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At least 397 records · Page 22

Structural and optical properties of cubic GaN on U-grooved Si (100)

Cubic GaN epitaxy on large-area U-grooved silicon (100) dies is demonstrated by metalorganic chemical vapor deposition, and its structural and optical properties are reported. Scanning electron, atomic force, and transmission electron microscopy studies reveal that cubic GaN shows no discernible threading dislocations and a low stacking fault density of 3.27 ± 0.18 × 10 4 cm –1 . Temperature-dependent photoluminescence studies reveal as-grown cubic GaN band edge emission internal quantum efficiency as 25.6% ± 0.9%. Selective etching of the low-temperature AlN buffer layer, SiO 2 sidewalls, and hexagonal-phase GaN is demonstrated, which increases the cubic GaN band edge emission internal quantum efficiency to 31.6% ± 0.8%. This increase is attributed to the decrease in the radiative recombination lifetime via the removal of defective hexagonal-phase GaN. Altogether, cubic GaN on U-grooved silicon with high structural and optical quality is reported, promising its suitability for next-generation devices.

36 MATERIALS SCIENCE↗

Adherence of sputtered titanium carbides

Sputtered coatings of the refractory metal carbides are of great interest for applications where hard wear-resistant materials are desired. The usefulness of sputtered refractory carbides is often limited, in practice, by spalling or interfacial separation. In this work improvements in the adherence of refractory carbides on iron, nickel and titanium based alloys were obtained by using oxidation, reactive sputtering or sputtered interlayers to alter the coating-substrate interfacial region. X-ray photoelectron spectroscopy and argon ion etching were used to characterize the interfacial regions, and an attempt was made to correlate adherence as measured in wear tests with the chemical nature of the interface.

Brainard, W. A.↗

Improved adhesion of sputtered refractory carbides to metal substrates

Sputtered coatings of the refractory metal carbides are of great interest for applications where hard wear-resistant materials are desired. The usefulness of sputtered refractory carbides is often limited in practice by spalling or interfacial separation. In this work improvements in the adherence of refractory carbides on iron, nickel and titanium base alloys were obtained by using oxidation, reactive sputtering or sputtered interlayers to alter the coating-substrate interfacial region. X-ray photoelectron spectroscopy and argon ion etching were used to characterize the interfacial regions, and an attempt was made to correlate adherence as measured in wear tests with the chemical nature of the interface.

Wheeler, D. R.↗

A V-grooved GaAs solar cell

V-grooved GaAs solar cells promise the benefits of improved optical coupling, higher short-circuit current, and increased tolerance to particle radiation compared to planar cells. A GaAs homojunction cell was fabricated by etching a V-groove pattern into an n epilayer (2.1 x 10 to the 17th power per cu cm) grown by metalorganic chemical vapor deposition (MOCVD) on an n+ substrate (2.8 x 10 to the 18th power per cu cm) and then depositing and MOCVD p epilayer (4.2 x 10 to the 18th power per cu cm). Reflectivity measurements on cells with and without an antireflective coating confirm the expected decrease in reluctance of the microgrooved cell compared to the planar structure. The short circuit current of the V-grooved solar cell was 13 percent higher than that of the planar control.

Bailey, S. G.↗

Feasibility Study to Dissolve Additively Manufactured Inconel 718 Support Structures

Additive manufacture (AM) component design face constrains due to support structure removal. Interior passages or delicate geometries require supports yet cannot be removed without compromising the design or complicating post-processing. A process was developed to dissolve metal AM supports where a sensitizing agent is applied post-build. During stress relief the sensitizing agent diffuses into the surface and alters the chemical composition of the top 100 to 200 μm. During an electrochemical dissolution process the sensitized region is susceptible to corrosion/dissolution and the etching reaction self-terminates once the sensitized region is dissolved. Support thickness varies from 80 to 200 μm, resulting in total dissolution or sufficiently weakened to facilitate removal. The objective of this project was to demonstrate a support structure dissolution process for IN718 components built using AM and to characterize the impact on mechanical properties, microstructure, and surface finish.

Omar R Mireles↗

A V-grooved GaAs solar cell

V-grooved GaAs solar cells promise the benefits of improved optical coupling, higher short-circuit current, and incrased tolerance to particle radiation compared to planar cells. A GaAs homojunction cell was fabricated by etching a V-groove pattern into an n-epilayer (2.1 x 10 to the 17th power per cu cm) grown by metalorganic chemical vapor deposition (MOCVD) on an n+ substrate (2.8 x 10 to the 18th power per cu cm) and then depositing an MOCVD p epilayer (4.2 x 10 to the 18th power per cu cm). Reflectivity measurements on cells with and without an antireflective coating confirm the expected decrease in reflectance of the microgrooved cell compared to the planar structure. The short-circuit current of the V-grooved solar cell was 13 percent higher than that of the planar control.

