Search NASA⌕ Search

SEARCH · Search NASA

Results for “Surface Passivation”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 289 records · Page 16

Effect of Surface Texture on Pinhole Formation in SiO x -Based Passivated Contacts for High-Performance Silicon Solar Cells

High-efficiency silicon solar cells rely on some form of passivating contact structure to reduce recombination losses at the crystalline silicon surface and losses at the metal/Si contact interface. One such structure is polycrystalline silicon (poly-Si) on oxide, where heavily doped poly-Si is deposited on a SiO x layer grown directly on the crystalline silicon (c-Si) wafer. Depending on the thickness of the SiO x layer, the charge carriers can cross this layer by tunneling (<2 nm SiO x thickness) or by direct conduction through disruptions in the SiOx, often referred to as pinholes, in thicker SiO x layers (>2 nm). In this work, we study structures with tunneling- or pinhole-like SiO x contacts grown on pyramidally textured c-Si wafers and expose variations in the SiOx layer properties related to surface morphology using electron-beam-induced current (EBIC) imaging. Using EBIC, we identify and mark regions with potential pinholes in the SiO x layer. We further perform high-resolution transmission electron microscopy on the same areas, thus allowing us to directly correlate locally enhanced carrier collection with variations in the structure of the SiO x layer. Our results show that the pinholes in the SiO x layer preferentially form in different locations based on the annealing conditions used to form the device. With greater understanding of these processes and by controlling the surface texture geometry, there is potential to control the size and spatial distribution of oxide disruptions in silicon solar cells with poly-Si on oxide-type contacts; usually, this is a random phenomenon on polished or planar surfaces. Such control will enable us to consistently produce high-efficiency devices with low recombination currents and low junction resistances using this contact structure.

14 SOLAR ENERGY↗

Nanoscale Mg-Depleted Layers Slow Carbonation of Forsterite (Mg 2 SiO 4 ) When Water Is Limited

Passivation of silicate surfaces by accumulated reaction products is an obstacle to efficient CO 2 mineralization. In this study, we investigate a unique passivation effect during the carbonation of the basalt mineral forsterite (Mg 2 SiO 4 ) in humid supercritical CO 2 (50 °C, 90 bar). Using in situ high-pressure infrared spectroscopy, we demonstrate that dissolution of forsterite into a thin water film slows significantly after reaction for ˜24 h, even under far-from-equilibrium conditions. Further, 29 Si magic angle spinning nuclear magnetic resonance spectroscopy detects a highly polymerized amorphous silica at this stage. On the basis of transmission electron microscopy and energy dispersive X-ray spectroscopy, we show that the silica is present as a Mg-depleted layer that is just 2–3 nm thick on the reacted forsterite particles. The decrease in the level of forsterite dissolution in the presence of an extraordinarily thin Mg-depleted layer can be strongly linked to properties of the thin fluid film at the surface, highlighting the importance of water during mineral carbonation. This study furthers our understanding of silicate mineral carbonation under select low-water, humidified fluid conditions relevant to basaltic geologic reservoirs, recovery of critical elements by carbonation of mafic ores, and sequestration of atmospheric CO 2 by enhanced rock weathering.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Gas-phase surface modification to control catalyst structure and yields in methane dehydroaromatization

Methane dehydroaromatization (MDA) is a promising approach for direct methane transformation to aromatics and hydrogen. The benchmark catalyst Mo/H-ZSM-5 struggles to find commercial adoption because of thermodynamically-limited yields and rapid coking on Brønsted acid and molybdenum carbide species, especially on zeolite external surfaces. Here, gas-phase atomic layer deposition (ALD) overcoats H-ZSM-5 external surfaces with SiO 2 or Al 2 O 3 . NH 3 -TPD, HRTEM, and textural properties show that these overcoats exclusively passivate zeolite external surfaces. Under MDA conditions, SiO 2 gives softer coke and increases cumulative benzene yields by 25%, while Al 2 O 3 strongly decreases yields. H 2 -TPR and UV-visible and Raman spectroscopy show how the overcoats redisperse the MoO x precatalysts, especially over multiple deactivation and isothermal oxidative regeneration cycles. Combined with 27 Al-MAS NMR, MoO x redistribution and dealumination are seen as the causes of long-term deactivation over multiple regeneration cycles, and this process continues to occur regardless of the overcoat. Altogether, the deposition of a small amount of silica on the outer surface of Mo/H-ZSM-5 reduces the formation of hard coke, which could be regenerated by milder methods such as hydrogen treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phase stabilization and oxidation of a continuous composition spread multi-principal element (AlFeNiTiVZr) 1-x Cr x alloy

