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Coupled Roles of Surface Chemistry and Hydrogen-Assisted Cycling in Ruthenium Atomic Layer Deposition on Silicon Oxides

Ruthenium (Ru) is a promising interconnect material for advanced semiconductor technologies due to its favorable scaling characteristics, including a short electron mean free path and strong electromigration resistance. In semiconductor integration, silicon oxide-based dielectrics serve as dominant insulating materials and constitute ubiquitous interfaces for metallization; however, their formation-dependent surface chemistry and its impact on Ru growth remain insufficiently explored. Here, we investigate Ru ALD on native oxide SiO x (N-SiO x ) and thermally grown SiO 2 (T-SiO 2 ) as model substrates using bis(ethylcyclopentadienyl)ruthenium(II) [Ru(EtCp) 2 ] under two distinct reactant-sequence environments: AB-type (Ru(EtCp) 2 /O 2 ) and hydrogenassisted ABC-type (Ru(EtCp) 2 /O 2 /H 2 ). Under the AB-type process, both N-SiO x and T-SiO 2 exhibit pronounced nucleation delay. N-SiO x shows earlier nucleation and higher nucleation density than T-SiO 2 , plausibly attributed to differences in surface hydroxyl populations. Similar temperature-dependent phase evolution is observed on both substrates, with mixed Ru and RuO 2 phases at 250 °C and predominantly metallic Ru at 300 °C accompanied by increased morphological roughening. In contrast, incorporating an H 2 subpulse (ABC-type) mitigates nucleation delay, particularly on hydroxyl-deficient T-SiO 2 , thereby reducing the substratedependent disparity observed under AB cycling. Moreover, RuO 2 formation is suppressed even at 250 °C on both substrates, shifting growth toward more metallic Ru with reduced resistivity (∼20 μΩ·cm at ∼ 20 nm on N-SiO x ). These trends suggest that H 2 influences the surface reaction pathway, contributing to enhanced metallic stabilization and altered early stage growth kinetics. Overall, this work clarifies the coupled roles of substrate chemistry and reactant-sequence design in governing Ru nucleation and early stage film evolution, providing insight relevant to next-generation interconnect integration and future area-selective deposition strategies.

36 MATERIALS SCIENCE↗

Deciphering the Mechanism of Base-Triggered Conversion of Ammonia to Molecular Nitrogen and Methylamine to Cyanide

Here we report an in-depth investigation into the ammonia oxidation mechanism by the catalyst [Ru III (tpy)(dmabpy)NH 3 ] 3 + ([Ru(NH 3 )] 3 + ). Stoichiometric reactions of [Ru(NH 3 )] 3 + were carried out with exogenous noncoordinating bases to trigger a proposed redox disproportionation reaction, which was followed using variable-temperature NMR spectroscopy. An intermediate species was identified as a dinitrogen-bridged complex using 15 N NMR and Raman spectroscopy on isotopically labeled complexes. This intermediate is proposed to derive from coupling of nitridyl species formed upon sequential redox disproportion reactions. Acetonitrile displaces the dinitrogen bridge to yield free N 2 . DFT calculations support this lower-energy pathway versus that previously reported for ammonia oxidation by the parent [Ru III (tpy)(bpy)NH 3 ] 3 + complex. These experimental and computational results are consistent with the interpretation of redox disproportionation involving sequential hydrogen atom transfer reactions by an amide/aminyl intermediate, [Ru(NH 2 ) – ] + $\Leftrightarrow$ [Ru(NH 2 ) • ] + , formed upon deprotonation of the parent complex. Control experiments employing a large excess of ammonia as a base indicate this new proposed lower-energy pathway contributes to the oxidation of ammonia to dinitrogen in conditions relevant to electrocatalysis. In addition, analogous methylamine complexes, [Ru(NH 2 CH 3 )] 2 + /3 + , were prepared to further test the proposed mechanism. Treating [Ru(NH 2 CH 3 )] 3 + with a base cleanly yields two products [Ru(NH 2 CH 3 )] 2 + and [Ru(CN)] + in an ~3:1 ratio, fully consistent with the proposed cascade of hydrogen atom transfer reactions by an intermediate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Fundamental Studies of Bifunctional Catalysts for Tandem Reactions

