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NASA NTRS1985

Modulated voltage metastable ionization detector

The output current from a metastable ionization detector (MID) is applied to a modulation voltage circuit. An adjustment is made to balance out the background current, and an output current, above background, is applied to an input of a strip chart recorder. For low level concentrations, i.e., low detected output current, the ionization potential will be at a maximum and the metastable ionization detector will operate at its most sensitive level. When the detected current from the metastable ionization detector increases above a predetermined threshold level, a voltage control circuit is activated which turns on a high voltage transistor which acts to reduce the ionization potential. The ionization potential applied to the metastable ionization detector is then varied so as to maintain the detected signal level constant. The variation in ionization potential is now related to the concentration of the constituent and a representative amplitude is applied to another input of said strip chart recorder.

Carle, G. C.↗

NASA NTRS1991

Metastable phase formation in undercooled liquid lead alloys

During non-equilibrium processes metastable phases are formed instead of stable phases due to the operation of various kinetic or structural constraints. By removing the most effective nucleation sites for the stable phase using emulsified droplet samples, stable phase formation can be prohibited in a broad range of undercooling and the phase space available in the metastable regime can be mapped out. With this method the thermodynamic properties of the undercooled liquid and the metastable phase boundaries corresponding to reversible metastable (solid + liquid) phase equilibria are examined from experimental data. The analysis reveals important implications for the nucleation kinetics and the choice of the kinetically most favored solidification path.

Fecht, Hans J.↗

NASA NTRS2012

Crystallographic Stability of Metastable Phase Formed by Containerless Processing in REFeO3 (RE: Rare-Earth Element)

Undercooling a melt often facilitates a metastable phase to nucleate preferentially. Although the classical nucleation theory shows that the most critical factor for forming a metastable phase is the interface free energy, the crystallographic stability is also indispensable for the phase to be frozen at ambient temperature. In compound materials such as oxides, authors have suggested that the decisive factors for forming a critical nucleus are not only the free energy difference but also the difference of the entropy of fusion between stable and metastable phases. In the present study, using REFeO3 (RE: rare-earth element) as a model material, we investigate the formation of a metastable phase from undercooled melts with respect to the competitive nucleation and crystallographical stabilities of both phases.

Kuribayashi, Kazuhiko↗

DOE OSTI2025

Pressure-driven density match nucleates metastable r8 phases from amorphous Si and Ge

The pressure–temperature phase behavior of covalent disordered solids such as amorphous silicon and germanium is complex. Questions remain on possible glass transitions, on polyamorphism via amorphous–amorphous transitions, on connections with liquid–liquid transitions, on structure-behavior relationships, and on their potential as precursor for novel methods for material discovery. Here we demonstrate experimentally the nucleation of a metastable, four-fold coordinated rhombohedral r8 phase from pure amorphous silicon and germanium upon room temperature compression at pressures below 10 GPa. Accompanying theory reveals a strong pressure-driven distortion of the bond angle transforming the starting tetrahedral low-density amorphous network to a distorted four-fold coordinated medium-density state. This state is of lower density than metallic high-density networks, resembles the crystalline r8 phase and initiates its nucleation. Our finding shows that polyamorphism is not the only possible transformation mode for these amorphous solids and that instead nucleation of interesting functional phases at potentially useful pressures is possible. Such novel access modes to metastable structures are critical for future exploitability and could be useful for other tetrahedral materials including carbon, where the related (bc8) post-diamond phase remains elusive. Our observed density match between an amorphous and a metastable crystalline phase clearly allows for a new phase transition pathway, while corresponding theory demonstrates how carefully validated atomistic simulations can guide prediction, discovery and synthesis of novel material structures.

