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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.

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At least 937 records · Page 52
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

CdTe-based thin film photovoltaics: Recent advances, current challenges and future prospects

Cadmium telluride (CdTe)-based cells have emerged as the leading commercialized thin film photovoltaic technology and has intrinsically better temperature coefficients, energy yield, and degradation rates than Si technologies. More than 30 GW peak (GWp) of CdTe-based modules are installed worldwide, multiple companies are in production, modules are shipping at up to 18.6% efficiency, and lab cell efficiency is above 22%. We review developments in the science and technology that have occurred over approximately the past decade. These achievements were enabled by manufacturing innovations and scaling module production, as well as maximizing photocurrent through window layer optimization and alloyed CdSe x Te 1-x (CST) absorbers. Improved chlorine passivation processes, film microstructure, and serendipitous Se defect passivation significantly increased minority carrier lifetime. Efficiencies >22% have been realized for both Cu and As doped CST-based cells. The path to further efficiency gains hinges primarily on increasing open circuit voltage (V oc ) and fill factor (FF) through innovations in materials, fabrication methods, and device stacks. Replacing the longstanding Cu doping with As doping is resulting in better module stability and is being translated to large-scale production. To realize 25% efficiency and >1 V V oc , research and development is needed to increase the minority carrier lifetime beyond 100 ns, reduce grain boundary and interface recombination, and tailor band diagrams at the front and back interfaces. Many of these goals have been realized separately however combining them together using scalable manufacturing approaches has been elusive to date. We review these achievements and outstanding opportunities for this remarkable photovoltaic technology.

14 SOLAR ENERGY↗
DOE OSTI2024

Formation and degradation mechanism of methylammonium lead iodide perovskite thin film fabricated by electrospray technique

Electrospray deposition technique has been reported previously for fabricating effective and stable perovskite thin film, leading to efficient perovskite solar cells. Here, in this work, a comprehensive investigation of the formation mechanism of methylammonium lead iodide perovskite (CH 3 NH 3 PbI 3 ) film by electrospray technique is demonstrated and compared to the formation mechanism through the conventional spin coating technique. In the electrospray process, charged MAI nanoparticles are gradually introduced onto the PbI 2 film, intercalating within the PbI 2 structure to produce the perovskite film. In contrast, the spin-coating method involves supplying the MAI solution in bulk, leading to perovskite crystal formation through the dissolution of the PbI 2 layer by the MAI solution, followed by recrystallization into perovskite oriented in the [110] direction, 30° inclined to the substrate. The impact of charge and the electric field on the formation of perovskite film using the electrospray is explored. Furthermore, the intrinsic stability of perovskite films is monitored in real-time in a highly humid environment (≥80 % relative humidity (RH)) using in-situ Grazing Incidence Wide Angle X-ray Scattering (GIWAXS), and a degradation mechanism is proposed to enhance the durability of the perovskite-based devices. The study further delves into the comparison of the stability of electrosprayed and spin-coated perovskite film, and the impact of humidity level and the presence of a hole-transporting layer on the stability of the perovskite layer. Overall, this work provides a detailed understanding of the formation and humidity-induced degradation mechanism of electrosprayed perovskite films, offering insights that can extend to various applications of perovskite materials.

14 SOLAR ENERGY↗
DOE OSTI2022

Core-level binding energy shifts between interior, terrace and edge atoms in MnO(001) thin films

Understanding the physical origin of core-level photoemission line shapes can offer valuable information about the chemical and physical properties of surfaces. For instance, in a large number of transition metals oxides, changes in the line shape allow the accurate determination of their oxidation states and cation site symmetry. Yet, despite this importance, experimental investigations on core-level shifts have been much neglected in recent years. In order to provide further evidence of the physical relevance, we have, in this contribution, introduced a new aspect of interior-, terrace- and edge- atom core-level binding energy shifts to describe monolayers of MnO(001) films grown on an Au(111) substrate. By this means we were able to distinguish the line shape contributions related to different types of atomic sites. Here we show that their relative intensities and energy shifts are able to provide information about the relative amount of under coordinated atoms on the surface and, thus give insights into their catalytic properties. Our findings reveal the importance of a detailed surface science characterization to provide the correct interpretation of distinct photoemission line shapes when considering thin film samples as well as nanostructures in general.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Electronic and reactivity changes in epitaxially grown Ce 1-x Zr x O 2-δ (111) thin films