During the past few years of our funding from DOE Basic Energy Sciences, we have focused on the catalytic conversion of biomass-derived 5-hydroxymethyl furfural (HMF) as a platform molecule for sustainable synthesis of value-added chemicals. The combination of the diene and aldehyde functionalities in HMF enables catalytic production of acetalized HMF derivatives with diol or epoxy reactants to allow reversible synthesis of norcantharimide derivatives upon Diels-Alder reaction with maleimides. Whereas the electron-withdrawing nature of aldehyde group inhibits the reactivity of diene group in HMF to undergo Diels-Alder reactions with dienophiles, by converting the aldehyde group in HMF to an electron-donating hydroxyl group, HMF can append maleimide-based chemicals through Diels-Alder coupling. Acetalization of HMF not only produces an electron-rich diene for Diels-Alder reaction, but it also alters the reversibility of acetal formation and thereby allows for the controlled release of chemicals by hydrolysis. Therefore, we synthesized various norcantharimide derivatives from biomass-derived HMF by acetalization over an acid catalyst, Amberlyst-15, followed by Diels-Alder reaction with maleimide. The norcantharimides release the starting materials by retro Diels-Alder reaction that is triggered by acetal hydrolysis under acidic (≤pH 3) conditions. In subsequent work, we explored the synthesis and properties of functional polyurethanes and polyesters with tunable properties from biomass-derived (HMF)-Acetone-HMF (HAH) monomers. HAH can be selectively hydrogenated over Cu and Ru catalysts to produce partially-hydrogenated HAH (PHAH) and fully-hydrogenated HAH (FHAH). HAH contains functional groups, including hydroxyl, furan, enone, and ketone functionalities, that can be exploited to further tune the polymer properties. The π-electron conjugation between the enone and furan groups in HAH monomer stabilizes the furan group to prevent the uncontrolled degradation of furans during reactions, such as etherification. Therefore, HAH is a renewable monomer that can be used to synthesize polymers, having high molecular weight, symmetric functionalities, an inexpensive production price, and being derived from renewable resources without competition with food resources. We demonstrated the synthesis of functional polyurethanes and a renewable polyester from HAH-derived monomers, and 4,4’-methylenebis(phenyl isocyanate) (MDI). We showed that it is essential to be able to selective hydrogenate C=C double bonds in HAH to be able to achieve effective Diels Alder reactions of the furan ring. Therefore, we studied the hydrogenation at temperatures from 313 – 393 K of HAH over Pd, Ru, and Cu based catalysts. HAH was selectively hydrogenated to produce partially-hydrogenated monomers (PHAH) over Cu and Ru catalysts and to fully-hydrogenated HAH monomers (FHAH) over the Ru catalyst. Pd based catalysts yielded a mixture of partially and fully hydrogenated monomers. Reaction kinetics models were employed to quantify the kinetic behavior for hydrogenation over Ru, Cu, and Pd catalysts. A 5-step pathway exhibited over Pd and Ru catalysts consists of both series and parallel reaction steps, where HAH is both converted to fully hydrogenated products sequentially via series reactions of partially hydrogenated intermediates, as well as converted directly in parallel reactions to form the fully hydrogenated products. In contrast, a 3-step pathway over the Cu catalyst consists only of the consecutive reaction steps, where the final product was formed via series reactions of intermediate products. Additionally, reaction over the Cu catalyst did not hydrogenate the furan rings of the HAH molecule and yielded a different final product than those hydrogenation over Pd and Ru catalysts. Using the results from our detailed reaction kinetics studies, we developed universal conditions for the maximum production of the various hydrogenated products for both batch and plug flow systems. In subsequent work, we employed reaction schemes to optimize the yields of products from selective hydrogenations of HAH in isopropanol solvent and in the presence of liquid water. Reaction schemes consisting of 7, 9, and 11 steps were examined to describe the rates of formation of the observed products and reaction intermediates for hydrogenation of HAH over Ru and Pd catalysts, and a 3-step scheme was studied over Cu catalysts. Rate constants and activation energies were calculated using these reaction schemes, and we then apply these reaction schemes to explore the effects of water addition on the hydrogenation pathways. The effects of water addition to isopropanol (IPA) solvents on the hydrogenation of HAH were markedly different over Pd, Ru, and Cu catalysts. Over the Pd catalyst, the addition of water to IPA increased hydrogenation rates and promoted hydrogenation of furan rings. The addition of water to IPA yielded significant carbon losses over the Ru catalyst, and slowed hydrogenation steps over Cu, while significantly inhibiting hydrogenation of the ketone group. This behavior opened routes toward increased production rates of PHAH=O (a partially hydrogenated form of HAH containing a C=O bond), a product in which the diene groups of the furan rings were not hydrogenated. Addition of water also allowed increased feed concentrations of HAH that were previously not possible in pure IPA solvents.

