Dependent Electronic Properties

Electron transport in organic molecules and biomolecules is governed by electronic structure and molecular conformations. Despite recent progress, key challenges remain in understanding the role of intramolecular interactions and three-dimensional (3D) conformations on the electron transport behavior of organic molecules. In this work, the electronic properties of aromatic amide foldamers are characterized that organize into distinct 3D structures, including an extended secondary amide that adopts a trans-conformation and a folded N-methylated tertiary amide that adopts a cis-conformation. Results from single-molecule electronic experiments show that the extended secondary amide exhibits a fourfold enhancement in molecular conductance compared to the folded N-methylated tertiary amide, despite a longer contour length. The results show that extended amide molecules are governed by a through-bond electron transport mechanism, whereas folded amide molecules are dominated by through-space transport. Bulk spectroscopic characterization and density functional theory calculations further reveal that extended amides have a smaller HOMO–LUMO gap and larger transmission values compared to folded amides, consistent with single-molecule electronic experiments. Overall, this work shows that 3D molecular conformations significantly influence the electronic properties of single-molecule junctions.

electron transport↗

DOE OSTI2026

4-Electron Oxygen Reduction Reaction (ORR) with Iron Phthalocyanine (FePc) Functionalized Nanowire Templated-3D Fuzzy Graphene (NT-3DFG)

Iron phthalocyanine (FePc) is a promising alternative to platinum-based catalysts for sustainable energy devices; however, the plane-symmetry of Fe-N 4 sites, random aggregation, and poor conductivity of FePc present major barriers for their application as oxygen reduction reaction (ORR) electrocatalysts. Here, we report the synergistic effects of FePc electrocatalysts supported by a nanowire-templated three-dimensional fuzzy graphene (FePc@NT-3DFG) substrate. The in situ functionalized oxygen groups (iFOGs) at the edge of NT-3DFG localize Fe active sites in FePc under alkaline ORR conditions. With a uniform FePc distribution through many single layers of graphene, the NT-3DFG substrates improve O 2 adsorption and catalytic activity while stabilizing the electrochemical activity during reactions. The FePc@NT-3DFG catalyst exhibits fast ORR kinetics with an extremely low Tafel slope of 28.3 ± 2.7 mV dec −1 , a higher half-wave potential of 0.911 ± 0.004 V (vs RHE), and notable long-term stability at 0.5 V (vs RHE) of 96.0 ± 0.4% retention after 30 h. Surface chemistry spectra validate electronic configuration modification of Fe at the iFOGs. Density functional theory calculations indicate that the extra layers of graphene improve oxygen adsorption. Moreover, additional exploration of other transition metal phthalocyanines supports the effects of iFOGs through the transition toward 4e − ORR. This work offers an expanded strategy for active site modification through edge-based graphene substrates for 4e − ORR.

X-ray absorption spectroscopy↗

DOE OSTI2026

Measurement of the longitudinal flow-plane decorrelation using multiplane cumulants in $\sqrt{s_{NN}}$ = 200 GeV Au+Au, Ru+Ru, and Zr+Zr collisions

