Etching Process Research Articles

Combination of scanning electron microscopy and digital image correlation for micrometer-scale analysis of shear-loaded adhesive joints

ABSTRACT To understand adhesive bonds and their macroscopic behavior, a new experimental method is presented in this paper that allows to investigate micromechanical effects down to nanometer scale under load. The method combines ion milled cross sections, low-voltage scanning electron microscopy (SEM), digital image correlation, and a miniaturized testing machine in the SEM-chamber. Experimental results from shear-loaded adhesively bonded carbon fiber-reinforced polymer specimens illustrate the method’s benefits. Through a plasma etching process, the specimen cross section is textured, creating a stochastically distributed speckle pattern visible in SEM images. A miniaturized testing machine placed in the SEM is used to apply a load to the specimens while capturing images simultaneously. The resulting image series can be analyzed by image correlation algorithms. This method enables precise statements regarding strain distribution on the specimen at micro- and nanometer scales. While conventional coupon tests on bonded specimens can only depict the effects of a composite in a homogenized manner, the new method allows to gain additional insights into the underlying mechanisms.

Laser Produced Hydrophilic and Hydrophobic Silicon Surfaces

Two lasers were utilized for silicon processing using photoelectrochemical etching and laser texturing in order to produce nano/micro structures, respectively. Photoelectrochemical etching process utilizes a CW diode laser of 532 nm wavelength was used to support electrochemical etching for both n-type and p-type conductivity. While laser texturing process was employed using pulsed fiber laser of 1064 nm wavelength. Various characterization methods were devoted to examine silicon micro/nanostructures surfaces produced by lasers. These methods include AFM, SEM and Raman scattering to provide clear evidence about formation of micro/nanostructures abundant at silicon surfaces. Moreover, FTIR analysis for the laser produced silicon surfaces could emphasize whether the resultant silicon surface is hydrophilic or hydrophobic. Image analysis software adopted a side view micro image was used to measure the contact angle between the water droplet and silicon micro/nano-surfaces. It is found that the laser produced silicon nanostructure by photoelectrochemical etching creates a hydrophobic surface and even super hydrophobic with contact angle of 130 degrees for 50 nm average size. In addition, utilizing fiber laser of high repetition rate for laser texturing produces microstructures that are super hydrophilic with contact angle could reach 8 degrees for a surface dimension of 50 μm.

Identification and trimming of the eccentric mass in shell resonators

This paper presents a novel method to identify and suppress the undesired spurious mode caused by the 1st and 3rd harmonics of eccentric mass defects in shell resonators. This approach eliminates the need for pre-trimming of frequency split, simplifying the identification and trimming process, with the advantages of high efficiency and minimal structural damage. Firstly, the influence of the mass defects on the dynamics of resonators is analyzed using the mass ring model. The shear force caused by the 1st and 3rd harmonics of the eccentric mass, as well as the axial force caused by the 2nd harmonic, result in forced bending vibration and axial vibration of resonators. These two types of vibrations are superimposed as spurious modes with the operating mode. The bending vibration caused by eccentric mass is decoupled from the mixed vibration signal by analyzing the dynamic characteristics. An analytic scheme is proposed to identify the 1st and 3rd harmonics without eliminating frequency split. To validate the proposed scheme, the identification and trimming process for eccentric mass is simulated by the finite element method based on the geometric model with preset first four harmonics. Finally, experimental identification and trimming of the eccentric mass for the hemispherical resonator are performed based on the laser Doppler vibrometer and ion beam etching process. After multiple iterations, the 1st and 3rd harmonics are reduced by 87.2% and 49.8%, and the quality factors of the operating modes increase by 26.7% and 40.7%, respectively, demonstrating the effectiveness of the proposed method.

