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At least 487 records · Page 27

Damage Evolution of Double-Sided Copper Conductor on Multi-layer Flexible Substrate Under Bending

Abstract—Thin-film conductors continue to play an important role in flexible electronics, and thus, the performance and reliability of such conductors under mechanical loading such as stretch, bend, and twist need to be studied through experiments as well as simulations. This paper focuses on the damage evolution of the thin-film conductors under cyclic bending. Four types of double-sided copper conductors: straight trace without coverlay, straight trace with coverlay, notched trace without coverlay, and notched trace with coverlay on multi-layer substrates were studied in this work. The adaptive curvature flexure test method, which is suitable for thin-film bending, was employed in this work. Adaptive curvature flexure test is one where the flexible substrate with its conductor is positioned between two parallel plates, and the parallel plates are moved relative to each other such that the gap distance between the parallel plates changes in one of the configurations of the adaptive curvature flexure test. Different strain levels can be achieved easily in such an adaptive curvature flexure test by controlling the gap distance between the parallel plates. By subjecting flexible substrates with thin conductors to such bend tests, the fatigue life of the specimen was determined for different magnitudes of strain ranges. The results were then compared among the four types of conductors. Specimens were designed such that the conductors were placed on both sides of the substrate so that the one of the conductors would undergo tensile straining, while the other one would undergo compressive straining. It was shown that the fatigue life was highly dependent on the magnitude of strain range, and that the conductor on the compressive side failed sooner than that on the tensile side. The failed specimens were examined in a microscope at different number of cycles. Also, the resistance of the conductors, which is directly related to the reliability of thin-film conductors, was monitored in-situ during bending. The resistance change with the strain range change as well as the resistance progression with the number of cycles in tensile as well as compressive mode were determined, and such information is then used to create failure prediction models for thin-film conductors on flexible substrates.

damage evolution, flexible conductor, multi-layer ↗

Substrate‐Dependent Molecular and Nanostructural Orientation of Nafion Thin Films

Abstract The effects of film thickness and substrate composition on the ionomer structure in porous electrodes are critical in understanding pathways toward developing higher performance electrochemical devices, including fuel cells and batteries. Insights are gained into the molecular and nanostructural orientation dependence for thin Nafion films (12–300 nm thick) on gold, platinum, and SiO 2 model substrates. Molecular orientation is determined from the birefringence measured using spectroscopic ellipsometry, while the nanostructural orientation of the ionic domains is measured using grazing‐incidence small‐angle X‐ray scattering. Density functional theory calculations for the molecular polarizability of the Nafion backbone and side chain show complimentary contributions to the measured birefringence values for the material. Nafion films prepared on SiO 2 substrates exhibit a nearly isotropic molecular and nanostructural orientation. Films on gold and platinum display parallel backbone orientations, relative to the substrate, with decreasing film thickness. However, a birefringence transition toward molecular isotropy is observed for 30 nm thick films on Au and Pt; while the ionic nanostructured domains continuously align parallel to the substrate. This apparent isotropic molecular orientation with increasing domain orientation highlights the difference between the backbone and side chain orientation, a key finding for elucidating transport in confined films at the interfaces.

Kushner, Douglas I.↗

Long-Life Lithium-Sulfur Batteries with a Bifunctional Cathode Substrate Configured with Boron Carbide Nanowires

Developing high-energy-density lithium–sulfur (Li–S) batteries relies on the design of electrode substrates that can host a high sulfur loading and still attain high electrochemical utilization. Herein, a new bifunctional cathode substrate configured with boron-carbide nanowires in situ grown on carbon nanofibers (B 4 C@CNF) is established through a facile catalyst-assisted process. The B 4 C nanowires acting as chemical-anchoring centers provide strong polysulfide adsorptivity, as validated by experimental data and first-principle calculations. Meanwhile, the catalytic effect of B 4 C also accelerates the redox kinetics of polysulfide conversion, contributing to enhanced rate capability. As a result, a remarkable capacity retention of 80% after 500 cycles as well as stable cyclability at 4C rate is accomplished with the cells employing B 4 C@CNF as a cathode substrate for sulfur. Moreover, the B 4 C@CNF substrate enables the cathode to achieve both high sulfur content (70 wt%) and sulfur loading (10.3 mg cm -2 ), delivering a superb areal capacity of 9 mAh cm -2 . In addition, Li–S pouch cells fabricated with the B 4 C@CNF substrate are able to host a high sulfur mass of 200 mg per cathode and deliver a high discharge capacity of 125 mAh after 50 cycles.

