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At least 19 records

Columnar and subsurface silicide growth with novel molecular beam epitaxy techniques

We have found novel growth modes for epitaxial CoSi2 at high temperatures coupled with Si-rich flux ratios or low deposition rates. In the first of these modes, codeposition of metal and Si at 600-800 C with excess Si leads to the formation of epitaxial silicide columns surrounded by single-crystal Si. During the initial stages of the deposition, the excess Si grows homoepitaxially in between the silicide, which forms islands, so that the lateral growth of the islands is confined. Once a template layer is established by this process, columns of silicide form as a result of selective epitaxy of silicide on silicide and Si on Si. This growth process allows nanometer control over silicide particles in three dimensions. In the second of these modes, a columnar silicide seed layer is used as a template to nucleate subsurface growth of CoSi2. With a 100 nm Si layer covering CoSi2 seeds, Co deposited at 800C and 0.01 nm/s diffuses down to grow on the buried seeds rather than nucleating surface silicide islands. For thicker Si caps or higher deposition rates, the surface concentration of Co exceeds the critical concentration for nucleation of islands, preventing this subsurface growth mode from occurring. Using this technique, single-crystal layers of CoSi2 buried under single-crystal Si caps have been grown.

Fathauer, R. W.↗

Stability, metallicity, and magnetism in niobium silicide nanofilms

Modern superconducting qubits based on two-dimensional (2D) transmons typically involve the growth of Nb thin films on high-resistivity Si substrates. Since imperfections at the Nb-Si heterointerface have been implicated as a source of two-level systems that limit quantum coherence times, detailed characterization and understanding of niobium silicide interfacial layers are critical to improving superconducting qubit technology. While bulk binary intermetallic niobium silicide phases are well understood, the thermodynamic phase stability and properties of ultrathin niobium silicides, such as those found at the Nb-Si heterointerface in 2D transmons, have not yet been explored. Here, we report finite-sized effects for ultrathin niobium silicide films using density functional theory calculations and predict nanoscale stabilization of Nb 6 Si 5 over the bulk α-Nb 5 Si 3 phase. This result is consistent with our experimental observations of a niobium silicide interfacial layer between a sputtered Nb thin film and the underlying Si substrate. Furthermore, our calculations show that Nb 6 Si 5 nanofilms are nonmagnetic, making them superior to nanofilms of α-Nb 5 Si 3 that exhibit antiferromagnetic correlations detrimental to long coherence times in superconducting qubits. Furthermore, by providing atomic-scale insight into niobium silicide nanofilms, this paper can help guide ongoing efforts to optimize Nb-Si heterointerfaces for long coherence times in superconducting qubits.

36 MATERIALS SCIENCE↗

Direct Transformation of SiH 4 to a Molecular L(H) 2 Co=Si=Co(H) 2 L Silicide Complex

The synthesis of bimetallic molecular silicide complexes is reported, based on the use of multiple Si–H bond activations in SiH 4 at the metal centers of 14-electron LCo I fragments (L = Tp", HB(3,5-diisopropylpyrazolyl) 3 – ; [BP 2 tBu Pz], PhB(CH 2 P t Bu 2 ) 2 (pyrazolyl)). Upon exposure of (Tp"Co) 2 (μ-N 2 ) (1) to SiH 4 , a mixture of (Tp"Co) 2 (μ-H) (2) and (Tp"Co) 2 (μ-H) 2 (3) was formed and no evidence for Si–H oxidative addition products was observed. In contrast, [BP 2 tBu Pz]-supported Co complexes led to Si–H oxidative additions with the generation of silylene and silicide complexes as products. Notably, the reaction of ([BP 2 tBu Pz]Co) 2 (μ-N 2 ) (5) with SiH 4 gave the dicobalt silicide complex [BP 2 tBu Pz](H) 2 Co=Si=Co(H) 2 [BP 2 tBu Pz] (8) in high yield, representing the first direct route to a symmetrical bimetallic silicide. Here, the effect of the [BP 2 tBu Pz] ligand on Co–Si bonding in 7 and 8 was explored by analysis of solid-state molecular structures and density functional theory (DFT) investigations. Upon exposure to CO or DMAP (DMAP = 4-dimethylaminopyridine), 8 converted to the corresponding [BP 2 tBu Pz]Co(L) x adducts (L = CO, x = 2; L = DMAP, x = 1) with concomitant loss of SiH 4 , despite the lack of significant Si–H interactions in the starting complex. On heating to 60 °C, 8 underwent reaction with MeCl to produce small quantities of Me x SiH 4–x (x = 1–3), demonstrating functionalization of the μ-silicon atom in a molecular silicide to form organosilanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface morphology of erbium silicide

