Metal-assisted Chemical Etching Research Articles

AFM interlaboratory comparison for nanodimensional metrology on silicon nanowires

Abstract Silicon nanowires (NWs) with a cylindrical form are fabricated by means of nanospheres lithography and metal-assisted chemical etching to obtain high aspect ratio nanostructures (diameter of about 100 nm and length of more than 15 µm) on cm2 area.
The nanodimensional characterization of individual NWs is performed by using several techniques, because dimensions at the nanoscale strictly relate to functional performances. In this study, we report the results of an interlaboratory comparison between measurements from a metrological atomic force microscope (AFM) and research AFMs located in different national metrology institutes (NMIs) across Europe and in a university.
The purpose of this study is to characterize two measurands: (i) sidewall roughness (Ra, Rq, Rz, Rsk, Rku parameters), extracted from the top profile measured along the nanowire length, and (ii) diameter of the nanowires measured as top-height. To this goal, the nanowires are spread horizontally on a silicon substrate, which has several areas labelled with a pattern of crosses and letters facilitating the measurement of the same NW, in order to study the reproducibility due to different instruments.
Measurements show a good agreement between the different NMIs, with a combined standard uncertainty of top-height diameter less than 3%, and with a combined standard uncertainty of roughness parameters well within 5% for Ra and Rq values.

Dichloro-tin (IV) hexadeca-fluoro-phthalocyanine (F16PcSnCl2) thin film on porous silicon layers by ultrasonic spray pyrolysis, for possible application in optoelectronics devices

Phthalocyanines represent a significant class of organic semiconductors that have garnered attention for their potential applications in conducting polymers and organic electronics. The unique structural characteristics of phthalocyanines, coupled with the intriguing chemical behavior and variations in bandgap associated with different substitution sites, offer exciting prospects for designing novel application devices. In this study, we have successfully fabricated a heterostructure incorporating dichloro tin (IV) hexa deca fluoro phthalocyanine (F16PcSnCl2) on both porous silicon (PS) and crystalline silicon (c-Si). The PS substrate was prepared using metal-assisted chemical etching. To explore the optoelectronic applications, we thoroughly characterized the optical, electrical, and morphological properties of the heterostructure. F16PcSnCl2 exhibits the lowest reflectance within the visible light spectrum, making it highly advantageous for photosensitive applications that necessitate efficient light absorption, diffusion, or scattering. The morphological analysis of the F16PcSnCl2 film reveals the presence of nanosphere-type structures uniformly distributed on both PS and c-Si substrates. The absorbance spectrum exhibits three distinct bands, which serve as typical indicators of the F16PcSnCl2 complex. Several hybrid heterostructures were fabricated for electrical characterization, displaying rectifying ohmic behavior and demonstrating a photocurrent effect in the I-V curves. Notably, when the heterostructures were polarized at 1 V, a pronounced response to pulses of white light was observed in the current–time curves. Overall, the integration of organic and inorganic materials in heterostructures holds great promise for innovative applications in optoelectronics.

Rapid graphene oxide assisted chemical etching of silicon in HF/H2O2 solution

In recent years, graphene oxide assisted etching silicon has been considered a potential method to replace metal-assisted chemical etching. This work demonstrated the catalytic ability of graphene oxide synthesized by the Hummers method to promote chemical etching of silicon. By adjusting HF/H2O2 ratio of the solution and reaction temperature, a minimum weighted average reflectance of 9.9% in the wavelength range of 300–1100 nm was obtained. An etching rate of 10 μm h−1, faster than those in others’ reports, was obtained in an optimized acidic solution at 80 °C. Finally, a four-electron model for graphene oxide assisted etching mechanism was proposed to explain our research results.

Silver-Assisted Chemical Etching for the Fabrication of Porous Silicon N-Doped Nanohollow Carbon Spheres Composite Anodes to Enhance Electrochemical Performance.