Materials discovery↗

DOE OSTI2025

Interplay Between Metastability and Mechanically Induced Structural Instability in CsPbBr 3 Photovoltaic Perovskite

An atomic-level understanding of the underlying structural metastability is still absent in halide perovskite photovoltaic systems. Focusing on the model material CsPbBr 3 , the impact of mechanically induced atomic structure alteration is elucidated through structural modeling and X-ray diffraction measurements. Sudden Cs–Br bond breaking drives the system metastability, where the first-order transition arises from cation-halide bond strain relief by severing the corner connectivity of the PbBr 6 units. The pressure–volume and entropy terms govern the Gibbs free-energy landscape in halide perovskites. In conclusion, metastability is revealed as a critical factor limiting the performance of lead halide perovskites under extreme but natural environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Symmetry-protected electronic metastability in an optically driven cuprate ladder

Optically excited quantum materials exhibit non-equilibrium states with remarkable emergent properties, but these phenomena are usually transient, decaying on picosecond timescales and limiting practical applications. Advancing the design and control of non-equilibrium phases requires the development of targeted strategies to achieve long-lived, metastable phases. Here, in this study, we report the discovery of symmetry-protected electronic metastability in the model cuprate ladder Sr 14 Cu 24 O 41 . Using femtosecond resonant X-ray scattering and spectroscopy, we show that this metastability is driven by a transfer of holes from chain-like charge reservoirs into the ladders. This ultrafast charge redistribution arises from the optical dressing and activation of a hopping pathway that is forbidden by symmetry at equilibrium. Relaxation back to the ground state is, hence, suppressed after the pump coherence dissipates. Our findings highlight how dressing materials with electromagnetic fields can dynamically activate terms in the electronic Hamiltonian, and provide a rational design strategy for non-equilibrium phases of matter.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Metal–Organic Frameworks at the Edge of Stability: Mediating Node Distortion to Access Metastable Nanoparticle Polymorphs

Metal-organic frameworks (MOFs) are emerging as unconventional precursors for nanoparticle synthesis, with potential to leverage their tunable structures and chemistry to achieve nanomaterials with structures and compositions inaccessible via traditional synthetic routes. Here we use in situ synchrotron X-ray diffraction and pair distribution function (PDF) measurements to investigate how the dynamic structure of MOFs at the edge of stability influences their transformation into different metastable polymorphs. Our study reveals that the local structural features of metal-oxo MOF nodes at elevated temperatures are linked to the resulting nanoparticle structures formed under mild conditions. Focusing on the titanium-based MOF MIL-125, we demonstrate that manipulating the chemical environment to facilitate transformation of the Ti8 node geometry promotes formation of metastable, nanometer-scale TiO2 brookite rather than the more common anatase and rutile TiO2 polymorphs typically produced through MOF pyrolysis at high temperature. These findings highlight the potential to harness the MOF topology and chemical environment to design and control node distortions and enable access to exotic metastable nanoparticle states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

UV-Induced Degradation and Associated Metastability in TOPCon Photovoltaic Modules: Understanding Kinetics and Cell Variance

Tunnel oxide passivated contact (TOPCon) silicon photovoltaic (PV) modules are dominating the PV market, but they may be susceptible to degradation under ultraviolet (UV)-containing light. Quantifying the impacts of UV-induced degradation (UVID) is complicated by an associated metastability causing further degradation under dark storage and rapid recovery under sunlight. Here, we study modules that have -2.3% to -3.2% nonrecoverable UVID loss after 60 kWh/m2 dose of 340 nm light and additional recoverable loss under dark storage. We use in situ electroluminescence (EL) imaging to characterize the post-UVID metastability at the module level. The cell-by-cell dark degradation and recovery kinetics span a wide range from +6% to -70% changes in EL intensity after 520 h of dark storage, which returns to +- 4% of the initial post-UVID EL intensity after illumination. The kinetics follow double exponential rates with dark storage degradation time constants of 345 and 45 h, and UV light recovery time constants of 5 min and 36 s. We propose that this is consistent with prior reports of kinetics for light-soaking metastability in Al2O3 passivation. Finally, we further show that cells having high UVID also have injection-dependent effective carrier lifetimes and significant intra-cell variance, suggesting possible origins of processing inconsistency.

14 SOLAR ENERGY↗

DOE OSTI2025

Basin-Size Mapping: Prediction of Metastable Polymorph Synthesizability Across TaC–TaN Alloys

