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At least 775 records · Page 43

Passivation-driven speciation, dealloying and purification

Thin passivating surface oxide layers on metal alloys form a dissipation horizon between dissimilar phases, hence harbour an inherent free energy and composition gradient. We exploit this gradient to drive order and selective surface separation (speciation), enabling redox-driven enrichment of the core by selective conversion of low standard reduction potential (E°) components into oxides. Additionally, coupling this oxide growth to volumetric changes during solidification allows us to create oxide crystallites trapped in a metal (‘ship-in-a-bottle’) or extrusion of metal fingerlings on the heavily oxidized particle. We confirm the underlying mechanism through high temperature X-ray diffraction and characterization of solidification-trapped particle states. We demonstrate that engineering the passivating surface oxide can lead to purification via selective dealloying with concomitant enrichment of the core, leading to disparate particle morphologies.

36 MATERIALS SCIENCE↗

Ultrathin alumina passivation for improved photoelectrochemical water oxidation catalysis of tin oxide sensitized by a phosphonate-functionalized perylene diimide first without, and then with, CoOy

Previously, a photoanode composed of nanostructured SnO 2 coated with the perylene diimide dye N,N'-bis(phosphonomethyl)-3,4,9,10-perylenediimide (PMPDI) plus photoelectrochemically deposited cobalt oxide (CoO y ) was shown to photoelectrochemically oxidize water at 31 ± 7% faradaic efficiency. A non-ideal part of that prior system is that the addition of the known CoO y water oxidation catalyst (WOC) resulted in a reduction of the total photocurrent rather than the anticipated increase, due to an increase in charge-carrier recombination. Herein, we show deposition of an ultrathin alumina overlayer applied by atomic layer deposition (ALD) on the SnO 2 /PMPDI photoanode can improve the photoactivity and catalytic activity of the system; the addition a ca. 1 nm-thick AlO x layer deposited on a 4000 nm (i.e., 4 micron) thick mesoporous anode system can and does have a positive, 2.5-fold improvement in the steady-state photocurrent with 29 ± 9% faradaic efficiency vs. the control anode without alumina passivation by reducing charge-carrier recombination. Moreover, ALD-deposited AlO x layer does help support the understanding of the “anti-catalysis” of co-depositing a CoO y WOC on the SnO 2 /PMPDI DS-PECs—specifically the picture of direct CoO y –SnO 2 contact-mediated recombination—but that AlO x layer was unable to improve the photocurrent in a net SnO 2 /PMPDI/AlO x (/CoO y ) system. We attribute the lack of a performance enhancement by CoOy WOC to incomplete coverage of each SnO 2 nanoparticle by the AlO x . Overall, we find the addition of an optimized ultrathin AlOx layer (0.6 nm thick; deposited at 85 °C) improves the SnO 2 /PMPDI/AlO x system's photoactivity by a factor of up to ca. 3-fold with reduced recombination. These results document that metal-oxide passivation by low-temperature ALD can be an effective strategy for improving the water oxidation performance of even nanostructured dye sensitized-photoelectrochemical cell.

36 MATERIALS SCIENCE↗

Electrochemical quantification of phosphonic acid passivated surface sites of NiO x for perovskite solar cells

Nickel oxide (NiO x ) is among the few p-type metal oxide semiconductors considered a strong candidate for hole transport layers in halide perovskite solar cells (PSCs). However, its reactivity with perovskite ions poses significant challenges to achieving high efficiency and long-term stability. Here, we investigate passivation of detrimental reactive surface sites on NiO x by carbazole phosphonic acids. We leverage electrochemical cyclic voltammetry (CV) of NiO x electrodes as a proxy measure for the redox activity that afflicts PSCs. From the CVs, we derive a metric, N (units cm −2 ), that relates to the number of redox active sites on NiO x surfaces. We observe a statistically significant negative correlation between PSC efficiency and N-value that indicates PSCs are more efficient on NiO x with lower electrochemical reactivity. The new mechanistic insight into NiO x passivation demonstrates it requires a reducing agent and Brønsted acid combination, providing a broadly applicable approach for evaluating and enhancing the stability and performance of NiO x -based interfaces in photovoltaics.