Ceria composite catalysts have long been used for ketonization reactions, which is a valuable chemistry for the upgrading of biomass-derived carboxylates. To better understand the interaction of zirconia with ceria in the context of ketonization, thin epitaxial films of ceria-zirconia mixed metal oxide Ce 1-x Zr x O 2-δ (x = 0-1) were grown on a Pt(111) substrate in ultrahigh vacuum conditions and studied with X-ray photoelectron spectroscopy (XPS). Core level and valence band XPS results suggest a strong interaction between ceria and zirconia cations, possibly due to increased filling of unoccupied 4f 0 orbitals of ceria from neighboring Zr cations in the lattice structure. This leads to a partial reduction of ceria from Ce 4+ to Ce 3+ , with Zr remaining predominantly in the 4+ oxidation state. Ketonization of acetic acid was studied using temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). These results found ketonization over mixed Ce-Zr composite oxides exhibited lower activation energies than for pure CeO 2 and ZrO 2 , with Ce 0.38 Zr 0.62 O 2-δ exhibiting the highest yield of acetone among the studied surfaces. In conclusion, these results suggest the high activity of Ce-Zr catalysts appears to be a result of oxygen vacancy formation, stabilized by electron donation from Zr cations.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Fracture toughness evaluation for thin-shell stainless steel weldment

Integrity of spent nuclear fuel (SNF) interim storage canisters are very important to the safety of the back-end nuclear fuel cycle. Stress corrosion cracking (SCC) potential of interim storage canister has been considered as a high priority. Because no post-weld heat treatment was required for forming these canisters, the high tensile residual stress existed within these canister welds. This can change the fracture resistance capacity significantly as well as increase SCC potential. Due to relative thin shell thickness of a canister weldment, the spiral notch torsion test (SNTT) method of small specimen approach was used to estimate the canister weldment fracture toughness. Most SNTT weldment samples fracture initiation sites are at heat-affected zone (HAZ) regions. The estimated fracture toughness $J_Q'$ for the baseline SS304 steel is at 283 kJ/m 2 . The estimated $J_Q'$ for the SS304/308 weld from HAZ and weld specimens are 126 kJ/m 2 and 148.9 kJ/m 2 , respectively.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Disorder driven variations in magnetoresistance and planar Hall effect in Bi 2 Te 3 thin films

The degenerately doped sesquichalcogenide Bi 2 Te 3 , a well-known thermoelectric material, has attracted much attention in recent years as a topological insulator in which conducting surface states lead to exotic electronic transport. Here, in this study, we report the observation of anisotropic magnetoresistance (AMR) and planar Hall effect (PHE) in polycrystalline thin films of Bi 2 Te 3 over a broad range of temperature and magnetic field strength. The values of AMR, PHE and the Hall mobility (μ H ) are compared with results of similar measurements on single crystals and epitaxial films of Bi 2 Te 3 , where these properties are understood in the framework of electronic transport in the topologically protected conducting surface states. Our textured polycrystalline films show a robust metallic character with a carrier density (n s ) and mobility μ H of 9×10 20 cm -3 and 16.7 cm 2 V -1 s -1 respectively. This carrier density is higher and the mobility lower by an order of magnitude compared to the reported values of n s and μ H in epitaxial films and single crystals. However, we see a comparable AMR and PHE in our films for which the concept of conducting surface states is ill-defined due to their polycrystallinity and disordered structure. We suggest that an anisotropic backscattering of charge carriers in the strongly spin – orbit coupled electronic states of this heavy-metal-based non-magnetic compound may lead to the measured resistivity anisotropy. The observation of AMR and PHE in polycrystalline films may be important for scalable production of Bi 2 Te 3 based AMR and PHE sensors of magnetic fields.