Measurements of the variation of anisotropic flow-plane angles (𝛹 𝑛 ) with rapidity, commonly known as the flow-plane decorrelation, provide important insights into the initial conditions of the matter produced in heavy-ion collisions. Here, in this paper, using data collected by the STAR experiment, we report the first measurement of the four-plane correlator observable 𝑇 𝑛 ⁡{𝑏⁢𝑎;𝑑⁢𝑐}=⟨⟨sin⁡[𝑛⁢(𝛹$^𝑏_𝑛$ − 𝛹$^𝑎_𝑛$)]⁢sin⁡[𝑛⁢(𝛹$^𝑑_𝑛$ − 𝛹$^𝑐_𝑛$)]⟩⟩, where superscripts 𝑎, 𝑏, 𝑐, and 𝑑 denote sequential pseudorapidity (𝜂) regions with 𝑎 corresponding to the most backward region, 𝑏 and 𝑐 close to mid-rapidity with 𝜂 𝑏 < 0 and 𝜂 𝑐 > 0, and 𝑑 being the most forward. The measurement is performed for the elliptic and triangular flow (i.e.~𝑛 = 2 and 3) in Au+Au and isobar (Ru+Ru, Zr+Zr) collisions at $\sqrt{s_{NN}}$=200~GeV. The goal of calculating the correlation of the flow-plane angle variations from backward to mid-central, and from mid-central to forward regions, is to probe the systematic variation of flow angle over a wide 𝜂 range. In mid-central collisions (10−30% centrality), we find 𝑇 2 ⁡{𝑏⁢𝑎;𝑑⁢𝑐} =−0.004 ±0.001⁢(s⁢t⁢a⁢t) ±0.002⁢(s⁢y⁢s⁢t) independent of the collision system. Such a small value of 𝑇 2 favors a random-walk'' variation of the flow-plane angles, where the rapidity correlation length is smaller than the entire region under study. These measurements provide new information on the decorrelation patterns in the system and offer a quantitative estimate of possible systematic variations in anisotropic flow angles such astwist’’ between forward and backward regions. This opens new opportunities for understanding the three-dimensional structure and the time evolution of the quark-gluon plasma created in heavy-ion collisions.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2025

Breaking the Linear Scaling Relations for the Oxygen Reduction Reaction with a Dual‐Atom Catalyst Composed of a MnFe‐Porphyrrole Aerogel

Bimetallic catalysts offer enhanced catalytic performance through synergistic interactions between the two metals, allowing them to break the linear scaling relations and reach high electrocatalytic activity. This study presents bimetallic aerogel-based catalyst synthesized as a covalent, three-dimensional framework containing neighboring iron and manganese sites. The aerogel structure provides a high surface area and porosity, facilitating an ultra-high active site density and efficient mass transport. The MnFe porphyrrole's unique structure is obtained by alternately linking Mn-porphyrin and Fe-corrole complexes. It exhibited outstanding performance with an onset potential of 0.99 V RHE . Comparative studies with a free-base Fe porphyrrole catalyst (E onset 0.97 V RHE ) revealed that while Mn incorporation led to only a slight improvement in half-cell performance, it resulted in significantly enhanced performance in anion exchange membrane fuel cell. The MnFe catalyst achieved an OCV of 0.97 V and a peak power density of 0.27 W cm −2 , outperforming the free-base Fe counterpart. Using density functional theory calculations, we show that the higher ORR activity of MnFe-porphyrrole is due to charge transfer between Mn and Fe atoms, which is absent in the reference free-base Fe-porphyrrole. These findings underscore the advantages of bimetallic catalysts in improving ORR activity and fuel cell efficiency by leveraging synergistic effects.

Aerogel↗

DOE OSTI2025

MURR LEU structural and thermal hydraulics analyses: Part I – Preliminary irradiation thermo-mechanical behavior

The University of Missouri Research Reactor (MURR) is expected to be converted from highly enriched uranium (HEU, ≥ 20 wt% U-235) U-Al x dispersion fuel to low-enriched uranium (LEU, < 20 wt% U-235) with U-10Mo monolithic fuel. This work introduces high-fidelity irradiation thermo–mechanical (T-M) analysis of the MURR LEU focusing on changes in coolant channel gap thickness. Three-dimensional (3D) finite element (FE) models were developed to simulate the irradiation T-M behavior of the MURR LEU element with all 23 curved fuel plates, the two side plates, and the combs. It was shown that channel gap thickness changes were influenced not only by plate thickness variations due to fuel swelling and creep but also by the radial displacement of consecutive MURR LEU plates. Modeling the fuel element assembly captured side plate displacements, which were shown to reduce radial fuel plate displacements towards the convex side. The maximum local radial displacement in the element was predicted at the end of life (EOL) as 23.7 mil (602.0 µm) on the lateral centerline of plate 23 towards the convex side. The maximum stripe-averaged reduction in channel gap thickness, particularly relevant for thermal hydraulics (TH) safety analysis, was calculated as 15.9 mil (403.9 µm) in single-side heated channel 24 (the outermost channel). These results account for the thermal resistance from the oxide build-up on cladding surfaces which was shown to be up to 0.82 mil (20.8 µm) thick. It was demonstrated that accounting for oxide layer thermal resistance led to a 10 °C higher peak fuel temperature and a 4.4 mil (111.8 µm) greater maximum local radial displacement. The impact of the calculated channel gap thickness changes on the MURR LEU TH safety analysis is evaluated in Part II.