Drag increase behavior of micro-textured concave titanium surface generated by oblique laser etching

Titanium alloy has been widely used in the clinical preparation of artificial jawbone implants due to its excellent mechanical properties and biocompatibility. Artificial bone implantation drug-carrying research can realize the targeted release of drugs at the lesion, however, it is still at the technical bottleneck in inhibiting the sudden release of drugs. In this paper, based on the typical wettability model, a drug-loading and release-retarding method for artificial titanium jawbone drug-storage microcapacitor has been proposed by studying the oblique laser etching process of the inner surface of the drug-storage capsule and by investigating the resistance-enhancing mechanism of the texturization of concave surface of the inner wall. Using the oblique laser etching texture, the contact angle measurement reveals that when the laser frequency is 40KHz, the laser pulse width is 11 ns, the scanning speed is 130 mm/s, and the laser incidence angle is kept at 30° and the number of processing is one, the minimum surface contact angle can be obtained is only 8°. By combining the “3 + 2″ nanosecond laser etching device with the laser depth of focus theory, a curved surface laser etching process method was proposed. A titanium alloy jawbone with drug-carrying cavities was printed using SLM 3D printing technology, and the drag-enhancing effect of the texture was verified using sodium fluorescein labeling method, and it was found that the hydrophilic microtexture had a significant drag-enhancing effect on the liquid flow in the microfluidic channel.

Formation of low-dimensional nanopit structures on atomically flat surfaces of diamond (111) by nickel nanoparticles

Diamond nanoprocessing technologies are essential for the development of diamond-based devices. However, the existing etching processes damage the diamond crystal, adversely affecting the characteristics of the corresponding device. Herein, we focused on the Ni–C solid-solution reaction as a nondamaging fabrication method. Ni films (10, 3, and 1 nm) were deposited on atomically flat surfaces (AFSs) of diamond (111) and annealed under H2 gas flow. The Ni film aggregated into particles, and as the particle size decreased, Ni particles moved around, etching the diamond surface. Interestingly, when the diameter of the Ni nanoparticles was less than a few tens of nanometers, they dug one-dimensional (1D) nanopits with a linear trench shape on diamond AFS. We discuss the mechanism for the formation of these 1D nanopits in detail from the perspective of the etching-morphology dependence on the annealing time, Ni thickness, and gas atmosphere. The results of this study will improve our understanding of the Ni–C solid-solution reaction at the nanoscale and promote the development of damage-free nanofabrication techniques for diamond-based device applications.

Investigation of an electrode-driven hydrogen plasma method for in situ cleaning of tin-based contamination

To prolong the service life of optics, the feasibility of in situ cleaning of the multilayer mirror (MLM) of tin and its oxidized contamination was investigated using hydrogen plasma at different power levels. Granular tin-based contamination consisting of micro- and macroparticles was deposited on silicon via physical vapor deposition (PVD). The electrode-driven hydrogen plasma at different power levels was systematically diagnosed using a Langmuir probe and a retarding field ion energy analyzer (RFEA). Moreover, the magnitude of the self-biasing voltage was measured at different power levels, and the peak ion energy was corrected for the difference between the RFEA measurements and the self-biasing voltage ( ). XPS analysis of O 1s and Sn 3d peaks demonstrated the chemical reduction process after 1 W cleaning. Analysis of surface and cross-section morphology revealed that holes emerged on the upper part of the macroparticles while its bottom remained smooth. Hills and folds appeared on the upper part of the microparticles, confirming the top-down cleaning mode with hydrogen plasma. This study provides an in situ electrode-driven hydrogen plasma etching process for tin-based contamination and will provide meaningful guidance for understanding the chemical mechanism of reduction and etching.

Fabrication of Bulk Tungsten Microstructure Arrays for Hydrophobic Metallic Surfaces Using Inductively Coupled Plasma Deep Etching.

Hydrophobic surfaces have attracted great attention due to their ability to repel water, and metallic surfaces are particularly significant as they have several benefits, for example they self-clean and do not corrode in marine environments, but also have several applications in the aircraft, building and automobile industries. Tungsten is an ideal material for metallic surfaces due to its remarkable mechanical properties. However, conventional micromachining methods of micro- or nanostructures, including mechanical fabrication and laser and wet etching are incapable of balancing functionality, consistency and cost. Inspired by the etching process of silicon, deep etching of bulk tungsten has been developed to achieve versatile microstructures with the advantages of high efficiency, large scale and low cost. In this article, fabrication methods of tungsten-based hydrophobic surfaces using an ICP deep etching process were proposed. Micro- or hierarchical structure arrays with controllable sidewall profiles were fabricated by optimizing etching parameters, which then exhibited hydrophobicity with contact angles of up to 131.8°.