The surface of rare-earth silicides (Er, Tb, etc.), formed by the reaction of thin-film metal layers with a silicon substrate, is typically dominated by deep penetrating, regularly shaped pits. These pits may have a detrimental effect on the electronic performance of low Schottky barrier height diodes utilizing such silicides on n-type Si. This study suggests that contamination at the metal-Si or silicide-Si interface is the primary cause of surface pitting. Surface pits may be reduced in density or eliminated entirely through either the use of Si substrate surfaces prepared under ultrahigh vacuum conditions prior to metal deposition and silicide formation or by means of ion irradiation techniques. Silicide layers formed by these techniques possess an almost planar morphology.

Lau, S. S.↗

A [CoSiH 2 ] Silylene Synthon Provides Modular Access to Homo- and Heterobimetallic [Co=Si=M] (M = Co, Fe) Silicide Complexes

Base-stabilized [BP 3 iPr ](H) 2 CoSiH 2 (DMAP) (1, [BP 3 iPr ] = PhB(CH 2 P i Pr 2 ) 3 – ; DMAP = 4-dimethylaminopyridine) is a rare instance of a synthon for the simplest “parent” silylene complex (LM=SiH 2 ). Complex 1 was accessed in high yields via double Si–H bond activation in SiH 4 by [BP 3 iPr ]Co(DMAP), and in solution, it undergoes rapid exchange between bound and free DMAP by an associative mechanism (as determined by variable-temperature 1 H NMR dynamic studies). The DMAP ligand of 1 is readily displaced by metal-based fragments that bind silicon and cleave the Si–H bonds of the SiH 2 moiety to produce bimetallic [Co=Si=M] (M = Co, Fe) molecular silicides. Thus, treatment of 1 with 0.5 equiv of (LCo I ) 2 (μ-N 2 ) (L = a tripodal ligand) resulted in the spontaneous formation of [BP 3 iPr ](H) 2 Co=Si=Co(H) 2 L (L = [BP 2 tBu Pz], PhB(CH 2 P t Bu 2 ) 2 (pyrazolyl) - (3); Tp", HB(3,5-diisopropylpyrazolyl) 3 – (4)) with the concomitant release of DMAP. The symmetrical silicide [BP 3 iPr ](H) 2 Co=Si=Co(H) 2 [BP 3 iPr ] (5) was prepared by treatment of a mixture of 1 and [BP 3 iPr ]Co(DMAP) with 2 equiv of Ph 3 B, which in this case is required to sequester DMAP as the elimination product Ph 3 B-DMAP. A heterobimetallic silicide, [BP 3 iPr ](H) 2 Co=Si=Fe(H) 2 [SiP 3 iPr ] (7; [SiP 3 iPr ] = PhSi(CH 2 P i Pr 2 ) 3 ), was obtained via in situ KC 8 reduction of [SiP 3 iPr ]FeCl and subsequent addition of 1 and Ph 3 B. These transformations involving a metal–SiH 2 derivative demonstrate a fundamentally new type of reactivity for silylene complexes and provide a unique synthetic method for construction of molecular silicide complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Substrate effects on phase formation and interfacial stability in superconducting vanadium silicide thin films

