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At least 235 records · Page 13

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DOE OSTI2023

Controlled Growth of Single‐Crystal Graphene Wafers on Twin‐Boundary‐Free Cu(111) Substrates

Single-crystal graphene (SCG) wafers are needed to enable mass-electronics and optoelectronics owing to their excellent properties and compatibility with silicon-based technology. Controlled synthesis of high-quality SCG wafers can be done exploiting single-crystal Cu(111) substrates as epitaxial growth substrates recently. However, current Cu(111) films prepared by magnetron sputtering on single-crystal sapphire wafers still suffer from in-plane twin boundaries, which degrade the SCG chemical vapor deposition. Here, in this study, it is shown how to eliminate twin boundaries on Cu and achieve 4 in. Cu(111) wafers with ≈95% crystallinity. The introduction of a temperature gradient on Cu films with designed texture during annealing drives abnormal grain growth across the whole Cu wafer. In-plane twin boundaries are eliminated via migration of out-of-plane grain boundaries. SCG wafers grown on the resulting single-crystal Cu(111) substrates exhibit improved crystallinity with >97% aligned graphene domains. As-synthesized SCG wafers exhibit an average carrier mobility up to 7284 cm 2 V −1 s −1 at room temperature from 103 devices and a uniform sheet resistance with only 5% deviation in 4 in. region.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Mechanistic Studies on the Insertion of Carbonyl Substrates into Cu‐H: Different Rate‐Limiting Steps as a Function of Electrophilicity

Abstract We report mechanistic studies on the insertion reactions of [(NHC)Cu(μ‐H)] 2 complexes with carbonyl substrates by UV‐vis and 1 H NMR spectroscopic kinetic studies, H/D isotopic labelling, and X‐ray crystallography. The results of these comprehensive studies show that the insertion of Cu‐H with an aldehyde, ketone, activated ester/amide, and unactivated amide consist of two different rate limiting steps: the formation of Cu‐H monomer from Cu‐H dimer for more electrophilic substrates, and hydride transfer from a transient Cu‐H monomer for less electrophilic substrates. We also report spectroscopic and crystallographic characterization of rare Cu‐hemiacetalate and Cu‐hemiaminalate moieties from the insertion of an ester or amide into the Cu−H bond.

Tran, Ba L.↗

DOE OSTI2025

Is a Malleable Active Site Loop the Key to High Substrate Promiscuity? Hybrid, Biocatalytic Route to Structurally Diverse Taxoid Side Chains with Remarkable Dual Stereocontrol

Abstract These studies reveal the first structure ofClostridium acetobutylicumalcohol dehydrogenase (CaADH), a protein exhibiting remarkable substrate promiscuity and stereochemical fidelity. The CaADH enzyme is utilized here for synthesizing 20 potential aryl isoserine side chains for the Taxotere family of tubulin‐binding chemotherapeutics. The approach involves dynamic reductive kinetic resolution (DYRKR) upon the corresponding α‐chloro‐β‐keto esters, showing high D‐synstereoselectivity, including those leading to the clinically relevant milataxel (Ar = 2‐furyl) and simotaxel (Ar = 2‐thienyl) side chains. Furthermore, various cross‐coupling chemistries performed on thep‐bromophenyl isoserine side chain significantly enhance the structural diversity of the taxoid side chain library obtained (16 additional taxoid side chains). The CaADH structure is notable: (i) the nicotinamide cofactor is bound in ananti‐conformation, with the amide carbonyl occupying the ketone binding pocket, and (ii) a flexible loop near the active site likely contributes to the remarkable substrate promiscuity observed in CaADH. We present our perspective on the dynamic nature of the CaADH active site through molecular dynamics simulation, proposing a halogen bonding model as a potential mechanism for the remarkable selectivity for an (S)‐configured C─Cl bond, in addition to the D‐facial selectivity, demonstrated across 20 diverse substrates by this remarkable short‐chain dehydrogenase enzyme.