Silicon (Si) shows great potential as an anode material for lithium-ion batteries. However, it experiences significant expansion in volume as it undergoes the charging and discharging cycles, presenting challenges for practical implementation. Nanostructured Si has emerged as a viable solution to address these challenges. However, it requires a complex preparation process and high costs. In order to explore the above problems, this study devised an innovative approach to create Si/C composite anodes: micron-porous silicon (p-Si) was synthesized at low cost at a lower silver ion concentration, and then porous silicon-coated carbon (p-Si@C) composites were prepared by compositing nanohollow carbon spheres with porous silicon, which had good electrochemical properties. The initial coulombic efficiency of the composite was 76.51%. After undergoing 250 cycles at a current density of 0.2 A·g-1, the composites exhibited a capacity of 1008.84 mAh·g-1. Even when subjected to a current density of 1 A·g-1, the composites sustained a discharge capacity of 485.93 mAh·g-1 even after completing 1000 cycles. The employment of micron-structured p-Si improves cycling stability, which is primarily due to the porous space it provides. This porous structure helps alleviate the mechanical stress caused by volume expansion and prevents Si particles from detaching from the electrodes. The increased surface area facilitates a longer pathway for lithium-ion transport, thereby encouraging a more even distribution of lithium ions and mitigating the localized expansion of Si particles during cycling. Additionally, when Si particles expand, the hollow carbon nanospheres are capable of absorbing the resulting stress, thus preventing the electrode from cracking. The as-prepared p-Si utilizing metal-assisted chemical etching holds promising prospects as an anode material for lithium-ion batteries.

Fabrication of humidity monitoring sensor using porous silicon nitride structures for alkaline conditions

Porous silicon nitride structures were fabricated for a humidity sensor. The porous silicon structures were fabricated by the metal-assisted chemical etching process, and the conformal silicon nitride thin film was deposited by the atomic layer deposition process. The optimized porous sensor with the 10 nm-thick silicon nitride thin film had a hydrophilic surface and compared to other sensors, had an excellent humidity sensing response. Especially, it showed a superior humidity sensing response at 1 kHz with fast response and recovery times of 13.3 s and 12.4 s, respectively, were observed. Based on the electrochemical impedance spectroscopy results, the equivalent circuits and humidity sensing mechanism were discussed. The chemical stability of the silicon nitride was characterized using Tafel analysis in alkaline electrolytes. Additionally, the sensor's humidity sensing capabilities were tested under cement-embedded conditions.

Platinum-Particle-Assisted Etching of Low-, Moderately-, and Highly-Doped p-Type Silicon: Change of Composite Porous Structure

Metal-assisted etching (metal-assisted chemical etching) is an efficient method to fabricate porous silicon (Si). When using platinum (Pt) particles as metal catalysts in metal-assisted etching, a composite porous structure of straight macropores formed beneath the Pt particles and a mesoporous layer formed on the entire surface of Si can be fabricated. The formation mechanism of the composite structure is still open to discussion. We previously demonstrated that the ratio of mesoporous layer thickness to macropore depth showed a large value (approximately 1.1) in the case of highly-doped p-Si. In this study, we investigated the composite structure formation by using p-Si substrates with different doping densities and etching solutions with different concentrations of hydrogen peroxide (H2O2). There was not significant difference in the structures formed on low- and moderately-doped Si, despite the large difference in doping density. The ratio of mesoporous layer thickness to macropore depth increased within the range approximately from 0.1 to 0.4 with increasing the H2O2 concentration in the case of low- and moderately-doped Si, but it did not change in the case of highly-doped Si. We discussed the observation results based on the spatial distribution of hole consumption and the band structures at Pt/Si and Si/electrolyte interfaces.

Controllable Fabrication of Silicon Solar Cells with Inverted or Upright Pyramid Structures by a One-Step Copper Catalysis Method

Silicon has garnered significant attention as the primary material for solar cell preparation. Traditional alkaline etching solutions are limited to creating an upright pyramid structure on monocrystalline silicon surfaces. However, research indicates that an inverted pyramid structure exhibits superior light-trapping properties compared to the upright pyramid structure. In this study, we employed a one-step copper ion metal-assisted chemical etching process to fabricate an inverted pyramid structure on monocrystalline silicon wafers. This method allows for the customization of either inverted or upright pyramid structures by adjusting the concentration of specific solution components. Characterization of the textured silicon wafers reveals that the inverted pyramid structure exhibits lower reflectivity than both the upright pyramid structure and polished silicon. By integrating this texturing technique into the solar cell production line, we successfully produced solar cells with both inverted and upright pyramid structures. Evaluation of various solar cell parameters demonstrates that the inverted pyramid structure outperforms the upright pyramid structure, showcasing lower reflectivity and higher photoelectric conversion efficiency.