Irradiation thermo-mechanical analysis↗

DOE OSTI2026

Mesoscale atomic engineering in a crystal lattice

Controlling individual atoms using lasers, ion traps and scanning probe tips has transformed our understanding of matter and enabled breakthroughs in quantum science. Extending this control into three-dimensional (3D) solids and across mesoscopic scales, however, remains a foundational challenge. Electron irradiation in electron microscopes is known to induce atomic displacements, and atomic manipulation has been proposed and demonstrated. Yet repeated and deterministic control has remained elusive. Here, in this study, we demonstrate deterministic atomic engineering in a 3D crystal, creating ordered arrangements of more than 40,000 user-defined defects within minutes across a 150 nm × 100 nm × 13 nm volume. By steering individual Cr atoms in the magnetic semiconductor CrSBr into selected interstitial sites using an electron beam directed with sub-20-pm-scale accuracy, we create vacancy–interstitial complexes. The resulting impurity array forms a mesoscale crystal embedded within the host lattice, a new form of engineered artificial matter that remains stable at room temperature and outside the microscope. By tracking Cr atom displacements, we identify conditions under which the defect structures are predictable. Our calculations suggest that these defects form correlated impurity states with intra-defect optical transitions and inter-defect kinetic and Coulomb interactions. This establishes a generalizable platform for atomic defect engineering at mesoscopic, and potentially macroscopic, scales, opening opportunities for scalable quantum technologies, including deterministic colour-centre placement, quantum simulation of many-body lattice models and atomic-scale manufacturing.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2025

Initial steady-state core simulation capability or thermal and pool-type molten salt reactors, coupling reactor physics, thermal-hydraulics, and evolving chemistry

This report presents the development and validation of an initial steady-state multiphysics capability for molten salt reactors (MSRs) under the Nuclear Energy Advanced Modeling and Simulation (NEAMS) program in Fiscal Year 2025. The framework integrates neutronics, thermal-hydraulics, species transport, and thermochemistry to capture the coupled dynamics of liquid-fueled systems. Implementation and testing were performed on two representative designs: the Molten Salt Reactor Experiment (MSRE), a thermal-spectrum, channeled-flow reactor, and the Lotus Molten Salt Reactor (L-MSR), a fast-spectrum, pool-type reactor. The modeling suite employs Griffin for reactor physics and depletion, Pronghorn and SAM for thermal-hydraulics, Thermochimica for chemistry, and Saline for thermophysical properties, with benchmarking and validation carried out against historical MSRE data, experimental flow-loop measurements, and reference depletion calculations from Monte Carlo codes. The framework demonstrated the ability to reproduce key reactor behaviors including temperature feedback, reactivity losses, delayed neutron precursor transport, xenon poisoning, and redox potential evolution. The results confirm the feasibility and accuracy of the coupled models in predicting steady-state and selected transient MSR behaviors. This latter ones are used in this report as a proxy indicating that the steady-state models from which the transient starts are accurate. For MSRE, validation showed good agreement with pump start-up and natural circulation tests, while for the L-MSR, benchmarking confirmed hydraulic calibration and consistency of neutronics–thermal coupling. The tools also provided new insights into species transport, noble metal deposition, and salt solidification dynamics. On the Xenon transport front, the code is validated against the steady state Xenon poisoining measurement and showed good agreement with the experimental value. Identified areas for future work include advanced void transport modeling, three-dimensional simulations, improved alloy corrosion models, and tighter integration with high-fidelity Monte Carlo codes. These developments provide a foundation for high-fidelity MSR simulations that can support reactor design optimization, safety assessments, and long-term operational strategies.

