Wet Etching Step Research Articles

Geometrically Controlled Microscale Patterning and Epitaxial Lateral Overgrowth of Nitrogen-Polar GaN.

In this Letter, we report on a novel two-step epitaxial growth technique that enables a significant improvement of the crystal quality of nitrogen-polar GaN. The starting material is grown on 4° vicinal sapphire substrates by metal-organic vapor-phase epitaxy, with an initial high-temperature sapphire nitridation to control polarity. The material is then converted to a regular array of hexagonal pyramids by wet-etching in a KOH solution and subsequently regrown to coalesce the pyramids back into a smooth layer of improved crystal quality. The key points that enable this technique are the control of the array geometry, obtained by exploiting the anisotropic behavior of the wet-etch step, and the use of regrowth conditions that preserve the orientation of the pyramids' sidewalls. In contrast, growth conditions that cause an excessive expansion of the residual (0001̅) facets on the pyramids' tops cause the onset of a very rough surface morphology upon full coalescence. An X-ray diffraction study confirms the reduction of the threading dislocation density as the regrowth step develops. The analysis of the relative position of the 0002̅ GaN peak, with respect to the 0006 sapphire peak, reveals a macroscopic tilt of the pyramids, probably induced by the large off-axis substrate orientation. This tilt correlates very well with an anomalous broadening of the 0002̅ diffraction peaks at the beginning of the regrowth step.

Uniform large-area surface patterning achieved by metal dewetting for the top-down fabrication of GaN nanowire ensembles

The dewetting of thin Pt films on different surfaces is investigated as a means to provide the patterning for the top-down fabrication of GaN nanowire ensembles. The transformation from a thin film to an ensemble of nanoislands upon annealing proceeds in good agreement with the void growth model. With increasing annealing duration, the size and shape uniformity of the nanoislands improves. This improvement speeds up for higher annealing temperature. After an optimum annealing duration, the size uniformity deteriorates due to the coalescence of neighboring islands. By changing the Pt film thickness, the nanoisland diameter and density can be quantitatively controlled in a way predicted by a simple thermodynamic model. We demonstrate the uniformity of the nanoisland ensembles for an area larger than 1 cm2. GaN nanowires are fabricated by a sequence of dry and wet etching steps, and these nanowires inherit the diameters and density of the Pt nanoisland ensemble used as a mask. Our study achieves advancements in size uniformity and range of obtainable diameters compared to previous works. This simple, economical, and scalable approach to the top-down fabrication of nanowires is useful for applications requiring large and uniform nanowire ensembles with controllable dimensions.

Fabrication of high aspect ratio AlN nanopillars by top-down approach combining plasma etching and wet etching

This study proposes a top-down approach for fabricating high aspect ratio AlN pillars with m-oriented nonpolar sidewalls, which will serve as the first building block for the fabrication of core-shell UV-LEDs. Such structures are achieved through a two-step process, combining a chlorine plasma etching, followed by a wet chemical etching with KOH. In this work, the mechanisms driving the AlN etching in chlorine plasma are discussed. In particular, we highlight the impact of the ratio between ion flux and radical flux on AlN etch rates, pillar profiles, and crystal orientation-dependent etching. We also identify two mechanisms of passivation layer formation on the pillar sidewalls that contribute to the pattern slope: redeposition of the carrier wafer etch by-products and Aluminium line of sight redeposition, both phenomena are also driven by the ionic bombardment. Low ionic bombardment (either low ion over radical flux ratio or low ion energy) has been identified as plasma conditions allowing the patterning of anisotropic AlN pillars but with the formation of a-nonpolar facets. Due to the inability to obtain m-oriented sidewalls using Cl2 plasma etching alone, we show that the use of a KOH wet etching treatment allows verticalizing the pillars and revealing smooth m-facets on the pillars’ sidewalls if suitable m-oriented hard mask is used. In this wet etching step, we highlight the key role played by the hard mask and its initial shape during the wet etching if straight and m-oriented pillars are desired.

