Anisotropic Wet Chemical Etching Research Articles

Unraveling Anisotropic and Pulsating Etching of ZnO Nanorods in Hydrochloric Acid via Correlative Electron Microscopy.

Despite much technical progress achieved so far, the exact surface and shape evolution during wet chemical etching is less unraveled, especially in ionically bonded ceramics. Herein, by using in situ liquid cell transmission electron microscopy, a repeated two-stage anisotropic and pulsating periodic etching dynamic is discovered during the pencil shape evolution of a single crystal ZnO nanorod in aqueous hydrochloric acid. Specifically, the nanopencil tip shrinks at a slower rate along [0001̅] than that along the ⟨101̅0⟩ directions, resulting in a sharper ZnO pencil tip. Afterward, rapid tip dissolution happens due to accelerated etching rates along various crystal directions. Concurrently, the vicinal base region of the original nanopencil tip emerges as a new tip followed by the repeated sequence of tip shrinking and removal. The high-index surfaces, such as {101̅m} (m = 0, 1, 2, or 3) and {21̅ 1̅n} (n = 0, 1, 2, or 3), are found to preferentially expose in different ratios. Our 3D electron tomography, convergent beam electron diffraction, middle-angle bright-field STEM, and XPS results indicate the dissociative Cl- species were bound to the Zn-terminated tip surfaces. Furthermore, DFT calculation suggests the preferential Cl- passivation over the {101̅1} and (0001) surfaces of lower energy than others, leading to preferential surface exposures and the oscillatory variation of different facet etching rates. The boosted reactivity due to high-index nanoscale surface exposures is confirmed by comparatively enhanced chemical sensing and CO2 hydrogenation activity. These findings provide an in-depth understanding of anisotropic wet chemical etching of ionic nanocrystals and offer a design strategy for advanced functional materials.

Etch and growth rates of GaN for surface orientations in the crystallographic zone: Step flow and terrace erosion/filling via the Continuous Cellular Automaton

Compared to other methods, we present the benefits of the Continuous Cellular Automaton (CCA) to describe in a simple and flexible manner anisotropic wet chemical etching of GaN as a combination of step flow and terrace erosion. In fact, the simplicity of the approach enables accounting for epitaxial growth of GaN based on the equivalent perspective of step flow and terrace filling (or build-up). A key ingredient is the direct removal/deposition of GaN groups of atoms, which directly enables describing etching/growth via the removal/deposition of a small number of different crystallographic cell types, each with a different removal/deposition rate. We focus on the derivation of mathematical expressions for the etch rates of the surface orientations contained in the <0001> crystallographic zone as a function of the removal rates of the various cell types, then describing their use also for growth. A least squares approach is used to determine optimal values for the removal/deposition rates of the various cell types. For the first time, Focused Ion Beam (FIB) etching is used to manufacture a well-known, vertically micromachined wagon-wheel structure for subsequent use in wet etching, thus enabling a comparison between the CCA-derived etch rates and the experimental values. For growth, the comparison is performed against data from the literature. The combination of average step flow and average terrace erosion/filling, as inherently contained in the CCA method, explains well the anisotropy of both etching and growth of GaN in the <0001> crystallographic zone.

Rapid anisotropic chemical etching for quick formation of novel octagonal pyramids on silicon surface for photovoltaics

A novel octagonal micro pyramid structure was formed by etching a monocrystalline silicon wafer (100) by employing a wet chemical anisotropic etching process. The main objective is to reduce the silicon wafer's front surface reflectance, improve surface morphology, enhance wettability, and increase the coverage area of the octagonal pyramids on the surface of silicon wafers. The reaction time of the etching process was kept precise under strict observation and control. The experimental results demonstrate a significant reduction in silicon wafers' optical surface reflectance, achieving the lowest reflectance of 8.87%, along with improved surface morphology, periodicity, and coverage of more than 88%. While adding hydrofluoric acid together with magnetic stirring (mechanical agitation) at 300 rpm was advantageous in forming the octagonal silicon pyramid with a high etch rate of 0.41 um/min and significantly reducing the reaction time.

