Partial Etching Research Articles

Scalable High‐Performance Nanolaminated SERS Substrates Based on Multistack Vertically Oriented Plasmonic Nanogaps

AbstractMetallic nanogap structures can support gap surface plasmon modes and strongly concentrate optical fields to enable surface‐enhanced Raman spectroscopy (SERS) for label‐free biochemical analysis down to single molecule level. However, current scalable SERS substrates based on horizontally oriented plasmonic nanogaps still face challenges for accurate sub‐10 nm control of in‐plane nanostructures. Here, we report a new type of scalable high‐performance SERS substrate based on multistack vertically oriented nanogap hotspots in metal–insulator–metal nanolaminated plasmonic crystals. In contrast to horizontally oriented nanogaps, vertically oriented plasmonic nanogaps can be controlled at subnanometer resolution in the multilayered thin‐film deposition process. After a partial etching of dielectric layers, embedded nanogap hotspots in nanolaminated SERS substrates can be exposed to further increase SERS enhancement factors (EFs) by over one order of magnitude from ≈1 × 107 to ≈1.6 × 108. Moreover, oxygen plasma can be used to regenerate clean nanogap hotspots for repeated SERS measurements with maintained high SERS EFs (>1 × 108). Therefore, this work presents a novel out‐of‐plane plasmonic engineering approach to design and manufacture scalable high‐performance reusable SERS substrates for various biochemical analysis applications that prefer high spatial‐temporal resolution and good hotspot uniformity.

Transmission spectrum alteration of a silica fiber taper while covering lateral surface with heterostructure of ZnTe/Bi2Te3 thin film

Short tapered fiber sections 3–10 mm in length and 12–20 microns in diameter were fabricated through the partial etch removal of the outer silica cladding. ZnTe and Bi2Te3 crystalline films 1–60 nm thick were subsequently applied to the surface of the tapered fiber sections using metalorganic chemical vapor deposition. Transmission spectra of the taper were recorded within the wavelength region of 1–1.6 μm at regular intervals whilst the deposition. Strong decreases in transmission in relatively narrow spectral bands were observed. The results can be applied to lossy mode resonance fiber sensors and passively mode-locked pulsed fiber laser designs.

A novel silicon heterojunction IBC process flow using partial etching of doped a‐Si:H to switch from hole contact to electron contact in situ with efficiencies close to 23%

AbstractWe present a novel process sequence to simplify the rear‐side patterning of the silicon heterojunction interdigitated back contact (HJ IBC) cells. In this approach, interdigitated strips of a‐Si:H (i/p+) hole contact and a‐Si:H (i/n+) electron contact are achieved by partially etching a blanket a‐Si:H (i/p+) stack through an SiOx hard mask to remove only the p+ a‐Si:H layer and replace it with an n+ a‐Si:H layer, thereby switching from a hole contact to an electron contact in situ, without having to remove the entire passivation. This eliminates the ex situ wet clean after dry etching and also prevents re‐exposure of the crystalline silicon surface during rear‐side processing. Using a well‐controlled process, high‐quality passivation is maintained throughout the rear‐side process sequence leading to high open‐circuit voltages (VOC). A slightly higher contact resistance at the electron contact leads to a slightly higher fill factor (FF) loss due to series resistance for cells from the partial etch route, but the FF loss due to J02‐type recombination is lower, compared with reference cells. As a result, the best cell from the partial etch route has an efficiency of 22.9% and a VOC of 729 mV, nearly identical to the best reference cell, demonstrating that the developed partial etch process can be successfully implemented to achieve cell performance comparable with reference, but with a simpler, cheaper, and faster process sequence.

Enhanced Electromagnetic Microwave Absorption Property of Peapod-like MnO@carbon Nanowires

Investigating lightweight electromagnetic microwave absorption materials is still urgent because of the issue related to the electromagnetic pollution or military defense. Our findings indicate that core-shell MnO@carbon nanowires (MnO@C NWs) achieve substantially enhanced microwave absorption, suggesting the suitable impedance matching induced by the synergetic effect between MnO and carbon. Furthermore, the peapod-like MnO@C NWs with internal void space can be facially synthesized by partial etching of core-shell MnO@C NWs. The peapod-like MnO@C NWs with internal voids/cavities exhibit dramatically enhanced electromagnetic microwave absorption property when the carbon content is about 64 wt %, a minimum reflection loss (RL) of -55 dB at 10 wt % loading was observed at 13.6 GHz, and the bandwidth of RL less than -10 dB (90% absorption) covers 6.2 GHz at the thickness of 2 mm. The excellent electromagnetic microwave absorption performance is superior to the most of MnO x/C composites in the literatures, which probably benefits from the dielectric polarization among conductive network structure between MnO and carbon, as well as the multiple reflection and absorption induced by internal void space. Our work is expected to pave an effective way to extend the electromagnetic microwave absorption performance of MnO/C composites through partial etching to create a void space.