Thin films of vanadium silicide (V-silicide) in the A15 cubic phase (V 3 Si) are promising for superconducting quantum devices due to their high transition temperature and potential compatibility with scalable semiconductor fabrication. However, solid-phase synthesis often yields secondary silicide phases that degrade performance. Here, in this study, we investigate the influence of substrate properties using two silicon-on-insulator architectures: one with a polycrystalline HfO 2 buried layer (group A) and the other with amorphous SiO 2 (group B). Both systems exhibit superconductivity consistent with V 3 Si formation, yet structural analysis reveals mixed-phase films in both cases. Crucially, only group A maintains an atomically sharp and chemically stable interface, a prerequisite for phase purity. Prolonged annealing in group A reduces the unwanted V 5 Si 3 phase but also leads to the emergence of Si-rich VSi 2 , likely due to localized substrate degradation. Preliminary atomic-resolution imaging suggests that HfO 2 crystallinity may promote local phase-selective nucleation. These findings highlight the importance of substrate design in promoting phase control and maintaining interfacial integrity in superconducting silicides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Silicide surface phases on gold

The crystalline silicide layers formed on (111) and (100) surfaces of Au films on various Si single-crystal substrates are studied by LEED and AES in conjunction with sputter-depth profiling as a function of annealing temperature. On the (111) surface, three basic silicide structures are obtained corresponding to layers of various thicknesses as obtained by different preparation conditions. The (100) surface shows only two different structures. None of the structures is compatible with the various bulk silicide structures deduced from X-ray diffraction. Using LEED as a criterion for the presence or absence of silicide on the surface, smaller layer thicknesses are obtained than reported previously on the basis of AES studies.

Green, A. K.↗

Chromium silicide formation by ion mixing

The formation of CrSi2 by ion mixing was studied as a function of temperature, silicide thickness and irradiated interface. Samples were prepared by annealing evaporated couples of Cr on Si and Si on Cr at 450 C for short times to form Si/CrSi2/Cr sandwiches. Xenon beams with energies up to 300 keV and fluences up to 8 x 10 to the 15th per sq cm were used for mixing at temperatures between 20 and 300 C. Penetrating only the Cr/CrSi2 interface at temperatures above 150 C induces further growth of the silicide as a uniform stoichiometric layer. The growth rate does not depend on the thickness of the initially formed silicide at least up to a thickness of 150 nm. The amount of growth depends linearly on the density of energy deposited at the interface. The growth is temperature dependent with an apparent activation energy of 0.2 eV. Irradiating only through the Si/CrSi2 interface does not induce silicide growth. It is concluded that the formation of CrSi2 by ion beam mixing is an interface-limited process and that the limiting reaction occurs at the Cr/CrSi2 interface.

Shreter, U.↗

Palladium silicide formation under the influence of nitrogen and oxygen impurities

The effect of impurities on the growth of the Pd2Si layer upon thermal annealing of a Pd film on 100 line-type and amorphous Si substrates is investigated. Nitrogen and oxygen impurities are introduced into either Pd or Si which are subsequently annealed to form Pd2Si. The complementary techniques of Rutherford backscattering spectrometry, and N-15(p, alpha)C-12 or O-18(p, alpha)N-15 nuclear reaction, are used to investigate the behavior of nitrogen or oxygen and the alterations each creates during silicide formation. Both nitrogen and oxygen retard the silicide growth rate if initially present in Si. When they are initially in Pd, there is no significant retardation; instead, an interesting snow-plowing effect of N or O by the reaction interface of Pd2Si is observed. By using N implanted into Si as a marker, Pd and Si appear to trade roles as the moving species when the silicide front reaches the nitrogen-rich region.

Ho, K. T.↗

Phase transformations in ion-irradiated silicides

The present investigation has three objectives. The first is concerned with the phase transformation of CoSi2 under ion implantation and the subsequent crystallization characteristics during annealing, taking into account epitaxial and nonepitaxial recrystallization behavior. The second objective is related to a study of the general trend of implantation-induced damage and crystallization behavior for a number of commonly used silicides. The last objective involves a comparison of the recrystallization behavior of cosputtered refractory silicides with that of the ion-implanted silicides. It was found that epitaxial regrowth of ion-irradiated CoSi2 occurred for samples with an epitaxial seed left at the Si/CoSi2 interface. A structural investigation of CoSi2 involving transmission electron microscopy (TEM) showed that after high-dose implantation CoSi2 is amorphous.