42 - ENGINEERING↗

DOE OSTI2025

Three-Dimensional Heat Flux and Thermal Analysis of Angled Tungsten Samples on DIII-D

ITER-grade tungsten and dispersoid-strengthened tungsten samples with the top surface angled at ~15° towards the incident plasma flux were exposed to 9 H-mode discharges with edge-localized modes (ELMs) in the lower divertor of DIII-D tokamak using the Divertor Material Evaluation System (DiMES). Surface damage included cracking and flaking of material on the two samples farthest away from the plasma strike point, and significant melting of the two samples closest to the strike point. Heat flux and thermal analysis tools new to DIII-D have been applied to better understand this material response and to help optimize the exposure conditions for future experiments. SMITER field-line tracing simulations based on IRTV data and EFIT equilibria estimate an average inter-ELM perpendicular heat flux, 𝑞⊥,𝑖nter−𝐸LM , on the angled surfaces of 10.1 – 19.6 MW/m² for a majority of the 9 discharges, increasing to 15.6 – 24.5 MW/m² for the single, higher-power shot where samples melted. Fast camera data showed shallow intra-ELM melting and re-solidification, which transitioned to bulk inter-ELM melting with melt motion in the 𝐽⃗ 𝑥 𝐵⃗ direction. About 50% of the protruding volume of the most affected sample was displaced via melt-motion. SIERRA thermal modeling software was able to reproduce an onset time of melting consistent with fast camera data and final sample conditions, within < 200 ms. Maximum surface temperatures of 3122 K and 2787 K are estimated for the samples farthest away from the strike point, while the closest samples achieve melting at 4067 ms and 4750 ms into the ~5000 ms plasma exposure. A +10% increase in both the SMITER 𝑞⊥,𝑖nter−𝐸LM calculations and the estimated ELM heat loads 𝑞⊥, 𝐸LM was required to achieve this result, which is within the uncertainty of the diagnostic data but likely accounts for non-ideal geometry effects plus other physics uncertainties not included in this first iteration of modeling. This work provided valuable estimates of the 3D temperature evolution to help better understand the observed surface morphology and internal recrystallization of samples, which are discussed in detail in a complementary manuscript [1]. Benchmarking efforts with more diagnosed DIII-D experiments are underway to further refine the SMITER and SIERRA models for DiMES. Future use of these tools will enable researchers to precisely target heat flux exposure conditions in DIII-D to test, but not exceed, the thermomechanical limitations of novel plasma-facing materials.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2025

Integrated Molten Salt Reactor Modeling Capabilities in NEAMS Thermal Hydraulics Tools

The DOE neams program supports a full range of computational thermal fluids analysis capabilities and code developments for a broad range of advanced reactor concepts. The research and development approach under the thermal fluids technical area synergistically combines three length and time scales in a hierarchical multi-scale approach. To enable multi-scale thermal fluids capability using these codes, a key joint effort has been underway to develop an integrated system- and engineering-scale thermal fluids analysis capability, through integration of SAM and Pronghorn codes, both based on the MOOSE framework. This report summarizes recent advances in developing an integrated system- and engineering-scale modeling capability for the msr concept, which has gained significant interest in recent years. A consistent framework was established by coupling Pronghorn and SAM through the Saline interface, with thermophysical properties provided by the Molten Salt Thermal Property Database (MSTDB-TP). Further improvements were made to the coupling schemes and domain-overlapping strategies, enhancing the stability and robustness of multi-code simulations. Verification and validation efforts demonstrate the accuracy of this integration across a range of benchmark problems, including one-dimensional heated pipe flows, three-dimensional natural convection loops with evolving isotopic compositions, and \gls{msre} demonstration cases. Within Pronghorn, new capabilities were introduced to model corrosion and noble-metal plating phenomena, supported by an extended thermal-hydraulics framework and refined turbulence treatments. To capture two-phase flow behavior, a multiphase Euler–Euler model was implemented in Pronghorn, including advanced closure relations, high-resolution advection techniques, and capillary force reconstruction. Preliminary verification cases confirm the fidelity of the approach, while planned validation efforts target canonical multiphase benchmarks and application to msr components such as the msre pump bowl. Finally, updates to SAM’s msr mass transfer modeling were extended to consider noble gas migration into porous structures like graphite. The point kinetics model was updated to include reactivity feedback contributions from any defined species, such as xenon. The gas transport model was expanded for applicability to gas mixtures, bubble efflux phenomena, and species transport between liquid and gas phases. A selection of multi-scale Sherwood number correlations from MOSCATO/NekRS and multi-phase correlations from literature have been added for improved accuracy in calculating mass transfer coefficients. A companion effort on developing system-level redox corrosion has also been incorporated into SAM. Collectively, these enhancements strengthen the predictive capability of SAM and Pronghorn for simulating MSR thermal-hydraulics, corrosion, multiphase behavior, and fission-product transport, providing a more complete toolset for design, safety analysis, and licensing support of next-generation \gls{msr}s.

