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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 451 records · Page 25
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Characterizing novel Indium Phosphide pad detectors with focused X-ray beams and laboratory tests

Future tracking systems in High Energy Physics experiments will require large instrumented areas with low radiation length. Crystalline silicon sensors have been used in tracking systems for decades, but are difficult to manufacture and costly to produce for large areas. We are exploring alternative sensor materials that are amenable to fast fabrication techniques used for thin film devices. Indium Phosphide pad sensors were fabricated at Argonne National Lab using commercially available InP:Fe 2-inch mono-crystal substrates. Current-voltage and capacitance-voltage characterizations were performed to study the basic operating characteristics of a group of sensors. Micro-focused X-ray beams at Canadian Light Source and Diamond Light Source were used to study the response to ionizing radiation, and characterize the uniformity of the response for several devices. Electrical test results showed a high degree of performance uniformity between the 48 tested devices. X-ray test beam results showed good performance uniformity within tested devices after accounting for spatially-local defects and edge fields. As a result, this motivates further studies into thin film devices for future tracking detectors.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Lithium indium diselenide — An advanced material for neutron detection

Here, this paper describes the synthesis, crystal growth, detector fabrication, radiation hardening studies, MCNP modeling, and characterization of lithium indium diselenide or LiInSe 2 . This newly-developed room temperature thermal neutron detector has semiconducting and scintillating properties and it is suitable for neutron detection application. LiInSe 2 was synthesized starting from elemental Li, In, Se in two steps due to high reactivity of Li. A single crystal of LiInSe 2 was grown using the Vertical Bridgman method. The room temperature band gap was found to be 2.8 eV using optical absorption measurements. Bulk resistivity was measured at ∼5 × 10 11 Ωcm. Photoconductivity measurements of LiInSe 2 wafers identified a peak in the photocurrent around 445 nm. Nuclear radiation detectors were fabricated from single crystal wafer and the responses to alpha particles at various biases were measured. The mobility-lifetime product was estimated. Gamma irradiation studies were performed with calculated absorbed doses ranging from 0.2126 to 21,262 Gy. The characterization of the two wafers for their scintillator performance was conducted after each irradiation. The gamma irradiation produced a reduction of the light yield that translated to a lower channel number for the centroid of alpha detection spectra. It also showed a considerable reduction of the decay time after the first irradiation. These are the first studies on gamma radiation hardening with this material.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Simultaneously Enhancing Exciton/Charge Transport in Organic Solar Cells by an Organoboron Additive

Efficient exciton diffusion and charge transport play a vital role in advancing the power conversion efficiency (PCE) of organic solar cells (OSCs). Here, a facile strategy is presented to simultaneously enhance exciton/charge transport of the widely studied PM6:Y6-based OSCs by employing highly emissive trans-bis(dimesitylboron)stilbene (BBS) as a solid additive. BBS transforms the emissive sites from a more H-type aggregate into a more J-type aggregate, which benefits the resonance energy transfer for PM6 exciton diffusion and energy transfer from PM6 to Y6. Transient gated photoluminescence spectroscopy measurements indicate that addition of BBS improves the exciton diffusion coefficient of PM6 and the dissociation of PM6 excitons in the PM6:Y6:BBS film. Transient absorption spectroscopy measurements confirm faster charge generation in PM6:Y6:BBS. Moreover, BBS helps improve Y6 crystallization, and current-sensing atomic force microscopy characterization reveals an improved charge-carrier diffusion length in PM6:Y6:BBS. Finally, owing to the enhanced exciton diffusion, exciton dissociation, charge generation, and charge transport, as well as reduced charge recombination and energy loss, a higher PCE of 17.6% with simultaneously improved open-circuit voltage, short-circuit current density, and fill factor is achieved for the PM6:Y6:BBS devices compared to the devices without BBS (16.2%).