The sizes of the basins of attraction on the potential energy surface are helpful indicators in determining the experimental synthesizability of metastable phases. In principle, these basins can be controlled with changes in thermodynamic conditions such as composition, pressure, and surface energy. Herein, we use random structure sampling to computationally study how alloying smoothly perturbs basin of attraction sizes. The TaC 1-x N x pseudobinary is an ideal test system given the structural and polymorphic contrast of its parent compounds and their technological relevance as epitaxial substrates for Al 1-x Ga x N. While we find limited thermodynamic stability across all computationally observed phases, random structure sampling shows a significant composition region where the rocksalt basin dominates. As such, we predict the potential for the nonequilibrium synthesis of metastable rocksalt TaC 1-x N x alloys as substrates for Al 1-x Ga x N. At higher nitrogen concentrations, other low-energy metastable polymorphs emerge that continue to retain the hexagonal close packing suitable for III-N growth. Confidence in these trends was established through uncertainty quantification of the basin sizes and energy distributions; such analysis utilized the Beta and Dirichlet distributions. In conclusion, we also find (a) polymorph basin sizes can be rationalized in terms of energetic preferences for different coordination environments; and (b) basin sizes universally shrink with increasing nitrogen content, making the system more prone to amorphous growth.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Band Gap Engineering and Metastable Phase Discovery in Cu 2 BaSnS 4– x Se x Nanocrystals via Topotactic Anion Exchange

Earth-abundant multinary inorganic chalcogenides, such as Cu 2 BaSnS 4–x Se x (CBTSSe), have emerged as promising absorbers for next-generation solar cells. However, accessing colloidal CBTSSe nanocrystals, including metastable polymorphs with more favorable optoelectronic properties, remains a critical synthetic challenge. Herein, we report the first use of topotactic anion exchange to access metastable crystal structures in soft chemistry syntheses. By varying the stoichiometry of selenium precursors, we directly synthesize Cu 2 BaSnS 4–x Se x (0 ≤ x ≤ 4) nanocrystals with a broad band gap tunability of 1.51–2.04 eV. At x = 4, a new metastable trigonal phase of Cu 2 BaSnSe 4 is isolated. This phase arises via an in-situ topotactic anion exchange from sulfur-rich Cu 2 BaSnS 4–x Se x intermediates, while retaining both the cation sublattice and overall nanocrystal morphology. The trigonal Cu 2 BaSnSe 4 exhibits a nearly direct band gap that is 280 meV lower than its thermodynamically stable orthorhombic counterpart, aligning more closely with the optimal band gap for single-junction solar cells. In contrast, a post-synthetic anion exchange route leads to the thermodynamically preferred orthorhombic polymorph, pointing to the critical nature of the in-situ transformation. Our findings open a versatile pathway for both polymorphic and morphological control in colloidal nanocrystals, expanding the synthetic design space for new optoelectronic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Single-Electron Transfer Stabilizes Metastable Alane in a Bipyridine-Functionalized MOF Nanopore

Nanoconfinement of metastable hydrides such as alane (AlH 3 ) in functionalized porous frameworks represents a promising yet largely untapped strategy for high-capacity energy storage. Despite its potential, the underlying mechanisms responsible for the thermodynamic stabilization of metastable hydrides are poorly understood. Here, in this study, concepts from solution Lewis acid–base chemistry were applied to a crystalline metal–organic framework (MOF) to stabilize AlH 3 . The long-range order and synthetically versatile pore chemistry enabled us to reveal the intimate details of the hydride-host interactions. Powder X-ray diffraction (PXRD) of AlH 3 -infiltrated UiO-67bpy (Zr 6 O 4 (OH) 4 (bpydc) 6 ; bpydc 2– = 2,2′-bipyridine-5,5′-dicarboxylate) confirms that the framework maintains its crystallinity up to 250 °C and is stable under 70 MPa H 2 pressure. We find that thermodynamic stabilization arises from coupled single-electron and hydrogen-atom transfer from AlH 3 to bipyridine-containing linkers. Electron paramagnetic resonance detects a bipyridyl radical with an anisotropic g-tensor (g values of 2.00132, 2.00215, and 2.00275), consistent with Bader charge analysis predicting 0.82 e – transferred from the hydride to the MOF. These findings establish critical structure–property relationships underpinning AlH 3 stabilization and suggest general strategies for tuning the thermodynamics and kinetics of metastable materials.