The “LED‐version” of the electron gun

SummaryWe report on our progress to develop and optimize electron sources for practical applications. A simple fabrication process is introduced based on a wafer dicing saw and a wet chemical etch step without the need for a clean room. Due to the formation of crystal facets the samples show a homogeneous geometry throughout the array. Characterization techniques are developed to systematically compare various arrays. A very defined measurement procedure based on current controlled IV‐sweeps as well as lifetime measurements at various currents is proposed. To investigate the current distribution in the array a commercial CMOS detector is used and shows the potential for in depth analysis of the arrays. Finally, a compact hermetically sealed housing is presented enabling electron generation in atmospheric pressure environments.

Abstract 3297: Deep reactive ion etched microneedle array for in-vivo melanoma cancer monitoring via cancer exosome isolation

Abstract This study reports a deep-reactive-ion-etched microneedle device (ExoNeedle chip) coated with a hybrid hydrogel that can directly capture cancer-associated extracellular vesicles (EVs) in interstitial fluid (ISF) in a minimally invasive manner, as opposed to conventional liquid biopsy methods involving sample extraction and EV isolation in-vitro or tissue biopsies for melanoma. Tumor derived EVs give insight into a tumor’s mutational burden and provide both prognostic and diagnostic value as a liquid biopsy tool. Melanoma is an aggressive cancer with a lack of promising markers for early detection, onset of metastasis, and monitoring of recurrence. The ExoNeedle chip is intended to pierce through the epidermis and parts of the dermis to isolate melanoma secreted EVs from the ISF to alleviate these unmet needs. The microneedle arrays were created through the Deep Reactive Ion Etching (DRIE) process and a subsequent wet etching step to sharpen the needles. A 4 inch silicon wafer spin coated with 3 microns of positive photoresist was lithographically patterned and etched by DRIE using the standard Bosch processes to expose arrays of cylindrical pillars. Next, the cylindrical features were sharpened using an isotropic wet etch consisting of a mixture of hydrofluoric and nitric acid. The microneedle arrays were made and cleaved into individual patches. Meanwhile, hybrid hydrogel solution was made from Polyvinyl alcohol (PVA) and alginate by dissolving each of them separately in water under heat, followed by mixing the solutions. After centrifuging and filtering the hydrogel, it was conjugated with Annexin V (Av) protein to give it affinity for cancerous exosomes. Lastly, this hydrogel complex was added onto the microneedle patches and gelated with the help of a humidifier that deposited Ca2+ ion vapor over the hydrogel. The microneedles were first optimized and validated using melanoma cell line secreted EVs. Melanoma EVs were successfully isolated and quantified to evaluate the efficacy of the microneedle patches yielding above an 80% capture efficiency from purified serum samples. The microneedle patches were DiO stained, fluorescently imaged, visualized in a scanning electron microscope, and protein concentration was determined respectfully. Additionally, the functional hydrogel coatings on the microneedles are dissolved in ethylenediaminetetraacetic acid (EDTA), subsequently unbinding EVs from Av due to EDTA-based Ca2+ chelation. The dissolved solution is then used for enumeration and quantification of EVs by nanoparticle tracking analysis. We are further validating these patches in skin mimicking models and patient derived xenograft models of melanoma. The technology developed in this study for the isolation of melanoma EVs can broadly pave the way for minimally invasive point of care cancer diagnostics and tracking for melanoma patients. Citation Format: Scott M. Smith, Abha Kumari, Thiago Reis, Yoon-Tae Kang, Sunitha Nagrath. Deep reactive ion etched microneedle array for in-vivo melanoma cancer monitoring via cancer exosome isolation [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2023; Part 1 (Regular and Invited Abstracts); 2023 Apr 14-19; Orlando, FL. Philadelphia (PA): AACR; Cancer Res 2023;83(7_Suppl):Abstract nr 3297.