Chemistry↗

DOE OSTI2026

Biocatalytic Carboxylic Acid Reduction and Transamination in Cell‐Free Lysates at High Substrate Loading

Chemoselective reduction of stable carboxylic acids to reactive aldehydes is of interest across many industries. While carboxylic acid reductases (CARs) are promising biocatalysts for this chemistry, poor chemoselectivity and low yield are commonly obtained when using less expensive crude lysate preparations and prerequisite ATP and NADPH regeneration systems. Here, in this work, we developed a highly chemoselective multienzyme cascade featuring a CAR and an ω-transaminase (TA) in crude lysate format, with conversion of the dicarboxylic acid terephthalic acid (TPA) into the diamine para -xylylenediamine (pXDA) as the model chemistry. We improved chemoselectivity for pXDA using engineered aldehyde-stabilizing Escherichia coli strains, though desired product yields remained modest. We next found that CAR activity was limited at high substrate loadings and overcame this bottleneck by modulating the ratio of polyphosphate (polyP 6 ) to Mg 2+ , enabling volumetric scaling and increased substrate loading up to 50 mM TPA. We then showcased the portability of this platform across substrates, resulting in the synthesis of four other high-value amines from carboxylate precursors. The combination of high carboxyl group turnover, up to 93.5 mM under the tested conditions, and the simplicity of crude enzyme preparation is a promising platform for sustainable functional group interconversion.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2021

Substrate, temperature, and geographical patterns among nearly 2000 natural yeast isolates

Yeasts have broad importance as industrially and clinically relevant microbes and as powerful models for fundamental research, but we are only beginning to understand the roles yeasts play in natural ecosystems. Yeast ecology is often more difficult to study compared to other, more abundant microbes, but growing collections of natural yeast isolates are beginning to shed light on fundamental ecological questions. In this work, we used environmental sampling and isolation to assemble a dataset of 1962 isolates collected from throughout the contiguous United States of America (USA) and Alaska, which were then used to uncover geographic patterns, along with substrate and temperature associations among yeast taxa. We found some taxa, including the common yeasts Torulaspora delbrueckii and Saccharomyces paradoxus, to be repeatedly isolated from multiple sampled regions of the USA, and we classify these as broadly distributed cosmopolitan yeasts. A number of yeast taxon-substrate associations were identified, some of which were novel and some of which support previously reported associations. Further, we found a strong effect of isolation temperature on the phyla of yeasts recovered, as well as for many species. We speculate that substrate and isolation temperature associations reflect the ecological diversity of and niche partitioning by yeast taxa.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Measurement of High Density Electrons Above a Helium Film on an Amorphous Metal Substrate

Here we have measured two-dimensional electron systems bound to a thin helium film supported by a metallic substrate. We report on our measurement of electron density obtained via a Kelvin probe technique. The underlying metallic substrate is an amorphous metallic alloy (TaWSi), which can support large uniform densities due to its low surface roughness and homogeneous work function. We find that this substrate is able to support high enough densities that the electrons are expected to be Fermi-degenerate.

42 ENGINEERING↗

DOE OSTI2020

Controlling substrate temperature with infrared heating to improve mechanical properties of large-scale printed parts

Additively manufactured parts made with polymer extrusion techniques can be 50-75% weaker in the z-direction (across layers) than in the x- and y-directions. This has been attributed to poor mobility of polymer chains and a low degree of entanglement across a cold deposition interface. This is particularly a challenge when printing large-scale parts, such as with the Big Area Additive Manufacturing (BAAM) system, because layer times can exceed several minutes. The current work presents a method for controlling the temperature of the substrate material on the BAAM just prior to deposition using infrared heating lamps. Additionally, long layer times were simulated by actively cooling the material following deposition of each layer. The effect of substrate temperature on the z-direction mechanical properties of 20% carbon fiber reinforced acrylonitrile butadiene styrene (ABS) was measured for an initial temperature ranging from 50 °C to 150 °C and a preheated temperature ranging from 150 °C to 220 °C. Infrared preheating proved to be very effective when applied to substrates that had cooled considerably, almost doubling the tensile strength and increasing the fracture toughness by a factor of 7x.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Effects of substrate bias and tilt on magnetron sputtered boron carbide films

Maintaining high density and good mechanical properties at oblique angles for magnetron sputtered amorphous boron carbide films remains a challenge. In this study, we investigate the effect of the substrate bias on density, residual stress, mechanical properties, and morphology of boron carbide films deposited via direct current magnetron sputtering with a full-face erosion magnetron source in a mixed Ar-Ne plasma. Results show that films deposited at oblique substrate tilt angles on substrates biased at -50 V possess significantly lower oxygen content, superior mechanical properties, and higher density compared to their electrically grounded counterparts. In conclusion, these enhancements observed at oblique angles, while promising, come at the cost of larger residual compressive stress and higher Ne incorporation in films.