Bailey, S. G.↗

Conversion efficiency improvement of ELO GaAs solar cell, deposited on water soluble sacrificial buffer

Here, we demonstrate the improvement of power conversion efficiency of an epitaxially-lifted-off single junction GaAs solar cell deposited on a water-soluble sacrificial buffer architecture by introducing an additional germanium (Ge) interlayer between GaAs and the fluoride buffer. The epitaxial lift-off (ELO) technique has been extensively used to separate III-V device layers from their single crystal GaAs substrates. However, conventional ELO requires the use of concentrated hydrofluoric acid (HF) for extended times to etch out the sacrificial layer, subsequently degrading the surface roughness of the parent wafer. As a result, the wafer has to undergo expensive and intensive chemical mechanical polishing (CMP) processes, costing about 25% of a pristine 6-inch GaAs substrate. In our previous work, we demonstrated a method to eliminating the need for CMP post-processing by using water-assisted ELO (H 2 O-ELO). A water-soluble, 3-layer buffer architecture was developed using alkaline earth compounds. However, devices suffered low performance due to a high defect density in the GaAs active layers. A Ge interlayer was introduced to provide a more favorable surface energy for GaAs growth, which leads to an improvement of GaAs crystal quality. The Ge deposition conditions were optimized to achieve a high-quality Ge layer on triple-layer fluoride buffer. Single junction GaAs devices fabricated on Ge/(Ca,Sr)F 2 /BaF 2 /(Ca,Sr)F 2 showed improvement of solar cell performance parameters featuring increases in V oc by 23.7%, and fill factor (F.F.) by 4.9%, which results in an overall improvement of power conversion efficiency from 10.3% to 12.69%.

14 SOLAR ENERGY↗

Operando XPS in reactive plasmas: The importance of the wall reactions

In this article, advancements in differential pumping and electron optics over the past few decades have enabled x-ray photoelectron spectroscopy (XPS) measurements at (near-)ambient pressures, bridging the pressure gap for characterizing realistic sample chemistries. Recently, we have demonstrated the capabilities of an ambient pressure XPS setup for in situ plasma environment measurements, allowing plasma-surface interactions to be studied in operando rather than using the traditional before-and-after analysis approach. This new “plasma-XPS” technique facilitates the identification of reaction intermediates critical for understanding plasma-assisted surface processes relevant to semiconductor nanomanufacturing, such as physical vapor deposition, etching, atomic layer deposition, and many other plasma applications. In this paper, we apply the plasma-XPS approach to monitor real-time surface chemical changes on a model Ag(111) single crystal exposed to oxidizing and reducing plasmas. We correlate surface-sensitive data with concurrent gas-phase XPS measurements and residual gas mass-spectrum analysis of species generated during plasma exposure, highlighting the significant role of plasma-induced chamber wall reactions. Ultimately, we demonstrate that plasma-XPS provides comprehensive insights into both surface and gas-phase chemistry, establishing it as a versatile and dynamic characterization tool with broad applications in microelectronics research. Finally, we outline potential enhancements and future metrology directions to advance plasma-XPS investigations further.

36 MATERIALS SCIENCE↗

The correlation of alkalis and aluminum during high-temperature volatilization of albite and nepheline

Our previous study of high-temperature evaporation of mafic targets has shown a systematic enrichment of newly-formed condensates in silicon and alkalis and depletion in refractory elements (Al, Ca, Ti). This effect, which is consistent with the volatility of the elements, was also tested for several experiments with acidic targets. In one case it was the impact evaporation of granite targets using a light-gas gun facility. Analyses of the condensate which was collected during the impact show that it was enriched in Al and Na so that the composition of the condensate became close to nepheline. In the work of Nagahara, an incongruent evaporation of alkali feldspars under stationary conditions has been also proposed. These discoveries required a more detailed study of high-temperaure evaporation of monomineralic Al-silicate targets. In these experiments, we have used samples of oligoclase and of nepheline. Vaporization of samples was performed in a hermetic cell filled with helium at normal temperature and pressure using a powerful Nd-laser focused on the sample. Laser pulses had the following parameters: luminous energy approximately 600 J, duration approximately 10(exp -3) s, density of luminosity was approximately 5 x 10(exp 6) W/sq cm, the temperature of vaporization is about 3000-4000 K. About 4 cm from the sample, a nickel foil was placed on which the condensate was collected. Films of condensate were analyzed using X-Ray Photo-Electron spectrometer ES-2401. The measurement of internal chemical composition and of the charging state of elements through the whole depth of the condensed films was made layer by layer with argon-ion etching of 200 A of the film per step. Results of this study are given. The bottom layers of condensed film correspond to the front parts of the evaporated cloud or to condensation at the beginning of the evaporative process and surface layers to condensation at the end of the process.