25 ENERGY STORAGE↗

Achieving Electrode Smoothing by Controlling the Nucleation Phase of Metal Deposition Through Polymer‐Substrate Binding

Polymer additives [like polyethylene oxide (PEO)] are widely used for smooth electrode deposition in aqueous zinc and many other battery systems. However, the precise mechanism by which they regulate morphology and suppress dendrite formation remains unclear. In this study, the knowledge gap is addressed by using in situ electrochemical atomic force microscopy to directly observe the interfacial evolution during Zn electrodeposition and polymer adsorption on Cu substrates in the presence of varying concentrations of ZnSO 4 and PEO. Contrary to previous literature assumptions, which emphasize the binding to the growing Zn crystal surfaces or Zn 2+ ions, the results demonstrate that PEO smooths Zn films by promoting nucleation of (002)-oriented Zn platelets through interactions with the Cu substrate. Density functional theory simulations support this finding by showing that PEO adsorption on Cu modifies the interfacial energy of Zn/Cu/electrolyte interfaces, favoring the stabilization of Zn (002) on the Cu substrate, as well as confines Zn electrodeposition to a narrow near-surface region. In conclusion, these findings elucidate a novel design principle for electrode smoothing, emphasizing the importance of substrate selection paired with polymer additives that exhibit an attractive interaction with the substrate but minimal interaction with growing crystals, offering a mechanistic perspective for improved battery performance.

Electrodeposition↗

Revealing the Origin and Nature of the Buried Metal‐Substrate Interface Layer in Ta/Sapphire Superconducting Films

Abstract Despite constituting a smaller fraction of the qubit's electromagnetic mode, surfaces and interfaces can exert significant influence as sources of high‐loss tangents, which brings forward the need to reveal properties of these extended defects and identify routes to their control. Here, we examine the structure and composition of the metal‐substrate interfacial layer that exists in Ta/sapphire‐based superconducting films. Synchrotron‐based X‐ray reflectivity measurements of Ta films, commonly used in these qubits, reveal an unexplored interface layer at the metal‐substrate interface. Scanning transmission electron microscopy and core‐level electron energy loss spectroscopy identified an intermixing layer (≈0.65 ± 0.05 nm) at the metal‐substrate interface containing Al, O, and Ta atoms. Density functional theory modeling reveals that the structure and properties of the Ta/sapphire heterojunctions are determined by the oxygen content on the sapphire surface prior to Ta deposition for two atomic terminations of sapphire. Using a multimodal approach, we gained deeper insights into the interface layer between the metal and substrate, which suggests that the orientation of deposited Ta films depend on the surface termination of sapphire. The observed elemental intermixing at the metal‐substrate interface influences the thermodynamic stability and electronic behavior of the film, which may also affect qubit performance.

36 MATERIALS SCIENCE↗

Protein–Protein Complex Stability Controls Substrate Scope in a β‐Ketoacyl‐ACP Reductase Specific for Medium Chains

Assembly-line enzymes carry out multistep synthesis of important metabolites by using acyl carrier proteins (ACPs) to shuttle intermediates along defined sequences of active sites. Despite longstanding interest in reprogramming these systems for metabolic engineering and biosynthetic chemistry, the mechanisms underlying their reaction order remain poorly understood and difficult to control. In this work, we describe a β-ketoacyl-ACP reductase from Pseudomonas putida (PpFabG4) with an unusual selectivity for medium chains and use it to explore the molecular basis of substrate specificity in enzymes that pull intermediates from fatty acid synthesis, a common route to specialized products. X-ray crystallography shows no obvious barriers to short-chain binding. Molecular simulations and supporting mutational analyses indicate that substrate preference arises instead from a weak enzyme–ACP interaction that is stabilized by medium acyl chains but not by short chains. Indeed, mutations that strengthen this interaction for PpFabG4 or weaken it for EcFabG, an Escherichia coli β-ketoacyl-ACP reductase with a broad substrate specificity, can enhance or reduce activity on short-chain substrates by over 100-fold. Our findings show how the stability of enzyme-ACP interactions can control substrate scope in promiscuous enzymes and guide the exchange of intermediates between (and within) assembly-line systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Comparative performance of PETase as a function of reaction conditions, substrate properties, and product accumulation