Fabrication of P(100) silicon macro-pore and pillar array by wet electrochemical etching

In this paper, pyramidal notch array was pre-etched on P(100) silicon wafer using anisotropic wet chemical etching, then macro-pore/pillar array were successfully processed in the pyramidal notch array by an anodic electrochemical etching. The formation mechanism of macro-pore and pillar in pyramidal notch were investigated, it indicates that the silicon dissolution rate is proportional to electric field, while electric field is mainly concentrated on the tip, edges and corners of the pyramidal notch. Therefore, there is an etching rate difference between the notch corner and planar regions in the pyramid notch. The notch corners are preferentially etched at first, then a pore is formed in the notch. If the shape of the open window is truncated and the bottom size is large enough, four pores would initiate at the notch angels due to etching rate difference between the truncated pyramidal notch corner and notch center, consequently, a pillar is formed in the notch center.

Surface texturisation for the reduction of light reflection in ZnO/Si heterojunction

ABSTRACT In this paper, the impact of pyramidal texture on a silicon substrate in ZnO/p-Si heterojunction was investigated. The texturisation of p-type silicon (100) substrate was obtained using the KOH anisotropic wet chemical etching method for different etching times. The RF magnetron sputtering technique was used to deposit ZnO thin films on textured Si substrates and planar Si substrates to form ZnO/Si heterojunction. The surface morphology was studied with field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM). Optical properties were investigated using UV-Visible spectroscopy and photoluminescence (PL). The results show that the PL intensity in the visible region of the electromagnetic spectrum increases with the etching time, while a significant reduction is observed in the reflectance. Due to impressive anti-reflection response, ZnO/Si (textured silicon-TS) heterojunction can be effective in improving the efficiency of solar cells.

Microfabrication of Alkali Vapor MEMS Cells for chip-scale atomic clock

The technology of MEMS atomic cells containing rubidium or caesium vapors in an atmosphere of neon buffer gas has been developed. Two-chamber silicon cells containing an optical cavity, shallow filtration channels and a technical container for a solid-state alkali source have been implemented in a single-step process of anisotropic wet chemical etching. To prevent significant undercutting of the filtration channels during etching of the through silicon cavities, the shapes of the compensating elements at the convex corners of the silicon nitride mask have been calculated and the composition of the silicon etchant has been experimentally found. The sealing of the cells has been carried out by silicon-glass anodic bonding at a temperature of 250 °C. For this purpose the LK5 glass which has an increased ionic conductivity in comparison with the conventional glass Borofloat 33 was used. The best microfabricated cells allowed us to obtain estimates of the relative instability of the coherent population trapping resonance frequency at the level of 5 · 10-11 at 1 s.

Anisotropic wet-chemical etching for preparation of freestanding films on Si substrates for atom probe tomography: A simple yet effective approach

A major drawback of atom probe tomography (APT) experiments of complex samples is the demanding and rather time consuming specimen preparation via the lift-out process. It usually requires a skilled operator for focused ion beam (FIB) preparation, and frequently overbooked FIB workstations represent a major bottleneck in sample throughput. Within this work, the authors present an alternative approach for APT specimen preparation of functional films and coatings on Si substrates via anisotropic wet-chemical etching. Utilizing this simple, yet effective approach, a freestanding section of the film to be investigated can be fabricated in a few steps. After the etching procedure, freestanding film posts and subsequently APT specimen can be easily prepared by basic FIB milling operations without the need for a lift-out process. Hence, this approach reduces FIB efforts to a minimum in terms of complexity and required machine utilization.