Facile synthesis of RGO/TiO2 heterojunction on SiNWs on Si chip for near infrared detector

Here, a ternary nanostructure-based heterojunction was developed for the detection of infrared (IR) radiation in near wavelength range. During materials synthesis process, silicon nanowires (SiNWs) were developed using metal assisted chemical etching (MACE) technique whereas reduced graphene oxide (RGO) sheets and TiO2 nanoparticles were synthesized by chemical vapour deposition (CVD) and solvothermal method, respectively. Thereafter, RGO/TiO2 nanostructure was deposited over SiNWs to form a heterojunction. To analyse the stoichiometry, morphology, and internal structure, various characterization techniques were performed such as scanning electron microscope (SEM), transmission electron microscope (TEM), Energy dispersive spectrometer (EDS), X-Ray Diffractometer (XRD), UV–Vis spectrophotometer and X-Ray Photoelectron Spectrometer (XPS). The RGO/TiO2@SiNWs nanostructure-based heterojunction was used for the detection of near IR radiation where the responsivity (R) was found to be 17.22 × 10−3 A/W and detectivity (D) was measured to be 0.23 × 1011 Jones with response time < 1 s and recovery time < 3 s. These results were found comparatively better than pristine RGO@Si and RGO@SiNWs nanostructure-based sensors used for the near IR detection under same conditions. The photocurrent response was also recorded with 5 ON/OFF cycles which depicted a good reproducibility of the prepared detector. Hence, the SiNWs on Si chip based highly sensitive and selective photodetector can be used to set a new milestone for various near IR applications.

The nature of photocatalytic hydrogen generation on silicon nanowires prepared by MAWC

Highly n-doped silicon nanowires (SiNWs) exhibit excellent hydrogen generation. Our results indicate three hydrogen generation possibilities, i.e. SiNWs oxidation, photocatalysis and the cleavage of dangling H bonds, are jointly responsible for the efficient hydrogen generation. Oxidation accounts for about 80% of total hydrogen, photocatalysis contributes less than 20% of total hydrogen, and about 0.1% of total hydrogen is from cleavage of dangling H bonds. SiNWs were oxidized in water and form SiOx (0 < X < 2) thin layer. Furthermore, the ratio of photo-generated hydrogen to photo-generated oxygen is about 2.4:1. It suggests that photocatalysis appears to be a process of water splitting. This study is significant to reveal the mechanism of hydrogen production on SiNWs prepared by Metal-Assisted Wet Chemical Etching (MAWC).

Growth of β-Ga2O3 nanostructures by thermal oxidation of GaN-on-sapphire for optoelectronic devices applications

Heterostructures of wide-bandgap semiconductors, like β-Ga2O3/ GaN, are being used in many high-power, high-frequency electronic and optoelectronic devices. This paper presents the growth of β-Ga2O3 thin film and nanostructures by thermally oxidizing (at 1000 °C) the planar and nano-structured GaN surfaces respectively. The nano-structures of GaN (having 300–500 nm long vertical nano-kinks) are fabricated by metal-assisted chemical etching of GaN surface for 1–2 hours. The thermally grown β-Ga2O3 samples are polycrystalline. The chemical analysis of the samples using X-ray photoelectron spectroscopy (XPS) showed enhancement of Ga-O peak intensity (at 20.21–20.3 eV) at the expense of the Ga-N peak intensity (at 19.2–19.7 eV) in the thermal oxidation process. The O1s XPS spectra of the oxidized samples exhibited prominent signature of O2- ions (530.7–530.9 eV) representing the formation of Ga2O3 with presence of adsorbed hydroxyl group at the surface (532.2 – 532.4 eV). The valance band XPS spectra disclosed the formation of an additional Ga(4 s)–O(2p) hybridization energy state, and the valence band maxima increased from 2.3 eV to 3.25 eV. The Raman spectra of the oxidized samples exhibited multiple Ag and Bg vibrational modes of β-Ga2O3 along with intense E2(high), A1(LO) modes of GaN. The time-resolved photoluminescence spectra of the samples demonstrated fast transition of charge carriers from excited state to ground state with 460–820 pico-seconds average career lifetime.

