Selective Wet Etching Research Articles

Large-Scale Plasmonic Hybrid Framework with Built-In Nanohole Array as Multifunctional Optical Sensing Platforms.

Light coupling with patterned subwavelength hole arrays induces enhanced transmission supported by the strong surface plasmon mode. In this work, a nanostructured plasmonic framework with vertically built-in nanohole arrays at deep-subwavelength scale (6 nm) is demonstrated using a two-step fabrication method. The nanohole arrays are formed first by the growth of a high-quality two-phase (i.e., Au-TiN) vertically aligned nanocomposite template, followed by selective wet-etching of the metal (Au). Such a plasmonic nanohole film owns high epitaxial quality with large surface coverage and the structure can be tailored as either fully etched or half-way etched nanoholes via careful control of the etching process. The chemically inert and plasmonic TiN plays a role in maintaining sharp hole boundary and preventing lattice distortion. Optical properties such as enhanced transmittance and anisotropic dielectric function in the visible regime are demonstrated. Numerical simulation suggests an extended surface plasmon mode and strong field enhancement at the hole edges. Two demonstrations, including the enhanced and modulated photoluminescence by surface coupling with 2D perovskite nanoplates and the refractive index sensing by infiltrating immersion liquids, suggest the great potential of such plasmonic nanohole array for reusable surface plasmon-enhanced sensing applications.

Scalable Synthesis of Ti3C2Tx 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 (Ti3C2Tx) 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.

Flexible four-junction inverted metamorphic AlGaInP/AlGaAs/ In0.17Ga0.83As/In0.47Ga0.53As solar cell

A flexible four-junction (4 J) AlGaInP/AlGaAs/In0.17Ga0.83As/In0.47Ga0.53As solar cell with the band gap energy of 1.92/1.53/1.18/0.82eV was fabricated. Taking advantages of aluminum (Al)-contained material as well as metamorphic growth, the design of multiple junction solar cells became much easier and more flexible. In order to accommodate lattice mismatch between two InGaAs sub cells, compositionally step-graded AlGaInAs buffer layers were applied to release the mismatch strain during the inverted metamorphic (IMM) 4 J solar cells growth. A flexible 4 J solar cell on a 50 μm thick polyimide (PI) film was successfully fabricated by using temporary bonding and epitaxial layer lift-off via selective wet chemical etching. A conversion efficiency of 25.76% (AM1.5G) with an open circuit voltage of 3.46V, a short-circuit current density of 9.07 mA/cm2 and a fill factor of 82.14% was obtained without anti-reflection coating (ARC), and it would be higher than 32% by ARC integration. The mass density of the 4 J flexible solar cell was only 467 g/m2, and the specific power was up to 550 W/kg.

MEMS-based thermal conductivity sensor for hydrogen gas detection in automotive applications

Accurate detection of hydrogen gas in vehicle interiors is very important for the future of a fuel cell car. Since this type of gas is highly volatile and flammable, the measurement methods have to be very reliable and precise due to safety reasons. In this paper a thermal conductivity sensor for hydrogen gas detection is presented, exhibiting a lower detection limit of 2000 ppm hydrogen in laboratory air. The sensor element is realized by micro-fabrication techniques on silicon wafers. The heated filament is exposed by a selective wet etching process creating a micro-hotplate on a thin membrane. In order to minimize power consumption, the sensor is operated in pulsed mode. Hydrogen gas detection was carried out using a synthetic gas testbench. Measurements of hydrogen contents ranging from 0% to 4% with an increment of 0.5% were successfully performed for ambient gas temperatures between −15°C and 84°C. Including humidity, high moisture contents have the greatest influence on thermal conductivity. This was predicted in theoretical investigations and confirmed in experiments. For evaluation, both the change in resistance ΔR as well as the time constant τ were taken as sensor output. For both quantities, the previously established theoretical relationship with thermal conductivity could be confirmed.