14 SOLAR ENERGY↗
DOE OSTI2025

Observation of Extraordinary Vibration Scatterings Induced by Strong Anharmonicity in Lead‐Free Halide Double Perovskites

Abstract Lead‐free halide double perovskites provide a promising solution for the long‐standing issues of lead‐containing halide perovskites, i.e., the toxicity of Pb and the low stability under ambient conditions and high‐intensity illumination. Their light‐to‐electricity or thermal‐to‐electricity conversion is strongly determined by the dynamics of the corresponding lattice vibrations. Here, the measurement of lattice dynamics is presented in a prototypical lead‐free halide double perovskite(Cs 2 NaInCl 6 ). The quantitative measurements and first‐principles calculations show that the scatterings among lattice vibrations at room temperature are at the timescale of ≈1 ps, which stems from the extraordinarily strong anharmonicity in Cs 2 NaInCl 6 . Further the degree of anharmonicity of each type of atom is quantitatively characterized in the Cs 2 NaInCl 6 single crystal, which stems from the interatomic forces, and demonstrate that this strong anharmonicity is synergistically contributed by the bond hierarchy, the tilting of the NaCl 6 and InCl 6 octahedral units, and the rattling of Cs + ions. Consequently, the crystalline Cs 2 NaInCl 6 possesses an ultralow thermal conductivity of ≈0.43 W mK −1 at room temperature, and a weak temperature dependence ofT −0.41 . These findings uncovered the underlying mechanisms behind the dynamics of lattice vibrations in double perovskites, which can largely benefit the design of optoelectronics and thermoelectrics based on halide double perovskites.

Chemistry↗
DOE OSTI2020

Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu 30 H 18 {E 2 P(OR) 2 } 12 ] (E=S or Se; R= n Pr, i Pr or i Bu)

Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Here, we describe the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu 30 H 18 {S 2 P(O n Pr) 2 } 12 ] ( 1 H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1 H reveals an unprecedented central Cu 12 hollow icosahedron. Six faces of this icosahedron are capped by Cu 3 triangles, the whole Cu 30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S 6 symmetry. The locations of the 18 hydrides in 1 H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ 3 -H, interstitial μ 4 -H (seesaw) and μ 5 -H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the 1 H NMR spectrum of 1 H are in line with their coordination environment in the solid state, retaining the S 6 symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu 30 H 18 {Se 2 P(OR) 2 } 12 ] ( 2 H : R= i Pr 3 H : R= i Bu) were synthesized from their sulfur relative 1 H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1 H – 3 H . In addition, the reaction of 1 H with [Pd(PPh 3 ) 2 Cl 2 ] in the presence of terminal alkynes led to the formation of new bimetallic Cu–Pd alloy clusters [PdCu 14 H 2 {S 2 P(O n Pr) 2 } 6 (C≡CR) 6 ] ( 4 : R=Ph; 5 : R = C 6 H 4 F).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Synthesis, Electronic Properties and Reactivity of [B 12 X 11 (NO 2 )] 2– (X=F–I) Dianions

Nitro-functionalized undecahalogenated closo-dodecaborates [B 12 X 11 (NO 2 )] 2– were synthesized in high purities and characterized by NMR, IR, and Raman spectroscopy, single crystal X-diffraction, mass spectrometry, and gas-phase ion vibrational spectroscopy. The NO 2 substituent leads to an enhanced electronic and electrochemical stability compared to the parent perhalogenated [B 12 X 12 ] 2– (X=F–I) dianions evidenced by photoelectron spectroscopy, cyclic voltammetry, and quantum-chemical calculations. The stabilizing effect decreases from X=F to X=I. Thermogravimetric measurements of the salts indicate the loss of the nitric oxide radical (NO . ). The homolytic NO . elimination from the dianion under very soft collisional excitation in gas-phase ion experiments results in the formation of the radical [B 12 X 11 O] 2–. . Theoretical investigations suggest that the loss of NO . proceeds via the rearrangement product [B 12 X 11 (ONO)] 2– . The O-bonded nitrosooxy structure is thermodynamically more stable than the N-bonded nitro structure and its formation by radical recombination of [B 12 X 11 O] 2–. and NO . is demonstrated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Heterogenous activation of dynamic recrystallization and twinning during friction stir processing of a Cu-4Nb alloy