Humidity Diode Sensors Based on 1D Nanosized Silicon Structures

Introduction. Humidity measurement is essential in microelectronics, aerospace, biomedical, and food industries, as well as in households for climate control. Currently, various types of devices have been used as humidity sensors: capacitive, resistive, diode, gravimetric, optical structures, field-effect transistors and devices based on surface acoustic waves.Problem Statement. Today, there is a need to develop IC-compatible humidity sensors that have high sensitivityand low cost. To this end, silicon nanowires have been successfully used in resistive and capacitive humidity sensors. However, there is a lack of research on the nanowire effect on device parameters of diode-type humidity sensors.Purpose. To develop diode sensors based on silicon nanowires and to determine the effect of process parameters of synthesis and structural features of nanowires on the performance of humidity sensors.Materials and Methods. The process of sensor fabrication includes several steps: chemical cleaning of silicon wafer, synthesis of silicon nanowires using standard or modified metal-assisted chemical etching, phosphorus diffusion to create a p-n junction, front and back metallization. The surface morphology of the nanostructures has been studied by scanning electron microscopy. The humidity-sensitive characteristics have been studied with theuse of salt hygrostats.Results. It has been shown that the addition of one-dimensional silicon nanostructures to the diode-type sensor signifi cantly improves its characteristics. The rectification ratio increases from 161 to 1807, the response ups from 4.5 to 25, the sensitivity grows from 1.6 to 4.02 (%RH)–1, while the response time and recovery time are reduced from 85/90 to 25/30 s, the hysteresis value goes down from 75 to 16%, the signal deviation after cycling drops from 15to 3%, and the signal fluctuation during continuous device operation decreases from 17 to 15%.Conclusions. The results have shown that the use of a simple and cheap nanowire synthesis technology is effective to produce humidity sensors.

Anisotropy of the conductivity of silicon nanowires

ABSTRACT This study reports the findings from an investigation into charge carrier transport within a silicon nanowire layer. The samples were prepared using the metal-assisted chemical etching method applied to crystalline silicon wafers with a resistance of 10–20 Ω·cm. The resulting silicon nanowires had a diameter of about 100 nm with a resistance of approximately 15 kΩ·cm. Electrical conductivity measurements were performed in both planar and sandwich configurations, revealing analogous conductivity mechanisms across different geometries. Frequency-dependent conductivity studies unveiled the presence of hopping conductivity. A hypothesis is proposed regarding the existence of a potential barrier at the interface between the nanowire layer and the substrate.

Demystifying metal-assisted chemical etching of GaN and related heterojunctions

GaN and related semiconductors have become an increasingly prominent material for a wide range of active and passive devices from optoelectronics to high frequency and power electronics as well as photocatalysis. Regardless of the application, anisotropic etching is required for micro and nano structuring, currently performed by reactive ion etching (RIE). Alternately, metal-assisted chemical etching (MacEtch) is an open-circuit plasma-free anisotropic etching method that has demonstrated high aspect ratio device structures devoid of plasma-induced damage found in RIE. This paper presents an in-depth study of the ensemble electrochemical mechanisms that govern the photo-enhanced MacEtch process of GaN and related heterojunctions. Through in-depth experimental investigations, modeling and simulations, the effects of local cathode and anode design, energy-band alignments, and solution chemistry on MacEtch are correlated with the underlying electronic mechanisms of carrier generation, annihilation, transport, and extraction, establishing a fundamental framework for parametrized prediction of system behavior. These findings carry profound implications for tailored design of photoelectrochemical processes employed not just for uniformly etching wide/ultrawide bandgap materials but more broadly for semiconductor-based photocatalytic reactions in general. One-pot photo-enhanced MacEtching of AlInGaN multi-heterojunction device structures including superlattices and multi-quantum wells are demonstrated.