GaAs Quantum Dot in a Parabolic Microcavity Tuned to 87Rb D1.

We develop a structure to efficiently extract photons emitted by a GaAs quantum dot tuned to rubidium. For this, we employ a broadband microcavity with a curved gold backside mirror that we fabricate by a combination of photoresist reflow, dry reactive ion etching in an inductively coupled plasma, and selective wet chemical etching. Precise reflow and etching control allows us to achieve a parabolic backside mirror with a short focal distance of 265 nm. The fabricated structures yield a predicted (measured) collection efficiency of 63% (12%), an improvement by more than 1 order of magnitude compared to unprocessed samples. We then integrate our quantum dot parabolic microcavities onto a piezoelectric substrate capable of inducing a large in-plane biaxial strain. With this approach, we tune the emission wavelength by 0.5 nm/kV, in a dynamic, reversible, and linear way, to the rubidium D1 line (795 nm).

GeTe photoresist films for both positive and negative heat-mode nanolithography

Binary chalcogenide phase change material GeTe was proposed and investigated as a novel high-resolution inorganic photoresist for laser heat-mode lithography. GeTe possesses both positive and negative photoresist characteristics based on alkaline or acid developing solutions, which can improve the flexibility in fabricating micro/nano devices. Different relief gratings with feature sizes in the range of nanometer to micron were fabricated, and the minimum linewidths can be reduced to 137 nm (positive tone) and 98 nm (negative tone) respectively. The selective wet etching mechanism was discussed with local oxygen concentration mapping of nanopatterns. Moreover, the patterns were successfully transferred onto Si substrate by plasma etching.

Selective Wet-Etching of Polymer/Fullerene Blend Films for Surface- and Nanoscale Morphology-Controlled Organic Transistors and Sensitivity-Enhanced Gas Sensors.

Surface and nanoscale morphology of thin poly(3-hexylthiophene) (P3HT) films are effectively controlled by blending the polymer with a soluble derivative of fullerene, and then selectively dissolving out the fullerene from the blend films. A combination of the polymer blending with fullerene and a use of diiodooctane (DIO) as a processing additive enhances the molecular ordering of P3HT through nanoscale phase separation, compared to the pristine P3HT. In organic thin-film transistors, such morphological changes in the blend induce a positive effect on the field-effect mobility, as the mobility is ~5–7 times higher than in the pristine P3HT. Simple dipping of the blend films in butyl acetate (BA) causes a selective dissolution of the small molecular component, resulting in a rough surface with nanoscale features of P3HT films. Chemical sensors utilizing these morphological features show an enhanced sensitivity in detection of gas-phase ammonia, water, and ethanol.

Surface and dislocation investigation of planar GaN formed by crystal reformation of nanowire arrays

In this paper we present a process of forming monolithic GaN surface from an ordered nanowire array by means of material redistribution. This process, referred to as reformation, is performed in a conventional MOVPE crystal growth system with the gallium supply turned off and allows a crystal nanostructure to change shape according to differences in surface energies between its facets. Using reformation, coalescence may proceed closer to thermodynamic equilibrium, which is required for fabrication of high-quality substrate material. Scanning probe techniques are utilized, complemented by cathodoluminescence and electron microscopy, to investigate structural and electrical properties of the surface after reformation, as well as to assess densities, location, and formation of different types of defects in the GaN film. Spatial variations in material properties such as intrinsic majority-carrier types can be attributed to the radical changes in growth conditions required for sequential transition between nanowire growth, selective shell growth, and reformation. These properties enable us to assess the impact of the process on densities, locations, and formation of different types of dislocations in the GaN film. We find a fraction of the nanowires to comprise of a single electrically neutral edge dislocation, propagating from the GaN buffer, while electrically active dislocations are found at coalesced interfaces between nanowires. By decreasing the mask aperture size and changing the nucleation conditions the prevalence of nanowires comprising edge dislocation was significantly reduced from $6%$ to $3%$, while the density of interface dislocations was reduced from $6\ifmmode\times\else\texttimes\fi{}{10}^{8}$ to $4\ifmmode\times\else\texttimes\fi{}{10}^{7}\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{\ensuremath{-}2}$. Using a sequential reformation process was found to create inversion domains with low surface potential N-polar regions in an otherwise Ga-polar GaN film. The inversion domains were associated with pinned dislocation pairs, and were further confirmed by selective wet etching in NaOH. This lateral polarity inversion was thoroughly eliminated in samples formed by a continuous reformation process. These results reveal a path and challenges for growing GaN substrates of superior crystal quality through nanowire reformation.