InGaN Laser Diodes with Etched Facets for Photonic Integrated Circuit Applications

The main objective of this work is to demonstrate and validate the feasibility of fabricating (Al, In) GaN laser diodes with etched facets. The facets are fabricated using a two-step dry and wet etching process: inductively coupled plasma-reactive ion etching in chlorine, followed by wet etching in tetramethylammonium hydroxide (TMAH). For the dry etching stage, an optimized procedure was used. For the wet etching step, the TMAH temperature was set to a constant value of 80 °C, and the only variable parameter was time. The time was divided into individual steps, each of 20 min. To validate the results, electro-optical parameters were measured after each step and compared with a cleaved reference, as well as with scanning electron microscope imaging of the front surface. It was determined that the optimal wet etching time was 40 min. For this time, the laser tested achieved a fully comparable threshold current (within 10%) with the cleaved reference. The described technology is an important step for the future manufacturing of photonic integrated circuits with laser diodes integrated on a chip and for ultra-short-cavity lasers.

Fabrication of Block Copolymer Templated Extended Surface Model Electrocatalysts By Atomic Layer Deposition and Physical Vapor Deposition

Templating platinum group metal (PGM) nanostructures from microphase separated block copolymers (BCPs) allows for electrocatalytic activity to be studied on highly ordered, model surfaces with precisely controlled feature sizes and morphologies, thereby allowing catalyst electroactivity and stability to be probed as a function of nanoscale geometry. In our previous work [1], BCP templated electrocatalysts fabricated via incipient wetness impregnation of PGM precursors were tested for hydrogen oxidation/evolution and water-splitting activity on interdigitated electrodes using liquid and solid polymer electrolytes. This talk presents the fabrication of such electrocatalysts via Atomic Layer Deposition (ALD) and Physical Vapor Deposition (PVD) techniques (e-beam evaporation and sputtering). Self-assembled lamellae of poly-(styrene-block-methylmethacrylate) (PSbPMMA) thin films on Si wafer and glassy carbon substrates were subjected to 5 - 15 ALD cycles with trimethylaluminium (TMA) precursor to induce selective growth of alumina in the PMMA domains via Sequential Infiltration Synthesis. Thereafter, the polymer template was removed via Reactive Ion Etching (RIE) with oxygen plasma. The resultant alumina nanostructures templated from self-assembled PSbPMMA was then used as a substrate either for Platinum ALD with (trimethyl)methylcyclopentadienylplatinum(IV) precursor atop a Titanium Nitride adhesive layer, or for sputtering of Pt atop a Ti adhesive layer to obtain conformal Pt coatings of up to 20 nm in thickness. When e-beam evaporation was used, The PMMA domains were selectively removed by successive wet and dry etch steps, followed by deposition and lift-off. The PGM electrocatalyst nanostructures were characterized via a combination of electron microcopy, X-ray diffraction, and X-ray photoelectron spectroscopy, and the Pt content of the catalysts were determined via microwave leaching and digestion of the electrocatalyst thin film followed by Inductively Coupled Plasma Mass Spectroscopy. The nanostructured electrocatalysts were tested for oxygen reduction (ORR) activity in a conventional rotating disk electrode setup using 0.1 M perchloric acid electrolyte, and the ORR mass activities and active surface area were obtained.[1] Bhattacharya, D., Arges, C. G., et al., Small, 2021, 17, 2100437

Transparency and icephobicity of moth eye-inspired tailored omniphobic surface

ABSTRACT In this work, we presented a facile method to introduce a transparent and anti-icing omniphobic surface fabricated on the glass substrate. The uniform moth eye-inspired structure was generated by the Deep Reactive Ion Etching method and followed by an additional wet etching step to enhance the sharpness of the nanostructure. A hydrophobe compound was assembled on the rough substrate by chemical vapor coating to achieve remarkable liquid-repellent properties. The tensile strength test was conducted using a designed apparatus to evaluate the anti-icing performance of functional surfaces compared to the as-received one. In addition, the optical performance in terms of transmittance and reflectance also was tested and revealed significant optical enhancement owing to the unique design of nanoarrays. The results demonstrated the great potential and proposed design for multifunctional surfaces.

Wet-based digital etching on GaN and AlGaN

Many advanced III-nitride devices, such as micro-LEDs, vertical FinFETs, and field emitters, require the fabrication of high aspect ratio vertical pillars or nanowires. Two-step etchings combining dry and wet etching steps have been used on vertical devices in the past, but they show poor control in vertical nanostructures with sub-50 nm diameter. In this work, we demonstrate a wet-chemical digital etching on GaN and AlGaN and apply it to both vertical nanostructure scaling and planar etching along the c-axis. In this digital etching process, a mixture of H2SO4 and H2O2 is applied to oxidize the III-nitrides surface, and the oxide layer is then removed by dilute HCl. This digital etching approach can finely sharpen vertical structures and does not require any vacuum or plasma systems, which will enable advanced device structures in the future.