Synthesis of Well-Ordered Functionalized Silicon Microwires Using Displacement Talbot Lithography for Photocatalysis.

Metal-assisted chemical etching (MACE) is a cheap and scalable method that is commonly used to obtain silicon nano- or microwires but lacks spatial control. Herein, we present a synthesis method for producing vertical and highly periodic silicon microwires, using displacement Talbot lithography before wet etching with MACE. The functionalized periodic silicon microwires show 65% higher PEC performance and 2.3 mA/cm2 higher net photocurrent at 0 V compared to functionalized, randomly distributed microwires obtained by conventional MACE at the same potentials.

Wetting Properties of Black Silicon Layers Fabricated by Different Techniques

The wettability of black silicon (BSi) layers fabricated by reactive ion etching (RIE), metal‐assisted chemical etching (MACE), and laser‐induced etching (LIE) techniques is studied. The contact angles of wetting on the samples with deionized water and methylammonium iodide‐based perovskite solutions are determined. It is found that the element composition and the enlargement area factor of BSi layers have a significant effect on their wettability. When tested with water, the RIE and MACE BSi layers exhibit hydrophobic properties, while the LIE BSi layer demonstrates hydrophilic properties due to the SiOx‐rich surface structures. It is also shown that aging leads to a decrease in the water contact angle. Upon exposure to perovskite solution droplets, BSi layers become highly lyophilic. Based on the Wenzel and Cassie–Baxter models, the mechanisms responsible for the wetting states of the fabricated samples are identified. In the results obtained, valuable insights are provided into the potential of using these layers in tandem perovskite/silicon solar cells.

Voltage- and Metal-assisted Chemical Etching of Micro and Nano Structures in Silicon: A Comprehensive Review.

Sculpting silicon at the micro and nano scales has been game-changing to mold bulk silicon properties and expand, in turn, applications of silicon beyond electronics, namely, in photonics, sensing, medicine, and mechanics, to cite a few. Voltage- and metal-assisted chemical etching (ECE and MaCE, respectively) of silicon in acidic electrolytes have emerged over other micro and nanostructuring technologies thanks to their unique etching features. ECE and MaCE have enabled the fabrication of novel structures and devices not achievable otherwise, complementing those feasible with the deep reactive ion etching (DRIE) technology, the gold standard in silicon machining. Here, a comprehensive review of ECE and MaCE for silicon micro and nanomachining is provided. The chemistry and physics ruling the dissolution of silicon are dissected and similarities and differences between ECE and MaCE are discussed showing thattheyare the two sides of the same coin. The processes governing the anisotropic etching of designed silicon micro and nanostructures are analyzed, and the modulation of etching profile over depthis discussed. The preparation of micro- and nanostructures with tailored optical, mechanical, and thermo(electrical) properties is then addressed, and their applications in photonics, (bio)sensing, (nano)medicine, and micromechanical systems are surveyed. Eventually, ECE and MaCE are benchmarked against DRIE, and future perspectives are highlighted.

Experimental study on flow boiling heat transfer performance of nanowire-printed substrates with porous-like structures

In this study, ZnO nanowires (NWs) were demonstrated to have considerable potential for heat transfer enhancement in flow boiling. Unlike the conventional NW fabrication method using metal-assisted chemical etching, we use the microcontact printing (µCP) method comprising solution-based growing methodologies to create ZnO NWs on different substrates, including bare Si-, Cu-, and Al-coated surfaces. This ZnO NW fabrication approach successfully overcomes the substrate limitation of typical NWs, such as Si- and Cu-NWs, which can be only formed on its intrinsic material following the high-cost fabrication approaches required by the metal catalyst. Additionally, a high pore-connected structure was observed on the interfacial area of the ZnO NWs, with the nanocore distribution area considerably enhanced by lengthening the NW length, beneficial to bubble nucleation and surface coolant supply during nucleate boiling. The length of the ZnO NW substrates is controllable by varying the growing period during the hydrothermal growth procedure. Further, the ZnO NW substrates reveal a remarkable enhancement in the flow boiling heat transfer regardless of the substrate variation, thereby exhibiting high variability in the substrate selection and potential of being used as the cooling approach for the thermal management of the high heat flux applications. We conducted a series of experiments related to the surface wettability, wicking, and bubble characteristics for different test substrates under saturated flow boiling conditions to explicitly determine the underlying mechanism in the heat transfer enhancement of the ZnO NWs.