Shivanna, Mohana [Sandia National Laboratories (SN↗

DOE OSTI2025

Enhancing nanoscale charged colloid crystallization near a metastable liquid binodal

Achieving predictive control over crystallization using non-classical nucleation while avoiding kinetic traps would be a step towards designing materials with new functionalities. We address these challenges by inducing the bottom-up assembly of nanocrystals into ordered arrays, or superlattices. Using electrostatics—rather than density—to tune the interactions between particles, we watch self-assembly proceed through a metastable liquid phase. Here, we systematically investigate the phase behaviour as a function of quench conditions in situ and in real time using small-angle X-ray scattering. By fitting to colloid, liquid and superlattice models, we extract the time evolution of each phase and the system phase diagram, which we find to be consistent with short-range attractive interactions. Using the predictive power of the phase diagram, we establish control of the self-assembly rate over three orders of magnitude, and we identify one- and two-step self-assembly regimes, with only the latter implicating the metastable liquid as an intermediate. The presence of the metastable liquid increases the superlattice formation rate relative to the equivalent one-step pathway, and the superlattice order increases with the rate, revealing a generalizable kinetic strategy for promoting and enhancing ordered assembly.

Tanner, Christian P. N. [University of California,↗

DOE OSTI2026

First-principles investigation of structure-property relationships in stable and metastable MXenes

Understanding the structure–property relationships in layered transition-metal carbides or nitrides, known as MXenes, is of critical importance for their rational design, synthesis, and application. However, the vast chemical and structural diversity of MXenes, stemming from their wide range of M and X elements, surface terminations, and different atomic coordination environments, makes it challenging to clearly understand these structure–property relationships. Here, in this work, we perform first-principles density functional theory (DFT) calculations and molecular dynamics (MD) simulations to comprehensively investigate the stability and a variety of physical properties of MXenes with different coordination environments. Using Ti- and Mo-based carbide MXenes as model systems, energetic calculations reveal that Ti-based MXenes are most stable in octahedral coordination, whereas Mo-based MXenes preferentially adopt prismatic coordination. This fundamental difference in preferred atomic coordination gives rise to markedly distinct properties between these two systems as a function of the fraction of octahedral and prismatic sites. For instance, the in-plane stiffness of Ti-based MXenes increases as octahedral coordination becomes dominant, but it decreases in the Mo-based MXenes under the same conditions. Additional stability analyses based on mechanical, lattice-dynamical, and temperature-dependent thermodynamic properties demonstrate that many metastable MXenes not only satisfy the strict stability criteria but can also undergo phase transitions among different structures and even become stabilized at elevated temperatures. Although surface terminations, such as F and O atoms, do not alter the energetic ordering or the overall stiffness trends among stable and metastable MXenes, they influence other material properties. For instance, O termination can induce semiconducting behavior in both stable and metastable Ti 2 ⁢CO 2 MXenes. This study significantly advances the fundamental understanding of structure–property relationships in MXenes and provides valuable guidance for developing coordination-based design principles to precisely engineer MXenes with improved properties.

Oyeniran, Noah [University of Alabama, Tuscaloosa,↗

DOE OSTI2025

Dynamic compression effects of H 2 ⁡O in a dynamic diamond anvil cell: Origin of metastable ice VII and its crystal growth kinetics

We report on the structural verification of metastable ice VII solidifying in the phase space of ice VI at 1.80 GPa at room temperature. Using time-resolved (TR) x-ray diffraction and TR ruby luminescence paired with high-speed microphotography utilizing a dynamic diamond anvil cell, an initial compression rate range from 0.12 to 95.84 GPa/s was explored. The solidification pressure of metastable ice VII has a potential sigmoidal dependence upon compression rate with a turnover compression rate of ∼80 GPa/s. The preferred crystallization of ice VII in the stability field of ice VI is due to the increased nucleation rate of ice VII over ice VI at 1.77 GPa that is driven by the surface energy difference between the liquid and solid phases along with the change in Gibbs free energy of solidification. The dynamic pressure-volume–compression behaviors of ice phases (VI and VII) show a lattice stiffening in both phases, especially during the compression loading. It is also found that the compression rate greatly affects the solid-solid phase transition between ice VI and VII but does not affect the liquid-solid transition between water and ice VI as much. Lastly, a third phase transition was found to occur after metastable ice VII transforms into high-density amorphous (HDA) ice, which could be a disordered hydrogen-bonded network configuration of ice VII forming out of HDA ice facilitated by the decoupling of the oxygen movement and reorientation of the H 2⁡ O molecule. These results demonstrate the complexity of a seemingly simple molecule H 2⁡ O, how it can readily change its static properties with the modification of (de)compression rate, and highlight the need to use multiple TR structural and spectroscopic probes at higher time resolutions to realize the most comprehensive understanding.

