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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

The Underlying Chemical Mechanism of Selective Chemical Etching in CsPbBr 3 Nanocrystals for Reliably Accessing Near-Unity Emitters

Reliably accessing nanocrystal luminophores with near-unity efficiencies aids in the ability to understand the upper performance limits in optoelectronic applications that require minimal nonradiative losses. Constructing structure-function relationships at the atomic level, while accounting for inevitable defects, allows for the development of robust strategies to achieve near-unity quantum yield luminophores. For CsPbBr 3 perovskite nanocrystals, bromine vacancies leave behind undercoordinated lead atoms that act as traps, limiting the achievable optical performance of the material. Here, we show that selective etching represents a promising path for mitigating the consequences of optical defects in CsPbBr 3 nanocrystals. A mechanistic understanding of the etching reaction is essential for developing strategies to finely control the reaction. We report a study of the selective etching mechanism of CsPbBr3 nanocrystal cubes by controlling the etchant chemical potential. We observe optical absorption and luminescence trajectories while varying the extent and rate of lead removal, removing in some cases up to 75% of the lead from the original nanocrystal ensemble. At modest etchant chemical potentials, the size and shape uniformity of the nanocrystal ensemble improves in addition to the quantum yield, proceeding through a layer-by-layer etching mechanism. Operating with excessively high etchant chemical potentials is detrimental to the overall optical performance as the etching transitions to nonselective, while too low of a chemical potential results in incomplete etching. Through this general approach, we show how to finely control selective etching to consistently access a steady state or chemical stability zone of near-unity quantum yield CsPbBr 3 nanocrystals postsynthetically, suggesting a practical framework to extend this treatment to other perovskite compositions and sizes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

O · , H · , and · OH radical etching probability of polystyrene obtained for a radio frequency driven atmospheric pressure plasma jet

Atmospheric pressure plasma jets have great potential for the surface modification of polymers. In this work, the authors report on polystyrene etching by a radio frequency driven atmospheric pressure plasma jet with a focus on the role of H · , O · , and · OH radicals in this process. The absolute flux of H · , O · , and · OH radicals reaching the surface of the polymer was determined by a COMSOL MULTIPHYSICS reacting fluid dynamics model incorporating detailed transport phenomena in the boundary layer near the substrate. The simulated results of H · and · OH densities in the jet effluent were experimentally verified by two-photon absorption laser induced fluorescence and laser induced fluorescence, respectively. The carbon atom removal flux from the polystyrene surface was taken from previously reported measurements using the same plasma source. The authors show that the boundary layer effects in the interfacial region above the substrate can have a significant impact on the calculated etching probabilities. The reaction probability (β) has a significant uncertainty although a variation of 2 orders of magnitude in β leads to uncertainties of approximately 1 order of magnitude variation in the determined etching probability. The etching probability of polystyrene by · OH radicals was confirmed to be at least an order of magnitude larger than the polystyrene etching probability by O · radicals. The authors also confirmed the weak polystyrene etching probability by H · radicals. The model suggests that the presence of a 30 ppm O 2 impurity can lead to the production of · OH radicals in the far effluent of the Ar + 1% H 2 plasma jet close to the substrate at sufficient densities to enable effective etching.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Using block-copolymer nanolithography as a tool to sensitively evaluate variation in chemical dry etching rates of semiconductor materials with sub-5 nm resolution

Ion implantation is a robust and established method to customize the electronic properties of Si. However, fabricating doped, ultrafine semiconductor nanostructures can be challenging. Ion implantation has well-established effects on the dry etch rates of Si, which becomes increasingly consequential as the target dimension shrinks below a few tens of nanometers. While dry etching arrays of block copolymer-templated nanoscale holes (pitch = 37.5 nm, diameter ~25 nm) into p-type, n-type, and undoped Si, we observed that the lateral etch rate was notably larger for the n-type regions than p-type or undoped regions. By doing image analyses on high resolution electron micrographs of the nanostructured hole arrays, we were able to extract the porosity and average radii of the holes with subnanometer sensitivity and compare the relative etch rates between different doping conditions. We found that degenerately doped n-type silicon consistently etches between approximately 17% and 27% faster in the lateral direction than p-type Si, resulting in significantly larger porosity and, consequently, less mechanical stability. Here, we demonstrate that top-down dimensional analysis of a densely packed porous nanostructure is a robust method for assessing extremely small differences in the lateral, chemical etch rate of doped Si to a degree of sensitivity that was previously unachievable. The minute, dense-packed nature of block copolymer self-assembled nanostructures is shown to be ideal for this application. This proposed method could be useful for designing fabrication processes for heterogeneous nanostructures, as slight dry etch rate variations that may be within process tolerance at the micrometer-scale appear to have nontrivial consequences at the nanometer scale.