09 BIOMASS FUELS↗

Developing a Fundamental Knowledge Base for the Interaction of Ruthenium with Natural and Engineered Iron-Bearing Materials

The intent of this project is to build a fundamental knowledge base concerning the redox coupling between Ru and Fe in heterogeneous systems with predictive applications towards the fate, speciation, and transport of Ru in the environment and its capture using available technologies. RuNOCl 3 and Fe 3+ are redox active over a broad range of pH. Initial assessment of effect of redox coupling between Ru and Fe indicates that Fe(III) in ferrihydrite can oxidize Ru 2+ in RuNOCl3 to Ru(IV) during coprecipitation at ambient conditions and alkaline pH. Further, evidence suggests that Ru(IV) is incorporated in the structure of fh. Likewise, Fe 3+ (aq) also reduces Ru 2+ in RuNOCl 3 in the homogenous system at acidic pH although the kinetics of reaction appear to be slow. Rufh annealed to 500 0C transforms to Ru(III) doped hematite. AIMD informed EXAFS indicates that Ru substitutes for Fe(III) in regular octahedral sites of hematite but requires three distinct configurations involving edge-sharing protonated Fe vacancies and straight substitution with no local defects. Fe 2+ (aq) appears to oxidize at the surface of RuO 2 , but the amount is too low to reasonably expect detectable reduced Ru. Future experiments at higher pH are warranted to make Fe 2+ (aq) less stable (i.e., make more redox active). We also demonstrated that we can functionalize Si aerogels with Fe(II) and Fe(III) but likely need to go to higher T to make Feo nanoparticles.

36 MATERIALS SCIENCE↗

A Transmission Electron Microscopy Study of a Refractory Metal Grain from a Calcium-Aluminum-Rich Inclusion in the Leoville CV3 Chondrite