Chemical bonding↗

DOE OSTI2025

Dynamics of metastable contact soliton dissipative exchange flows in one-dimensional ferromagnetic channels

Dissipative exchange flows (DEFs) are large-amplitude boundary value solutions of ferromagnetic channels. In their low-injection limit, DEFs reduce to spin superfluids. However, in the strong injection limit, nonlinearities dominate close to the injection site and a soliton is formed; this solution has been termed a contact soliton dissipative exchange flow (CS-DEF). Here, in this work, we numerically investigate CS-DEF solutions in a moderate injection regime and a finite injection width. We find a solution where two metastable solitons coexist in the injection region. This solution is metastable in the sense that any perturbation to the system will eject one of the solitons out of the injection region. Moreover, soliton dynamics can be excited when two injection regions are separated by a certain distance. We find that the ensuing DEF between the solitons induces a steady-state dynamics in which metastable solitons are continually ejected and nucleated. Furthermore, and depending on the relative signs of the spin injections, the soliton dynamics possess a particular handedness and frequency related to the spin transfer torque delivered by the DEF. Our results provide insights into the transport of spin current by DEFs - where the interaction between DEFs and solitons suggests a mechanism for detaching contact-solitons from the injection boundary. Although this study focuses on the "nonlocal" interaction between solitons, it may lead to the investigation of new mechanisms for inserting solitons in a DEF, e.g., for discrete motion and transport of information over long distances.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2024

Learning from metastable symmetric-tilt grain boundaries using physics-based descriptors

Grain boundaries (GBs) govern critical properties of polycrystalline materials. Although significant advancements have been made in characterizing minimum energy and ordered GBs, real GBs are seldom found in such well-defined states. This diversity of atomic arrangements in metastable states makes it challenging to establish structure-property relationships with physical insights. Here, to address this challenge, we use data-driven methods to explore these relationships and examine the underlying physics. In this study, we utilize a large atomistic database (~5000) of minimum energy and metastable states of symmetric-tilt copper GBs, combined with physically motivated local atomic environment (LAE) descriptors [strain functional descriptors (SFDs)], to predict GB properties and gain physical insights. Our regression models exhibit robust predictive capabilities using only 19 descriptors, generalizing to atomic environments in nanocrystals. A significant highlight of our work is the integration of an unsupervised method with SFDs to elucidate LAEs at GBs and their role in determining properties. The model, trained on these minimum energy and metastable GBs using SFDs, predicts the properties of unseen nanocrystals with good accuracy. Our research underscores the role of a physics-based representation of LAEs and the efficacy of data-driven methods in establishing GB structure-property relationships.

36 MATERIALS SCIENCE↗

NASA NTRS1972

Excitation of the metastable E(3 Sigma g plus) state of N2 by electron impact

The contribution of the N2(E(3 Sigma g plus)) state to the total metastable excitation function of N2 assessed on the basis of time-of-flight studies of metastable nitrogen molecules. The cross section for electron impact excitation state was determined in the domain of the resonance form threshold (11.87 eV) to an energy of about 13 eV. The maximum value of the cross section was found to be (7.0 + or - 4.0) x 10 to the -18th power sq cm at an energy of 12.2 eV. The measurement was made absolute by using the previously determined yield of the metastable detector, the lifetime of the E state, and by eliminating the energy spread in the electron beam from the raw data. The half-width (FWHM) of the resonance-like excitation function near threshold was found to be about 0.4 eV. No substantial evidence was obtained from the present data for the presence of the nonresonant part of the excitation function for the state studied.

Borst, W. L.↗

NASA NTRS1971

Dissociation-excitation reactions of argon metastables with carbon dioxide.

Results of a study showing that a metastable argon-carbon dioxide reaction results in dissociation of carbon dioxide and electronic excitation of one of the products, carbon monoxide or oxygen. A flow system using a 2450-MHz discharge was used to produce metastable argon atoms. Metastable argon in the afterglow was confirmed by adding nitrogen to the afterglow. Without addition of carbon dioxide no argon line emission, or any other emission, is observed from the reaction zone. Absence of argon line emission produced by recombination indicates the absence of charged species.

Starr, W. L.↗