Multi-Principal Element Alloys (MPEA) have been hypothesized to maintain a stable single alloy phase and resist corrosion at high temperatures, which are desirable in various functional applications, including material of turbine blades. However, studies into oxidation resistant alloys have been constrained to individual MPEA systems or a limited selection of compositions within those systems. Here, High-Throughput Experimental (HTE) techniques were utilized to rapidly assess phase stability and resistance to oxidation of an (AlFeNiTiVZr) 1-x Cr x continuous composition spread (CCS) thin-film alloy system. High-throughput synchrotron diffraction and Raman spectroscopy were used to identify phases, especially high symmetry structures and oxides, as a function of annealing time and composition. The formation of two distinct phase regions, R 1 and R 2 , across the CCS was observed. One of these phase regions, R 2 , exhibited a stable high symmetry BCC-like phase at Cr concentrations greater than 25.4 at%, and grew a passivating mixed metal surface oxide; whereas, the R 1 phase region, decomposed on oxidation to multiple oxides and reacted with the substrate to form silicides. The passivating mixed metal oxide layer appears to prevent destabilization of the (AlFeNiTiVZr) 1-x Cr x MPEA BCC solid solution. Furthermore, at longer annealing times the passivating phase was seen only above 29.2 at% Cr. High Cr-doped (AlFeNiTiVZr) 1-x Cr x appear to be a good candidate for high temperature, oxidation-resistant structural alloys.

36 MATERIALS SCIENCE↗

Evaluating the roles of electrolyte components on the passivation of silicon anodes

A protocol was recently developed to compare calendar life using a constant potential while monitoring the electrical current required to maintain the potential. Here, this calendar life protocol is used with electrolyte formulations containing various mole fractions of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and LiPF 6 to elucidate the role each component plays in passivation for high silicon anodes. Together, EC and LiPF 6 lead to higher currents, and thus poorer passivation, whereas EMC acts as a spectator. The variation of the components' mole fraction also changes the solid-electrolyte interphase (SEI) composition, as measured by x-ray photoelectron spectroscopy. Importantly, higher LiPF 6 content leads to increased LiF as well as increased current, indicating that higher LiF content does not enhance the passivation of the silicon surface. Finding that EC did not yield a passivating SEI, instead ethylene sulfite, sulfolane, and propylene carbonate (PC) were used in place of EC. Using ethylene sulfite and sulfolane resulted in poorer passivation compared to EC, whereas PC resulted in superior passivation. As a result, the superior passivation may be related to more stable lithium-solvent complexes.

25 ENERGY STORAGE↗

Catalytic open-circuit passivation by thin metal oxide films of p-Si anodes in aqueous alkaline electrolytes

Ni and NiO x -based protective thin films are shown to catalyze the oxidation of Si in the presence of O 2 in strongly alkaline KOH(aq) even in the absence of illumination. The O 2 in solution drove the open-circuit potential of the electrode to >0.4 V, which is positive of the Si passivation potential. The elevated electrochemical potential of the surface promoted formation of passive oxides on exposed Si regions of Si/Ni electrodes. Catalytic passivation of Si extended the durability of an np + -Si(100)/NiO x photoanode to >400 h while operating under simulated day/night cycles. In contrast, electrodes without a Ni(O x ) layer and/or without O 2 in solution displayed direct etching of the Si and corrosion pitting during non-illuminated, simulated nighttime episodes of day/night cycling. The O 2 -derived catalyzed passivation of Si using thin films can be generalized to multiple phases of NiO x as well as to materials other than Ni. Finally, relative to operation in aqueous alkaline conditions, decreasing the pH of the electrolyte decreased the dissolution rate of the protective oxide layer formed by the catalyzed passivation process, and consequently increased the durability of the photoanode, but yielded lower photoelectrode fill factors for water oxidation due to the relatively large kinetic overpotentials for the electrocatalyzed oxygen-evolution reaction at near-neutral pH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid Alloy Surface Engineering through Closed-Vessel Reagent Pyrolysis