An interplay between high degree of shear deformation and deformation-induced heating occurs during friction stir processing (FSP) of metals. In medium-to-low stacking fault energy Cu alloys, this can lead to a complex spatially heterogenous activation of dynamic recrystallization (DRX) and twinning mechanisms. Within the Cu-Nb system, the presence of Nb is further expected to influence the DRX mechanism of the Cu matrix. However, the microstructural changes induced by the co-deformation of Nb during FSP are still not well understood. So, this study uses a combination of multimodal microstructural characterization, solution thermodynamics-based predictions, and computational crystal plasticity simulation to reveal the various microstructural evolution mechanisms that can occur during FSP of a Cu-4at.%Nb binary model alloy. The formation of softer DRX zones, and harder shear localization regions are revealed using electron backscatter diffraction, transmission electron microscopy, atom probe tomography, and crystal plasticity modeling.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Advanced Characterization of Fuel-cladding Chemical Interaction between U-10Zr Fuel and HT9 Cladding Tested in Fast Flux Test Facility

Fuel cladding chemical interaction (FCCI) can greatly accelerate the cladding failure. However, due to the limited space in a fuel cladding assembly, it is historically challenging to gain an mechanistical understanding of the formation mechanism of FCCI and its influence on fuel and cladding performance. With the imminent need to qualify U-10Zr based metallic fuel cladded by HT-9 for advanced reactors demonstration project, it is of vital importance to use advanced characterization method to study FCCI in a unprecedent detailed manner and gain better mechanism understanding of FCCI. Mechanistic Fuel Failure (MFF) series of prototypic fuel elements irradiated in FFTF [1, 2] provides the best samples to study FCCI since the MFF-series assemblies had an axial fuel height the same as proposed length by industry partners. Jason et al. [3] has performed preliminary post-irradiation examination on a MFF fuel pin sample, which was extracted from the HT9 cladded U-10at.%Zr MFF-3 pin MFF-3 pin (#193045) at an axial location of X/L = 0.98. This sample has a peak burnup of 5.7 at.% and peak inner cladding temperature (PICT) of around 615 °C during in-core testing. Scanning electron microscope examination has identified visible FCCI region on more than half of the HT9 circumference [3]. The most striking feature are grain boundary attacking by apparently lanthanides (Lns) rich phase. However, SEM cannot provide accurate assessment of phase and concentration of grain boundary phases and prevented a better understanding of the formation mechanism of such attach. This study, by pairing transmission electron microscope (TEM) characterization and atom probe tomography (APT) techniques with in-situ micro-tensile testing in scanning electron microscope (SEM), aims at gaining in-depth understanding on the formed FCCI region. The identified FCCI region roughly consists of multilayers as illustrated in Figure 1 (c). The main findings are: (1) layer-B shows observable lanthanides (Lns) infiltration along grain boundaries and mechanical softening due to FCCI- and irradiation-induced microstructural and microchemistry changes, particularly the recovery of martensitic lath structure and dissolution of pre-existing M23C6 together with the formation of coarsened Laves phases, (Fe, Cr)2(Mo, W); (2) layer-C is Fe depleted but Lns significantly enriched, becoming very brittle; (3) layer-D is mainly composed of UFe2 and Lns; (4) three FCCI-induced intermetallic U-Fe-Zr phases, ? (Fe0.5Zr0.32U0.18), e (Fe0.3Zr0.4U0.3), ? (Fe0.06Zr0.23U0.71), were identified near layer-E; (5) the ? (Fe0.5Zr0.32U0.18) phase was characterized to be a face centered cubic (FCC) crystal structure. These results will help to better understanding the governing mechanism of FCCI and facilitating the development of theoretical model for assessing the performance of metallic fuel and cladding integrity.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Structurally Frustrated Remeika Phases: Tolerance Factor and Non-Kramers’ Ion Effects