Performance evaluation of GaN etching using Cl2-based plasma with bias pulsing

Reducing plasma-induced damage (PID) is one of the most challenging goals for the fabrication of GaN-based MOS-HEMT. In this paper, we propose a performance evaluation of a Cl2-based etching chemistry using bias pulsing mode for GaN applications. The plasma-induced damage using bias pulsing has been compared to conventional reactive ion etching (RIE) and atomic layer etching (ALE) processes using sheet resistance (Rsheet) measurements. This pulsing mode showed low plasma-induced damage, similar to ALE. In addition, it keeps an acceptable GaN etching rate, showing that pulsing mode has potential for industrial applications.

Digital etching of AlGaN/GaN heterostructures with GaN cap using inductively coupled oxygen plasma process combined with wet chemical treatment

In this work, AlGaN with a GaN cap has been etched in a cyclical process with ICP-RIE O2 plasma oxidation and wet etching in dilute HCl. The oxygen plasma ICP-RIE etching of the AlGaN at an ICP plasma power of 200 W and radio frequency bias power of 100 W led to an etch depth of ∼1.5 nm per digital cycle with increased surface roughness. The AlGaN remained unaffected by the wet etching process alone without any ICP-RIE O2 plasma oxidation, maintaining a surface roughness similar to that of the substrate. AlGaN was etched to a depth of ∼12 nm after six cycles of digital etching with an etch rate of 1.9–2.1 nm/cycle showing an improved surface roughness. The XPS analysis at each stage of the etching process reveals that the O2 plasma oxidation initially oxidizes the GaN cap and the AlGaN layer and is later effectively removed by the HCl solution. The digital etching method has proven effective in controlling etch depth and surface roughness, which are needed to fabricate AlGaN high electron mobility transistors.

Spatial confinement of Co1.67Te2 nanoparticles within porous carbon nanofibers enabling fast kinetics and stability for sodium dual-ion batteries

Owing to favorable cell voltage exceeding 3 V and cost-effectiveness, sodium dual-ion batteries (Na-DIBs) have gained increasing emphasis, however, they are hampered by the availability of suitable anode. Here, an exotic Na-DIB anode, composed of Co1.67Te2 nanoparticles embedded within porous carbon nanofibers (Co1.67Te2@PCFs), has been developed by a combination of electrostatic spinning and a specialized thermal etching process. The Co1.67Te2 nanoparticles within the confined space and porous carbon layers show energetic capability for Na+ storage and enhanced kinetic behavior of the cell, further verified by the density functional theory (DFT) calculations. Additionally, the formed thin, uniform, and inorganic-rich solid electrolyte interphase (SEI) on the surface of Co1.67Te2@PCFs after cycling reduces electrolyte consumption and facilitates the uniform flow of Na+. Electrochemically, the Co1.67Te2@PCFs anode exhibits a superior reversible capacity of 383.5 mAh g-1 and maintains stable cycling performance over 1000 cycles at 1 A g-1. Furthermore, the assembled Na-DIB can power a “SUST” pattern comprising 242 light-emitting diodes (LEDs) for two minutes, showcasing its operational potential. This study introduces a promising anode material for Na-DIBs and paves the way for spatially confined energy storage.

Improving Trace Detection of Methylene Blue by Designing Nanowire Array on Boron-Doped Diamond as Electrochemical Electrode

In this study, a boron-doped diamond nanowire array (BDD-NWA)-based electrode is prepared by using a microwave plasma chemical vapor deposition system and treated with inductively coupled plasma reactive ion etching. The BDD-NWA electrode is used for trace detection of methylene blue, which has a wide linear range of 0.04–10 μM and a low detection limit of 0.72 nM. Both the superhydrophilicity (contact angle ~0°) and the dense nanowire array’s structure after the etching process improve the sensitivity of the electrochemical detection compared to the pristine BDD. In addition, the electrode shows great repeatability (peak current fluctuation range of −3.3% to 2.9% for five detection/cleaning cycles) and stability (peak current fluctuation range of −5.3% to 6.3% after boiling) due to the unique properties of diamonds (mechanical and chemical stability). Moreover, the BDD-NWA electrode achieves satisfactory recoveries (93.8%–107.5%) and real-time monitoring in tap water.