42 - ENGINEERING↗

DOE OSTI2025

Lattice QCD Benchmark of Proton Helicity and Flavor-Dependent Unpolarized Transverse Momentum-Dependent Parton Distribution Functions at Physical Quark Masses

We present the first lattice QCD calculations of the isovector helicity transverse momentum-dependent parton distribution function (TMDPDF) and the flavor-dependent unpolarized TMDPDFs for up and down quarks in the proton. Our computations utilize domain-wall fermion discretization with physical quark masses. Employing Coulomb-gauge-fixed quark correlation functions within the large-momentum effective theory framework, we access nonperturbative transverse quark separations 𝑏 𝑇 up to approximately 1 fm, corresponding to transverse momenta as low as 200 MeV. Based on the quasi-TMD factorization theorem, we construct renormalization-group–invariant ratios that are equal to the corresponding light-cone TMDPDF ratios. At moderate 𝑥, our results reveal that the isovector helicity and unpolarized TMDPDFs exhibit nearly identical transverse structure up to a normalization factor, and the unpolarized distributions display only mild flavor dependence. These findings not only support key trends observed in recent global analyses but also provide robust, nonperturbative constraints that can distinguish between different parameterizations. This Letter establishes a first-principles benchmark for TMDPDFs, offering valuable input for ongoing and future experimental efforts to map the proton’s three-dimensional structure.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2025

Determining the Conformation of Supported Complexes Using an 17 O TEDOR-like NMR Experiment

Dynamic nuclear polarization surface-enhanced nuclear magnetic resonance (NMR) spectroscopy has enabled the determination of the three-dimensional configuration of surface sites, in particular supported metal complexes of relevance to single-site heterogeneous catalysis. These approaches have chiefly leveraged the application of NMR double-resonance experiments that either reveal the complex conformation via point-to-point intramolecular distances between spin-labeled atoms or the complex-surface orientation via distances between the spins and the surface plane. Either method typically requires expensive isotope labeling and each reports on different structural features. The application of an experiment that simultaneously reveals both types of distances with chemical resolution would be ideal. Here, in this article, we describe an 17 O{ 1 H} pseudo-3D correlation experiment that achieves this goal. Specifically, Si–O–Si and Si–O–M oxygens are well-resolved by 17 O NMR; therefore, distances can be simultaneously measured radially, between Si– 17 O–M and the 1 H’s of the ligands, and vertically to the Si– 17 O–Si linkages of the silica support. We demonstrate the experiment using supported yttrium and zirconium complexes. Good agreement is obtained when comparing the experimental results to theoretical predictions from density functional theory calculations, highlighting the reliability of this relatively simple experiment.

alkyls↗

DOE OSTI2025

Applying a Compact Porous Media Model to Numerically Derive Resistance Coefficients for Lattice Structures