Hewett, C. A.↗

Si-Ge Nano-Structured with Tungsten Silicide Inclusions

Traditional silicon germanium high temperature thermoelectrics have potential for improvements in figure of merit via nano-structuring with a silicide phase. A second phase of nano-sized silicides can theoretically reduce the lattice component of thermal conductivity without significantly reducing the electrical conductivity. However, experimentally achieving such improvements in line with the theory is complicated by factors such as control of silicide size during sintering, dopant segregation, matrix homogeneity, and sintering kinetics. Samples are prepared using powder metallurgy techniques; including mechanochemical alloying via ball milling and spark plasma sintering for densification. In addition to microstructural development, thermal stability of thermoelectric transport properties are reported, as well as couple and device level characterization.

thermoelectricity↗

Lessons Learned—Lithium Silicide Hydration Fire

Alkali metals, such as lithium, sodium, potassium, etc., are highly reactive elements. While researchers generally handle these metals with caution, less caution is taken when these elements have been “reacted”. In this work, a recent incident is examined in which a pair of researchers ignited a lithium silicide alloy sample that was assumed to be fully hydrated to lithium hydroxide and, thereby, no longer water-reactive. However, variations in the original chemical composition of the lithium compounds examined resulted in select mixtures failing to hydrate and react completely to lithium hydroxide in the time frame allowed. This gave rise to residual unreacted, water-sensitive lithium silicide which resulted in a violent exothermic reaction with water and autoignition of the produced hydrogen gas. This Article describes this incident and improvements that can be implemented to prevent similar incidents from occurring.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Automated reactor physics analysis framework of High Flux Isotope Reactor low-enriched uranium silicide dispersion fuel designs

The High Flux Isotope Reactor (HFIR) is a versatile research reactor that provides one of the highest steady-state neutron fluxes of any reactor in the world. The HFIR reactor physics team investigated the conversion of the current 93 wt% highly enriched uranium U 3 O 8 -Al dispersion fuel to a 19.75% low-enriched uranium (LEU) U 3 Si 2 -Al dispersion fuel. The team continuously develops a Python module to streamline the analysis steps required for an LEU core design to ensure reproducible and agile design iteration. The Python module automates the data processing between analysis steps and automates the input perturbation for branch calculations and design changes. The automated framework has proven to significantly increase the efficiency and reproducibility of the reactor physics team to design High Flux Isotope Reactor (HFIR) LEU cores and thoroughly analyze performance metrics, safety metrics, and thermal safety margins. Consequently, the team can now respond rapidly to fuel fabrication engineer and thermal-hydraulic-structural analyst requests. Numerous combinations of LEU fuel designs are explored, of which two LEU fuel designs are presented here in this paper: a low density silicide design, and a high-density silicide design. Results show that both designs meet or exceed safety and performance metrics with exception for minor differences caused by the hardened spectrum from LEU.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Thin-film synthesis of superconductor-on-insulator A15 vanadium silicide

Abstract We present a new method for thin-film synthesis of the superconducting A15 phase of vanadium silicide with critical temperature higher than 13 K. Interdiffusion between a metallic vanadium film and the underlying silicon device layer in a silicon-on-insulator substrate, at temperatures between 650 and 750 °C, favors formation of the vanadium-rich A15 phase by limiting the supply of available silicon for the reaction. Energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction verify the stoichiometry and structure of the synthesized thin films. We measure superconducting critical currents of more than 10 6 amperes per square centimeter at low temperature in micron-scale bars fabricated from the material, and an upper critical magnetic field of 20 T, from which we deduce a superconducting coherence length of 4 nm, consistent with previously reported bulk values. The relatively high critical temperature of A15 vanadium silicide is an appealing property for use in silicon-compatible quantum devices and circuits.