14 SOLAR ENERGY↗

Photovoltage behaviour of p-Sb 2 S 3 photocathodes for hydrogen evolution: effect of n-In 2 S 3 passivation layers

The 1.76 eV band gap of antimony(iii) sulphide (Sb 2 S 3 ) makes this semiconductor material a promising light absorber for photoelectrochemical water splitting, but scalable fabrication approaches to efficient devices are still lacking. Here we show that compact Sb 2 S 3 films on FTO can be obtained by electrochemical growth from aqueous colloidal sulphur and antimony trichloride solutions, followed by mild annealing. These films can be converted into hydrogen evolution photocathodes after coating with In 2 S 3 passivation layers and the addition of Pt proton reduction co-catalysts. For the first time, vibrating Kelvin probe surface photovoltage (VKP-SPV) spectroscopy is used to observe the carrier dynamics in such photoelectrodes. While the bare Sb 2 S 3 films suffer from high surface recombination rates and poor electron extraction, the In 2 S 3 overlayer is found to raise the photovoltage and cathodic photocurrent density, due to passivation of surface defects and formation of a p–n heterojunction. In thick In 2 S 3 films, these benefits are offset by shading and slow electron transfer. Also, we find that O 2 strongly affects the band bending in the Sb 2 S 3 –air and In 2 S 3 –air junctions and their photovoltage. The optimised devices evolve H 2 at 77.5% Faradaic efficiency and with 0.084% applied bias photon-to-current efficiency (ABPE) at 0.12 V vs. RHE. The low ABPE value is attributed to Sb 2 S 3 sub-bandgap defects visible in SPV spectra, the random orientation of Sb 2 S 3 crystallites in the films, which inhibits charge transport, the absence of crystal facets of Sb 2 S 3 , and a detrimental Schottky junction at the FTO|Sb 2 S 3 interface.

de Araújo, Moisés A. [University of California, Da↗

Evaluation of the Passive Cooling Potential of Thermal Mass Inherent in Medium to Large Commercial Buildings

Typical commercial construction inherently contains large surface areas of relatively thin mass located in the floor slabs. This research asks how effective this mass could be for passive cooling, relative to other mass depths, if it were to be exposed and used as thermal mass. Although much of the rich literature on thermal mass has been conducted with far greater mass depths, a more limited amount of research suggests that because the surface heat transfer rate is limited, the focus should be on the surface area of exposed mass, not its depth. This presents an opportunity for more buildings to behave more thermally massively, if the mass inherent in typical floor slabs contains utility, particularly over diurnal cycles. In all climates analyzed, it was found that there is a pronounced shoulder where energy savings from passive cooling of increasing mass depths was steep until roughly 7.5–10 cm, and beyond this point the achieved energy savings diminished rapidly. When considering the embodied energy of concrete, the incremental benefit of added mass beyond a typical topping slab of 10 cm does not justify the incremental embodied energy cost from a total energy standpoint alone.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Improved Stability Of Amorphous Zinc Tin Oxide Thin Film Transistors Using Molecular Passivation

The role of back channel surface chemistry on amorphous zinc tin oxide (ZTO) bottom gate thin film transistors (TFT) have been characterized by positive bias-stress measurements and x-ray photoelectron spectroscopy. Positive bias-stress turn-on voltage shifts for ZTO-TFTs were significantly reduced by passivation of back channel surfaces with self-assembled monolayers of n-hexylphosphonic acid (n-HPA) when compared to ZTO-TFTs with no passivation. These results indicate that adsorption of molecular species on exposed back channel of ZTO-TFTs strongly influence observed turn-on voltage shifts, as opposed to charge injection into the dielectric or trapping due to oxygen vacancies.

Environmental Molecular Sciences Laboratory↗

Effect of sidewall surface recombination on the quantum efficiency in a Y{sub 2}O{sub 3} passivated gated type-II InAs/GaSb long-infrared photodetector array

Y{sub 2}O{sub 3} was applied to passivate a long-wavelength infrared type-II superlattice gated photodetector array with 50% cut-off wavelength at 11 μm, resulting in a saturated gate bias that was 3 times lower than in a SiO{sub 2} passivated array. Besides effectively suppressing surface leakage, gating technique exhibited its ability to enhance the quantum efficiency of 100 × 100 μm size mesa from 51% to 57% by suppressing sidewall surface recombination. At 77 K, the gated photodetector showed dark current density and resistance-area product at −300 mV of 2.5 × 10{sup −5} A/cm{sup 2} and 1.3 × 10{sup 4} Ω cm{sup 2}, respectively, and a specific detectivity of 1.4 × 10{sup 12} Jones.

36 MATERIALS SCIENCE↗

Passively Q-switching induced by the smallest single-walled carbon nanotubes

We report a passively Q-switched erbium-doped fiber laser (EDFL) by using the smallest single-walled carbon nanotubes (SWNTs) with a diameter of 0.3 nm as the saturable absorber. These small SWNTs are fabricated in the nanochannels of a ZnAPO-11 (AEL) single crystal. By inserting one of the AEL crystal into an EDFL cavity pumped by a 980 nm laser diode, stable passive Q-switching is achieved for a threshold pump power of 206.2 mW, and 4.73 μs pulses with a repetition rate of 41.78 kHz and an average output power of 3.75 mW are obtained for a pump power of 406 mW.