Introduction: Calcium-aluminum-rich inclusions (CAIs) are an important component of chondritic meteorites. They can contain materials that are thermodynamically predicted and isotopically age dated to be among the first-formed solids in our solar system [1-5]. Observed in some CAIs are micron to sub-micron sized inclusions rich in Fe, Ni, and high-Z elements such as Pt, Os, Ir and W, in the form of refractory metal nuggets (RMNs), fremdlinges, and ‘nugget like objects’ (NLOs) [1,6]. Refractory siderophile elements such as Os, Ir and Ru are thermodynamically predicted to condense at temperatures well in excess of the major CAI phases such as melilite, perovskite, spinel and hibonite [2,7-9]. These refractory metal inclusions in CAIs can therefore serve as probes into the thermodynamic landscape of the early solar protoplanetary disk. Here we report on a refractory grain identified in a CAI of the Leoville CV3 chondrite. This work is part of an ongoing effort to gain insight into the thermochemistry of the early solar system through systematic analyses of the structure and chemistry of various components in CAIs [10-13]. Sample and Analytical Techniques: A fluffy type A CAI (Fig. 1A) was identified in a section of the Leoville, CV3 chondrite (Center for Meteorite Studies, Arizona State University collection, #821_C_3) using a JOEL-JXA 8530F electron microprobe at Arizona State University. Backscattered electron (BSE) imaging and energy-dispersive X-ray spectroscopy (EDS) were used to identify refractory metal grains in the CAI using a Thermo Fisher (formerly FEI) Helios NanoLab 660 G3 focused-ion-beam scanning-electron microscope (FIBSEM) located at the Kuiper Materials Imaging and Characterization Facility (KMICF) at the Lunar and Planetary Laboratory, University of Arizona. The FIB is equipped with an EDAX EDS system. We selected one of the larger (micron-sized) refractory metal grains, designated as ‘Spud’ (Fig. 1B) for further analysis. ‘Spud’ was extracted and thinned to electron transparency (<100 nm) using the FIB-SEM located in KMICF, following methods described by [14- 15]. The FIB section was analyzed using a 200 keV Hitachi HF5000 scanning transmission electron microscope (S/TEM) located at KMICF. The HF5000 is equipped with cold-field emission gun, 3rd-order spherical aberration corrector for STEM imaging, and an Oxford Instruments X-Max N 100 TLE energydispersive spectroscopy (EDS) system with dual 100 mm2 windowless silicon-drift detectors (Ω = 2.0 sr). Selected-area electron-diffraction (SAED) patterns were acquired to aid in determination of crystallinity and phase. Results: The mineralogy, texture, and morphology of the CAI are consistent with that of a fluffy type A (FTA) CAI [16]. BSE imaging at high magnifications revealed grains with high contrast, indicative of compositions rich in elements of higher atomic number relative to surrounding material. These high-Z grains have sizes that range from ∼250 nm to 4 µm. EDS analyses confirm that the bright grains are metal-rich inclusions. A minor fraction of the grains are composed of only Fe and Ni, but the majority (∼60%) of the identified inclusions also contained various refractory siderophiles including Os, Ru, Zr, Ir and Mo. EDS analysis on the FIB-SEM of Spud shows that it contains Fe, Ni, Mo and Ru. High-angle annular dark-field (HAAFD) imaging and EDS mapping in the TEM (Fig. 2) show that Spud occurs in melilite (Ca1.9Al1.99Si1.06O7). Spud contains a subhedral to anhedral morphology and is compositionally heterogenous (polyphasic, Fig. 2). Local spatial correlation occurs among Fe, Ni, and Pt, and also among Os, Ru, and Mo. SAED patterns show that the Fe-Ni-Pt, Fe-Os-Mo-Ru and Fe-Pt regions are crystalline. Discussion: CAIs can contain various types of inclusions rich in Fe, Ni and refractory siderophiles such as Os, Ru, W and Pt [1]. RMNs are micron-sized, single phase alloy grains and can contain Os, Ir, Ru and Rh [1,7,17]. NLOs are also micron-sized inclusions, but contain two phases, a refractory metal, and an oxide [6]. Fremdlinge are the largest of such inclusions (tens of microns in size) and are complex aggregates of Fe-Ni alloy, silicates, oxides, and sulfides [1,17]. While the size of Spud matches previous descriptions of RMNs and NLOs, Spud is neither a single-phase alloy like RMNs, nor does it contain one metal phase and one oxide like NLOs. Spud does not match the above described categories of refractory metal inclusions. The presence of refractory siderophiles such as Mo, Os, Ru, and Pt suggests a high-temperature origin. Thermodynamic modelling by [7] indicates condensation temperatures of 1917 K, 1693 K, 1613 K and 1415 K for Os, Mo, Ru and Pt respectively. These models also show that following the initial condensation of a refractory metal, alloying of solutes such as Fe, Ni and W, occurs in levels proportional to their partial pressures in the surrounding gas. Such alloying occurs at temperatures above the condensation temperatures of common CAI phases such as melilite (1529 K), perovskite (1441 K), spinel (197 K) and forsterite (1354 K) [2]. The polyphasic nature of Spud could be the result of such high-temperature alloying, possibly shortly after the condensation of Mo and Ru at 1693 K and 1613 K respectively. That Spud occurs as an inclusion is consistent with it having formed prior to and at temperature above that of its host melilite in this FTA CAI, which is qualitatively consistent with such prior thermodynamic modeling. Further, the polyphasic nature of Spud is similar to refractory grains from a FTA CAI in the Northwest Africa (NWA) 8323, CV3 chondrite [11-13]. These data suggest that such refractory metal grains could have been widespread in the inner and early solar protoplanetary disk and represent some of the earliest formed solids to have condensed. Acknowledgments: Research and instrumentation supported by NASA grants #NNX12AL47G, #NNX15AJ22G and #80NSSC19K0509, and NSF grants #1531243 and #0619599. Fig 2. STEM data on ‘Spud’. HAADF Image (Top) False-color EDS Maps (Bottom) References: [1] MacPherson G. J. (2014) T. of Geochem. Vol I: Met. And Cosmochem. Processes, 139-179. [2] Lodders K. (2003) ApJ, 591, 1220-1247. [3] Ebel D. S. (2006) Met. & the Early S. Sys. II., 253- 277. [4] Amelin Y. (2002) Science, 297, 1678-1683. [5] Connelly J.N. et.al. (2012) Science, 338, 651-655. [6] Schwander D. et al. (2015) GCA, 18, 70-87. [7] Palme H. and Wlotzka F. (1976) EPSL, 33, 45-60. [8] Berg T. et al. (2009) ApJ, 702, 172-176. [9] Liffman K. et al. (2021) Icarus, 221, 89-105. [10] Zega T.J. et al. (2021) PSJ, 2, 115. [11] Ramprasad T. et al. (2020) LPSC LI, Abstract #2472. [12] Ramprasad T. et al. (2021) Microscopy & Microanalysis, S1, 2792-2794. [13] Ramprasad T. et al. (2021) 84th MetSoc, Abstract #6123. [14] Zega T.J. et al. (2007) MAPS, 42, 1373-1386. [15] Ramprasad T. et al. (2022) MAPS, in revision. [16] Grossman L. (1975), GCA, 39, 433-454. [17] El Goresy A. et al. (1978) LPSC IX, Abstract#1100