Selective Wet Etching of Silicon Germanium in Composite Vertical Nanowires.

Silicon germanium (SixGe1-x or SiGe) is an important semiconductor material for the fabrication of nanowire-based gate-all-around transistors in the next-generation logic and memory devices. During the fabrication process, SiGe can be used either as a sacrificial layer to form suspended horizontal Si nanowires or, because of its higher carrier mobility, as a possible channel material that replaces Si in both horizontal and vertical nanowires. In both cases, there is a pressing need to understand and develop nanoscale etching processes that enable controlled and selective removal of SiGe with respect to Si. Here, we developed and tested solution-based selective etching processes for SiGe in composite (SiNx/Si0.75Ge0.25/Si) vertical nanowires. The etching solutions were formed by mixing acetic acid (CH3COOH), hydrogen peroxide (H2O2), and hydrofluoric acid (HF). Here, CH3COOH and H2O2react to form highly oxidizing peracetic acid (PAA orCH3 CO3H). The hydrofluoric acid serves both as a catalyst for PAA formation and as an etchant for oxidized SiGe. Our study shows that an increase in anyofthe two oxidizer(H2O2 and PAA)concentrations increases the etch rate, and the fastest etch rate of SiGe is associated with the highest PAA concentration. Moreover, using in situ liquid-phase TEM imaging, we tested the stability of nanowires during wet etching and identified the SiGe/Si interfaceto be the weakest plane; we found that once the diameter of the 160-nm-tall Si0.75Ge0.25 nanowire reaches ∼15 nm during the etching, the nanowire breaks at or very close to this interface. Our study provides important insight into the details of the nanoscale wet etching of SiGe and some of the associated failure modes that are becoming extremely relevant for the fabrication processes as the size of the transistors shrink with every new device generation.

Effect of SiO2 Etching Inhibitor to H3PO4 for the Selective Si3N4 Wet Etching of 3D NAND

As the number of stacked layers of the 3D NAND structure increases, the memory density of 3D NAND flash memory device increases [1]. In the fabrication of 3D NAND device, it is essential to selectively etch Si3N4 by an etchant flowing along a narrow slit followed by metal deposition. However, as the number of Si3N4/SiO2 multi-stack increases, selective etching of Si3N4 becomes difficult. In order to increase the Si3N4-to-SiO2 etch selectivity, SiO2 etching inhibitor should be added to H3PO4. Unfortunately, most of SiO2 etching inhibitors added to H3PO4 generate oxide regrowth around SiO2 layer on the Si3N4/SiO2 multi-stack structure. In this study, the mechanism of oxide regrowth occurred on the 3D NAND structure was investigated. Patterned Si3N4/SiO2 multi-stack structures were prepared. Etching experiments were performed using coupon wafers in 85% H3PO4 or etching inhibitor-added H3PO4 at 160 °C. The Si3N4 and SiO2 etching rates and Si3N4-to-SiO2 etch selectivity were measured using spectroscopic ellipsometry and oxide regrowth on the Si3N4/SiO2 multi-stack structure was analyzed using FE-SEM and HR-TEM. When the Si3N4/SiO2 multi-stack structure was etched in the SiO2 etching inhibitor-added H3PO4, oxide regrowth was observed on the SiO2 layered trenches on the Si3N4/SiO2 multi-stack structure, as shown in Fig. 1. The oxide regrowth occurred intensively at the corner of SiO2 layered trench and oxide regrowth occurred heavily at the bottom of Si3N4/SiO2 multi-stack structure as compared to the top. The overall amount of oxide regrowth on the SiO2 layered trench increased as the concentration of SiO2 etching inhibitor added to H3PO4 increased. In addition, it is shown that generation rate of etching product is an important factor to occur oxide regrowth. Based on the results, it is suggested that etching inhibitor addition and high generation rate of etching product and mass transfer limitation are responsible for the oxide regrowth. Through their optimization, selective Si3N4 etching on the Si3N4/SiO2 multi-stack structure without oxide thinning and regrowth could be obtained, as shown in Fig. 2.