42 ENGINEERING↗
DOE OSTI2020

A study of damage-free in-situ etching of GaN in metalorganic chemical vapor deposition (MOCVD) by tertiarybutylchloride (TBCl)

This paper reports a study of the effect of NH 3 flow rate and reactor temperature on the tertiarybutylchloride (TBCl) etching of patterned GaN-on-sapphire templates. It is found that a reduced NH 3 flow rate and an elevated reactor temperature can eliminate islands or dots on the surface, while at the same time, enhance the etching around dislocations. TBCl etching was also performed on planar bulk GaN templates with much lower dislocation density. We find an atomically flat and layer-by-layer etching behavior within the region free of dislocations. Surface kinetics analysis reveals a short diffusion length of etching products. Room-temperature photoluminescence (PL) and x-ray photoelectron spectroscopy (XPS) measurements confirm that TBCl etching is capable of removing the damage and impurities induced by plasma etching without introducing additional damage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Inhibition of AlF3·3H2O Impurity Formation in Ti3C2Tx MXene Synthesis under a Unique CoFx/HCl Etching Environment

MXenes, most commonly transition metal carbides, are a family of two-dimensional (2D) materials with promising potential in, among other applications, supercapacitors and batteries. MXenes are synthesized by etching of aluminum or gallium layers in its parent MAX phase directly by HF or by HF in situ formation using a fluoride salt and strong acid. A commonly undesired byproduct of MXene synthesis is AlF3·3H2O. To relieve MXenes from AlF3·3H2O impurity, it is important to elucidate the factors that drive its formation. Here, we dually deduce the conditions that lead to AlF3·3H2O formation while exploring etching with cobalt fluorides (CoF2/CoF3). Previously uncharacterized, etching with cobalt fluorides offers a forthright method to etch MXenes while intercalating cobalt cations. The influence of this etching environment and AlF3·3H2O formation on MXene’s structure, morphology, and surface bonding is investigated. Ionic strength of solution used for etching is found to be a critical driving factor in the formation of AlF3·3H2O impurity formation. Specifically, when the ionic strength falls between ~8.5 and 10 M, AlF3 complexation is stable. As a result, Ti3C2Tx MXene phase with AlF3·3H2O impurity is obtained. In contrast, near-pure MXene is the only solid state product when I is smaller than 8.5 M or larger than 10 M. Hence, high purity MXene phase can be synthesized by subtle compositional tuning to manipulate the ionic strength of the etching environment.

Cockerham, Cody B.↗
DOE OSTI2020

Genesis and Propagation of Fractal Structures During Photoelectrochemical Etching of n-Silicon

The genesis, propagation, and dimensions of fractal-etch patterns that form anodically on front- or back-illuminated n-Si(100) photoelectrodes in contact with 11.9 M NH 4 F (aqueous) have been investigated during either a linear potential sweep or a constant potential hold ( E = +6.0 V versus Ag/AgCl). Optical images collected in situ during electrochemical experiments reflected the location and underlying mechanism of initiation and propagation of the structures on the surface. X-ray photoelectron spectroscopic (XPS) data collected for samples emersed from the electrolyte at varied times provided detailed information about the chemistry of the surface during fractal etching. The fractal structure was strongly influenced by the orientation of the crystalline Si sample. Furthermore, the etch patterns were initially generated at points along the circumference of bubbles that formed upon immersion of n-Si(100) samples in the electrolyte, most likely due to the electrochemical and electronic isolation of areas beneath bubbles. XPS data showed the presence of a tensile-stressed silicon surface throughout the etching process as well as the presence of SiO x F y on the surface. The two-dimensional fractal dimension, D f,2D , of the patterns increased with etching time to a maximum observed value of D f,2D = 1.82. Promotion of fractal etching near etch masks that electrochemically and electronically isolated areas of the photoelectrode surface enabled the selective placement of highly branched structures at desired locations on an electrode surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Fabrication and field emission properties of vertical, tapered GaN nanowires etched via phosphoric acid