T. Ramprasad↗

Materials Data on TiPRu by Materials Project

TiRuP crystallizes in the hexagonal P-62m space group. The structure is three-dimensional. Ti is bonded in a 11-coordinate geometry to six equivalent Ru and five P atoms. There are two shorter (2.78 Å) and four longer (2.92 Å) Ti–Ru bond lengths. There are one shorter (2.61 Å) and four longer (2.63 Å) Ti–P bond lengths. Ru is bonded in a 12-coordinate geometry to six equivalent Ti, two equivalent Ru, and four P atoms. Both Ru–Ru bond lengths are 2.72 Å. There are two shorter (2.39 Å) and two longer (2.42 Å) Ru–P bond lengths. There are two inequivalent P sites. In the first P site, P is bonded in a 9-coordinate geometry to three equivalent Ti and six equivalent Ru atoms. In the second P site, P is bonded in a 9-coordinate geometry to six equivalent Ti and three equivalent Ru atoms.

36 MATERIALS SCIENCE↗

Materials Data on HfPRu by Materials Project

HfRuP crystallizes in the hexagonal P-62m space group. The structure is three-dimensional. Hf is bonded in a 11-coordinate geometry to six equivalent Ru and five P atoms. There are two shorter (2.88 Å) and four longer (3.01 Å) Hf–Ru bond lengths. There are one shorter (2.68 Å) and four longer (2.71 Å) Hf–P bond lengths. Ru is bonded to six equivalent Hf, two equivalent Ru, and four P atoms to form a mixture of distorted corner, edge, and face-sharing RuHf6P4Ru2 cuboctahedra. Both Ru–Ru bond lengths are 2.75 Å. All Ru–P bond lengths are 2.47 Å. There are two inequivalent P sites. In the first P site, P is bonded in a 9-coordinate geometry to six equivalent Hf and three equivalent Ru atoms. In the second P site, P is bonded in a 9-coordinate geometry to three equivalent Hf and six equivalent Ru atoms.

36 MATERIALS SCIENCE↗

Materials Data on ScPRu by Materials Project

ScRuP crystallizes in the hexagonal P-62m space group. The structure is three-dimensional. Sc is bonded in a 11-coordinate geometry to six equivalent Ru and five P atoms. There are two shorter (2.91 Å) and four longer (2.97 Å) Sc–Ru bond lengths. There are four shorter (2.69 Å) and one longer (2.70 Å) Sc–P bond lengths. Ru is bonded in a 12-coordinate geometry to six equivalent Sc, two equivalent Ru, and four P atoms. Both Ru–Ru bond lengths are 2.78 Å. There are two shorter (2.43 Å) and two longer (2.53 Å) Ru–P bond lengths. There are two inequivalent P sites. In the first P site, P is bonded in a 9-coordinate geometry to six equivalent Sc and three equivalent Ru atoms. In the second P site, P is bonded in a 9-coordinate geometry to three equivalent Sc and six equivalent Ru atoms.

36 MATERIALS SCIENCE↗

Materials Data on Pu5Ru3 by Materials Project

Pu5Ru3 crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. there are two inequivalent Pu sites. In the first Pu site, Pu is bonded in a 6-coordinate geometry to six Ru atoms. There are a spread of Pu–Ru bond distances ranging from 2.91–3.25 Å. In the second Pu site, Pu is bonded to four equivalent Ru atoms to form distorted edge-sharing PuRu4 tetrahedra. All Pu–Ru bond lengths are 2.66 Å. There are two inequivalent Ru sites. In the first Ru site, Ru is bonded in a 10-coordinate geometry to ten Pu atoms. In the second Ru site, Ru is bonded in a 10-coordinate geometry to eight equivalent Pu atoms.

36 MATERIALS SCIENCE↗

Materials Data on Sm(Sn3Ru2)2 by Materials Project

Sm(Ru2Sn3)2 crystallizes in the tetragonal I-42m space group. The structure is three-dimensional. Sm is bonded in a 12-coordinate geometry to four equivalent Ru and twelve Sn atoms. All Sm–Ru bond lengths are 3.30 Å. There are a spread of Sm–Sn bond distances ranging from 3.39–3.77 Å. Ru is bonded in a 7-coordinate geometry to one Sm, two equivalent Ru, and six Sn atoms. Both Ru–Ru bond lengths are 2.85 Å. There are a spread of Ru–Sn bond distances ranging from 2.60–2.80 Å. There are two inequivalent Sn sites. In the first Sn site, Sn is bonded in a 6-coordinate geometry to two equivalent Sm and four equivalent Ru atoms. In the second Sn site, Sn is bonded in a 5-coordinate geometry to two equivalent Sm and four equivalent Ru atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ce5Ge2Ru by Materials Project