Fabrication and Characterization of Inverted Silicon Pyramidal Arrays with Randomly Distributed Nanoholes

We report the fabrication, electromagnetic simulation and measurement of inverted silicon pyramidal arrays with randomly distributed nanoholes that act as an anti-reflectivity coating. The fabrication route combines the advantages of anisotropic wet etching and metal-assisted chemical etching. The former is employed to form inverted silicon pyramid arrays, while the latter is used to generate randomly distributed nanoholes on the surface and sidewalls of the generated inverted silicon pyramidal arrays. We demonstrate, numerically and experimentally, that such a structure facilitates the multiple reflection and absorption of photons. The resulting nanostructure can achieve the lowest reflectance of 0.45% at 700 nm and the highest reflectance of 5.86% at 2402 nm. The average reflectance in the UV region (250–400 nm), visible region (400–760 nm) and NIR region (760–2600 nm) are 1.11, 0.63 and 3.76%, respectively. The reflectance at broadband wavelength (250–2600 nm) is 14.4 and 3.4 times lower than silicon wafer and silicon pyramids. In particular, such a structure exhibits high hydrophobicity with a contact angle up to 132.4°. Our method is compatible with well-established silicon planar processes and is promising for practical applications of anti-reflectivity coating.

Study of Black Silicon Wafer through Wet Chemical Etching for Parametric Optimization in Enhancing Solar Cell Performance by PC1D Numerical Simulation

Black silicon (BSi) fabrication via surface texturization of Si-wafer in recent times has become an attractive concept regarding photon trapping and improved light absorption properties for photovoltaic applications. In this study, surface texturization has been conducted on mono-crystalline Si(100) wafer using a wet chemical anisotropic etching process with IPA:KOH solution to form micro-pyramidal surface structures. Moreover, the optimized properties of the fabricated BSi wafers are used for numerical simulation using PC1D software to analyze the performance of the solar cell and establish the correlation among relevant parameters. Effects such as doping concentration, texturization, passivation, and anti-reflection coating of BSi on the solar cell performance have numerically been investigated. Results show that textured surface obtained from the wet chemical anisotropic etching process has successfully reduced the reflectance of the BSi wafer and surpassed the solar cell efficiency by 2%, which is mainly attributed to the optical confinement of the textured pyramids on the surface with a height of 1–2 μm and angles of 70 degrees. Furthermore, the doping concentration of the p-type wafer and n-type emitter were optimized to be 1 × 1016 cm−3 and 1 × 1018 cm−3, respectively. In the case of device optimization, the SiO2 passivation layer with a refractive index of 1.48 and the Si3N4 ARC layer with a refractive index of 2.015 has been identified as the best combination for the solar cell performance. These optimized parameters eventually result in 23.14% conversion efficiency from numerical simulation for solar cells that use black silicon wafers as fabricated in this study.

On the Operation Modes of Dual-Gate Reconfigurable Nanowire Transistors

We investigate the operation of dual-gate reconfigurable field-effect transistor (RFET) in the programgate at drain (PGAD) and program-gate at source (PGAS) configurations. To this end, dual-gate silicon nanowire (SiNW) FETs are fabricated based on anisotropic wet chemical silicon etching and nickel silicidation yielding silicide-SiNW Schottky junctions at source and drain. Whereas in PGAD-configuration ambipolar operation is suppressed, switching is deteriorated due to the injection through a Schottky-barrier. Operating the RFET in PGAS configuration yields a switching behavior close to a conventional MOSFET. This, howewer, needs to be traded off against strongly non-linear output characteristics for small bias.

Silicon field emitters fabricated by dicing-saw and wet-chemical-etching

Silicon field emitter arrays (FEAs) with different tip sizes and quantities were fabricated by saw dicing and anisotropic wet chemical etching by tetramethylammonium hydroxide. The tip is formed by the different etching rates of the crystal facets leading to a sharp pyramid based on {103} planes on the top and a hexadecagon based on {331} and {221} planes on the bottom. Electrical measurements at 10−5 mbar up to 10 μA show good reproducibility for FEAs with the same process parameters and higher uniformity and stability with an increasing number of tips. Constant current measurements at the same conditions and 10 μA show a mean electric field increase of about 0.06(3) V/(μm h) for p-type FEAs with a tip quantity of 3600. The shift increases with lower tip quantity and is higher for n-type FEAs compared to p-type. The degradation during the constant current measurement of n-type samples is found to be partly reversible by heating to 200 °C during emission. In contrast, heating of p-type FEAs induced further degradation instead of a regeneration effect.