36 MATERIALS SCIENCE↗
DOE OSTI2024

The Tribomechadynamics Research Challenge: Confronting blind predictions for the linear and nonlinear dynamics of a thin-walled jointed structure with measurement results

The present article summarizes the submissions to the Tribomechadynamics Research Challenge announced in 2021. The task was a blind prediction of the vibration behavior of a system comprising a thin plate clamped on two sides via bolted joints. Both geometric and frictional contact nonlinearities are expected to be relevant. Provided were the CAD models and technical drawings of all parts as well as assembly instructions. The main objective was to predict the frequency and damping ratio of the lowest-frequency mode as function of the amplitude. Many different prediction approaches were pursued, ranging from well-known methods to very recently developed ones. After the submission deadline, the system has been fabricated and tested. The aim of this article is to evaluate the current state of the art in modeling and vibration prediction, and to provide directions for future methodological advancements.

42 ENGINEERING↗
DOE OSTI2021

EBSD of Rough Native CuInGaSe2 Thin-Films

The polycrystalline Cu (In, Ga) Se2, or CIGS, based thin-film materials system has long been studied for use in photovoltaic technologies, where its bandgap tunability, mechanical flexibility, and relatively low production costs are all appealing. Nonetheless, significant defect populations, which serve to reduce efficiency, create performance instabilities, and increase concerns about long-term reliability, have hindered wide-scale adoption. Prior work, including application of a scanning probe based deep level trap spectroscopy (SP-DLTS) defect mapping technique and scanning transmission electron microscope (STEM) based electron energy loss spectroscopy (EELS), has shown that the most detrimental defects, with energy level near mid-gap (thus serving as a carrier recombination center), are most likely caused by CuIn/Ga antisites and tend to cluster at or around certain grain boundaries [1,2]. However, the exact nature of these particular boundaries — their structures, chemistries, or even the relative misorientation of their associated grains — and their relation to this defect clustering and/or its formation is yet unknown. As such, electron backscatter diffraction (EBSD) orientation mapping, directly correlated with defect-sensitive techniques like SP-DLTS and/or STEM-EELS, could prove critical for providing the final missing links toward understanding the mechanisms behind these defects. Indeed, recent studies using correlative electron beam induced current (EBIC) with EBSD have been able to identify boundaries, and their relative misorientations, that possess detrimental electronic properties [3]. However, because EBIC is unable to resolve the defect energy levels, many questions are left unanswered. Furthermore, this study, and others like it, employed focused ion beam (FIB) milling to flatten the natively-rough CIGS [3-5], which may run the risk of changing the nature of any near-surface defect structures.

14 SOLAR ENERGY↗
DOE OSTI2020

Surface Passivation by Excess Sulfur for Controlled Synthesis of Large, Thin SnS Flakes

Tin sulfide (SnS) is part of the group IV chalcogenides (SnX, GeX; X: S, Se), a family of anisotropic layered materials considered for thin film photovoltaics, optoelectronics, and valleytronics, and predicted narrow bandgap multiferroic materials. Large ultrathin SnS flakes, suitable for a variety of applications, are challenging to synthesize because of the enhanced surface reactivity due to the open layer structure of SnS which gives rise to a competition between lateral and vertical growth. Here we investigate the effects of added sulfur on passivating the surface and modifying the balance between lateral expansion and thickening of SnS flakes in chemical vapor transport from a SnS precursor. In addition, we investigate the growth of SnS flakes and compare the results of synthesis from a pure SnS precursor with growth, in which a slight excess of sulfur is supplied in different ways. Our results demonstrate that small amounts of excess sulfur can profoundly affect the size and thickness distributions of SnS flakes. The largest and thinnest flakes are obtained if (i) traces of sulfur are added and (ii) the sulfur source consists either of small Sx fragments released at high temperatures from the reactor walls, or atomic S supplied by sublimation from SnS 2 . The likely mechanism for the observed growth modifications is a transient surface passivation of SnS flakes during growth, which reduces the reactivity of the top facet of the flakes, limits vertical growth, and thus gives rise to ensembles with increased lateral size and reduced thickness.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Resolving the Evolution of Atomic Layer-Deposited Thin-Film Growth by Continuous In Situ X-Ray Absorption Spectroscopy