Ce5RuGe2 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are four inequivalent Ce sites. In the first Ce site, Ce is bonded in a 5-coordinate geometry to two equivalent Ru and three equivalent Ge atoms. There are one shorter (2.74 Å) and one longer (3.07 Å) Ce–Ru bond lengths. There are a spread of Ce–Ge bond distances ranging from 3.21–3.33 Å. In the second Ce site, Ce is bonded to one Ru and four equivalent Ge atoms to form distorted edge-sharing CeGe4Ru square pyramids. The Ce–Ru bond length is 3.11 Å. There are two shorter (3.05 Å) and two longer (3.07 Å) Ce–Ge bond lengths. In the third Ce site, Ce is bonded in a 5-coordinate geometry to one Ru and four equivalent Ge atoms. The Ce–Ru bond length is 2.70 Å. There are two shorter (3.12 Å) and two longer (3.16 Å) Ce–Ge bond lengths. In the fourth Ce site, Ce is bonded in a 5-coordinate geometry to one Ru and four equivalent Ge atoms. The Ce–Ru bond length is 2.82 Å. There are two shorter (3.10 Å) and two longer (3.13 Å) Ce–Ge bond lengths. Ru is bonded in a 7-coordinate geometry to seven Ce atoms. Ge is bonded in a 9-coordinate geometry to nine Ce atoms.

36 MATERIALS SCIENCE↗

Materials Data on Bi4RuBr2 by Materials Project

RuBi4Br2 crystallizes in the monoclinic C2/m space group. The structure is one-dimensional and consists of two RuBi4Br2 ribbons oriented in the (0, 1, 0) direction. Ru is bonded in a 8-coordinate geometry to one Ru and eight Bi atoms. The Ru–Ru bond length is 2.88 Å. There are a spread of Ru–Bi bond distances ranging from 2.79–2.94 Å. There are four inequivalent Bi sites. In the first Bi site, Bi is bonded in a 2-coordinate geometry to two equivalent Ru and two equivalent Bi atoms. Both Bi–Bi bond lengths are 3.04 Å. In the second Bi site, Bi is bonded in a 2-coordinate geometry to two equivalent Ru and two equivalent Bi atoms. In the third Bi site, Bi is bonded in a 4-coordinate geometry to two equivalent Ru and two Br atoms. There are one shorter (3.01 Å) and one longer (3.03 Å) Bi–Br bond lengths. In the fourth Bi site, Bi is bonded in a 4-coordinate geometry to two equivalent Ru and two Br atoms. There are one shorter (3.01 Å) and one longer (3.04 Å) Bi–Br bond lengths. There are two inequivalent Br sites. In the first Br site, Br is bonded in a 2-coordinate geometry to two Bi atoms. In the second Br site, Br is bonded in a 2-coordinate geometry to two Bi atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ba6Ru3(ClO6)2 by Materials Project

Ba6Ru3Cl2O12 crystallizes in the trigonal P-3m1 space group. The structure is three-dimensional. there are three inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded in a 7-coordinate geometry to three equivalent O2- and four equivalent Cl1- atoms. All Ba–O bond lengths are 2.57 Å. There are one shorter (3.22 Å) and three longer (3.53 Å) Ba–Cl bond lengths. In the second Ba2+ site, Ba2+ is bonded in a 10-coordinate geometry to nine O2- and one Cl1- atom. There are three shorter (2.69 Å) and six longer (2.99 Å) Ba–O bond lengths. The Ba–Cl bond length is 3.15 Å. In the third Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with six equivalent BaO12 cuboctahedra, corners with three equivalent RuO6 octahedra, faces with three equivalent BaO12 cuboctahedra, and faces with six RuO6 octahedra. The corner-sharing octahedral tilt angles are 12°. There are a spread of Ba–O bond distances ranging from 2.96–3.07 Å. There are two inequivalent Ru+4.67+ sites. In the first Ru+4.67+ site, Ru+4.67+ is bonded to six O2- atoms to form RuO6 octahedra that share corners with three equivalent BaO12 cuboctahedra, faces with three equivalent BaO12 cuboctahedra, and a faceface with one RuO6 octahedra. There are three shorter (1.91 Å) and three longer (2.10 Å) Ru–O bond lengths. In the second Ru+4.67+ site, Ru+4.67+ is bonded to six equivalent O2- atoms to form RuO6 octahedra that share faces with six equivalent BaO12 cuboctahedra and faces with two equivalent RuO6 octahedra. All Ru–O bond lengths are 2.02 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 5-coordinate geometry to four Ba2+ and one Ru+4.67+ atom. In the second O2- site, O2- is bonded in a 6-coordinate geometry to four Ba2+ and two Ru+4.67+ atoms. Cl1- is bonded to five Ba2+ atoms to form a mixture of distorted edge and corner-sharing ClBa5 trigonal bipyramids.