Additive Manufacturing allows for exploring various geometries to achieve specific engineering criteria. Lattices are one geometry with unique properties, including being periodically repeating structures which allow flow through them to be represented as a porous media according to Darcy-Forchheimer equations. These equation’s coefficients are generally experimentally derived, but this work demonstrates the ability to numerically derive them with CFD. Simulations were performed using three-dimensional stead state Reynolds-averaged Navier-Stokes with a k-ω Shear Stress Transport turbulence model using Ansys Fluent. Three lattice geometries were investigated and drag coefficients were derived. The method was validated against externally published data for similar geometries demonstrating strong agreement, and grid convergence for all simulations was calculated with a Grid Convergence Index method. Wall roughness is demonstrated to have a non-negligible impact on results and roughness values are considered for the primary focus Octahedral geometry where both smooth wall and rough wall coefficients were derived. The porosity coefficients for the Octahedral geometry at 1.0 [m/s] were found to be 2.89×10 6 and 2.90×10 6 [1/(Pa*m*s)] for the permeability coefficients, 6.37×10 1 and 5.44×10 1 [m 2 /kg] for the inertial resistance coefficients, and with a max pressure drop of 5116.7 [Pa] and 4429.5 [Pa] for the smooth walls and rough walls, respectively. The derived numerical method enables rapid exploration and optimization of new lattice designs for diverse engineering applications.

42 ENGINEERING↗

DOE OSTI2024

Effect of insulator end cap thickness on time-dependent Hartmann flow in a rotating mirror

We present a framework for analysing plasma flow in a rotating mirror. By making a series of physical assumptions, we reduce the magnetohydrodynamic (MHD) equations in a three-dimensional cylindrical system to a one-dimensional system in a shallow, cuboidal channel within a transverse magnetic field, similar to the Hartmann flow in ducts. We then solve the system both numerically and analytically for a range of values of the Hartmann number and calculate the dependence of the plasma flow speed on the thickness of the insulating end cap. We observe that the mean flow overshoots and decelerates before achieving a steady-state value, a phenomenon that the analytical model cannot capture. This overshoot is directly proportional to the thickness of the insulating end cap and the external electric field, with a weak dependence on the external magnetic field. Our simplified model can act as a benchmark for future simulations of the supersonic mirror device CMFX (centrifugal magnetic fusion experiment), which will employ more sophisticated physics and realistic magnetic field geometries.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2025

Pb:Sn Ratio-Driven Polytypism and Band Modulation in Photoresponsive Hexagonal Perovskitoids

Three-dimensional (3D) perovskites of the formula AMX 3 are known for their excellent optoelectronic properties, but their design is limited by the narrow range of A-site cations that can template the 3D corner-sharing structure, and many of the viable options have already been explored. These materials also face structural instability under environmental conditions. In contrast, 3D hexagonal perovskitoids, with the same chemical formula, may offer enhanced stability and richer structural diversity through a range of corner- and face-sharing octahedral configuration options, providing greater opportunities for structural design; however, challenges such as synthesis complexity and wide band gaps have hindered optoelectronic performance achieved to date. Herein, we synthesized a structural homologous series of mixed-metal hexagonal perovskitoids with the formula APb 1-x Sn x I 3 (x = 0, 0.25, 0.50, 0.75, 1; A = ethylammonium, guanidinium) and identified three polytypes (9R, 12R, 6H) using single-crystal X-ray diffraction (SCXRD). These structures exhibited increasing corner-sharing connectivity with higher Sn content, revealing a previously unobserved relationship between metal composition and structural evolution in perovskitoid materials. The incorporation of Sn reduced the band gap (tunable from 2.51 eV to 1.87 eV) and drove structural transformations, a trend seen also in density functional theory (DFT) calculations, which suggest a thermodynamic preference for Pb at face-sharing sites and Sn at corner-sharing sites. DFT band structure calculations and optical spectroscopy also reveal an anomalous behavior in these materials, which we term polytypic band modulation. This phenomenon combines conventional band bowing with the structural transformations that occur as Sn content increases, as observed in the band gap and in photoluminescence spectra. Photodiodes fabricated from thin films of these materials exhibited stable and pronounced photoresponses across various light intensities over time. Furthermore, the combination of templating 3D perovskitoids with multiple cations and alloying Pb and Sn, suggests a vastly underexplored phase space that offers new parameters to tune perovskitoids.