In situ synchrotron X-ray absorption near-edge structure characterization of thin-film titania growth by atomic layer deposition (ALD) over ZnO nanowires reveals persistent low-coordinated Ti motifs leading to a new picture of ALD growth. Through the design of growth and measurement cycles, Ti K-edge spectral data are continuously recorded so as to characterize the film evolution as a function of ALD cycle number and the surface changes within the time scale of the ALD cycle. A unified set of analysis tools is developed to interpret the time-series of spectral data. A prenucleation stage of growth, a transition region, and then a steady-state growth stage are observed with distinguishable features. Multivariate curve resolution analysis, that is physically constrained, demonstrates two specific spectral components with associated, time-dependent concentrations. The bulk-film component tracks the stages of growth. The surface and interface components, present throughout the stages of growth, reveal a significant coverage of relatively isolated or loosely networked tetrahedrally coordinated Ti atomic motifs. Lastly, spectral signatures for the intra-cycle growth kinetics are reconstructed at a time resolution of ~1 s and demonstrate that the transient Ti motifs on the growing surface stabilize within a few seconds of the Ti precursor pulse.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Solvent and A-Site Cation Control Preferred Crystallographic Orientation in Bromine-Based Perovskite Thin Films

Preferred crystallographic orientation in polycrystalline films is desirable for efficient charge carrier transport in metal halide perovskites and semiconductors. However, the mechanisms that determine the preferred orientation of halide perovskites are still not well understood. In this work, we investigate crystallographic orientation in lead bromide perovskites. We show that the solvent of the precursor solution and organic A-site cation strongly affect the preferred orientation of the deposited perovskite thin films. Specifically, we show that the solvent, dimethylsulfoxide, influences the early stages of crystallization and induces preferred orientation in the deposited films by preventing colloidal particle interactions. Additionally, the methylammonium A-site cation induces a higher degree of preferred orientation than the formamidinium counterpart. We use density functional theory to show that the lower surface energy of the (100) plane facets in methylammonium-based perovskites, compared to the (110) planes, is the reason for the higher degree of preferred orientation. In contrast, the surface energy of the (100) and (110) facets is similar for formamidinium-based perovskites, leading to lower degree of preferred orientation. Furthermore, we show that different A-site cations do not significantly affect ion diffusion in bromine-based perovskite solar cells but impact ion density and accumulation, leading to increased hysteresis. Our work highlights the interplay between the solvent and organic A-site cation which determine crystallographic orientation and plays a critical role in the electronic properties and ionic migration of solar cells.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Coherence in Polycrystalline Thin Films of Twisted Molecular Crystals

Helicoidal crystallites in rhythmically banded spherulites manifest spectacular optical patterns in small molecules and polymers. It is shown that concentric optical bands indicating crystallographic orientations typically lose coherence (in-phase twisting) with growth from the center of nucleation. Here, coherence is shown to increase as the twist period decreases for seven molecular crystals grown from the melt. This dependence was correlated to crystallite fiber thickness and length, as well as crystallite branching frequency, a parameter that was extracted from scanning electron micrographs, and supported by numerical simulations. Hole mobilities for 2,5-didodecyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP-C12) measured by using organic field-effect transistors demonstrated that more incoherent boundaries between optical bands in spherulites lead to higher charge transport for films with the same twist period. This was rationalized by combining our growth model with electrodynamic simulations. This work illustrates the emergence of complexity in crystallization processes (spherulite formation) that arises in the extra variable of helicoidal radial twisting. The details of the patterns analyzed here link the added complexity in crystal growth to the electronic and optical properties of the thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Thin Water Films Enable Low-Temperature Magnesite Growth Under Conditions Relevant to Geologic Carbon Sequestration