There is keen interest to develop new technologies to recycle the plastic poly(ethylene terephthalate) (PET). To this end, the use of PET-hydrolyzing enzymes has shown promise for PET deconstruction to its monomers, terephthalate (TPA) and ethylene glycol (EG). Here, we compare the Ideonella sakaiensis PETase wild-type enzyme to a previously reported improved variant (W159H/S238F). We compare the thermostability of each enzyme and describe a 1.45 Å resolution structure of the mutant, highlighting changes in the substrate binding cleft compared to the wild-type enzyme. Subsequently, the performance of the wild-type and variant enzyme was compared as a function of temperature, substrate morphology, and reaction mixture composition. These studies show that reaction temperature has the strongest influence on performance between the two enzymes. We also show that both enzymes achieve higher levels of PET conversion for substrates with moderate crystallinity relative to amorphous substrates. Finally, we assess the impact of product accumulation on reaction progress for the hydrolysis of both PET and bis(2-hydroxyethyl) terephthalate (BHET). Each enzyme displays different inhibition profiles to mono(2-hydroxyethyl) terephthalate (MHET) and TPA, while both are sensitive to inhibition by EG. Overall, this work highlights the importance of reaction conditions, substrate selection, and product accumulation for catalytic performance of PET-hydrolyzing enzymes, which have implications for enzyme screening in the development of enzyme-based polyester recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantum Efficiency Enhancement of Bialkali Photocathodes by an Atomically Thin Layer on Substrates

Quantum efficiency (QE) enhancement in accelerator technology relevant to antimonide photocathodes (K 2 CsSb) is achieved by interfacing them with atomically thin 2D crystal layers. The enhancement occurs in a reflection mode, when a 2D crystal is placed in between the photocathodes and optically reflective substrates. Specifically, the peak QE at 405 nm (3.1 eV) increases by a relative 10%, whereas the long wavelength response at 633 nm (2.0 eV) increases by a relative 36% on average and up to 80% at localized “hot spot” regions when photocathodes are deposited onto graphene–coated stainless steel. There is a similar effect for photocathodes deposited on hexagonal boron nitride monolayer coatings using nickel substrates. The enhancement does not occur when reflective substrates are replaced with optically transparent sapphire. Optical transmission, X–ray diffraction (XRD), and X–ray fluorescence (XRF) revealed that thickness, crystal orientation, quality, and elemental stoichiometry of photocathodes do not appreciably change due to 2D crystal coatings. Furthermore these results suggest that optical interactions are responsible for the QE enhancements when 2D crystal sublayers are present on reflective substrates, and provide a pathway toward a simple method of QE enhancement in semiconductor photocathodes by an atomically thin 2D crystal on substrates.

43 PARTICLE ACCELERATORS↗

Growth of Crystallographically Aligned PbSe Films of Controlled Thickness on Amorphous Substrates

Lead selenide (PbSe) has extensively been investigated due to its thermoelectric and photoconductive properties. More recently, predictions of emergent properties have focused synthetic efforts on preparing ultra-smooth layers of crystallographically aligned PbSe layers with a thickness equal to an integer number of monolayers. While rough films are typically formed through Volmer-Weber growth on heated substrates, we report the data presented herein indicates that a crystallographically aligned, ultrathin layer with a defined number of PbSe layers forms on mostly amorphous Mo-Se and V-Se coated Si substrates during nominally room temperature deposition. Since the films are uniform in thickness, the number of PbSe bilayers formed depends on the amount of Pb (or Se) deposited. If the amount of Pb deposited is close to that required for an integral number of unit cells and there is sufficient Se, Laue oscillations are present in the as-deposited samples. The Laue oscillations reflect the quality and uniformity of the crystalline PbSe domains. This study demonstrates that the substrate does not need to be crystalline to form uniform, crystallographically aligned, integer monolayer thick PbSe films. These results suggest that tuning the strength of interactions be-tween substrate and growing film is necessary to form smooth, crystallographically aligned layers. The substrate does not need to be crystalline for these interactions to be strong enough to enable growth of crystallographically aligned films.