Cations↗

DOE OSTI2025

Dimensional Evolution Guides Property Control in the A n Cu 4– n TiS 4 Semiconductor Series

Through progressive reduction of the three-dimensional (3D) covalent network of Cu 4 TiS 4 , we isolate seven new members of the A n Cu 4–n TiS 4 family (A = alkali metal; n = 0–4), spanning 3D, 2D, 1D, and 0D structural fragments. The dimensional reduction is rational, as it preserves the edge-sharing connectivity between [CuS 4 ] 7– and [TiS 4 ] 4– tetrahedra across the series. This structural evolution is driven by the stepwise substitution of Cu with alkali metals, guiding the formation of fragments with reduced dimensionality. The effects of “n” and “A” on the crystal structures, stabilities, electronic structures, and optoelectronic properties are profound, demonstrating that the manipulation of alkali metal size and A n Cu 4–n TiS 4 stoichiometry enables predictable variations in structure and properties. For example, the n = 0 and n = 4 end members of the A n Cu 4–n TiS 4 family set the range of achievable band gaps with 2.00 eV for Cu 4 TiS 4 , 2.60 eV for Na 4 TiS 4 , and intermediate values for the n = 1–3 members. Notably, CsCu 3 TiS 4 exhibits exceptional air stability and congruent melting, with density functional theory (DFT) calculating moderate hole and electron effective masses in specific crystallographic directions (mh = 1.24m 0 , me = 0.87m 0 ). Additionally, A 3 CuTiS 4 (A = Na, K, Rb) displays direct band gap behavior and long photoluminescence lifetimes of 2.3–8.6 μs, and K 3 CuTiS 4 has a PLQY of 5.19%. These findings underscore the potential of the A n Cu 4–n TiS 4 family for applications in optoelectronics and demonstrate widely applicable design concepts that unveil rational stoichiometries within a given composition space to generate a series of crystal structures related through an evolving covalent dimensionality that corresponds to a predictable electronic structure and property progression.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Single nuclear spin detection and control in a van der Waals material

Optically active spin defects in solids are leading candidates for quantum sensing and quantum networking. Recently, single spin defects were discovered in hexagonal boron nitride (hBN), a layered van der Waals (vdW) material. Owing to its two-dimensional structure, hBN allows spin defects to be positioned closer to target samples than in three-dimensional crystals, making it ideal for atomic-scale quantum sensing, including nuclear magnetic resonance (NMR) of single molecules. However, the chemical structures of these defects remain unknown and detecting a single nuclear spin with a hBN spin defect has been elusive. Here we report the creation of single spin defects in hBN using 13 C ion implantation and the identification of three distinct defect types based on hyperfine interactions. We observed both S = 1/2 and S = 1 spin states within a single hBN spin defect. We demonstrated atomic-scale NMR and coherent control of individual nuclear spins in a vdW material, with a π-gate fidelity up to 99.75% at room temperature. By comparing experimental results with density functional theory (DFT) calculations, we propose chemical structures for these spin defects. Our work advances the understanding of single spin defects in hBN and provides a pathway to enhance quantum sensing using hBN spin defects with nuclear spins as quantum memories.

Quantum metrology↗

DOE OSTI2025

Quantum Spin Ice in Three-Dimensional Rydberg Atom Arrays

Quantum spin liquids are exotic phases of matter whose low-energy physics is described as the deconfined phase of an emergent gauge theory. With recent theory proposals and an experiment showing preliminary signs of Z 2 topological order [G. Semeghini , ], Rydberg atom arrays have emerged as a promising platform to realize a quantum spin liquid. In this work, we propose a way to realize a U(1) quantum spin liquid in three spatial dimensions, described by the deconfined phase of U(1) gauge theory in a pyrochlore lattice Rydberg atom array. We study the ground state phase diagram of the proposed Rydberg system as a function of experimentally relevant parameters. Within our calculation, we find that by tuning the Rabi frequency, one can access both the confinement-deconfinement transition driven by a proliferation of “magnetic” monopoles and the Higgs transition driven by a proliferation of “electric” charges of the emergent gauge theory. We suggest experimental probes for distinguishing the deconfined phase from ordered phases. This work serves as a proposal to access a confinement-deconfinement transition in three spatial dimensions on a Rydberg-based quantum simulator. Published by the American Physical Society 2025

Shah, Jeet (ORCID:0000000158738129)↗