The controlled fabrication of vertical, tapered, and high-aspect ratio GaN nanowires via a two-step top-down process consisting of an inductively coupled plasma reactive ion etch followed by a hot, 85% H 3 PO 4 crystallographic wet etch is explored. The vertical nanowires are oriented in the $[0001]$ direction and are bound by sidewalls comprising of $\{33\bar{6}2\}$ semipolar planes which are at a 12° angle from the [0001] axis. High temperature H3PO4 etching between 60 °C and 95 °C result in smooth semipolar faceting with no visible micro-faceting, whereas a 50 °C etch reveals a micro-faceted etch evolution. High-angle annular dark-field scanning transmission electron microscopy imaging confirms nanowire tip dimensions down to 8–12 nanometers. The activation energy associated with the etch process is 0.90 ± 0.09 eV, which is consistent with a reaction-rate limited dissolution process. The exposure of the $\{33\bar{6}2\}$ type planes is consistent with etching barrier index calculations. The field emission properties of the nanowires were investigated via a nanoprobe in a scanning electron microscope as well as by a vacuum field emission electron microscope. Finally, the measurements show a gap size dependent turn-on voltage, with a maximum current of 33 nA and turn-on field of 1.92 V nm -1 for a 50 nm gap, and uniform emission across the array.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Shape tuning of large area silicon nanotip arrays through reactive ion etching

Nanostructures formed in silicon form an important class of structures that span a broad spectrum of application areas. Of these, columnar structures of silicon featuring tiplike apexes have their own niche applications. Here, the ability to afford shape tunability for these structures further enhances their application potential. In this paper, we present our findings on the large area fabrication of silicon nanotips defined through microsphere lithography and shape tuned through a combination of different reactive ion etching (RIE) techniques. The self-sharpening mechanism of the tips when using nonplanar etch masks (microspheres) under anisotropic etching conditions is elucidated. We further show that depending on the manner of etching (continuous versus discrete multistep etch), identical anisotropic etching recipes produce vastly different tip morphologies. Hourglass-shaped silicon tips were obtained when silicon was subjected to anisotropic followed by isotropic etching conditions. Sharp silicon tips with tip apex radii on the order of 2 nm have been successfully realized when the RIE shape tuned tips were subjected to a series of oxidative sharpening steps.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2024

Communication—Controlling Etching of Germanium through Surface Charge Manipulation

Potassium hydroxide (KOH) aqueous solutions can effectively etch germanium. Etch rates were determined in an electrolytic etch cell. Electrically isolated Ge wafers were subject to an etch rate of 1.45 ± 0.07 nm min −1 , increasing to 12.6 ± 0.2 nm min −1 when grounded, 97 ± 2 nm min −1 when biased at −0.9 V, and 138 ± 2 nm min −1 with periodic biasing. Results suggest that the previously reported limited etching in KOH is associated with the recombination of holes with electrons injected from the surface reaction. The results of this study demonstrate that changing the hole concentration through biasing is an effective tool to control electrolytic etch rates, enabling future selective etching processes for germanium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1985

Ion-beam-assisted etching of diamond

The high thermal conductivity, low RF loss, and inertness of diamond make it useful in traveling wave tubes operating in excess of 500 GHz. Such use requires the controlled etching of type IIA diamond to produce grating like structures tens of micrometers deep. Previous work on reactive ion etching with O2 gave etching rates on the order of 20 nm/min and poor etch selectivity between the masking material (Ni or Cr) and the diamond. An alternative approach which uses a Xe(+) beam and a reactive gas flux of NO2 in an ion-beam-assisted etching system is reported. An etching rate of 200 nm/min was obtained with an etching rate ratio of 20 between the diamond and an aluminum mask.

Efremow, N. N.↗
DOE OSTI2024

Method to control the etching rate of materials

A method for etching materials in which organic solvents are added to the etching mixture and combined in a mixing arrangement. When agitated organic materials mix with the etching agent and interact with the underlying material to form a shield around the etched areas that prevents the additional interaction of water with the newly etched areas and enables the etching of silicon oxides (SiOx) but does not oxidize Si. This method leads to milder reactions with less heat generation and avoids the safety hazards associated with conventional etching methods.