36 MATERIALS SCIENCE↗

Building Zr-based metallic glass part on Ti-6Al-4V substrate by laser-foil-printing additive manufacturing

Through using Zr intermediate layers, Zr 65.7 Ti 3.3 Al 3.7 Ni 11.7 Cu 15.6 metallic glass (MG) parts are successfully built on Ti-6Al-4V substrates by laser-foil-printing (LFP) additive manufacturing technology in which MG foils are laser welded layer-by-layer onto the substrate. The printed MG part is free of porosity, cracking and crystallization; additionally, its glass transition temperature, crystallization temperature, micro-hardness, and tensile strength are very similar to the original MG material. The Zr intermediate layers are aimed at preventing direct interaction between the first layer of MG foil and the Ti substrate; otherwise, the welded MG foils would peel off from the substrate due to the formation of hard and brittle intermetallic compounds. Finally, with the use of Zr intermediate layers, the bonding strength between the printed MG part and the Ti substrate can reach 758 MPa owing to the formation of α-Zr phase.

36 MATERIALS SCIENCE↗

Structural basis for substrate specificity of meso-diaminopimelic acid decarboxylase from Corynebacterium glutamicum

Highlights: • We determined a crystal structure of meso-Diaminopimelic acid decarboxylase from Corynebacterium glutamicum (CgDAPDC). • Binding mode of the PLP cofactor of CgDAPDC were elucidated. • Substrate binding mode of CgDAPDC were elucidated. l-lysine is an essential amino acid that is widely used as a food supplement for humans and animals. meso-Diaminopimelic acid decarboxylase (DAPDC) catalyzes the final step in the de novo l-lysine biosynthetic pathway by converting meso-diaminopimelic acid (meso-DAP) into l-lysine by decarboxylation reaction. To elucidate its molecular mechanisms, we determined the crystal structure of DAPDC from Corynebacterium glutamicum (CgDAPDC). The PLP cofactor is bound at the center of the barrel domain and forms a Schiff base with the catalytic Lys75 residue. We also determined the CgDAPDC structure in complex with both pyridoxal 5′-phosphate (PLP) and the l-lysine product and revealed that the protein has an optimal substrate binding pocket to accommodate meso-DAP as a substrate. Structural comparison of CgDAPDC with other amino acid decarboxylases with different substrate specificities revealed that the position of the α15 helix in CgDAPDC and the residues located on the helix are crucial for determining the substrate specificities of the amino acid decarboxylases.

60 APPLIED LIFE SCIENCES↗

Structure of a [NiFe] hydrogenase maturation protease HycI provides insights into its substrate selectivity

Highlights: • TkHycI adopts a three-layer α/β/α fold with the conserved key residues. • TkHycI retains a larger loop than TkHybD, thereby creating a broad and deep cleft. • The sizable cleft of TkHycI is probably associated with its substrate recognition. The immature large subunit of [NiFe] hydrogenases undergoes C-terminal cleavage by a specific protease in the final step of the post-translational process before assembly with other subunits. It has been reported that the [NiFe] hydrogenase maturation protease HycI from Thermococcus kodakarensis (TkHycI) has the catalytic ability to target the membrane-bound hydrogenase large subunit MbhL from T. kodakarensis. However, the detailed mechanism of its substrate recognition remains elusive. We determined the crystal structure of TkHycI at 1.59 Å resolution to clarify how TkHycI recognizes its own substrate MbhL. Although the overall structure of TkHycI is similar to that of its homologous protease TkHybD, TkHycI adopts a larger loop than TkHybD, thereby creating a broad and deep cleft. We analyzed the structural properties of the TkHycI cleft probably involved in its substrate recognition. Our findings provide novel and profound insights into the substrate selectivity of TkHycI.