36 MATERIALS SCIENCE↗

Dense nanoimprinted silicon nanowire arrays with passivated axial p-i-n junctions for photovoltaic applications

We report on the fabrication and photovoltaic characteristics of vertical arrays of silicon axial p-i-n junction nanowire (NW) solar cells grown by vapor-liquid-solid (VLS) epitaxy. NW surface passivation with silicon dioxide shell is shown to enhance carrier recombination time, open-circuit voltage (V{sub OC}), short-circuit current density (J{sub SC}), and fill factor (FF). The photovoltaic performance of passivated individual NW and NW arrays was compared under 532 nm laser illumination with power density of ∼10 W/cm{sup 2}. Higher values of V{sub OC} and FF in the NW arrays are explained by enhanced light trapping. In order to verify the effect of NW density on light absorption and hence on the photovoltaic performance of NW arrays, dense Si NW arrays were fabricated using nanoimprint lithography to periodically arrange the gold seed particles prior to epitaxial growth. Compared to sparse NW arrays fabricated using VLS growth from randomly distributed gold seeds, the nanoimprinted NW array solar cells show a greatly increased peak external quantum efficiency of ∼8% and internal quantum efficiency of ∼90% in the visible spectral range. Three-dimensional finite-difference time-domain simulations of Si NW periodic arrays with varying pitch (P) confirm the importance of high NW density. Specifically, due to diffractive scattering and light trapping, absorption efficiency close to 100% in the 400–650 nm spectral range is calculated for a Si NW array with P = 250 nm, significantly outperforming a blanket Si film of the same thickness.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Passive shielding effect on space profile of magnetic field emissions for wireless power transfer to vehicles

Magnetic fields emitted by wireless power transfer systems are of high importance with respect to human safety and health. Aluminum and ferrite are used in the system to reduce the fields and are termed as passive shielding. In this paper, the influence of these materials on the space profile has been investigated with the help of simulations on Comsol for the four possible geometries—no shielding, ferrite, aluminum, and full shielding. As the reflected impedance varies for the four geometries, the primary current is varied accordingly to maintain constant power transfer to the secondary side. Surrounding magnetic field plots in the vertical direction show that maxima's of the two coils for the no shielding geometry are centered at the respective coils and for the remaining three are displaced closer to each other. This closeness would lead to more effective addition of the two coil fields and an increase in the resultant field from space point of view. This closeness varies with distance in the horizontal direction and vertical gap between the coils and is explained in the paper. This paper provides a better understanding of effect of the passive shielding materials on the space nature of magnetic fields for wireless power transfer for vehicle applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Prediction of subsurface fracture in mining zone of Papua using passive seismic tomography based on Fresnel zone

Fracture prediction in a block cave of underground mine is very important to monitor the structure of the fracture that can be harmful to the mining activities. Many methods can be used to obtain such information, such as TDR (Time Domain Relectometry) and open hole. Both of them have limitations in range measurement. Passive seismic tomography is one of the subsurface imaging method. It has advantage in terms of measurements, cost, and rich of rock physical information. This passive seismic tomography studies using Fresnel zone to model the wavepath by using frequency parameter. Fresnel zone was developed by Nurhandoko in 2000. The result of this study is tomography of P and S wave velocity which can predict position of fracture. The study also attempted to use sum of the wavefronts to obtain position and time of seismic event occurence. Fresnel zone tomography and the summation wavefront can predict location of geological structure of mine area as well.

58 GEOSCIENCES↗

Integration of quantum cascade lasers and passive waveguides

We report on monolithic integration of active quantum cascade laser (QCL) materials with passive waveguides formed by using proton implantation. Proton implantation reduces the electron concentration in the QCL layers by creating deep levels that trap carriers. This strongly reduces the intersubband absorption and the free-carrier absorption in the gain region and surrounding layers, thus significantly reducing optical loss. We have measured loss as low as α = 0.33 cm{sup −1} in λ = 9.6 μm wavelength proton-implanted QCL material. We have also demonstrated lasing in active-passive integrated waveguides. This simple integration technique is anticipated to enable low-cost fabrication in infrared photonic integrated circuits in the mid-infrared (λ ∼ 3–16 μm)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Passive mode locking of a GaSb-based quantum well diode laser emitting at 2.1 μm

We demonstrate passive mode locking of a GaSb-based diode laser emitting at 2.1 μm. The active region of the studied device consists in two 10-nm-thick GaInSbAs/GaAlSbAs quantum wells. Passive mode locking has been achieved in a two-section laser with one of the sections used as a saturable absorber. A microwave signal at 20.6 GHz, measured in the electrical circuit of the absorber, corresponds to the fundamental photon round-trip frequency in the laser resonator. The linewidth of this signal as low as ∼10 kHz has been observed at certain operating conditions, indicating low phase noise mode-locked operation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Passive microrheology of soft materials with atomic force microscopy: A wavelet-based spectral analysis