Effect of SiO2 Etching Inhibitor to H3PO4 for the Selective Si3N4 Wet Etching of 3D NAND

3D NAND has a vertically stacked semiconductor structure to increase the memory density of semiconductor devices. 3D NAND devices are based on the multiply stacked silicon nitride (Si3N4) and silicon dioxide (SiO2) structure, and it is essential to high selectively etch Si3N4-to-SiO2 in the fabrication process. Hot phosphoric acid (H3PO4) has been typically used in the Si3N4-to-SiO2 selective etching process and the etch selectivity can increase by adding SiO2 etching inhibitors in H3PO4. In order to increase etching rate of Si3N4 and Si3N4-to-SiO2 etch selectivity, additives can be added in H3PO4. However, SiO2 etching inhibitors to increase Si3N4-to-SiO2 etch selectivity may occur by-product redeposition issue around the SiO2-layered trenches of Si3N4/SiO2 multi-stack structure. In this study, the etching behavior of the Si3N4/SiO2 multi-stack structures in SiO2 etching inhibitor-added H3PO4 was investigated. In addition, high selective Si3N4 etching with the control of redeposition was performed on the Si3N4/SiO2 multi-stack structure by adding proper SiO2 etching inhibitor in H3PO4.

A High Sensitive Flexible Pressure Sensor Designed by Silver Nanowires Embedded in Polyimide (AgNW-PI).

Silver nanowires (AgNW) have excellent electrical conductivity, transparency, and flexing endurance, and are broadly used in flexible electrodes and flexible sensors. This study mixed the silver nanowires and polyimide (PI) polymer using an in situ synthesis method, effectively reducing the problem of silver nanowires falling off the substrate. The selective wet etching method was firstly used to process the surface of AgNW-PI films, greatly enhancing the surface conductivity of AgNW-PI films. A flexible pressure sensor with high sensitivity was designed with two face-to-face AgNW-PI ultrathin layers. The experimental results show that our sensor presented a high sensitivity of about 1.3294 kPa−1 under a pressure of about 600 Pa, and when pressure continued to increase, the sensitivity decreased rapidly and reached saturation. Our flexible pressure sensor has the properties of low cost, high sensitivity, excellent repeatability, durability, and can detect various types of mechanical forces which could be utilized for flexible electronics.

Study of wet and dry etching processes for antimonide-based photonic ICs

We report on the dry etch process parameters and the associated etch rates for target and mask materials, as well as surface roughness in an inductively coupled plasma (ICP) for the (AlGaIn)(AsSb)-compounds. The essential chemistry is based on Cl2 with the addition of N2 for sidewall passivation. The optimized ICP etch process is capable of producing high aspect ratio structures with smooth sidewalls. In situ reflectance monitoring with a 670-nm-wavelength laser was used to enable stop-etching at a material interface with high accuracy. Given the additional need for highly selective wet chemical etchants in the fabrication of GaSb based electronic and optoelectronic devices, an extensive investigation was also performed to examine numerous etch solutions. These etchants were listed with etch rates, selectivities, and surface roughness in order to validate their suitability for intended applications. Despite the frequent use of GaSb or InAsSb materials for etch stop layers against each other, devices where their unique type-II broken bandgap alignment is undesired require new selective wet etchants between GaSb and AlGaAsSb with good selectivity. All of the wet chemical and dry etching processes described here were optimized using an n-type GaSb substrate.