Terahertz Emission of Gallium Arsenide on Textured p-type Silicon (100) Substrates Grown via Molecular Beam Epitaxy

This study presents the terahertz (THz) emission of molecular beam epitaxy (MBE)-grown Gallium Arsenide (GaAs) on surface textured p-type Silicon (p- Si) (100) substrates. Surface texturing was achieved by anisotropic wet chemical etching using 5% wt Potassium Hydroxide (KOH): Isopropyl alcohol (IPA) (50:1) solution for 15, 30, 45, and 60 minutes. Reflectivity measurements for the textured p-Si(100) substrates indicated that the overall texturing increases with longer etching times. Raman spectroscopy of the post-growth samples confirmed GaAs growth. The THz emission intensities were the same order of magnitude. The GaAs grown on p-Si(100) textured for 60 minutes exhibited the most intense THz emission attributed to the increased absorption from a larger surface-to-volume ratio due to surface texturing. All GaAs on textured p-Si(100) samples had frequency bandwidth of ~2.5 THz.

The Maximum Positive Curvature Recognition Method to Determine Etch Profiles in Wet Etching of Quartz on AT and BT Cuts

This paper presents a method to quickly determine the transient and stable profiles of trenches, cavities, and mesas formed by anisotropic wet chemical etching on AT and BT cut quartz wafers. Since most quartz orientations have low etch rates and both AT and BT cuts have no trigonal symmetry (unlike the Z cut), it is typically difficult to explain which sidewalls will appear on a given trench for a particular mask alignment on these cuts. By considering the complete etch rate distribution obtained from an etched quartz hemisphere we show that a maximum positive curvature recognition method can be used in order to determine a small number of key orientations, which will directly appear as the transient and stable sidewalls in the experimental trench profiles on both the AT and BT cuts. Similarly, the proposed method accurately explains the formation of complex facets on square cavities as well as on the top, middle and bottom regions of micro-needle arrays etched on the AT and BT cuts. This indicates that the etch profiles of any cut of the trigonal crystal can be determined by using the location of the proposed key orientations. [2017-0254]

Theoretical Study for Characteristic Surface Morphologies Fabricated by Anisotropic Chemical Etching.

The technique of the anisotropic wet chemical etching had turned into one of the widely used processes for manufacturing the functional materials in microelectromechanical systems. To better understand the issues of growth mechanisms for the characteristic surface morphologies during an anisotropic chemical etching, in this study the formation and evolution of surface structures were investigated by numerical simulation methods. A chemical etching model was established on the basis of chemical reaction and atomic diffusion. Affecting by the anisotropy of the crystalline structure and etching rate, various featured surface morphologies, including the rippling surface, cusp-like hillock, and nano-pyramid, were numerically developed in accordance with the etching conditions. These characteristic structures were also in well agreements with the corresponding experiments. From the theoretical point of view, the surface morphologies were critically influenced by the kinetic factors of the anisotropic etching rate and the atomic diffusion. With the enhancement of theoretical work in the formation mechanism for the anisotropic chemical etching, the practical technique would possess a more competitive advantage for the wide applications in the fields of the functional materials fabrication.