36 MATERIALS SCIENCE↗

Materials Data on Ba4Ho(RuO4)3 by Materials Project

Ba4Ho(RuO4)3 is (Cubic) Perovskite-derived structured and crystallizes in the trigonal R-3m space group. The structure is three-dimensional. there are two inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with nine BaO12 cuboctahedra, corners with three equivalent RuO6 octahedra, faces with seven BaO12 cuboctahedra, faces with three equivalent HoO6 octahedra, and faces with four equivalent RuO6 octahedra. The corner-sharing octahedral tilt angles are 13°. There are a spread of Ba–O bond distances ranging from 2.90–3.13 Å. In the second Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with nine BaO12 cuboctahedra, corners with three equivalent RuO6 octahedra, faces with seven BaO12 cuboctahedra, a faceface with one HoO6 octahedra, and faces with six RuO6 octahedra. The corner-sharing octahedral tilt angles are 13°. There are a spread of Ba–O bond distances ranging from 2.98–3.11 Å. Ho3+ is bonded to six equivalent O2- atoms to form HoO6 octahedra that share corners with six equivalent RuO6 octahedra and faces with eight BaO12 cuboctahedra. The corner-sharing octahedral tilt angles are 2°. All Ho–O bond lengths are 2.21 Å. There are two inequivalent Ru+4.33+ sites. In the first Ru+4.33+ site, Ru+4.33+ is bonded to six O2- atoms to form RuO6 octahedra that share corners with three equivalent BaO12 cuboctahedra, corners with three equivalent HoO6 octahedra, faces with seven BaO12 cuboctahedra, and a faceface with one RuO6 octahedra. The corner-sharing octahedral tilt angles are 2°. There are three shorter (1.95 Å) and three longer (2.06 Å) Ru–O bond lengths. In the second Ru+4.33+ site, Ru+4.33+ is bonded to six equivalent O2- atoms to form RuO6 octahedra that share corners with six equivalent BaO12 cuboctahedra, faces with six equivalent BaO12 cuboctahedra, and faces with two equivalent RuO6 octahedra. All Ru–O bond lengths are 2.03 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted linear geometry to four Ba2+, one Ho3+, and one Ru+4.33+ atom. In the second O2- site, O2- is bonded in a 6-coordinate geometry to four Ba2+ and two Ru+4.33+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ba4Tb(RuO4)3 by Materials Project

Ba4Tb(RuO4)3 is (Cubic) Perovskite-derived structured and crystallizes in the trigonal R-3m space group. The structure is three-dimensional. there are two inequivalent Ba2+ sites. In the first Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with nine BaO12 cuboctahedra, corners with three equivalent RuO6 octahedra, faces with seven BaO12 cuboctahedra, faces with three equivalent TbO6 octahedra, and faces with four equivalent RuO6 octahedra. The corner-sharing octahedral tilt angles are 13°. There are a spread of Ba–O bond distances ranging from 2.91–3.17 Å. In the second Ba2+ site, Ba2+ is bonded to twelve O2- atoms to form BaO12 cuboctahedra that share corners with nine BaO12 cuboctahedra, corners with three equivalent RuO6 octahedra, faces with seven BaO12 cuboctahedra, a faceface with one TbO6 octahedra, and faces with six RuO6 octahedra. The corner-sharing octahedral tilt angles are 13°. There are a spread of Ba–O bond distances ranging from 2.98–3.11 Å. Tb3+ is bonded to six equivalent O2- atoms to form TbO6 octahedra that share corners with six equivalent RuO6 octahedra and faces with eight BaO12 cuboctahedra. The corner-sharing octahedral tilt angles are 2°. All Tb–O bond lengths are 2.23 Å. There are two inequivalent Ru+4.33+ sites. In the first Ru+4.33+ site, Ru+4.33+ is bonded to six O2- atoms to form RuO6 octahedra that share corners with three equivalent BaO12 cuboctahedra, corners with three equivalent TbO6 octahedra, faces with seven BaO12 cuboctahedra, and a faceface with one RuO6 octahedra. The corner-sharing octahedral tilt angles are 2°. There are three shorter (1.95 Å) and three longer (2.06 Å) Ru–O bond lengths. In the second Ru+4.33+ site, Ru+4.33+ is bonded to six equivalent O2- atoms to form RuO6 octahedra that share corners with six equivalent BaO12 cuboctahedra, faces with six equivalent BaO12 cuboctahedra, and faces with two equivalent RuO6 octahedra. All Ru–O bond lengths are 2.03 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted linear geometry to four Ba2+, one Tb3+, and one Ru+4.33+ atom. In the second O2- site, O2- is bonded in a 6-coordinate geometry to four Ba2+ and two Ru+4.33+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Ce2(Al5Ru)3 by Materials Project