Materials science↗

DOE OSTI2020

CO as a substrate and inhibitor of H + reduction for the Mo-, V-, and Fe-nitrogenase isozymes

Three known nitrogenase isozymes, Mo-, V-, and Fe-, catalyze biological reduction of dinitrogen (N 2 ) to ammonia (NH 3 ). All three utilize the same reductive elimination mechanism: an intermediate with two metal-bound hydrides reductively-eliminates hydrogen gas (H 2 ) in a reaction coupled to binding and activation of N 2 . Nonetheless, the three isozymes show dramatically different relative rates of H 2 formation and N 2 reduction, revealing important differences in reactivity with substrates. Carbon monoxide (CO) has been characterized as both an inhibitor and substrate for Mo- and V-nitrogenases, but not for the Fe-nitrogenase. In this work, we present a comparative study of the reactivity of the three isozymes with CO, examining CO both as a substrate and as an inhibitor of proton (H + ) reduction under steady-state conditions. For Mo-nitrogenase, there is neither detectable reduction of CO nor inhibition of H + reduction. Fe- and V-nitrogenase show CO reduction and inhibition of H + reduction that depends on the CO partial pressure. For V-nitrogenase, ethylene (C 2 H 4 ) is the major reduction product with a maximum specific activity of ~7.5 nmol C 2 H 4 /nmol VFe protein/min at 1 atm CO. The major product of CO reduction for Fe-nitrogenase is methane (CH 4 ) with a maximum specific activity of ~4.8 nmol CH 4 /nmol FeFe protein/min at 0.05 atm CO. The rate of CH 4 production by Fe-nitrogenase progressively increases to a maximum at 0.05 atm CO and then declines to ~10% with increasing CO partial pressure up to 1 atm. CO does not inhibit proton reduction in Mo-nitrogenase but shows 16% inhibition for V-nitrogenase and 35% for Fe-nitrogenase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Spin canting of Ni/CoO/Fe films grown on curved MgO(0 0 1) substrate

Using element-resolved x-ray magnetic circular dichroism (XMCD) and x-ray magnetic linear dichroism (XMLD) measurements, we determined the spin orientations of Ni, CoO and Fe films in Ni/CoO/Fe films grown on a curved MgO(0 0 1) substrate. We find that the vicinal surface of MgO(0 0 1) substrate results in a spin canting towards out-of-plane direction in the Ni and CoO films as a result of the interfacial coupling. The Ni spin canting angle increases monotonically with the vicinal angle in the studied range of 0–17° and the CoO spin canting angle increases more rapidly towards saturation only at a few degrees of the vicinal angle. The uniaxial magnetic anisotropy induced in the Ni layer by the Ni/CoO interfacial coupling is quantitatively determined and is shown to increase monotonically with the vicinal angle. Our result provides a new pathway for tailoring the spin orientation by modifying the substrate surface symmetry in combining with the ferromagnetic/antiferromagnetic interfacial interaction in thin-film based spintronic devices.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Decoupling the effects of substrate hardness and roughness upon particle adhesion in cold spray

There are two stages of particle adhesion relevant to cold spray: adhesion of the first layer to the substrate, followed by inter-particle adhesion during subsequent deposition. In this work we study the second of these, in which particles strike a previously-deposited layer that is roughened and hardened by prior particle impacts. Specifically, we decouple the effects of surface roughness and hardness on particle adhesion for copper-on-copper impacts. We measure changes to the critical velocity, V cr , in single particle impacts produced by the Laser Induced Particle Impact Test on several surfaces including a cold sprayed surface and a polished version of that surface. We find that increases in both substrate roughness and hardness suppress particle adhesion to higher velocities, indeed in rather equal proportion by ∼10–15% each. This suggests that there is a higher V cr associated with coating build-up (particle-particle bonding) that is overall ∼30% higher than V cr for particle-substrate adhesion.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Assessing the impact of substrate-level enzyme regulations limiting ethanol titer in Clostridium thermocellum using a core kinetic model