Rapid Fabrication by Digital Light Processing 3D Printing of a SlipChip with Movable Ports for Local Delivery to Ex Vivo Organ Cultures.

SlipChips are two-part microfluidic devices that can be reconfigured to change fluidic pathways for a wide range of functions, including tissue stimulation. Currently, fabrication of these devices at the prototype stage requires a skilled microfluidic technician, e.g., for wet etching or alignment steps. In most cases, SlipChip functionality requires an optically clear, smooth, and flat surface that is fluorophilic and hydrophobic. Here, we tested digital light processing (DLP) 3D printing, which is rapid, reproducible, and easily shared, as a solution for fabrication of SlipChips at the prototype stage. As a case study, we sought to fabricate a SlipChip intended for local delivery to live tissue slices through a movable microfluidic port. The device was comprised of two multi-layer components: an enclosed channel with a delivery port and a culture chamber for tissue slices with a permeable support. Once the design was optimized, we demonstrated its function by locally delivering a chemical probe to slices of hydrogel and to living tissue with up to 120 µm spatial resolution. By establishing the design principles for 3D printing of SlipChip devices, this work will enhance the ability to rapidly prototype such devices at mid-scale levels of production.

Design, fabrication, and characterisation of a silicon microneedle array for transdermal therapeutic delivery using a single step wet etch process

The fabrication of silicon in-plane microneedle arrays from a simple single wet etch step is presented. The characteristic 54.7° sidewall etch angle obtained via KOH etching of (100) orientation silicon wafers has been used to create a novel microneedle design. The KOH simultaneously etches both the front and back sides of the wafer to produce V shaped grooves, that intersect to form a sharp pyramidal six-sided microneedle tip. This method allows fabrication of solid microneedles with different geometries to determine the optimal microneedle length and width for effective penetration and minimally invasive drug delivery. A modified grooved microneedle design can also be used to create a hollow microneedle, via bonding of two grooved microneedles together, creating an enclosed hollow channel. The microneedle arrays developed, effectively penetrate the skin without significant indentation, thereby enabling effective delivery of active ingredients via either a poke and patch application using solid microneedles or direct injection using hollow microneedles. This simple, scalable and cost effective method utilises KOH to etch the silicon wafer in-plane, allowing microneedles with variable length of several mm to be fabricated, as opposed to out-of-plane MNs, which are geometrically restricted to dimensions less than the thickness of the wafer. These microneedle arrays have been used to demonstrate effective delivery of insulin and hyaluronic acid into the skin.

Suspended germanium waveguides with subwavelength-grating metamaterial cladding for the mid-infrared band.

In recent years, sensing and communication applications have fueled important developments of group-IV photonics in the mid-infrared band. In the long-wave range, most platforms are based on germanium, which is transparent up to ∼15-µm wavelength. However, those platforms are limited by the intrinsic losses of complementary materials or require complex fabrication processes. To overcome these limitations, we propose suspended germanium waveguides with a subwavelength metamaterial lateral cladding that simultaneously provides optical confinement and allows structural suspension. These all-germanium waveguides can be fabricated in one dry and one wet etch step. A propagation loss of 5.3 dB/cm is measured at a wavelength of 7.7 µm. These results open the door for the development of integrated devices that can be fabricated in a simple manner and can potentially cover the mid-infrared band up to ∼15µm.