Dikov, Yu. P.↗

CIGS2 Thin-Film Solar Cells on Flexible Foils for Space Power

CuIn(1-x)Ga(x)S2 (CIGS2) thin-film solar cells are of interest for space power applications because of the near optimum bandgap for AM0 solar radiation in space. CIGS2 thin film solar cells on flexible stainless steel (SS) may be able to increase the specific power by an order of magnitude from the current level of 65 Wkg(sup -1). CIGS solar cells are superior to the conventional silicon and gallium arsenide solar cells in the space radiation environment. This paper presents research efforts for the development of CIGS2 thin-film solar cells on 127 micrometers and 20 micrometers thick, bright-annealed flexible SS foil for space power. A large-area, dual-chamber, inline thin film deposition system has been fabricated. The system is expected to provide thickness uniformity of plus or minus 2% over the central 5" width and plus or minus 3% over the central 6" width. During the next phase, facilities for processing larger cells will be acquired for selenization and sulfurization of metallic precursors and for heterojunction CdS layer deposition both on large area. Small area CIGS2 thin film solar cells are being prepared routinely. Cu-rich Cu-Ga/In layers were sputter-deposited on unheated Mo-coated SS foils from CuGa (22%) and In targets. Well-adherent, large-grain Cu-rich CIGS2 films were obtained by sulfurization in a Ar: H2S 1:0.04 mixture and argon flow rate of 650 sccm, at the maximum temperature of 475 C for 60 minutes with intermediate 30 minutes annealing step at 120 C. Samples were annealed at 500 C for 10 minutes without H2S gas flow. The intermediate 30 minutes annealing step at 120 C was changed to 135 C. p-type CIGS2 thin films were obtained by etching the Cu-rich layer segregated at the surface using dilute KCN solution. Solar cells were completed by deposition of CdS heterojunction partner layer by chemical bath deposition, transparent-conducting ZnO/ZnO: Al window bilayer by RF sputtering, and vacuum deposition of Ni/Al contact fingers through metal mask. PV parameters of a CIGS2 solar cell on 127 micrometers thick SS flexible foil measured under AM 0 conditions at NASA GRC were: V(sub oc) = 802.9 mV, J(sub sc) = 25.07 mA per square centimeters, FF = 60.06%, and efficiency 0 = 8.84%. For this cell, AM 1.5 PV parameters measured at NREL were: V(sub oc) = 788 mV, J(sub sc) = 19.78 mA per square centimeter, FF = 59.44%, efficiency 0 = 9.26%. Quantum efficiency curve showed a sharp QE cutoff equivalent to CIGS2 bandgap of approximately 1.50 eV, fairly close to the optimum value for efficient AM0 PV conversion in the space.