Injecting supercritical CO2 (scCO2) into basalt formations for long-term storage is a promising strategy for mitigating CO2 emissions. Mineral carbonation can result in permanent entrapment of CO2; however, carbonation kinetics in thin H2O films in humidified scCO2 is not well understood. We investigated forsterite (Mg2SiO4) carbonation to magnesite (MgCO3) via amorphous magnesium carbonate (AMC; MgCO3·xH2O, 0.5 < x < 1), with the goal to establish the fundamental controls on magnesite growth rates at low H2O activity and temperature. Experiments were conducted at 25, 40, and 50 °C in 90 bar CO2 with a H2O film thickness on forsterite that averaged 1.78 ± 0.05 monolayers. In situ infrared spectroscopy was used to monitor forsterite dissolution and the growth of AMC, magnesite, and amorphous SiO2 as a function of time. Geochemical kinetic modeling showed that magnesite was supersaturated by two to three orders of magnitude and grew according to a zero-order rate law. The results indicate that the main drivers for magnesite growth are sustained high supersaturation coupled with low H2O activity, a combination of thermodynamic conditions not attainable in bulk aqueous solution. This improved understanding of reaction kinetics can inform subsurface reactive transport models for better predictions of CO2 fate and transport.

Kerisit, Sebastien N.↗
DOE OSTI2020

Electronic Structure, Optical Properties, and Photoelectrochemical Activity of Sn-Doped Fe 2 O 3 Thin Films

Hematite (Fe 2 O 3 ) is a well-known oxide semiconductor suitable for photoelectrochemical (PEC) water splitting and industry gas sensing. It is widely known that Sn doping of Fe 2 O 3 can enhance the device performance, yet the underlying mechanism remains elusive. In this work, we determine the relationship between electronic structure, optical properties and PEC activity of Sn doped Fe 2 O 3 by studying highly crystalline, well-controlled thin films prepared by pulsed laser deposition (PLD). We show that Sn doping substantially increases the n-type conductivity of Fe 2 O 3 , and the conduction mechanism is better described by small-polaron hoping (SPH) model. Only 0.2% Sn doping significantly reduce the activation energy barrier for SPH conduction from at least 0.5 eV for undoped Fe 2 O 3 to 0.14 eV for doped ones. A combination of X-ray photoemission, X-ray absorption spectroscopy and DFT calculations reveals the Fermi level gradually shifts toward the conduction band minimum with Sn doping. A localized Fe 2+ like gap state is observed at the top of valence band, accounting for the SPH conduction. Interestingly, in contrast to the literature, we find that only 0.2% Sn doping in Fe 2 O 3 significantly improves the PEC activity, while more Sn decreases it. The improved PEC activity is partially attributed to an increased band bending potential which facilitates the charge separation at space charge region. The reduced activation energy barrier for SPH will facilitate the transport of photo-excited carriers for the enhanced PEC, which is of interest for further carrier dynamics study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Radiolysis of Thin Water Ice in Electron Microscopy

Little is known about the radiolysis of water ice, especially as compared to the radiolysis of liquid water. In this study, the radiolytic decomposition of thin water ice films is probed for an initial 80 keV electron beam using electron energy loss spectroscopy, EELS. Pre-peaks in the oxygen K-edge spectra give the relative intensities of most of the oxygen containing species produced by radiolytic water decomposition. Contrary to expectations from the extrapolation of liquid water radiolysis data to high dose rates where significant H 2 O 2 production is expected, the main molecular product observed in the oxygen K-edge EELS spectra of water ice is O 2 . Significant mass loss of water and decomposition of most of its radiolytic products are observed for higher exposures, and the O atom seems to have a major role in the subsequent chemistry. An inverse relationship between the formation of O 2 and of ·OH is observed. A new high-dose reaction scheme is proposed. Furthermore, the significance of our results with respect to the radiolysis of water ice and for electron microscopy studies is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