High-Sensitive TM Modes in Photonic Crystal Nanobeam Cavity with Horizontal Air Gap for Refractive Index Sensing

We propose a new type of refractive index sensing based on the transverse magnetic (TM) modes in the photonic crystal (PhC) nanobeam (NB) cavity with a horizontal air gap. The electric field of the resonant TM mode is strongly confined within the horizontal air gap present at the PhC NB cavity. In order to increase the quality (Q) factor and the sensitivity (S) of the refractive index change in the air simultaneously, the cavity structure is fully optimized. Because of the trade-off between the Q-factor and S of the TM mode in the PhC NB cavity with an air gap, there is an optimal thickness of the air gap in the dielectric slot. From the numerical simulation results, S can exceed 1000 nm/RIU with Q > 40,000. When the dielectric slot becomes thin, S could be higher than 1200 nm/RIU. For practical applications, we suggest an Si-based PhC NB cavity with a horizontal SiO2 slot structure which can also provide high S with a high Q-factor after a very fine selective wet etching process. This new type of TM resonant mode in the PhC NB cavity can be an ideal platform for compact sensors in photonic integrated circuits for TM waveguide systems.

Selective Atomic-Level Etching on Short S-Glass Fibres to Control Interfacial Properties for Restorative Dental Composites

Interfacial bonding between fibre and matrix is most critical to obtain enhanced mechanical properties of the resulting composites. Here we present a new surface tailoring method of selective wet etching and organosilicon monomers (3-(Trimethoxysilyl) propyl methacrylate, TMSPMA) deposition process on the short S-Glass fibre as a reinforcing material, resulting in increased mechanical retention and strong chemical bonding between glass fibres and polymer resin (a mixture of triethylene glycol dimethacrylate (TEGDMA) and urethane dimethacrylate (UDMA) monomers). The effect of surface modification on fibre matrix interfacial strength was investigated through microdroplet tests. An S-Glass fibre treated with piranha solution (a mixture of H2O2 and H2SO4) for 24 hours followed by TMSPMA surface silanization shows highest increase up to 39.6% in interfacial shear strength (IFSS), and critical fibre length could be reduced from 916.0 µm to 432.5 µm. We find the optimal surface treatment condition in that the flexural strength of dental composites reinforced by the S-Glass fibres enhanced up to 22.3% compared to the composites without fibre surface treatments. The significant elevation in strength is attributed to changes in the surface roughness of glass fibres at atomic scale, specifically by providing the multiplied spots of the chemical bridge and nano-mechanical interlocking. The findings offer a new strategy for advanced tailoring of short S-Glass fibres to maximise the mechanical properties of biomedical and dental composites.

Facile fabrication of periodic arrays of vertical Si nanoholes on (001)Si substrate with broadband light absorption properties

This study presents a facile and straightforward approach to fabricating periodic arrays of Au nanodisks and vertically aligned, depth- and morphology-controllable Si nanoholes on (001)Si substrates by combining self-assembled nanosphere lithography, selective Au wet etching, and Au nanodisk-catalyzed Si etching processes. All of the etching experiments were carried out in aqueous solutions at room temperature without using complex photolithography and hard-mask patterning processes. The shape, diameter, and spacing of the produced vertical Si nanoholes corresponded well to those of the catalytic Au nanodisks used, and the nanohole depth could be readily tuned from sub-micrometer to several micrometers by adjusting the Au nanodisk-catalyzed Si etching time. The Si substrates with nanohole-textured surfaces exhibited depth-dependent hydrophobic behaviors and broadband (400–1650 nm) light absorption properties. The measured integrated absorptance was found to increase with increasing the depth of Au nanodisk-embedded Si nanoholes and can reach up to 95% in the visible light region and 60% in the near-IR region. The resulting broadband absorption enhancement can be attributed to the combined effects of multiple scattering of light and localized surface plasmon resonance. The obtained results present the exciting prospects that the new combined approach proposed here would offer potential applications in constructing various high-efficiency nanohole array-based optoelectronic and photovoltaic devices.