Yi, Ran↗
DOE OSTI2025

Etching-assisted upcycling of Ni-lean to Ni-rich cathode materials

Upcycling is recognized as a sustainable recycling approach for spent lithium-ion batteries. However, existing upcycling methods typically involve intricate pretreatment or post-treatment steps, complicating their practical application. Here, in this study, we propose a straightforward, etching-assisted upcycling method that effectively transforms polycrystalline Ni-lean cathodes into high-performance single crystal Ni-rich cathodes. During the etching step, nickel acetate was dissolved into acetic acid and then polycrystalline NMC111 are etched in the solution. Finally, polycrystalline NMC111 are converted into single crystal particles coated with amorphous nickel acetate. This significantly enhances elemental diffusion during subsequent sintering by minimizing both particle size and the contact distance between NMC111 and nickel acetate. As elemental diffusion is improved and acetate ions decompose completely during sintering, the process requires neither additional pretreatment nor post-treatment. The resulting cathode materials (Etched-UP622) exhibit superior structural and electrochemical properties compared to the Control622, achieving an energy density of 719.7 Wh/kg, approximately 56.7 mAh/g higher than Control622 and 125.5 Wh/kg higher than NMC111. Etched-UP622 also delivers higher discharge capacity, improved rate performance and cycling stability, surpassing Control622 and NMC111. Meanwhile, NMC811 also can be synthesized by the proposed strategy, and the discharge capacity can reach 166.9 mAh/g at 1C, similar to 14 mAh/g higher than Control811. Overall, this etching-assisted strategy simplifies the upcycling process and offers a scalable, sustainable route for producing high-quality cathode materials.

Acid etching↗
DOE OSTI2025

Enhancement to the conductivity of surface transfer-doped (111) diamond through thermochemical surface etching

The use of a transition metal catalyzed thermochemical etching method for improving the carrier transport properties of the near-surface two-dimensional (2D) hole gas in surface transfer-doped hydrogen-terminated (111) diamond is demonstrated. Using Ni 0.8 Cr 0.2 films deposited and annealed to a temperature of 900 °C, with up to three etch cycles, preferential (111) surface etching produces large terraces exceeding 10 μm in size with a surface microroughness, σ 2 RMS λ, that is two orders of magnitude lower than for the pre-etched (111) surface. Magnetotransport measurements on hydrogen-terminated Hall bars engineered on the pre- and post-etched surfaces and rendered conductive by the adsorbed water layer formed on exposure to ambient conditions demonstrate that this etching causes an improvement in the hole mobility by an order of magnitude, resulting in a measured sheet resistivity of 1.04 kΩ/sq at a temperature of 4.2 K without gating.

42 ENGINEERING↗
DOE OSTI2023

Dynamics of plasma atomic layer etching: Molecular dynamics simulations and optical emission spectroscopy

Atomic layer etching is intrinsically dynamic as it involves sequential and repeated exposures of a surface to be etched with different species at different energies. The composition and structure of the near surface region change in both time and depth. Full understanding of this process requires resolving both temporal and spatial variations. In this work, we consider silicon (Si) atomic layer etching (ALE) by alternating exposure to chlorine gas (Cl 2 ) and argon ions (Ar + ). Molecular dynamics (MD) simulations are compared to experimental measurements with the aim of better understanding the dynamics of ALE and to test the simulation procedure. The simulations help to more fully interpret the experimental measurements. Further, optical emission measured just above the surface being etched can be related to etch products and can, therefore, be directly compared to simulation predictions. The simulations capture the measured initial product distribution leaving the surface and match the measured etch per cycle reasonably well. While simulations demonstrate the importance of ion-induced surface damage and mixing into a layer below the surface, the depth of which depends mainly on ion energy, the experiments suggest there is more Cl mixed into the layer than the MD procedure predicts.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Vertical Etching of Scandium Aluminum Nitride Thin Films Using TMAH Solution