60 APPLIED LIFE SCIENCES↗

Crystal structure of hypothetical protein PA4202 from Pseudomonas aeruginosa PAO1 in complex with nitroethane as a nitroalkane substrate

Highlights: • Crystal structure of PA4202 protein in complex with FMN and NE was determined. • A kinetic study reveals that the PA4202 enzyme may catalyze a neutral nitroalkane. • Our results provide the first structure-based substrate binding property of PA4202. Nitroalkane oxidase (NAO) and nitronate monooxygenase (NMO) are two different types of nitroalkane oxidizing flavoenzymes identified in nature. A previous study suggested that the hypothetical protein PA4202 from Pseudomonas aeruginosa PAO1 is NMO and utilizes only anionic nitronates. However, the structural similarity between the PA4202 protein and Streptomyces ansochromogenes NAO has motivated investigation for what features of the two enzymes differentiate between the NAO and NMO activities. Herein, we report the crystal structure of PA4202 in a ternary complex with a neutral nitroethane (NE) and flavin mononucleotide (FMN) cofactor to elucidate the substrate recognition mechanism using a site-directed mutagenesis. The ternary complex structure indicates that the NE is bound with an orientation, which is poised for the proton transfer to H183 (which is the essential first catalytic step with nitroalkanes), and subsequent reactions with FMN. Moreover, a kinetic study reveals that the catalytic reactions of the wild type and H183 mutants PA4202s with nitroalkane substrates may yield the products of hydrogen peroxide and nitrite that are specified to NAO, although they show a low catalytic efficiency. Our results provide the first structure-based molecular insight into the substrate binding property of the hypothetical protein PA4202, including the interactions with neutral nitroalkanes as the substrate.

60 APPLIED LIFE SCIENCES↗

Multiple mutations in the aglycone binding pocket to convert the substrate specificity of dalcochinase to linamarase

Highlights: • Dalcochinase and linamarase are β-glucosidases with distinct substrate specificities. • Substrate specificities could be converted by substitution of 2–3 key residues. • The I185A mutation is needed to fit substrates with tri-functional aglycone moieties. • The N189F mutant showed a potential for enzymatic synthesis of alkyl glucosides. • β-Glucosidases could be tailored to suit desired hydrolytic or synthetic applications. Dalcochinase from Dalbergia cochinchinensis Pierre and linamarase from Manihot esculenta Crantz are β-glucosidases which share 47% sequence identity, but show distinct substrate specificities in hydrolysis and transglucosylation. Previously, three amino acid residues of dalcochinase, namely I185, N189 and V255, were identified as being important for determining substrate specificity. In this study, kinetic analysis of the ensuing double and triple mutants of dalcochinase showed that only those containing the 185A mutation could appreciably hydrolyze linamarin as well as transfer glucose to 2-methyl-2-propanol. So, the space provided by the I185A mutation appeared to be a prerequisite for accommodation of the aglycone moiety containing three substituents at the carbinol carbon. However, quantitative analysis of the energy parameters revealed mostly antagonistic interactions between these mutations. In addition, the N189F mutant showed a potential for use in enzymatic synthesis of alkyl glucosides via transglucosylation and reverse hydrolysis reactions. Thus, substitution of only 2–3 key residues in the aglycone binding pocket of dalcochinase could convert its specificities to that of linamarase, as well as to be suitable for any chosen hydrolytic or synthetic applications.

60 APPLIED LIFE SCIENCES↗

Evaluation of different getter substrates using two-dimensional gas chromatography with time of flight mass spectrometry

We report while understanding hydrogen uptake by organic based getters such as 1,4-bis(phenylethynyl)benzene (DEB) combined with a palladium(0)bis(dibenzylideneacetone) (Pd(dba) 2 ) catalyst is essential, another crucial element to understand is the decomposition of the DEB, Pd(dba) 2 , and/or substrate material. The breakdown of these materials may create unwanted volatiles, which may interact with and lead to deterioration of sensitive materials. Moreover, it is critical to understand if different substrates cause the getter and/or catalyst to degrade in different manners. Utilizing comprehensive two-dimensional gas chromatography (GC×GC) with time-of-flight mass spectrometry (TOFMS), the presence of volatiles located in the headspace of various DEB/Pd(dba) 2 getter substrates is examined. These samples include a getter infused silicone foam, a hydrogenated getter infused silicone foam, an activated carbon getter pellet, and a hydrogenated activated carbon getter pellet. Application of Fisher ratio (F-ratio) analyses lead to the identification of several compounds that are generated or consumed through the hydrogenation process. These include benzene derivatives such as bibenzyl, benzaldehyde, and vinyl benzoate in the activated carbon pellets and 1,5-diphenyl-3-pentanone, toluene, styrene, and 1–1'(2-pentene 1,5-diyl)bis benzene in the silicone foams, and alkane/alkene derivatives such undecane, 4-tridecene, and decane in the activated carbon pellets and 2,6-dimethyl undecane in the silicone foams. Further comparison of the different hydrogenated getter substrates (e.g. activated carbon pellet and silicone foam) indicates that the different substrates alter the decomposition products created from the degradation of the DEB and Pd(dba) 2 .