Quantum materials that are found on the verge of structural, magnetic, and electronic instabilities are deep reservoirs for exotic phenomena. Our criteria to study the reported Ln 5 Ru 6 Sn 18 (Ln = Gd, Tb) are guided by the tolerance factor for Remeika phases─a class of intermetallic compounds with the general formula A 3 M 4 X 13 (where A = rare-earth element, M = transition metal, and X = tetrel), which can be viewed as structural analogues of pseudoperovskites (4 × ABX 3 ), with one of the tetrel atoms occupying the A-site. We have grown single crystals, up to 0.5 cm on the largest facet, of Gd 5 Ru 6 Sn 18 (a = 13.8052(12) Å) and Tb 5 Ru 6 Sn 18 (a = 13.7825(9) Å), which we expect to be on the verge of a formation instability. Bulk magnetic, heat capacity, and electrical transport measurements reveal unusual behavior that originates from the trivalent Gd and Tb ions, with deviations from typical metallic behavior and magnetic ordering that is short-range or disrupted in some other way. Furthermore, to better understand these phenomena, single-crystal neutron diffraction is investigated, which reveals short-range correlations among the partially occupied Tb and Sn sublattices, with 3D-ΔPDF analysis supporting direction-dependent local order. Taken together, these measurements show the utility of using tolerance factors in identifying materials that are likely to exhibit complex phenomena and uncover environments where a formation instability may strongly impact emergent bulk magnetic and electronic phenomena.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Distinguishing Desirable and Undesirable Reactions in Multicomponent Systems for Redox Activation of the Uranyl Ion

Although it has been established that covalent functionalization of the U–O bonds in the uranyl dication (UO 2 2+ ) generally requires use of strong reductants and electrophiles, little work has examined how interactions between the individual reaction components could affect final outcomes in solution. Here, the patterns of such reactivity have been studied in a UO 2 2+ -containing model system supported by a workhorse pentadentate ligand, 2,2′-[(methylimino)bis(2,1-ethanediylnitrilomethylidyne)]bis-phenol. Oxo activation and functionalization have been tested with (i) electrochemical and chemical reduction, and (ii) coordinating and noncoordinating solvents. In acetonitrile, uranyl reduction was achieved cleanly, but treatment of the reduced species with tris(pentafluorophenyl)borane (BCF) resulted in a mixture of products arising from direct electron transfer to BCF. In dichloromethane (CH 2 Cl 2 ), electrochemical reduction of uranyl was achieved cleanly, but clean chemical reactivity was inaccessible. Despite these challenges, one trinuclear and oxo-deficient uranium-containing product was crystallized from CH 2 Cl 2 solution and characterized; thus, desirable electrophilic reactivity can proceed to some degree in CH 2 Cl 2 with BCF. Computational studies were used to investigate the properties of the trinuclear uranium product and the changes that could be inducible by further reduction. Here, taken together, the reactivity patterns identified here could inform design of improved systems for actinyl oxo functionalization.

cations↗
DOE OSTI2024

New Nonreactive Force Field for Accurate Molecular Dynamics Simulations of TATB at Extreme Conditions

Insensitive high explosives based on TATB (1,3,5-triamino-2,4,6-trinitrobenzene) are needed in applications when safety is of paramount importance, but the basic material properties that give rise to its insensitivity are not fully understood. Molecular dynamics modeling using empirical force fields (FFs) has been the main route to characterize many complicated dynamical properties of TATB single crystal, but these FFs have not been comprehensively tested at extreme conditions typical of detonation. We collect a benchmark data set of (quasi)static TATB physical properties as determined by experiments and electronic structure calculations and apply this data set to validate four existing TATB FFs along with a new TATB FF that we develop here and denote as the CEA-LLNL-Missouri (CLM) FF. Benchmark data include vibrational spectra, the TATB crystal temperature–pressure–volume equation of state and lattice parameters, properties of TATB crystal polymorphs and transitions to the gaseous and liquid states, dimer energy landscapes, the pressure-dependent elastic tensor, and the energy landscape for inelastic deformation via sliding of TATB crystal layers. As a general assessment, we find that the two existing nonreactive FFs are more accurate in describing TATB’s physical properties compared to the two variants of the ReaxFF reactive FF considered. The new CLM FF is found to consistently yield similar or better agreement with experiments and electronic structure theory than any of the existing FF models, and it presents a distinct improvement in accurately modeling TATB elasticity and equation of state. So this work is expected to help improve the accuracy of FF-based modeling of complicated dynamic responses that ultimately govern the safety and performance characteristics of this material.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Assigning Optical Absorption Transitions with Light-Induced Crystal Structures: Case Study of a Single-Crystal Nanooptomechanical Transducer