36 MATERIALS SCIENCE↗

HFIR LEU High Density Silicide Dispersion Optimized Design Steady-State Heat Transfer Analyses

Steady-state heat transfer simulations of the Oak Ridge National Laboratory High Flux Isotope Reactor (HFIR) with the low-enriched uranium (LEU) high-density silicide dispersion Optimized fuel design were performed to support comprehensive performance and safety metric studies concerning this design. The LEU Optimized design operates at 95 MW to maintain HFIR’s current highly enriched uranium (HEU) core performance level at 85 MW. Full cycle Mode 1 full flow Case 1 (inlet temperature), Case 2 (flux-to-flow), and Case 3 (inlet pressure) safety limit analyses were performed to assess the margins to critical heat flux. Under the prescribed conditions, this LEU design meets the safety limit and limiting control setting requirements outlined in HFIR’s documented safety analysis; however, the safety margins are less than those for the 85 MW HEU core, and several assumptions were made where fuel fabrication and qualification data are currently lacking for the silicide fuel design. Effects of changes to pertinent fuel fabrication assumptions and uncertainty factors on thermal safety margins were also evaluated, showing that the margins are sensitive to many of these parameters. Power and pressure perturbations were also performed, indicating that significant steady-state thermal margins could be gained by increasing the coolant inlet pressure.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

COMSOL Results for the Nominal Steady-State Operation of the Proposed 95-MW LEU Silicide Core for HFIR Conversion

Engineering design studies are being performed to determine the feasibility of converting the High Flux Isotope Reactor (HFIR) from highly enriched uranium (HEU) to low-enriched uranium (LEU) fuel at Oak Ridge National Laboratory. This activity is sponsored by the Office of Reactor Conversion and Uranium Supply (ORCUS) under the auspices of the US Department of Energy National Nuclear Security Administration’s Office of Material Management and Minimization. HFIR is a very high flux, pressurized, light water–cooled and moderated, flux trap–type research reactor with a core made of involute shaped U 3 O 8 /Al cermet fuel plates and coolant channels. HFIR currently operates at a thermal power of 85 MW and supports key national and international missions in neutron scattering, isotope production, materials/fuels irradiation, neutron activation analysis, gamma irradiation, and neutrino research. Advanced multiphysics computational fluid dynamics models have been developed in the COMSOL Multiphysics software to simulate the steady-state operating conditions for the proposed low-and high-density LEU U 3 Si 2 -Al (uranium silicide dispersion) fuel designs. The COMSOL models for HFIR inner and outer fuel element models incorporate various essential inputs and physics such as spatially dependent nuclear heat deposition, multilayer heat conduction, conjugate heat transfer, turbulent flows (using Reynolds-averaged Navier Stokes turbulence models), structural mechanics (thermal–structural interactions and fuel swelling), and oxide layer build-up. This report presents the best-estimate thermal hydraulics results for the low- and high-density optimized silicide LEU core designs at 95 MW steady-state nominal operation.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Improved high-temperature silicide coatings

Special technique for applying silicide coatings to refractory metal alloys improves their high-temperature protective capability. Refractory metal powders mixed with a baked-out organic binder and sintered in a vacuum produces a porous alloy layer on the surface. Exposing the layer to hot silicon converts it to a silicide.

Klopp, W. D.↗

Development of fused slurry silicide coatings for tantalum reentry heat shields

A fused slurry silicide coating was developed to provide atmospheric reentry protection for the 90Ta-lOW alloy. Overlaying the silicide with a highly refractory glass greatly improved total lifetime and reliability of the coating system. Low pressure, slow cycle lifetimes in excess of 100 cycles were consistently recorded for 1700 K - 13 and 1300 N/sq m test conditions. A minimum of 25 cycles was obtained for 1810 K - 1300 N/sq m conditions. About 50 simulated reentry cycles (variable temperature, pressure, and stress) were endured by coated 1-inch miniature heat shield panels when exposed to a maximum of 1700 K and either internal or external pressure conditions.

Warnock, R. V.↗