A wide bandgap, an enhanced piezoelectric coefficient, and low dielectric permittivity are some of the outstanding properties that have made Sc x Al 1-x N a promising material in numerous MEMS and optoelectronics applications. One of the substantial challenges of fabricating Sc x Al 1-x N devices is its difficulty in etching, specifically with higher scandium concentration. In this work, we have developed an experimental approach with high temperature annealing followed by a wet etching process using tetramethyl ammonium hydroxide (TMAH), which maintains etching uniformity across various Sc compositions. The experimental results of etching approximately 730 nm of Sc x Al 1-x N (x = 0.125, 0.20, 0.40) thin films show that the etch rate decreases with increasing scandium content. Nevertheless, sidewall verticality of 85°~90° (±0.2°) was maintained for all Sc compositions. Based on these experimental outcomes, it is anticipated that this etching procedure will be advantageous in the fabrication of acoustic, photonic, and piezoelectric devices.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Investigation of dry-etch-induced defects in >600 V regrown, vertical, GaN, p-n diodes using deep-level optical spectroscopy

The effect of dry-etch-induced defects on the electrical performance of regrown, c-plane, GaN p-n diodes where the p-GaN layer is formed by epitaxial regrowth using metal-organic, chemical-vapor deposition was investigated. Diode leakage increased greatly for etched-and-regrown diodes compared to continuously grown diodes, suggesting a defect-mediated leakage mechanism. Deep level optical spectroscopy (DLOS) methods were used to identify energy levels and densities of defect states to understand etch-induced damage in regrown devices. DLOS results showed the creation of an emergent, mid-gap defect state at 1.90 eV below the conduction band edge for etched-and-regrown diodes. Reduction in both the reverse leakage and the concentration of the 1.90 eV mid-gap state was achieved using a wet chemical treatment on the etched surface before regrowth, suggesting that the 1.90 eV deep level contributes to increased leakage and premature breakdown but can be mitigated with proper post-etch treatments to achieve >600 V reverse breakdown operation.

42 ENGINEERING↗
DOE OSTI2024

Comparative S/TEM study of superconducting Ta quantum resonators by wet and dry etching types

Superconducting resonators play a pivotal role in various quantum technology applications, such as quantum computing and high-frequency communication systems. The performance of these resonators is closely tied to the properties of the superconducting films used in their fabrication. Here, in this study, we investigated the impact of wet and dry etching on tantalum (Ta) films leveraging advanced scanning transmission electron microscopy-based characterization methods and examined the morphological, chemical, and strain changes caused by the etching processes. Consequently, we report the significant differences between the two etching methods, with dry etching resulting in straight slanted sidewalls and a thinner oxidized layer, while wet etching produced curved sidewalls and undercuts. Both methods led to the formation of a residual Ta wedge at the lower part of the sidewall, causing lattice deformation, which could adversely influence the homogeneous operations of superconducting devices. These insights enhance our understanding of how etching influences superconducting films, offering valuable guidance for optimizing resonators and related devices. Our findings mark a significant stride in advancing quantum technologies and high-frequency communication by enhancing our practical understanding of superconducting material fabrication.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Temperature and oxygen concentration effects on anisotropy in chromium hard mask etching for nanoscale fabrication

Chromium and its oxides are valuable as functional materials and plasma-etching hard masks in micro- and nanofabrication. While the continuous decrease in feature sizes opens new opportunities for applications of patterned chromium, the demands placed on the patterning process require a new level of mechanistic understanding. In this work, we investigate plasma etching with chlorine/oxygen chemistry using temperature and oxygen concentration as a means to controllably pattern chromium at the nanometer level. Building on our previous studies on blanket film chromium etching, we look here at patterned trenches 15–100 nm wide in 20 and 10 nm thick chromium films. We vary oxygen concentrations from 1.5% to 81% at substrate temperatures of +20 and −50 °C, respectively. Feature and trench profiles are evaluated from high-resolution cross-sectional SEM images. The ternary chromium etch product shows very different profiles as oxygen, temperature, and feature size are varied. We find the highest anisotropy at −50 °C and 50% oxygen concentration. Etch results suggest that the redeposition of nonvolatile intermediate reaction compounds enhances anisotropy at low temperature, whereas re-emission of reactive species causes undercut at the higher etching temperature.

Staaks, Daniel (ORCID:0000000204825507)↗