Novel metallization processes for sub-100 nm magnetic tunnel junction devices

In this work, a novel method consisting of side-wall passivation and a top-metal reveal process is proposed for spintronics devices based on magnetic tunnel junctions (MTJs). The method can efficiently protect ferromagnetic metals and magnesium oxide, which are the key materials of MTJs, and effectively establish electrical contact with the interconnect metals for perpendicular MTJs (p-MTJs). The scheme consists of the passivation of MTJs with dual dielectrics – silicon nitride and silicon oxide – followed by planarization and selective wet etching. The proposed integration scheme was successfully demonstrated with 80-nm-diameter p-MTJ devices.

Hard X-ray photoelectron spectroscopy investigation of annealing effects on buried oxide in GaAs/Si junctions by surface-activated bonding

Hard X-ray photoelectron spectroscopy measurements are performed on ≈10-nm-thick GaAs film/Si substrate junctions fabricated by the surface activated bonding and selective wet etching. The chemical shifts of GaO and AsO signals in Ga 2p3/2 and As 2p3/2 core spectra indicate that oxides are formed in a part of GaAs films neighboring GaAs/Si interfaces due to the surface activation process. Analyses of GaO and AsO signals show that the thickness of such buried oxides is decreased due to a post-bonding annealing at temperatures up to 400 °C. This means that the electrical properties of bonding interfaces, which are in the meta-stable states, are improved by the annealing. The thickness of oxides is different from that of amorphous-like transition layers at the GaAs/Si interfaces observed by transmission electron microscopy.

Process optimization of selective wet etching for fabrication of high-aspect-ratio and uniform multilayer grating reference materials

Background: The multilayer gratings are considered as the potential length-standard-traceable lateral scales for calibrating the next-generation critical dimension scanning electron microscope (CD-SEM) magnification. As a key step in the fabrication of multilayer gratings, selective wet etching determines the final grating structure formation. However, the effects of the etching process parameters on the multilayer gratings in several nanometer scales have not been reported in detail. Aim: By optimizing the process of selective wet etching, we should fabricate high-aspect-ratio and uniform multilayer gratings to obtain high-contrast secondary electron signals and stable secondary electron images while also obtaining measurement accuracy from the small line edge roughness. Approach: Based on the analysis of the important factors in the etching process and SEM and TEM measurement results, we evaluate the effects of ultrasonic agitation, HF acid concentration, etch time, and linewidth scale on the aspect-ratio and uniform of multilayer gratings. Results: We recommend to etching the multilayer films with an HF acid concentration of about 2% during the ultrasonic agitation for uniformity. Moreover, selective wet etching reaction is limited by scale when the linewidth is below 20 nm. Despite the fact that the grating structure is fragile and easy to be broken down, for linewidths of about 10 and 5 nm, the aspect ratio of multilayer gratings can reach about 3 and 2, respectively. Conclusions: By focusing on the optimum conditions of ultrasonic agitation, HF acid concentration, and linewidth scale in the selective wet etching, selective wet etching can be used to fabricate high-aspect-ratio and uniform multilayer gratings with linewidth below 20 nm.

Four-step fabrication of SERS-active microfluidic channels

We present a technique to fabricate SERS substrates fully integrated with microfluidic channels. The fabrication of microsized dielectric channels was based on selective wet etching of a poled/unpoled silicate glass while silver nanoisland film was grown on the bottom of the channels via out-diffusion technique. Different combinations of fabrication steps were studied to optimize the channels’ depth, formation of the metal nanoislands and the roughness of the channels’ bottom.