Compared to active microrheology where a known force or modulation is periodically imposed to a soft material, passive microrheology relies on the spectral analysis of the spontaneous motion of tracers inherent or external to the material. Passive microrheology studies of soft or living materials with atomic force microscopy (AFM) cantilever tips are rather rare because, in the spectral densities, the rheological response of the materials is hardly distinguishable from other sources of random or periodic perturbations. To circumvent this difficulty, we propose here a wavelet-based decomposition of AFM cantilever tip fluctuations and we show that when applying this multi-scale method to soft polymer layers and to living myoblasts, the structural damping exponents of these soft materials can be retrieved.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Structural and optical properties of the naked and passivated Al{sub 5}Au{sub 5} bimetallic nanoclusters

The structural and optical properties of both the naked and passivated bimetallic Al{sub 5}Au{sub 5} nanoclusters have been analyzed based on data obtained from ab initio density functional theory and quantum molecular dynamics simulations. It has been found that the Al{sub 5}Au{sub 5} nanocluster possesses a hollow shaped minimum energy structure with segregated Al and Au layered domains, the former representing the electrophilic domain and the latter the nucleophilic domain. In particular, it has been shown that alkali metal cations attach in the nucleophilic domain and hop from one Au site to the next one in the picoseconds time scale, while anions are bound tightly to the Al atoms of the electrophilic domain. Simulating annealing studies are very suggestive of the proneness of the nanocluster towards coalescence into large cluster units, when the cluster is left unprotected by appropriate ligands. Further passivation studies with NaF salt suggest, nonetheless, the possibility of the isolation of the Al{sub 5}Au{sub 5} cluster in molten salts or ionic liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and chemistry of passivated SiC/SiO{sub 2} interfaces

Here, we report on the chemistry and structure of 4H-SiC/SiO{sub 2} interfaces passivated either by nitric oxide annealing or Ba deposition. Using aberration corrected scanning transmission electron microscopy and spectroscopy, we find that Ba and N remain localized at SiC/SiO{sub 2} interface after processing. Further, we find that the passivating species can introduce significant changes to the near-interface atomic structure of SiC. Specifically, we quantify significant strain for nitric oxide annealed sample where Si dangling bonds are capped by N. In contrast, strain is not observed at the interface of the Ba treated samples. Finally, we place these results in the context of field effect mobility.

36 MATERIALS SCIENCE↗

Optical and electrical characterizations of a single step ion beam milling mesa devices of chloride passivated PbS colloidal quantum dots based film

Colloidal Quantum Dots (CQDs) are of increasing interest, thanks to their quantum size effect that gives rise to their usage in various applications, such as biological tagging, solar cells and as the sensitizing layer of night vision devices. Here, we analyze the optical absorbance of chloride passivated PbS CQDs as well as revealing a correlation between their photoluminescence and sizes distribution, using theoretical models and experimental results from the literature. Next, we calculate the CQDs resistivity as a film. Although resistivity can be calculated from sheet resistance measurement using four point probes, such measurement is usually carried-out on the layer’s surface that in most cases has dangling bonds and surface states, which might affect the charges flow and modify the resistivity. Therefore; our approach, which was applied in this work, is to extract the actual resistivity from measurements that are performed along the film’s thickness (z-direction). For this intent, we fabricated gold capped PbS mesas devices using a single step Ion Beam Milling (IBM) process where we milled the gold and the PbS film continually, and then measured the vertical resistance. Knowing the mesas’ dimensions, we calculate the resistivity. To the best of our knowledge, no previous work has extracted, vertically, the resistivity of chloride passivated PbS CQDs using the above method.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Zirconium oxide surface passivation of crystalline silicon

This letter reports effective passivation of crystalline silicon (c-Si) surfaces by thermal atomic layer deposited zirconium oxide (ZrO x ). The optimum layer thickness and activation annealing conditions are determined to be 20 nm and 300 °C for 20 min. Cross-sectional transmission electron microscopy imaging shows an approximately 1.6 nm thick SiO x interfacial layer underneath an 18 nm ZrO x layer, consistent with ellipsometry measurements (~20 nm). Capacitance-voltage measurements show that the annealed ZrO x film features a low interface defect density of 1.0 × 10 11 cm -2 eV -1 and a low negative film charge density of -6 × 10 10 cm -2 . Effective lifetimes of 673 μs and 1.1 ms are achieved on p-type and n-type 1 Ω cm undiffused c-Si wafers, respectively, corresponding to an implied open circuit voltage above 720 mV in both cases. The results demonstrate that surface passivation quality provided by ALD ZrO x is consistent with the requirements of high efficiency silicon solar cells.

36 MATERIALS SCIENCE↗