Collective evolution of submicron hillocks during the early stages of anisotropic alkaline wet chemical etching of Si(1 0 0) surfaces

We address experimentally the large-scale dynamics of Si(1 0 0) surfaces during the initial stages of anisotropic wet (KOH) chemical etching, which are characterized through atomic force microscopy. These systems are known to lead to the formation of characteristic pyramids, or hillocks, of typical sizes in the nanometric/micrometer scales, thus with the potential for a large number of applications that can benefit from the nanotexturing of Si surfaces. The present pattern formation process is very strongly disordered in space. We assess the space correlations in such a type of rough surface and elucidate the existence of a complex and rich morphological evolution, featuring at least three different regimes in just 10 min of etching. Such a complex time behavior cannot be consistently explained within a single formalism for dynamic scaling. The pyramidal structure reveals itself as the basic morphological motif of the surface throughout the dynamics. A detailed analysis of the surface slope distribution with etching time reveals that the texturing process induced by the KOH etching is rather gradual and progressive, which accounts for the dynamic complexity. The various stages of the morphological evolution can be accurately reproduced by computer-generated surfaces composed by uncorrelated pyramidal structures. To reach such an agreement, the key parameters are the average pyramid size, which increases with etching time, its distribution and the surface coverage by the pyramidal structures.

Au nanoparticle-decorated silicon pyramids for plasmon-enhanced hot electron near-infrared photodetection

The heterojunction between metal and silicon (Si) is an attractive route to extend the response of Si-based photodiodes into the near-infrared (NIR) region, so-called Schottky barrier diodes. Photons absorbed into a metallic nanostructure excite the surface plasmon resonances (SPRs), which can be damped non-radiatively through the creation of hot electrons. Unfortunately, the quantum efficiency of hot electron detectors remains low due to low optical absorption and poor electron injection efficiency. In this study, we propose an efficient and low-cost plasmonic hot electron NIR photodetector based on a Au nanoparticle (Au NP)-decorated Si pyramid Schottky junction. The large-area and lithography-free photodetector is realized by using an anisotropic chemical wet etching and rapid thermal annealing (RTA) of a thin Au film. We experimentally demonstrate that these hot electron detectors have broad photoresponsivity spectra in the NIR region of 1200–1475 nm, with a low dark current on the order of 10−5 A cm−2. The observed responsivities enable these devices to be competitive with other reported Si-based NIR hot electron photodetectors using perfectly periodic nanostructures. The improved performance is attributed to the pyramid surface which can enhance light trapping and the localized electric field, and the nano-sized Au NPs which are beneficial for the tunneling of hot electrons. The simple and large-area preparation processes make them suitable for large-scale thermophotovoltaic cell and low-cost NIR detection applications.

Synergistically Enhanced Performance of Ultrathin Nanostructured Silicon Solar Cells Embedded in Plasmonically Assisted, Multispectral Luminescent Waveguides.

Ultrathin silicon solar cells fabricated by anisotropic wet chemical etching of single-crystalline wafer materials represent an attractive materials platform that could provide many advantages for realizing high-performance, low-cost photovoltaics. However, their intrinsically limited photovoltaic performance arising from insufficient absorption of low-energy photons demands careful design of light management to maximize the efficiency and preserve the cost-effectiveness of solar cells. Herein we present an integrated flexible solar module of ultrathin, nanostructured silicon solar cells capable of simultaneously exploiting spectral upconversion and downshifting in conjunction with multispectral luminescent waveguides and a nanostructured plasmonic reflector to compensate for their weak optical absorption and enhance their performance. The 8 μm-thick silicon solar cells incorporating a hexagonally periodic nanostructured surface relief are surface-embedded in layered multispectral luminescent media containing organic dyes and NaYF4:Yb3+,Er3+ nanocrystals as downshifting and upconverting luminophores, respectively, via printing-enabled deterministic materials assembly. The ultrathin nanostructured silicon microcells in the composite luminescent waveguide exhibit strongly augmented photocurrent (∼40.1 mA/cm2) and energy conversion efficiency (∼12.8%) than devices with only a single type of luminescent species, owing to the synergistic contributions from optical downshifting, plasmonically enhanced upconversion, and waveguided photon flux for optical concentration, where the short-circuit current density increased by ∼13.6 mA/cm2 compared with microcells in a nonluminescent medium on a plain silver reflector under a confined illumination.