For rapid surface engineering of Cr-containing alloys by low-temperature nitrocarburization, we introduce a process based on pyrolysis of solid reagents, e.g., urea, performed in an evacuated closed vessel. Upon heating to temperatures high enough for rapid diffusion of interstitial solute, but low enough to avoid second-phase precipitation, the reagent is pyrolyzed to a gas atmosphere containing molecules that (i) activate the alloy surface by stripping away the passivating Cr 2 O 3 -rich surface film (diffusion barrier) and (ii) rapidly infuse carbon and nitrogen into the alloy. We demonstrate quantitatively that this method can generate a subsurface zone with concentrated carbon and nitrogen comparable to what can be accomplished by established (e.g., gas-phase- or plasma-based) methods, but with significantly reduced processing time. As another important difference to established gas-phase processing, the interaction of gas molecules with the alloy surface can have auto-catalytic effects by altering the gas composition in a way that accelerates solute infusion by providing a high activity of HNCO. The new method lends itself to rapid experimentation with a minimum of laboratory equipment.

36 MATERIALS SCIENCE↗

Surface plasmon driven near- and midinfrared photoconductivity in ligand-free ITO nanocrystal films

Semiconductor nanocrystals (NCs) offer exciting opportunities to deploy infrared optoelectronic technology in a variety of applications that are off-limits to conventional single-crystalline materials. However, the performance and stability of state-of-the-art NC-based devices strongly depend on the details of the NC surface and its passivating ligands. Here, the authors use indium tin oxide NC films stripped of organic ligands and conformally coated with Al 2 O 3 to show that absorption enabled by infrared localized surface plasmon resonances permit infrared photoconduction. For Au electrodes, these metallic NC films exhibit stable photoconductive performance over months in ambient and under electrical stress.

36 MATERIALS SCIENCE↗

Stabilizing the Interphase in Cobalt–Free, Ultrahigh–Nickel Cathodes for Lithium–Ion Batteries

High-nickel layered oxide cathodes, such as LiNi 1-x-y Mn x Co y O 2 (NMC) and LiNi 1-x-y Co x Al y O 2 (NCA), are at the forefront for implementation in high-energy-density lithium-ion batteries. The presence of cobalt in both cathode chemistries, however, largely deters their application due to fiscal and humanitarian issues affiliated with cobalt sourcing. Increasing the Ni content drives down the Co content, but introduces additional structural and electrochemical problems attributed to high-Ni cathodes. Herein a dually modified cobalt-free ultrahigh-nickel cathode 0.02B-LiNi 0.99 Mg 0.01 O 2 (NBM) is presented with 1 mol% Mg and 2 mol% B that exhibits a high initial 1C discharge capacity of 210 mA h g –1 with a 20% capacity retention improvement over 500 cycles when benchmarked against LiNiO 2 (LNO) in pouch full cell configurations with graphite anode. Postmortem analyses reveal the enhanced performance stems from reduced active lithium inventory loss and localized surface reactivity in the NBM cathode. Here, the stabilized cathode-electrolyte interphase subsequently reduces transition-metal dissolution and ensuing chemical crossover to the graphite anode, which prevents further catalyzed parasitic reactions that harmfully passivate the anode surface. Altogether, this study aims to highlight the importance of electrode characterization and analysis from an interphasial viewpoint and to push the ongoing research to stabilize cobalt-free ultrahigh-Ni cathodes for industrial feasibility.

25 ENERGY STORAGE↗

Crown Ether Modulation Enables over 23% Efficient Formamidinium-Based Perovskite Solar Cells

The use of molecular modulators to reduce the defect density at the surface and grain boundaries of perovskite materials has been demonstrated to be an effective approach to enhance the photovoltaic performance and device stability of perovskite solar cells. Herein, we employ crown ethers to modulate perovskite films, affording passivation of undercoordinated surface defects. This interaction has been elucidated by solid-state nuclear magnetic resonance and density functional theory calculations. The crown ether hosts induce the formation of host-guest complexes on the surface of the perovskite films, which reduces the concentration of surface electronic defects and suppresses nonradiative recombination by 40%, while minimizing moisture permeation. As a result, we achieved substantially improved photovoltaic performance with power conversion efficiencies exceeding 23%, accompanied by enhanced stability under ambient and operational conditions. This work opens a new avenue to improve the performance and stability of perovskite-based optoelectronic devices through supramolecular chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self Assembled Monolayers for Passivated Contacts