Coal gasification fine slag derived porous carbon-silicon composite as an ultra-high capacity adsorbent for Rhodamine B removal

The extensive release of industrial solid wastes and organic dyes has led to severe environmental pollution, underscoring the urgent need to recycle these solid wastes and to remove the dyes. Herein, a porous carbon-silicon composite (PC-SiO2) is synthesized using coal gasification fine slag (CGFS) as a precursor via an alkali (KOH) activation and an acid (HCl) etching process, and used as an adsorbent for the Rhodamine B (RhB) removal. The as-synthesized PC-SiO2 possesses an ultra-high specific surface area of 1275.63 m2/g, a large pore volume of 0.26 cm3/g, and enriched reactive functional groups (e.g., Si-OH and –COOH). Due to these features, the actual adsorption capacity and removal ratio of the PC-SiO2 for RhB were as high as 1383.72 mg/g and 92.25 %, respectively, at 298.15 K and pH = 7. Further studies indicate that the adsorption of RhB on PC-SiO2 fits both the pseudo-second-order kinetic model and the Langmuir model, with the maximum equilibrium adsorption capacity being 1388.89 mg/g as predicted by the Langmuir model. The adsorption process involves the electrostatic attraction, hydrogen bonding, π-π interaction, and pore-filling mechanism. This work not only offers a novel approach for removing organic dyes from industrial wastewater but also provides an effective strategy for producing high-value-added materials from industrial solid wastes.

Size-Effect-Based Dimension Compensations in Wet Etching for Micromachined Quartz Crystal Microstructures.

Microfabrication technology with quartz crystals is gaining importance as the miniaturization of quartz MEMS devices is essential to ensure the development of portable and wearable electronics. However, until now, there have been no reports of dimension compensation for quartz device fabrication. Therefore, this paper studied the wet etching process of Z-cut quartz crystal substrates for making deep trench patterns using Au/Cr metal hard masks and proposed the first quartz fabrication dimension compensation strategy. The size effect of various sizes of hard mask patterns on the undercut developed in wet etching was experimentally investigated. Quartz wafers masked with initial vias ranging from 3 μm to 80 μm in width were etched in a buffered oxide etch solution (BOE, HF:NH4F = 3:2) at 80 °C for prolonged etching (>95 min). It was found that a larger hard mask width resulted in a smaller undercut, and a 30 μm difference in hard mask width would result in a 17.2% increase in undercut. In particular, the undercuts were mainly formed in the first 5 min of etching with a relatively high etching rate of 0.7 μm/min (max). Then, the etching rate decreased rapidly to 27%. Furthermore, based on the etching width compensation and etching position compensation, new solutions were proposed for quartz crystal device fabrication. And these two kinds of compensation solutions were used in the fabrication of an ultra-small quartz crystal tuning fork with a resonant frequency of 32.768 kHz. With these approaches, the actual etched size of critical parts of the device only deviated from the designed size by 0.7%. And the pattern position symmetry of the secondary lithography etching process was improved by 96.3% compared to the uncompensated one. It demonstrated significant potential for improving the fabrication accuracy of quartz crystal devices.

GO-based membranes with enhanced stability and permeability by implanting etched-MXene nanosheets: The role of binding energy in stabilizing 2D membranes

Graphene oxide (GO) stands out as a promising choice for the construction of next generation nanofiltration membranes in wastewater purification. Nevertheless, achieving the requisite stability and optimal permeability for effective separation of aqueous molecules and ions poses a formidable challenge for graphene oxide membranes. In this study, a series of GO/etched-MXene membranes with markedly enhanced stability and permeability was fabricated to provide high-level performance. Due to seemly etching process, the optimal GO/etched-MXene membrane featured additional nanochannels for faster mass transfer, consequently evincing a high water permeance of 88.2 ± 3.8 L m−2 h−1 bar−1 with an excellent dye/salt separation efficiency (CR/NaCl selectivity = 22.6, CR/Na2SO4 selectivity = 42.0). Noticeably, the introduction of etched-MXene nanosheets demonstrated a pronounced enhancement in stabilizing the GO membrane within aqueous environment. The density functional theory (DFT) calculations showed that the binding energy of MXene nanosheets (−7.68 eV) was significantly larger than GO nanosheets (−1.11 eV). According to charge difference density results, compared with GO nanosheets, the electrons transfer in MXene nanosheets was more concentrated. As a result, the specially-designed GO/etched-MXene membranes could maintain a stable separation performance during crossflow filtration, while the pristine GO membrane rapidly cracked. This approach is anticipated to establish a theoretical framework for comprehending the contribution of nanosheet binding energy in stabilizing two-dimensional membranes, fostering synergistic advantages in the advancement of GO membranes characterized by both elevated water permeance and requisite stability in water treatment.