Clostridium thermocellum is a promising candidate for consolidated bioprocessing because it can directly ferment cellulose to ethanol. Despite significant efforts, achieved yields and titers fall below industrially relevant targets. This implies that there still exist unknown enzymatic, regulatory, and/or possibly thermodynamic bottlenecks that can throttle back metabolic flow. By (i) elucidating internal metabolic fluxes in wild-type C. thermocellum grown on cellobiose via 13 C-metabolic flux analysis ( 13 C-MFA), (ii) parameterizing a core kinetic model, and (iii) subsequently deploying an ensemble-docking workflow for discovering substrate-level regulations, this paper aims to reveal some of these factors and expand our knowledgebase governing C. thermocellum metabolism. Generated 13 C labeling data were used with 13 C-MFA to generate a wild-type flux distribution for the metabolic network. Notably, flux elucidation through MFA alluded to serine generation via the mercaptopyruvate pathway. Using the elucidated flux distributions in conjunction with batch fermentation process yield data for various mutant strains, we constructed a kinetic model of C. thermocellum core metabolism (i.e. k-ctherm138). Subsequently, we used the parameterized kinetic model to explore the effect of removing substrate-level regulations on ethanol yield and titer. Upon exploring all possible simultaneous (up to four) regulation removals we identified combinations that lead to many-fold model predicted improvement in ethanol titer. In addition, by coupling a systematic method for identifying putative competitive inhibitory mechanisms using K-FIT kinetic parameterization with the ensemble-docking workflow, we flagged 67 putative substrate-level inhibition mechanisms across central carbon metabolism supported by both kinetic formalism and docking analysis.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Design of Planarizing Growth Conditions on Unpolished and Faceted (100)-Oriented GaAs Substrates Using Hydride Vapor Phase Epitaxy

Here we performed a design of experiments (DoE) analysis to determine the effect of various growth parameters on in situ planarizing overgrowth of rough substrates using hydride vapor phase epitaxy (HVPE). We used two types of rough (100)-oriented GaAs substrates to compare the effect of the initial morphology on the epitaxial growth behavior: an irregular, as-cut surface resultant from cutting the wafer from a GaAs boule and a regularly faceted surface produced by controlled spalling. The DoE analysis identified trends in the overgrowth behavior with changing growth conditions, and we used these trends to design favorable planarization growth conditions for each surface type. These favorable conditions enabled full planarization of a spalled surface with >2.5 um facet height within 10.8 min of growth. The root mean squared (RMS) surface roughness of the resulting (100) surface was 24.5 nm over a 286 um x 215 um area. Our results show that planarization growth by HVPE is a promising technique to enable device growth directly on rough substrates, and the trends revealed through DoE analysis indicate a path toward further optimization of planarization growth conditions for as-cut and spalled surfaces.

14 SOLAR ENERGY↗

DOE OSTI2026

Substrate-Mediated Evaporation and Stochastic Evolution of Supported Au Nanoparticles

Here, we use in situ transmission electron microscopy with automated tracking to study supported gold nanoparticles (NPs) during high-temperature vacuum annealing. The average mass loss per NP is governed by a flat, nearly size-independent substrate-mediated evaporation profile. On top of this mean shrinkage, individual NPs show significant fluctuations in apparent growth or shrinkage, and NP volume follows a random-walk-like trajectory. To rationalize both the ensemble-mean behavior and the particle-resolved variability, we develop a self-consistent theory that couples substrate-mediated evaporation to collective 2D Ostwald-type mass exchange through a shared adatom field, described in terms of a renormalized screening length and background concentration. In the experimentally relevant regime, the theory predicts an approximately size-independent mean shrinkage rate and clarifies how net mass loss suppresses classical coarsening. Superimposed on this deterministic drift, we quantify stochastic volume trajectories and capture their fluctuation spectrum with a minimal Langevin description consistent with intermittent adatom attachment and detachment events. In addition, we characterize the lateral diffusive motion of NPs, which is responsible for their coalescence. Altogether, our results highlight that stochasticity is intrinsic at the nanoscale and that predicting the evolution of supported NPs at early and intermediate times requires a unified framework combining substrate-mediated evaporation, collective mass exchange, and stochastic fluctuations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2025

Unraveling Enhanced Superconductivity in Single-Layer FeSe through Substrate Surface Terminations

Single-layer FeSe on SrTiO 3 (001) substrates shows a superconducting transition temperature much higher than that of bulk FeSe, which has been attributed to factors such as electron doping, interfacial electron–phonon coupling, and electron correlations. To pinpoint the primary driver, we grew single-layer FeSe films on SrTiO 3 (001) substrates with coexisting TiO 2 and SrO surface terminations. Scanning tunneling spectroscopy revealed a larger superconducting gap (17.0 meV) on the TiO 2 -termination than on the SrO-termination (10.5 meV). Tunneling spectroscopy also showed a larger work function on the SrO surface, resulting in reduced charge transfer to FeSe, as confirmed by angle-resolved photoemission spectroscopy. Scanning transmission electron microscopy further revealed distinctive interfacial atomic-scale structures, with the Se–Fe–Se tetrahedral angle changing from 109.5° on the SrO-termination to 104.9° on the TiO 2 -termination. Compared to dynamical mean field theory calculations, our results indicate that enhanced superconductivity in single-layer FeSe/TiO 2 arises from optimal electron correlations, in addition to sufficient charge transfer from the substrate.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2021