Passivated contacts mitigate defects typically encountered due metallization of solar cells. We deposit amorphous silicon (a-Si:H) on an oxidized silicon wafer via PECVD and anneal at high temperature to crystallize into polysilicon passivated contact. One drawback is the absorption of the polysilicon between grid fingers, so removal of this material is desirable to maximize Jsc. Alternatively, interdigitated back contact cells rely on a gap between n- and p- fingers, which is commonly etched to ensure electronic isolation. We utilize a self assembled monolayer (SAM) using hexamethyldisilazane (HMDS) as a precursor to pattern and etch amorphous silicon (a-Si:H) and polysilicon without the need for photoresist. Ultraviolet light exposure oxidizes the HMDS by photocleaving the organic groups [1] of the SAM leaving a patterned SiO2. Directly soaking this in TMAH will eventually etch the SAM and the silicon, where the SiO2 serves as an etch mask. Inversely, a dilute HF dip selectively etches this SiO2 and the SAM remains. A subsequent soak in TMAH selectively etches the underlying silicon, where the SAM serves as an etch mask. Importantly, we find that the SAM can remain intact for metallization, where we measure 10 mO-cm2 specific contact resistivity on n-type polysilicon.

passivation↗

Chalcogen back surface field layer

Kesterite photovoltaic devices having a back surface field layer are provided. In one aspect, a method of forming a photovoltaic device includes: forming a complete photovoltaic device having a substrate, an electrically conductive layer on the substrate, an absorber layer on the electrically conductive layer, a buffer layer on the absorber layer, and a transparent front contact on the buffer layer; removing the substrate and the electrically conductive layer from the complete photovoltaic device to expose a backside surface of the absorber layer; forming a passivating layer on the backside surface of the absorber layer; and forming a high work function back contact on the passivating layer. A photovoltaic device having a passivating layer is also provided.

14 SOLAR ENERGY↗

The Solid Electrolyte Interphase Dispersion Can Predict Cycle and Calendar Lifetimes in Silicon Anodes for Lithium-Ion Batteries

The solid electrolyte interphase (SEI) plays a critical role in lithium-ion battery (LIB) anodes. It is responsible for passivating the reactive surface of lithiated anodes against degradation of the electrolyte which enables long cycle and calendar lifetimes for LIBs. This role is especially important in high energy density anodes like silicon, that undergo massive volumetric changes during electrochemical cycling. The mechanism by which the SEI performs this role, however, is not clear which makes designing an SEI to passivate silicon anodes impossible. Through decades of research, dozens of chemical species have been identified within the SEI ranging from inorganic solids to polymeric coatings all of which simultaneously exist in a 'mosaic' composition at the anode surface. This mosaic creates a highly dispersive environment in which electrostatic screening of the anode surface from the electrolyte is not always complete. Here, we present an electrochemical technique to directly test the dispersion at the anode surface. We use this technique to screen more than 20 different electrolytes against silicon anodes and find correlations between both the cycle life and calendar life. The insights from this study offer a new framework to think about the SEI and a rapid screening method to test novel electrode/electrolyte combinations.

battery↗

Enhanced Reversibility of Iron Metal Anode with a Solid Electrolyte Interphase in Concentrated Chloride Electrolytes

Iron is a promising candidate for a cost-effective anode for large-scale energy storage systems due to its natural abundance and well-established mass production. Recently, Fe-ion batteries (FeIBs) that use ferrous ions as the charge carrier have emerged as a potential storage solution. The electrolytes in FeIBs are necessarily acidic to render the ferrous ions more anodically stable, allowing a wide operation voltage window. However, the iron anode suffers severe hydrogen evolution reaction with a low Coulombic efficiency (CE) in an acidic environment, shortening the battery cycle life. Herein, a hybrid aqueous electrolyte that forms a solid-electrolyte interphase (SEI) layer on the Fe anode surface is introduced. The electrolyte mainly comprises FeCl 2 and ZnCl 2 as cosalts, where the Zn-Cl anionic complex species of the concentrated ZnCl 2 allows dimethyl carbonate (DMC) to be miscible with the aqueous ferrous electrolyte. SEI derived from DMC's decomposition passivates the iron surface, which leads to an average CE of 98.3% and much-improved cycling stability. As a result, this advancement shows the promise of efficient and durable FeIBs.