Low temperature Topographically Selective Deposition by Plasma Enhanced Atomic Layer Deposition with ion bombardment assistance

Area selective deposition via atomic layer deposition (ALD) has proven its utility in elementary nanopatterning processes. In the case of complex 3D patterned substrates, selective deposition processes lead to vertical sidewall coverage only, or top and bottom horizontal surface coverage only, to enable advanced nanopatterning and further miniaturization of microelectronic devices. While many fabrication strategies for vertical only Topographically Selective Deposition (TSD) have already been developed, the horizontal TSD case needs further attention. In this work, we propose a versatile route for the TSD on 3D top and bottom horizontal surfaces along with a proof-of-concept for such selective Ta2O5 thin film deposition. The strategy at stake relies on a plasma enhanced atomic layer deposition process assisted by energetic ion bombardment during the plasma step and followed by a postgrowth wet etching step. The effectiveness of this strategy is based on a careful adjustment of processing temperatures purposely set at low temperature, most probably below the ALD temperature window. Anisotropic ion bombardment via substrate biasing during the plasma step provides an extra amount of thermal energy only to exposed horizontal surfaces, which in turn enables a selective densification of the thin film under growth. The difference in thin film density on horizontal and vertical surfaces enables the property-selective etching of vertical surfaces, generating horizontal TSD. A proof-of-concept for such low temperature TSD is shown in the case of 3D trenched substrates with an aspect ratio of 14.

Effects of Post-Etch Microstructures on the Optical Transmittance of Silica Ridge Waveguides.

Silica waveguides are often etched by reactive ion etch (RIE) processes. These processes can leave residual topography that can increase optical loss. We investigated the relation between optical loss and various RIE etch. A wet etch step meant to remove microstructures was also considered and compared. Ridge waveguides were fabricated in plasma enhanced chemical vapor deposited films by three different RIE processes, each with a different gas composition, pressure setting, and applied power setting. Half of each set of waveguides were also subjected to a hydrofluoric acid (HF) solution. The waveguides were tested for optical transmission via the cutback method. The transmission vs waveguide length measurements were plotted to fit an exponential curve and the optical loss and measurement uncertainty for each waveguide set was calculated. Clear distinctions in optical loss were found between the different RIE processes. The HF treatment also has an effect, significantly reducing optical loss for two processes and increasing it for the third. Of the tested RIE processes, one can be suggested for silica waveguides. It results in the lowest optical loss and coincidently has the fastest etch rate.

Fabrication of crystal plane oriented trenches in gallium nitride using SF6 + Ar dry etching and wet etching post-treatment

During the last few years and with the commercialization of the gallium nitride based high electron mobility transistor, research effort on gallium nitride has been strongly increasing. Besides activities regarding lateral devices like the gallium nitride high electron mobility transistor, progress in the growth of native gallium nitride substrates encourages the development of vertical devices. In particular, for power electronics above 600 V, vertical architecture shows superior performance compared to lateral devices. This makes the vertical approach interesting for the use in traction inverters in the rising market of e-mobility. A key aspect in the fabrication of most vertical devices is the formation and optimization of trenches in the semiconductor. In this work, the fabrication of 1.5–2μm deep, crystal plane oriented trenches in gallium nitride with lateral dimension as small as 1μm is demonstrated. The trenches were produced by means of plasma etching based on sulfur hexafluoride and argon as well as a subsequent wet etching step in tetramethylammonium hydroxide and potassium hydroxide. By accurately aligning the trenches along the [1¯010]- and [12¯10]-directions, the authors were able to evaluate the wet etching behavior of the respective crystal planes and achieved smooth vertical sidewalls.

Simulation-based optimization of out-of-plane, variable-height, convoluted quartz micro needle arrays via single-step anisotropic wet etching

Variable-height, out-of-plane, convoluted microneedle arrays with high aspect ratio, tapered shafts, sharp tips, and smooth surfaces are required for applications where the microneedle heights must conform to a specific target geometry. Here, we show that it is possible to achieve such convoluted microneedle arrays on a Z-cut quartz substrate by a single wet etching step in saturated NH4HF2 at 80 °C. Due to the low etch rate of quartz, the procedure is based on carefully controlling the dimensions of every needle-like structure by properly dimensioning the masked area on top. In particular, we show that the mask dimensions for all the microneedles can be optimized via a combination of Level Set (LS) simulations of wet etching and an Evolutionary Algorithm (EA) to search the optimal dimensions. As an example, we fabricate two different microneedle arrays, where the needle heights follow two different spherical surfaces. Our experiments confirm that (i) the LS method correctly predicts the evolution of the etch front for microneedles etched on AT, BT and Z quartz cuts; and (ii) the LS + EA approach provides a suitable procedure to determine an optimal collection of mask sizes for the fabrication of convoluted microneedle arrays on the Z cut.