In Situ Growth of Amorphous MnO2 on Graphite Felt via Mild Etching Engineering as a Powerful Catalyst for Advanced Vanadium Redox Flow Batteries.

Owing to the advantages of low cost, high safety, and a desirable cycling lifetime, vanadium redox flow batteries (VRFBs) have attracted great attention in the large-scale energy storage field. However, graphite felts (GFs), widely used as electrode materials, usually possess an inferior catalytic activity for the redox reaction of vanadium ions, largely limiting the energy efficiency and rate performance of VRFBs. Here, an in situ growth of amorphous MnO2 on graphite felt (AMO@GF) was designed for application in VRFBs via mild and rapid etching engineering (5 min). After the etching process, the graphite felt fibers showed a porous and defective surface, contributing to abundant active sites toward the redox reaction. In addition, formed amorphous MnO2 can also serve as a powerful catalyst to facilitate the redox couples of VO2+/VO2+ based on density functional theoretical (DFT) calculations. As a result, the VRFB using AMO@GF displayed an elevated energy efficiency and superior stability after 2400 cycles at 200 mA cm-2, and the maximum current density can reach 300 mA cm-2. Such a high-efficiency and convenient design strategy for the electrode material will drive the further development and industrial application of VRFBs and other flow battery systems.

Effective radioactive strontium removal using lithium titanate decorated Ti3C2Tx MXene/polyacrylonitrile beads

A lithium titanate-decorated Ti3C2Tx MXene (LTO-MX) composite was synthesized through etching and alkali processes, and subsequently immobilized using polyacrylonitrile (PAN) polymer via a phase inversion method. In the batch study, the strontium adsorption behavior followed the Redlich-Peterson isotherm and the pseudo-second-order kinetic models. The maximum adsorption capacity for strontium reached 24.05 mg/g. Furthermore, a continuous fixed-bed column study was performed using the LTO-MX PAN beads to remove strontium from aqueous solutions. The dynamic behavior of column adsorption was examined under various operating parameters such as initial strontium concentration, flow rate, and bed height. Dynamic modeling was employed to describe adsorption breakthrough properties based on these experimental data. Both the Thomas and Yoon-Nelson models accurately simulated the breakthrough curves. The proposed mechanisms for strontium adsorption included encapsulation, electrostatic attraction, cation exchange, and surface complexation. These results demonstrate the effectiveness of LTO-MX PAN beads as adsorbents for the continuous removal of strontium from radioactive wastewater.

Low-Cost Preparation of Diamond Nanopillar Arrays Based on Polystyrene Spheres.

Diamond nanopillar arrays can enhance the fluorescence collection of diamond color centers, playing a crucial role in quantum communication and quantum sensing. In this paper, the preparation of diamond nanopillar arrays was realized by the processes of polystyrene (PS) sphere array film preparation, PS sphere etching shrinkage control, tilted magnetron sputtering of copper film, and oxygen plasma etching. Closely aligned PS sphere array films were prepared on the diamond surface by the gas-liquid interfacial method, and the effects of ethanol and dodecamethylacrylic acid solutions on the formation of the array films were discussed. Controllable reduction of PS sphere diameter is realized by the oxygen plasma etching process, and the changes of the PS sphere array film under the influence of etching power, bias power, and etching time are discussed. Copper antietching films were prepared at the top of arrayed PS spheres by the tilted magnetron sputtering method, and the antietching effect of copper films with different thicknesses was explored. Diamond nanopillar arrays were prepared by oxygen plasma etching, and the effects of etching under different process parameters were discussed. The prepared diamond nanopillars were in hexagonal close-rowed arrays with a spacing of 800 nm and an average diameter of 404 nm, and the spacing, diameter, and height could be parametrically regulated. Raman spectroscopy and photoluminescence spectroscopy detection revealed that the prepared diamond nanopillar array still maintains polycrystalline diamond properties, with only a small amount of the graphite phase appearing. Moreover, the prepared diamond nanopillar array can enhance the photoluminescence of diamond color centers by approximately 2 times. The fabrication method of diamond nanopillar array structures described in this article lays the foundation for quantum sensing technology based on diamond nanostructures.