25 ENERGY STORAGE↗

Hydrogen Evolution on Restructured B-Rich WB: Metastable Surface States and Isolated Active Sites

Borides have been recently identified to be a class of earth-abundant and low-cost materials that are surprisingly active toward oxidative dehydrogenation and hydrogen evolution reaction (HER) catalysis. Here, we explain from first-principles calculations the HER activity of WB, an industrial material known for its superior physical properties and chemical inertness. We find that, compared to bulk termination, a major surface reconstruction takes place, leading to the off-stoichiometric B-rich surface termination that contains the active sites. The hydrogen adsorbate configurations are further investigated under various adsorbate coverages. Many competing configurations appear to be accessible in reaction conditions, and thus, a grand canonical ensemble is established to describe the catalytic system. A phase diagram of adsorbate coverages is constructed as a function of pH and the applied potential. A complex reaction network is presented based on the ensemble-averaged reaction rates, and the electrocatalytic activities are evaluated under different overpotentials. Here, the major contributors to the activity are found to be a few metastable surface states with a distinct electronic structure that are only accessible at high adsorbate coverages in reaction conditions. In addition, while the activity of the dominant active site is nearly the same as that on the unreconstructed WB, the B-rich formations play an important role of isolating the active sites and preventing the passivation of the surface with H 2 bubble formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Approaching the Radiative Efficiency Limit in Perovskite Solar Cells with Scalable Defect Passivation and Selective Contacts

This award aimed to enable perovskite solar cells to approach the radiative efficiency limit in scalable manufacturing environments by controlling recombination losses, especially surface recombination losses at electrodes and interfaces. The project combined organic molecular synthesis, perovskite film processing and characterization, and spectroscopic tool development for probing recombination centers. The project ultimately achieved record-low surface recombination velocity (SRV) in mixed cation methylammonium-free perovskite thin films, demonstrated photoluminescence as an effective process metrology tool to optimizing processing of device stacks, and showed that the aminopropyltrimethoxysilane (APTMS) is suitable for passivating the exposed perovskite interface in p-i-n stack devices. The project used combinations of phosphonic acids to modify the transparent conducting oxide and APTMS to passivate the perovskite/electron transport layer interface, thereby demonstrating reduction of SRVs in both partial and full device stacks. The project showed concomitant improvements in device performance, and demonstrated that APTMS passivation was compatible with large area coating of external stakeholder perovskite films using both scalable solution and vapor methods. Notably, the project also supplied surface passivating materials to a number of other US based and SETO-funded teams.

14 SOLAR ENERGY↗

Effects of open circuit immersion and vertex potential on potentiodynamic polarization scans of metallic biomaterials

Abstract Electrodes made of commercially pure titanium (CP-Ti) and a CoCrMo alloy are immersed at an open circuit in a phosphate buffer saline electrolyte at room temperature for different durations prior to electrochemical analyses. Open circuit potential measurements, electrochemical impedance spectroscopy measurements, and cyclic potentiodynamic polarization (CPP) scans are used to assess the impact of the immersion time on derived property values. Stable passivation layers formed on both materials during immersion. The corrosion potentials determined from the anodic legs of CPP scans become more cathodic, and the corrosion currents decrease to lower values after longer immersion times. Measured currents indicate the layers formed on CP-Ti stabilize during forward anodic scans and persist to the vertex potential, whereas passivation breakdown occurs during anodic scans with CoCrMo with active corrosion at voltages up to the vertex potential. The characteristics of the return cathodic legs of CPP scans represent the surface conditions at the vertex potential: characteristic corrosion property values derived from the test responses represent passive surfaces on CP-Ti and leached surfaces on CoCrMo rather than intrinsic properties of those materials.

36 MATERIALS SCIENCE↗

Facile Surface Coatings for Performance Improvement of NMC811 Battery Cathode Material

High nickel content layered oxide LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) is a promising cathode material with a high theoretical capacity of 200 mAh g -1 for use in high energy density lithium-ion batteries. However, its surface can easily get passivated by LiOH and Li 2 CO 3 due to its surface residual Li 2 O being reacting with ambient moisture and CO 2 . Herein, NMC811 was treated in a 3.0 M solution of lithium bis(fluorosulfonyl)imide (LiFSI) in dimethyl carbonate (DMC) at 60 °C for 8 h, 16 h and 24 h, respectively, resulting in coating of the NMC811 surface with LiF due to the basic nature of those residual lithium salts that react with LiFSI. The facile treatment of NMC811 in LiFSI/DMC not only improves the cycling stability but also enhances the capacity of the Li/NMC811 cells, mainly because of the thinning of the Li 2 CO 3 layer as suggested by cyclic voltammograms and impedance analyses. This method opens a new avenue for activation of passivated NMC811 particles for practical battery applications.

25 ENERGY STORAGE↗