47 OTHER INSTRUMENTATION↗

Effect of substrate orientation on CdS homoepitaxy by molecular dynamics

CdS homoepitaxy growth was performed by molecular dynamics using different substrate orientations and structures in order to analyze the CdS crystallinity. As anticipated from thermodynamics of homoepitaxy, highly crystalline films with only point defects were obtained on substrates with rectangular surface geometries, including View the MathML source[112¯] zinc blende (ZB), [101¯0] wurtzite (WZ), [112¯0] WZ, [110][110] ZB, [010][010] ZB, and View the MathML source[1101110] ZB. In contrast, films grown on substrates with hexagonal surface geometries, corresponding to the [0001][0001] WZ and [111][111] ZB growth directions, showed structures with a large number of defects including; anti-sites, vacancies, stacking faults, twinning, and polytypism. WZ and ZB transitions and grain boundaries are identified using a lattice identification algorithm and represented graphically in a structural map. A dislocation analysis was performed to detect, identify, and quantify linear defects within the atomistic data. Systematic simulations using different temperatures, deposition rates, and substrate polarities were perform to analyze the trends of dislocation densities on [0001][0001] WZ direction and showed persistent polytypism. As a result, the polytypism observed in the films grown on the substrates with hexagonal surface geometry is attributed to the similar formation energies of the WZ and ZB phases.

36 MATERIALS SCIENCE↗

SURFACE MODIFICATION OF ZIRCALOY-4 SUBSTRATES WITH NICKEL ZIRCONIUM INTERMETALLICS

Surfaces of Zircaloy-4 (Zr-4) substrates were modified with nickel-zirconium (NiZr) intermetallics to tailor oxidation performance for specialized applications. Surface modification was achieved by electroplating Zr-4 substrates with nickel (Ni) and then performing thermal treatments to fully react the Ni plating with the substrates, which resulted in a coating of NiZr intermetallics on the substrate surfaces. Both plating thickness and thermal treatment were evaluated to determine the effects of these fabrication parameters on oxidation performance and to identify an optimal surface modification process. Isothermal oxidation tests were performed on surface-modified materials at 290°, 330°, and 370°C under a constant partial pressure of oxidant (i.e., 1 kPa D2O in dry Ar at 101 kPa) for 64 days. Test results revealed an enhanced, transient oxidation rate that decreased asymptotically toward the rate of the Zr-4 substrate. Oxidation kinetics were analyzed from isothermal weight gain data, which were correlated with microstructure, hydrogen pickup, strength, and hardness.

Intermetallic↗

GaAs solar cells grown on acoustically spalled GaAs substrates with 27% efficiency

Acoustic spalling presents a potentially low-cost reuse pathway for III–V epitaxial growth substrates via exfoliation of device layers with recovery and reuse of the substrate. However, surface features formed during spalling can reduce the performance of subsequently grown devices. Here, we develop an understanding of how the surface morphology of acoustically spalled substrates affects GaAs solar cell performance and develop strategies to mitigate these impacts. We demonstrate that minor planarization of the surface by wet chemical etching and/or epitaxial growth, or the redesign of the device structure to thicken critical layers, prevents performance degradation. Using these strategies, we demonstrate a 0.25 cm 2 single-junction GaAs device with 26.9% ± 0.2% photovoltaic conversion efficiency under the AM1.5G spectrum grown on an acoustically spalled substrate. These results enable the growth of high-performance III–V devices on non-traditional substrates with the potential for significantly reduced device costs.

14 SOLAR ENERGY↗