Ce2(RuAl5)3 crystallizes in the hexagonal P6_3/mcm space group. The structure is three-dimensional. there are two inequivalent Ce sites. In the first Ce site, Ce is bonded in a 8-coordinate geometry to four equivalent Ru and fourteen Al atoms. All Ce–Ru bond lengths are 3.44 Å. There are a spread of Ce–Al bond distances ranging from 3.14–3.37 Å. In the second Ce site, Ce is bonded in a 12-coordinate geometry to eighteen Al atoms. There are a spread of Ce–Al bond distances ranging from 3.26–3.65 Å. Ru is bonded in a 10-coordinate geometry to two equivalent Ce and ten Al atoms. There are a spread of Ru–Al bond distances ranging from 2.58–2.70 Å. There are five inequivalent Al sites. In the first Al site, Al is bonded in a 2-coordinate geometry to one Ce, two equivalent Ru, and one Al atom. The Al–Al bond length is 2.72 Å. In the second Al site, Al is bonded in a 2-coordinate geometry to two equivalent Ce, two equivalent Ru, and two equivalent Al atoms. Both Al–Al bond lengths are 2.82 Å. In the third Al site, Al is bonded in a 2-coordinate geometry to three Ce, two equivalent Ru, and four equivalent Al atoms. There are two shorter (2.76 Å) and two longer (2.87 Å) Al–Al bond lengths. In the fourth Al site, Al is bonded in a distorted linear geometry to two equivalent Ce and two equivalent Ru atoms. In the fifth Al site, Al is bonded in a 2-coordinate geometry to two Ce, two equivalent Ru, and eight Al atoms. The Al–Al bond length is 2.73 Å.

36 MATERIALS SCIENCE↗

Materials Data on Si2Ru by Materials Project

RuSi2 crystallizes in the orthorhombic Cmce space group. The structure is three-dimensional. there are two inequivalent Ru sites. In the first Ru site, Ru is bonded in a 8-coordinate geometry to eight Si atoms. There are a spread of Ru–Si bond distances ranging from 2.46–2.49 Å. In the second Ru site, Ru is bonded in a 8-coordinate geometry to eight Si atoms. There are a spread of Ru–Si bond distances ranging from 2.46–2.53 Å. There are two inequivalent Si sites. In the first Si site, Si is bonded in a 4-coordinate geometry to four Ru and five Si atoms. There are a spread of Si–Si bond distances ranging from 2.58–2.70 Å. In the second Si site, Si is bonded in a 4-coordinate geometry to four Ru and five Si atoms. There are one shorter (2.55 Å) and one longer (2.59 Å) Si–Si bond lengths.

36 MATERIALS SCIENCE↗

Materials Data on BaCaRu2 by Materials Project

BaCaRu2 is Zintl Phase-derived structured and crystallizes in the cubic F-43m space group. The structure is three-dimensional. Ba is bonded in a 4-coordinate geometry to four equivalent Ca and ten Ru atoms. All Ba–Ca bond lengths are 3.06 Å. There are four shorter (3.06 Å) and six longer (3.53 Å) Ba–Ru bond lengths. Ca is bonded in a 4-coordinate geometry to four equivalent Ba and ten Ru atoms. There are four shorter (3.06 Å) and six longer (3.53 Å) Ca–Ru bond lengths. There are two inequivalent Ru sites. In the first Ru site, Ru is bonded to six equivalent Ba and four equivalent Ca atoms to form distorted RuBa6Ca4 tetrahedra that share corners with six equivalent RuBa6Ca4 tetrahedra, edges with twelve equivalent RuBa4Ca6 tetrahedra, and faces with sixteen RuBa6Ca4 tetrahedra. In the second Ru site, Ru is bonded to four equivalent Ba and six equivalent Ca atoms to form distorted RuBa4Ca6 tetrahedra that share corners with six equivalent RuBa4Ca6 tetrahedra, edges with twelve equivalent RuBa6Ca4 tetrahedra, and faces with sixteen RuBa6Ca4 tetrahedra.

36 MATERIALS SCIENCE↗