Dhere, Neelkanth G.↗

Abiotic Versus Biotic Weathering Of Olivine As Possible Biosignatures

We are investigating the weathering of silicate minerals by both purely inorganic, and biologically mediated processes using field-emission scanning electron microscopy (FESEM) and energy dispersive x-ray spectroscopy (EDS). By resolving surface textures and chemical compositions of weathered surfaces at the sub-micron scale we hope to be able to distinguish abiotic from biotic weathering processes and so establish a new biosignature applicable to the study of astromaterials including but not limited to the Martian meteorites. Sterilized olivine grains (San Carlos, Arizona) no more than 1-2 mm in their longest dimension were optically assayed to be uniform in color and free of inclusions were selected as weathering subjects. Prior to all experiments surface morphologies and Fe/Mg ratios were determined for each grain using FE-SEM and EDS. Experiments were divided into two categories abiotic and biotic and were compared with "naturally" weathered samples. For the preliminary experiments, two trials (open and closed to the ambient laboratory environment) were performed under abiotic conditions, and three trials under biotic conditions (control, day 1 and day 2). The open system abiotic trials used sterile grains heated at 98 C and 200 C for both 24 and 48 hours in 1L double distilled de-ionized water. The closed system abiotic trials were conducted under the same conditions but in a sealed two layer steel/Teflon "bomb" apparatus. The biotic trials used sterile grains mounted in a flow-through device attached to a wellhead on the Columbia River aquifer. Several discolored, altered, grains were selected to document "natural" weathering surface textures for comparison with the experimental samples. Preliminary results indicate there are qualitative differences in weathered surface textures among all the designed experiments. The olivine grains in abiotic trials displayed etching, pitting, denticulate margins, dissolution and clay formation. The scale of the features ranged from tens to a few microns with textures that remained relatively sharp and were crystallographically controlled. These results were comparable to that observed in the "naturally" weathered comparison/reference grains. Chemical analysis by EDS indicates these textures correlated with the relative loss of Mg and Fe cations by diffusional processes. In contrast the biotic results indicated changes in the etching patterns on the scale of hundreds of nm, which are neither sharp nor crystallographically controlled (nanoetching). Organisms, organic debris and/or extracellular polymeric substances (biofilm) were often in close proximity or direct contact with the nanoetching. While there are many poorly constrained variables in natural weathering experiments to contend with, such as the time scale, the chemistry of the fluids and degree of biologic participation, some preliminary observations can be made: (1) certain distinct surface textures appear correlated with the specific processes giving rise to these textures; (2) the process of diffusing cations can produce many similar styles of surface textural changes; and (3) the main difference between abiotic and biotically produced weathering is the scale (microns versus nanometers) and the style (crystallographically versus noncrystallographically controlled) of the textural features. Further investigation into nanosize scale surface textures should attempt to quantify both textures and chemical changes of the role of microorganisms in the weathering of silicates. Additional experiments addressing nanoscale textures of shock features for comparison with the current data set.

Longazo, Teresa G.↗

Techniques for increasing boron fiber fracture strain

Improvement in the strain-to-failure of chemical-vapor-deposition boron fibers is shown possible by contracting the tungsten boride core region and its inherent flaws. Results of three methods are presented in which etching and thermal-processing techniques were employed to achieve core flaw contraction by internal stresses available in the boron sheath. After commercially and treatment-induced surface flaws were removed from 203-micron (8-mil) fibers, the core flaw was observed to be essentially the only source of fiber fracture. Thus, fiber strain-to-failure was found to improve by an amount equal to the treatment-induced contraction on the core flaw. To date, average fracture strains and stresses greater than 1.4% and 5.5 GN/sq m (800 ksi), respectively, have been achieved. Commercial feasibility considerations suggest as the most cost-effective technique that method in which as-produced fibers are given a rapid heat treatment above 700 C. Preliminary results concerning the contraction kinetics and fracture behavior observed with this technique are presented and discussed for both high-vacuum and argon-gas heat-treatment environments.

Dicarlo, J. A.↗

Correlations between the interfacial chemistry and current-voltage behavior of n-GaAs/liquid junctions

Correlations between the surface chemistry of etched, (100) oriented n-GaAs electrodes and their subsequent photoelectrochemical behavior have been probed by high-resolution X-ray photoelectron spectroscopy. GaAs photoanodes were chemically treated to prepare either an oxide-free near stoichiometric surface, a surface enriched in zero-valent arsenic or a substrate-oxide terminated surface. The current-voltage (I-V) behavior of each surface type was subsequently monitored in contact with several electrolytes.

Tufts, Bruce J.↗

Scalable Synthesis of Ti 3 C 2 T x MXene

Scaling the production of synthetic 2D materials to industrial quantities has faced significant challenges due to synthesis bottlenecks whereby few have been produced in large volumes. These challenges typically stem from bottom‐up approaches limiting the production to the substrate size or precursor availability for chemical synthesis and/or exfoliation. In contrast, MXenes, a large class of 2D transition metal carbides and/or nitrides, are produced via a top‐down synthesis approach. The selective wet etching process does not have similar synthesis constraints as some other 2D materials. The reaction occurs in the whole volume; therefore, the process can be readily scaled with reactor volume. Herein, the synthesis of 2D titanium carbide MXene (Ti 3 C 2 T x ) is studied in two batch sizes, 1 and 50 g, to determine if large‐volume synthesis affects the resultant structure or composition of MXene flakes. Characterization of the morphology and properties of the produced MXene using scanning electron microscopy, X‐ray diffraction, dynamic light scattering, Raman spectroscopy, X‐ray photoelectron spectroscopy, UV–visible spectroscopy, and conductivity measurements show that the materials produced in both batch sizes are essentially identical. This illustrates that MXenes experience no change in structure or properties when scaling synthesis, making them viable for further scale‐up and commercialization.