The Triple Component Interface of Ni–Co–Ce: Growth, Chemical State, and Stability of NiCo Bimetallic Particles on Reducible CeO 2 (111) Thin Films

The growth of NiCo particles at low coverages over reducible CeO 2 (111) thin films producing a triple interface between Ni-Co-Ce was investigated by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS), which was compared to that of monometallic Ni and Co particles. XPS data show that deposition of either Ni or Co on CeO 2 at 300 K causes a partial reduction of Ce 4+ cations to Ce 3+ ions. At 0.3 monolayer (ML), XPS detects Co 2+ on CeO 2 . However, both Ni 0 and Ni 2+ are present as major species at 300 K and annealing causes a significant increase of Ni 2+ in Ni particles. Deposition of 0.3 ML Co over 0.3 ML Ni on CeO 2 at 300 K induces reduction of Ni 2+ to metallic Ni and Ni 0 was found as predominant species. Unlike for Co/CeO 2 , metallic Co was also present over the Co-Ni/CeO 2 surface in addition to Co 2+ . Further, this behavior indicates the formation of NiCo bimetallic particles with the possibility of Co diffusion to the interface of Ni/ceria. With heating, the intermixing of Ni and Co atoms in bimetallic particles on CeO 2 was facilitated. Furthermore, oxidation of both metals and ceria occurred as a result of the diffusion of lattice oxygen from the bulk of ceria to the surface. A slight increase in Ni 2+ was observed after heating Co-Ni/CeO 2 to 500 K or higher. Co became Co 2+ with heating to 800 K. Our STM results confirm the formation of NiCo bimetallic particles on CeO 2 at 300 K and further suggest that the addition of Co can help inhibit the sintering of Ni particles at higher temperatures. Bimetallic particles were also obtained by depositing Ni over existing Co particles on CeO 2 . However, our XPS data demonstrate that the deposition order of Co and Ni plays a role in the chemical state of these two metals in bimetallic particles, likely attributed to the difference in their compositions at the bimetallic particle surface as well as the metal-support interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Synthesis and Physical Properties of Manganese Chromium Nitride Thin Films Grown via Molecular Beam Epitaxy

Here, we demonstrate the ability to grow epitaxial thin films of manganese–chromium nitride (Mn x Cr 1–x N) across the entire composition range on magnesium oxide (MgO) (1 0 0) surfaces by molecular beam epitaxy. By independently controlling the ratio of the atomic fluxes of manganese and chromium, the compositional dependence of structural and electrical transport properties is determined. Soft X-ray absorption shows that the valence states of Cr( 3+ ) and Mn( 3+ ) remain identical among these MnCrN epitaxial films. The metallic transport behavior of binary manganese nitride (MnN) and chromium nitride (CrN) is suppressed in the ternary alloys. Changes in room temperature electrical resistivity of up to 100 times and 5 orders of magnitude at cryogenic temperatures are observed. This work expands the variety of nitride compounds available for epitaxial integration and could provide additional flexibility for the development of metal–semiconductor–insulator junctions for spintronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Oxidation and Reduction of Polycrystalline Cerium Oxide Thin Films in Hydrogen

This study investigates the oxidation state of ceria thin films' surface and subsurface under 100 mTorr hydrogen using ambient pressure X-ray photoelectron spectroscopy. We examine the influence of the initial oxidation state and sample temperature (25-450 °C) on the interaction with hydrogen. Our findings reveal that the oxidation state during hydrogen interaction involves a complex interplay between oxidizing hydride formation, reducing thermal reduction, and reducing formation of hydroxyls followed by water desorption. In all studied conditions, the subsurface exhibits a higher degree of oxidation compared to the surface, with a more subtle difference for the reduced sample. The reduced samples are significantly hydroxylated and covered with molecular water at 25 °C. We also investigate the impact of water vapor impurities in hydrogen. We find that although 1 × 10 -6 Torr water vapor oxidizes ceria, it is probably not the primary driver behind the oxidation of reduced ceria in the presence of hydrogen.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