Redesigned t-PFF-v device fabricated with one-step anisotropic chemical wet etching process: enhanced separation efficiency for colloidal particles in continuous-mode

A pinched flow fractionation device with trapezoid-shaped pinched segment and cross-flow side channels (t-PFF-v) was redesigned and fabricated with a one-stop anisotropic chemical wet etching process and its enhanced separation capability was demonstrated for spherical polystyrene (PS) particles with diameter ranges of 2–8 µm. The tilted sidewalls and vertical focusing channels of the t-PFF-v device led to an improved separation resolution (Rm,n) via enhanced separation distance of PS particles at the pinched segment (Δxm,n) and reduced effluent particle distribution width (sn). Using this t-PFF-v device with Wp (pinched segment width) of 25 µm, PS particles with diameters of 4, 6, and 8 µm were simultaneously separated with good separation resolution (R4,6 = 3.2 and R6,8 = 3.4). Moreover, by adapting even smaller pinched segment width (Wp = 15 µm), PS particles with diameters of 2 and 4 µm, not well separated in the previous studies, were clearly separated with 9.5-fold improvement in R2,4 compared with the normal PFF device (n-PFF). The effects of inlet flow rate ratio (Q2/Q1) on the separation efficiency were also carefully investigated and provided additional insight on the separation processes within the pinched segment of t-PFF-v device. The drain flow through the cross-flow v-channels helps better alignment of particles at the sidewall of pinched segment and resulted in significantly reduced distribution of effluent particles, even under the operating conditions with low Q2/Q1 values.

25 nm Single-Crystal Silicon Nanowires Fabricated by Anisotropic Wet Etching.

We report a top-down method for fabricating ultra-high aspect ratio single-crystal silicon nanowires. The fabrication method is based on the standard photolithography technique and anisotropic wet etching of the single-crystal silicon in KOH solution. SiO₂ mask nanolines used for patterning single-crystal silicon nanowires are formed by the undercut etching of thin SiO₂ layer in buffered hydrofluoric solution. The minimum width of the SiO₂ mask nanolines are 50 nm. The length of SiO₂ mask nanolines is 2 cm. The single-crystal silicon nanowires have been successfully transferred from the SiO₂ mask nanolines by KOH anisotropic wet-chemical etching. The minimum width of the silicon nanowire has obtained to be 25 nm. The fabricated single-crystal silicon nanowires have trapezoidal and triangular cross sections, which are useful for applications in nanoelectronic and nanophotonic elements.

V-Shaped InAs/Al0.5Ga0.5Sb Vertical Tunnel FET on GaAs (001) Substrate With I $_{\text {ON}}=\text {433}\,\,\mu$ A. $\mu$ m $^{-\text {1}}$ at V $_{\text {DS}}= \text {0.5}$ V

We report on the fabrication of a near broken InAs/Al0.5Ga0.5Sb vertical TUNNEL field effect transistor (TFET). The epitaxial structure is grown on a GaAs (001) substrate thanks to large mismatch accommodation at the GaSb/GaAs interface. The fabrication process involves an anisotropic and selective wet chemical etching of the InAs channel to form a V-shaped mesa with lateral side gates. This new architecture provides a large ON-current at room temperature while enabling an efficient pinch-off thanks to a reduced body thickness near the tunneling interface. With low temperature measurements, we identify the different mechanisms limiting the subthreshold slope at room temperature. At 77 K, where the impact of defects is reduced, a minimum subthreshold slope of 71 mV/decade is achieved for $\text{V}_{\mathrm{ DS}}=0.1$ V with an $\text{I}_{\mathrm{ ON}}/\text{I}_{\mathrm{ OFF}}$ current ratio larger than 6 decades demonstrating that a good trade-off between ON current and switching efficiency could be obtained with a near broken gap heterostructure based n-TFET.