Transfer-Free Synthesis of Atomically Precise Graphene Nanoribbons on Insulating Substrates

The rational bottom-up synthesis of graphene nanoribbons (GNRs) provides atomically precise control of widths and edges that give rise to a wide range of electronic properties promising for electronic devices such as field-effect transistors (FETs). Since the bottom-up synthesis commonly takes place on catalytic metallic surfaces, the integration of GNRs into such devices requires their transfer onto insulating substrates, which remains one of the bottlenecks in the development of GNR-based electronics. Herein, we report on a method for the transfer-free placement of GNRs on insulators. This involves growing GNRs on a gold film deposited onto an insulating layer followed by gentle wet etching of the gold, which leaves the nanoribbons to settle in place on the underlying insulating substrate. Scanning tunneling microscopy and Raman spectroscopy confirm that atomically precise GNRs of high density uniformly grow on the gold films deposited onto SiO 2 /Si substrates and remain structurally intact after the etching process. We have also demonstrated transfer-free fabrication of ultrashort channel GNR FETs using this process. A very important aspect of the present work is that the method can scale up well to 12 in. wafers, which is extremely difficult for previous techniques. Our work here thus represents an important step toward large-scale integration of GNRs into electronic devices.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Substrate-Directed Underlayer Growth of Bilayer MoS 2 Revealed by Mo Isotope Labeling

Direct control over the vertical formation sequence and stacking registry in van der Waals (vdW) bilayers is essential for device performance and moiré engineering yet difficult to resolve unambiguously with conventional probes. Here, we use Mo isotope labeling in a two-step chemical vapor deposition process to synthesize bilayer MoS 2 and trace its vertical formation on common substrates. By combining site-selective laser thinning, Raman spectroscopy, time-of-flight secondary ion mass spectrometry, and atomic-resolution scanning transimission electron microscopy (STEM), we find a clear substrate dependence: on SiO 2 /Si, the second layer nucleates and grows beneath the first (underlayer), whereas on sapphire, it forms on top (overlayer). Density functional theory indicates that a larger equilibrium interfacial separation and weaker MoS 2 –substrate interactions on amorphous SiO 2 permit confined interfacial diffusion and underlayer nucleation, whereas stronger interactions and smaller separations on sapphire favor overlayer growth. On SiO 2 , confined epitaxy templates commensurate 2H, 3R, and mixed bilayers, as confirmed by second harmonic generation spectroscopy and STEM. During underlayer coalescence, embedded mirror-twin grain boundaries stitch atomically sharp 2H|3R junctions via alternating 4|8 ring motifs. Molecular-dynamics simulations reveal that these alternating 4|8 motifs accommodate interlayer vdW coupling and locally modulate the stacking registry. These results provide mechanistic insight into confined epitaxial growth and establish isotope labeling as a powerful probe of two-dimensional materials synthesis.

MoS2↗

DOE OSTI2026

Production and Evaluation of Fluorophore-Doped Polymer Substrates to Screen for Plastic-Degrading Enzymes

Fast and sensitive analytical methods are the key to efficient screening of plastic-degrading enzymes. Here, we present a streamlined and affordable approach to assess the enzymatic deconstruction of insoluble synthetic polymers by blending them with a fluorescent dye, rhodamine 6G, and we evaluate this screening method using poly(ethylene terephthalate) (PET) as a model material. Our results indicate that enzymatic depolymerization of the rhodamine-doped PET can be observed in a high-throughput fashion by following release of the fluorophore. The fluorescence data obtained during the hydrolysis of rhodamine-doped PET by 14 PET hydrolases, produced with a robotic platform, correlated with the quantitative chromatographic analysis of PET degradation products. Remarkably, the use of the rhodamine-loaded PET substrate resulted in negligibly low background signals even when detecting PETase activity in crude cell lysates, suggesting suitability for screening of a wide variety of samples. Encouraged by these results, we next produced a selection of polyethylene- and nylon-based materials loaded with rhodamine 6G. While rapid leaching of fluorophore observed with nylon substrates limits the utility of the method for detecting nylonase activity, the rhodamine-loaded polyethylene showed promising performance in passive diffusion tests, indicating that this latter substrate may be used to screen for polyolefin-degrading enzymes.

09 BIOMASS FUELS↗