UV/vis absorption spectroscopy affords indirect structural information about the photochemistry and photophysics of molecules by inferring types of electronic transitions from spectral features. Direct structural information would become available, though, if light-induced crystal structures could be mapped against changes in optical absorption spectra as a photochemical process evolves. We present a series of light-induced crystal structures that track real-time changes in solid-state optical absorption spectra of a crystalline nanooptomechanical transducer, while the transduction process unfolds within its crystal lattice at 100 K. Results afford a combined structural and spectral mapping of its solid-state optical absorption, from which the operational mechanism of nanooptomechanical transduction is revealed. Metal-to-ligand and metal-centered charge-transfer bands are assigned to optical absorption peaks directly from their 3-D light-induced crystal structures. This approach could be used to characterize many solid-state optoelectronic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Cyclometalated Platinum Compounds from Competing C–H/C–X Bond Activation Pathways

X−C^N^N (X = Br, Cl) ligands were reacted with [Pt 2 Me 4 (μ- SMe 2 ) 2 ], 1, resulting in a six-coordinate cyclometalated platinum(IV) compound containing an anionic C^N^N ligand when X = Br and both a platinum(IV) and a platinum(II) product when X = Cl. The platinum(II) species was formed by C−H activation, followed by reductive elimination of methane. The platinum compounds were characterized by multinuclear NMR spectroscopy and single-crystal X-ray diffraction (SCXRD). Photophysical properties were explored by using UV/vis, emission, and transient absorption (TA) spectroscopies. DFT and TDDFT calculations were performed to examine the competition between C−H activation and C−X oxidative addition and compared to experimental results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Structure and bonding of a radium coordination compound in the solid state

The structure and bonding of radium (Ra) is poorly understood because of challenges arising from its scarcity and radioactivity. Here we report the synthesis of a molecular Ra 2+ complex using 226 Ra and the organic ligand dibenzo-30-crown-10, and its characterization in the solid state by single-crystal X-ray diffraction. The crystal structure of the Ra 2+ complex shows an 11-coordinate arrangement comprising the 10 donor O atoms of dibenzo-30-crown-10 and that of a bound water molecule. Under identical crystallization conditions, barium (Ba 2+ ) yielded a 10-coordinate ‘Pac-Man’-shaped structure lacking water. Furthermore, the bond distance between the Ra centre and the O atom of the coordinated water is substantially longer than would be predicted from the ionic radius of Ra 2+ and by analogy with Ba 2+ , supporting greater water lability in Ra 2+ complexes than in their Ba 2+ counterparts. In conclusion, barium often serves as a non-radioactive surrogate for radium, but our findings show that Ra 2+ chemistry cannot always be predicted using Ba 2+ .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Toward achieving cost-effective hexagonal BN semi-bulk crystals and BN neutron detectors via halide vapor phase epitaxy

Presently, thermal neutron detectors fabricated from boron-10 enriched hexagonal boron nitride (h-10BN) ultrawide bandgap semiconductor grown by metal organic chemical vapor deposition (MOCVD) hold the record high detection efficiency among all solid-state detectors at 59%. To overcome the short comings of MOCVD growth, including inherently low growth rate and unavoidable impurities such as carbon in metal organic source, we demonstrate here the growth of natural hexagonal boron nitride (h-BN) semi-bulk wafers using halide vapor phase epitaxy (HVPE), which is an established technique for producing GaN semi-bulk crystals at a high growth rate. Electrical transport characterization results revealed that these HVPE grown materials possess an electrical resistivity of 1 × 1013 Ω cm, and a charge carrier mobility and lifetime product of 2 × 10−4 cm2/V s. Detectors fabricated from a 100 μm thick h-BN wafer have demonstrated a thermal neutron detection efficiency of 20%, corresponding to a charge collection efficiency of ∼60% at an operating voltage of 500 V. This initial demonstration opens the door for mass producing high efficiency h-BN semiconductor neutron detectors at a reduced cost, which could create unprecedented applications in nuclear energy, national security, nuclear waste monitoring and management, the health care industry, and material sciences.