Fabrication of Metal Contacts on Silicon Nanopillars: The Role of Surface Termination and Defectivity.

The application of nanotechnology in developing novel thermoelectric materials has yielded remarkable advancements in material efficiency. In many instances, dimensional constraints have resulted in a beneficial decoupling of thermal conductivity and power factor, leading to large increases in the achievable thermoelectric figure of merit (ZT). For instance, the ZT of silicon increases by nearly two orders of magnitude when transitioning from bulk single crystals to nanowires. Metal-assisted chemical etching offers a viable, low-cost route for preparing silicon nanopillars for use in thermoelectric devices. The aim of this paper is to review strategies for obtaining high-density forests of Si nanopillars and achieving high-quality contacts on them. We will discuss how electroplating can be used for this aim. As an alternative, nanopillars can be embedded into appropriate electrical and thermal insulators, with contacts made by metal evaporation on uncapped nanopillar tips. In both cases, it will be shown how achieving control over surface termination and defectivity is of paramount importance, demonstrating how a judicious control of defectivity enhances contact quality.

Ultra Responsive NO2 silicon nanowires gas sensor

Nitrogen dioxide (NO2) is a hazardous gas emitted primarily from burning fossil fuels. When inhaled, it can have severe health implications, particularly for individuals with respiratory conditions such as asthma. It contributes to ground-level ozone formation, which can cause reduced lung function and increased susceptibility to respiratory infections. When in contact with water moisture in the air, NO2 is easily oxidized into nitric acid (HNO3), causing acid rain. Detection of NO2 levels is therefore important for monitoring air quality and protecting public health. Among the possible technical solutions for gas sensing, silicon nanowires (SiNWs) have proven to be a promising candidate, partly due to their high sensitivity, low manufacturing cost, and ability to perform in various air qualities. This paper presents using SiNWs, fabricated by metal-assisted chemical etching, as a fast, accurate, sensitive, robust, and cost-effective NO2 gas sensor. Our SiNWs gas sensor can experimentally detect 20 parts per billion (ppb) of NO2 under a wide range of relative humidity. Our sensor shows ultra-high sensitivity with fast response and recovery time.

Highly sensitive photoelectrochemical sensors for multichannel detection and uniform bioimaging based on fireworks-like silicon nanowires and its heterojunctions fabricated by MACE and sputtering processes

Photoelectrochemical (PEC) sensors have emerged as a promising candidate for biochemical detection. However, PEC sensors based on bulk semiconductors are limited by sensitivity and detection varieties, though they can provide uniform imaging; PEC sensors based on nanomaterials can meet the requirements of various analytes and sensitivity, but the inhomogeneity of their surface poses a challenge to imaging uniformity. In this work, metal-assisted chemical etching (MACE) and sputtering processes were used to directly fabricated PEC sensors with fireworks-like silicon nanowires (F-SiNWs) and their heterojunctions with excellent performance. Through regulating the etching and sputtering times, the structure and nanomaterials attachment of F-SiNWs can be well controlled. The photoelectric and sensing properties of F-SiNWs with different morphologies were investigated and optimized. Then, the sensor fabricated by optimal F-SiNWs can directly detect H2O2 and indirectly detect glucose under negative bias, while directly detect dopamine (DA) under positive bias. The detection of these three analytes do not interfere with each other, contributing to an excellent multichannel detection system. Subsequently, the multichannel detection of various secretions (H2O2, DA and glucose) of PC-12 cells was achieved by the sensor. Finally, the imaging uniformity of the sensor was demonstrated in different solutions. PEC bioimaging was successfully applied to monitor enzyme activity by bioimaging gradients and cell survival by bioimaging distribution. These results demonstrate the high sensitivity in multichannel detection and excellent stability and homogeneity in bioimaging of the sensor. Therefore, MACE and sputtering process can be a promising tool for constructing PEC sensor.