Buffered Oxide Etch: A Safer, More Effective Etchant for Additively Manufactured Ti-Alloys

Kroll’s reagent is effective for the metallographic etching of traditional Ti-alloys but struggles with the intricate, refined microstructures of newer Ti-alloy compositions like Ti-Cu and Ti-Mo alloys, which are created through additive manufacturing. The presence of fine intermetallic compounds in these alloys results in limited contrast between grains and phases when using Kroll’s reagent, highlighting the need for an alternative etchant. This study systematically investigates the use of buffered oxide etch, a common etchant for micro-electronics, on a range of additively manufactured Ti-alloys. The results show that buffered oxide etch provides superior etching outcomes compared to Kroll’s reagent and ammonium bifluoride, with a clear colour contrast between grains and fine phases. Furthermore, ammonium bifluoride with an F− ion concentration similar to 40% buffered oxide etch (5.60 mmol/ml) is found to reveal microstructural details effectively. These findings suggest that the buffered oxide etch is a reliable tint etchant for additively manufactured Ti-alloys, and could potentially be used to etch other additively manufactured alloy systems for metallographic studies. Both these etchants supply F− ions without the low pH, significantly improving safety by removing the need for HF in the etching process.

A Data-driven Deep Learning Approach for Remaining Useful Life in the ion mill etching Process

Prognostics and Health Management (PHM) is regarded as an essential element in the scope of intelligent manufacturing. Precise forecasting of the remaining useful life (RUL) of an ion mill is crucial in order to enhance the overall efficiency of the ion mill etching (IME) procedure. This paper proposed a Data-driven Deep Learning (DL) framework that integrates a Temporal Convolution Network (TCN), Long Short-Term Memory (LSTM), and self-attention mechanism to improve the accuracy of RUL prediction in the ion mill etching Process. Initially, sensor input data is divided into two parallel paths - one with TCN blocks for capturing long-range dependencies, and the other with LSTM layers for extracting temporal patterns. The outputs from both paths are then merged and input into an LSTM layer for enhanced learning, followed by a self-attention mechanism to highlight important features then fully connected layer for predicting RUL. The efficacy of this suggested model was assessed through the utilization of the 2018 PHM Data Challenge Dataset and juxtaposed against various Deep Learning models to demonstrate its efficacy. The results from the experiments indicate that ATCN-LSTM serves as a robust option for estimating the RUL in the ion mill etching Process as it outperformed all other models that were compared. The source code is publicly accessible at https://github.com/ion-mill-etching-Process.

Etching Rate Analysis Model Based on Quartz Bond Angle Characteristics

This paper proposes a method for classifying crystal planes based on the bond angle characteristics of quartz unit cells and constructs an etch rate model for quartz crystal planes at both macro and micro scales. By omitting oxygen atoms from the quartz cell structure, a method based on bond angle characteristics was established to partition the atomic arrangement of the crystal surface. This approach was used to analyze the etching processes of typical quartz crystal planes (R, r, m, and (0001)), approximating the etching process of crystals as a cyclic removal of certain bond angle characteristics on the crystal planes. This led to the development of an etch rate model based on micro-geometric parameters of crystal planes. Additionally, using the proposed bond angle classification method, the common characteristics of atomic configurations on the crystal plane surfaces within the X_cut type were extracted and classified into seven regions, further expanding and applying the etch rate model. The computational results of this model showed good agreement with experimental data, indicating the rationality and feasibility of the proposed method. These also provide a theoretical basis for understanding the microstructural changes during quartz-based MEMS etching processes.