Dual microelectrodes decorated with nanotip arrays: Fabrication, characterization and spectroelectrochemical sensing

Gold microelectrodes decorated with nanotips were developed for spectroelectrochemical experiments. These new dual probes were fabricated by combining fabrication processes of scanning near-field optical microscopy with photolithography. A nanotip array was produced at the surface of a coherent optical fiber bundle by a wet chemical etching step. The resulting nanostructured surface was sputter-coated with a thin gold layer. This gold film conferred plasmonic properties to the sharp nanotips and served as well as the electrode material to enable electrochemical reactions. A photolithographic process was used to delimit on the bundle surface nanotips-decorated microelectrodes with tunable dimensions (radii ranging between 20 μm and 3.5 μm) individually or in an array format. The resulting microelectrodes with a regular nanotip pattern were characterized first by cyclic voltammetry. Numerical simulation was used to assess the electrochemical properties of these platforms and the influences of the recessed geometry and of the nanotips. Approach curves were recorded in negative and positive feedback modes of scanning electrochemical microscopy (SECM) on insulating and conducting substrates. Finally, spatially resolved Raman imaging allowed us to detect a mercaptobenzoic acid monolayer adsorbed on the microelectrode surface, demonstrating a surface-enhanced Raman scattering (SERS) effect induced by the gold-coated nanotips with a typical enhancement factor of ∼7 × 104. Such an approach introduces a reproducible method to fabricate promising SERS-active platforms with microelectrode behavior for SECM experiments.

Control of diameter and numerical aperture of microlens by a single ultra-short laser pulse.

We demonstrate a versatile method for fast and flexible fabrication of either one or an array of microlenses. Multi-foci axial intensity distribution generated by a phase pattern displayed on a spatial light modulator irradiates silica, causing ablation and its internal modification. The following wet etching step defines the diameter r, while the radius of curvature R (hence, the focal length f) is maintained the same. As a result, the numerical aperture NA=r/f changes from 0.2 to 0.4 for the same pulse energy (but different number of multi-foci) during ablation. An isotropic wet etching of silica becomes highly anisotropic for the initial stages of etching following the irradiated pattern. Subsequent evolution of the shape is governed by an isotropic silica etch and forms a spherical lens. This method can be extended to other materials and geometries of micro-optical elements.

Pedestal microdisks in potassium yttrium double tungstate

KY(WO4)2 is an attractive material for integrated photonics due to its high refractive index and excellent non-linear and gain characteristics. High refractive index contrast structures increase light-matter interaction, reducing the threshold for lasing and non-linear effects. Furthermore, high refractive index contrast permits dispersion engineering for non-linear optics. In this work, we present a novel fabrication method to realize pedestal microdisk resonators in crystalline KY(WO4)2 material. The fabrication process includes swift heavy ion irradiation of the KY(WO4)2 with 9 MeV carbon ions and sufficient fluence (>2.7·1014 ion/cm2) to create a buried amorphous layer. After annealing at 350° C, microdisks are defined by means of focused ion beam milling. A wet etching step in hydrochloric acid selectively etches the amorphized barrier producing a pedestal structure. The roughness of the bottom surface of the disk is characterized by atomic force microscopy.

Preparation and physical properties of soft magnetic nickel-cobalt three-segmented nanowires

We review a method to produce cylindrical magnetic nanowires displaying several segments, with a large versatility in terms of segment diameter and length. It is based on electroplating in alumina templates, the latter being prepared by several steps of anodization, wet etching, and atomic layer deposition to produce, widen, or shrink pores, respectively. We propose an analytical model to analyze the in-plane and out-of-plane magnetization loops of dense assemblies of multisegmented wires. The model considers inter-wires dipolar fields and end-domain curling and predicts the switching field of individual wires with no adjustable parameter. Its ingredients are crucial to extract reliable parameters from the fitting of loops, such as magnetization or the porosity of the array.