Shuck, Christopher E.↗

Uptake of Pb and the Formation of Mixed (Ba,Pb)SO 4 Monolayers on Barite During Cyclic Exposure to Lead-Containing Sulfuric Acid

Barite (BaSO 4 ) is a common additive in lead-acid batteries, where it acts as a nucleating agent to promote the reversible formation and dissolution of PbSO 4 during battery cycling. However, little is known about the molecular-scale mechanisms the nucleation and cyclic evolution of PbSO 4 over a battery’s lifetime. In this study, we explore the responses of a barite (001) surface to cycles of high and low lead concentrations in the presence of 100 mM sulfuric acid using in-situ atomic force microscopy and high-resolution X-ray reflectivity. Here we find that PbSO 4 epitaxial films readily nucleate on the barite surface, even from solutions that are undersaturated relative to bulk PbSO 4 . Despite this, barite (001) proves to be an ineffective nucleator of bulk PbSO 4 , as multilayer growth is suppressed even in highly supersaturated solutions. Instead, we find evidence that Pb 2+ ions can directly exchange with Ba 2+ to create mixed (Ba,Pb)SO 4 surfaces. These chemically mixed surfaces do not host PbSO4 monolayers as readily as pristine barite, and the original reactivity is not regained until a fresh surface is reestablished by aggressive etching. Our results can be partly explained by traditional models of Stranski-Krastanov (S-K) growth, in which monolayer films are stabilized by a reduction in surface energy, but multilayer growth is inhibited by epitaxial strain. Complementary density functional theory calculations confirmed the basic energetic-terms of traditional S-K models, but also showed evidence form more complex, thickness-dependent, energetics than would be predicted from the S-K models. The experimental results can be better understood by extending the S-K model to consider the formation of mixed surfaces and films, which can have reduced strain and interfacial energies relative to pure films, while also being stabilized by entropy of mixing. These insights into non-stoichiometric heteroepitaxy will enable better predictions of how barite affects PbSO 4 nucleation in battery environments.

25 ENERGY STORAGE↗

Size-Dependent Electrical Transport Properties in Conducting Diamond Nanostripes

With the advances in nanofabrication technology, horizontally aligned and well-defined nitrogen-doped ultrananocrystalline diamond nanostripes can be fabricated with widths in the order of tens of nanometers. The study of the size-dependent electron transport properties of these nanostructures is crucial to novel electronic and electrochemical applications. In this paper, 100 nm thick n-type ultrananocrystalline diamond thin films were synthesized by microwave plasma-enhanced chemical vapor deposition method with 5% N2 gas in the plasma during the growth process. Then the nanostripes were fabricated using standard electron beam lithography and reactive ion etching techniques. The electrical transport properties of the free-standing single nanostripes of different widths from 75 to 150 nm and lengths from 1 to 128 μm were investigated. The study showed that the electrical resistivity of the n-type ultrananocrystalline diamond nanostripes increased dramatically with the decrease in the nanostripe width. The nanostripe resistivity was nearly doubted when the width was reduced from 150 nm to 75 nm. The size-dependent variability in conductivity could originate from the imposed diffusive scattering of the nanostripe surfaces which had a further compounding effect to reinforce the grain boundary scattering.

Zhou, Andrew F. (ORCID:0000000243050409)↗

Mechanical and spectroscopic properties of metal-containing polyimides

The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymerization or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.

Taylor, L. T.↗

Mechanical and spectroscopic properties of metal containing polyimides

The incorporation of specific metal ions into polyimides is described. Detailed studies have included various compounds of copper, lithium, and palladium as dopants. Addition of the metal during polymermzation or after formation of the polyamic acid precedes the thermal imidization step. With many dianhydride-diamine-dopant combinations high quality variously colored films are produced. Many metal doped films exhibit (1) improved high temperature adhesive properties, (2) increased electrical conductivity, (3) excellent thermal stability, (4) improved acid/base resistance, (5) increased modulus in flexible films and (6) excellent high temperature tensile strength. X-ray photo-electron spectroscopic study of these films suggests that many of the additives undergo chemical modification during thermal imidization. Palladium dopants appear to be partially reduced to the metallic state, while lithium and copper dopants are probably converted to their oxides. Ion etching experiments with Auger electron spectroscopy monitoring are discussed.

Taylor, L. T.↗