Physics↗
DOE OSTI2024

Structural anisotropy in Sb thin films

Sb thin films have attracted wide interest due to their tunable band structure, topological phases, high electron mobility, and thermoelectric properties. We successfully grow epitaxial Sb thin films on a closely lattice-matched GaSb(001) surface by molecular beam epitaxy. We find a novel anisotropic directional dependence on their structural, morphological, and electronic properties. The origin of the anisotropic features is elucidated using first-principles density functional theory (DFT) calculations. The growth regime of crystalline and amorphous Sb thin films was determined by mapping the surface reconstruction phase diagram of the GaSb(001) surface under Sb 2 flux, with confirmation of structural characterizations. Crystalline Sb thin films show a rhombohedral crystal structure along the rhombohedral (211) surface orientation parallel to the cubic (001) surface orientation of the GaSb substrate. At this coherent interface, Sb atoms are aligned with the GaSb lattice along the [1̄10] crystallographic direction but are not aligned well along the [110] crystallographic direction, which results in anisotropic features in reflection of high-energy electron diffraction patterns, misfit dislocation formation, surface morphology, and transport properties. Our DFT calculations show that the preferential orientation of the rhombohedral Sb (211) plane may originate from the GaSb surface, where Sb atoms align with the Ga and Sb atoms on the reconstructed surface. The formation energy calculations confirm the stability of the experimentally observed structures. Our results provide optimal film growth conditions for further studies of novel properties of Bi 1-x Sb x thin films with similar lattice parameters and an identical crystal structure, as well as functional heterostructures of them with III–V semiconductor layers along the (001) surface orientation, supported by a theoretical understanding of the anisotropic film orientation.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Dynamics and transport in the boundary-driven dissipative Klein-Gordon chain

Motivated by experiments on chains of superconducting qubits, we consider the dynamics of a classical Klein-Gordon chain coupled to coherent driving and subject to dissipation solely at its boundaries. As the strength of the boundary driving is increased, this minimal classical model recovers the main features of the "dissipative phase transition" seen experimentally. Between the transmitting and non-transmitting regimes on either side of this transition (which support ballistic and diffusive energy transport respectively), we observe additional dynamical regimes of interest. These include a regime of superdiffusive energy transport at weaker driving strengths, together with a "dissipative breather crystal" regime at stronger driving strengths, which is characterized by emergent translation symmetry, ballistic energy transport, and coherent oscillations of a nonlinear normal mode. Here, we propose a non-local Lyapunov exponent as an experimentally measurable diagnostic of many-body chaos in this system, and more generally in open systems that are only coupled to an environment at their boundaries.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Temperature- and Rate-Dependent Pathways in Formation of Metastable Silicon Phases under Rapid Decompression

High-pressure metallic beta-Sn silicon (Si-II), depending on temperature, decompression rate, stress, etc., may transform to diverse metastable forms with promising semiconducting properties under decompression. However, the underlying mechanisms governing the different transformation paths are not well understood. Here, two distinctive pathways, viz., a thermally activated crystal-crystal transition and a mechanically driven amorphization, were characterized under rapid decompression of Si-II at various temperatures using in situ time-resolved x-ray diffraction. Under slow decompression, Si-II transforms to a crystalline bc8/r8 phase in the pressure range of 4.3-9.2 GPa through a thermally activated process where the overdepressurization and the onset transition strain are strongly dependent on decompression rate and temperature. In comparison, Si-II collapses structurally to an amorphous form at around 4.3 GPa when the volume expansion approaches a critical strain via rapid decompression beyond a threshold rate. The occurrence of the critical strain indicates a limit of the structural metastability of Si-II, which separates the thermally activated and mechanically driven transition processes. The results show the coupled effect of decompression rate, activation barrier, and thermal energy on the adopted transformation paths, providing atomistic insight into the competition between equilibrium and nonequilibrium pathways and the resulting metastable phases.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