Low diffuse reflection of silver nanowire/ruthenium oxide nanosheet hybrid films for high-performance transparent flexible electrodes

Transparent conducting electrodes (TCEs) based on silver nanowire (AgNW) networks possess high conductance, transmittance, and mechanical flexibility. However, due to the relatively high diffuse reflection of incident light on AgNWs, they cannot be practically implemented in displays requiring low pattern visibility. One promising strategy for solving this problem is to place an optical stack with high refractive index underneath the AgNW layer. In this work, AgNW-RuO2 nanosheet hybrid TCEs with low diffuse reflections are fabricated using metallic RuO2 nanosheets as undercoats. As predicted by theoretical simulations, RuO2 nanosheets with high refractive indices reduce the diffuse reflections of AgNWs by almost 8%. Moreover, after the partial etching of AgNWs, the difference in the diffuse reflections of their etched and non-etched regions becomes equal to about 0.003, leading to the formation of an invisible pattern. The film consisting of micro-sized RuO2 nanosheets is not damaged during etching, but instead forms a current path between different AgNWs broken by cyclic bending, resulting in a tenfold decrease in the resistance of the AgNW TCE after 170 000 cycles. Further, RuO2 nanosheets suppress the diffusion of humid air from the outside, thus improving the environmental stability of the AgNW-RuO2 nanosheet hybrid TCEs.

Do total or partial etching procedures effect the rate of white spot lesion formation? A single-center, randomized, controlled clinical trial.

To determine whether total or partial etching procedures influence the appearance of white spot lesions (WSLs). This split-mouth, double-blind, controlled, randomized study included 20 patients (mean age 16.75 years), who had class I malocclusion, mild crowding, and satisfactory oral hygiene. A total of 40 maxillary quadrants were randomly allocated to be treated using a total etching (TE) or partial etching (PE) protocol. Quantitative light fluorescence images were captured at the beginning and at 3 (T1) and 6 (T2) months after beginning orthodontic treatmen, as well as when the debonding phase of orthodontic treatment was complete (T3). The presence of pre- and posttreatment WSLs was assessed with quantitative light fluorescence software and analyzed with Student's t-test. The analyses showed that, at T2, the total etching group had significantly higher ΔQ and A scores than the partial etching group ( P < .05). The ΔF scores increased significantly at all timepoints in the TE group, but only at T1 and T3 in the PE group. However, no differences were noted at T3 between the TE and PE groups ( P > .05). The inclusion of only right-handed people may have limited the generalizability of the findings. The absence of analyses of the plaque and gingivitis scores of patients was another limitation of this study. WSL formation was observed mostly in maxillary lateral incisor teeth irrespective of the etching technique. Although PE seems to be more successful in the first 6 months, no difference was observed between PE and TE in the long term for WSL formation.

Co3 O4 /Fe0.33 Co0.66 P Interface Nanowire for Enhancing Water Oxidation Catalysis at High Current Density.

Designing well-defined nanointerfaces is of prime importance to enhance the activity of nanoelectrocatalysts for different catalytic reactions. However, studies on non-noble-metal-interface electrocatalysts with extremely high activity and superior stability at high current density still remains a great challenge. Herein, a class of Co3 O4 /Fe0.33 Co0.66 P interface nanowires is rationally designed for boosting oxygen evolution reaction (OER) catalysis at high current density by partial chemical etching of Co(CO3 )0.5 (OH)·0.11H2 O (Co-CHH) nanowires with Fe(CN)6 3- , followed by low-temperature phosphorization treatment. The resulting Co3 O4 /Fe0.33 Co0.66 P interface nanowires exhibit very high OER catalytic performance with an overpotential of only 215 mV at a current density of 50 mA cm-2 and a Tafel slope of 59.8 mV dec-1 in 1.0 m KOH. In particular, Co3 O4 /Fe0.33 Co0.66 P exhibits an obvious advantage in enhancing oxygen evolution at high current density by showing an overpotential of merely 291 mV at 800 mA cm-2 , much lower than that of RuO2 (446 mV). Co3 O4 /Fe0.33 Co0.66 P is remarkably stable for the OER with negligible current loss under overpotentials of 200 and 240 mV for 150 h. Theoretical calculations reveal that Co3 O4 /Fe0.33 Co0.66 P is more favorable for the OER since the electrochemical catalytic oxygen evolution barrier is optimally lowered by the active Co- and O-sites from the Co3 O4 /Fe0.33 Co0.66 P interface.

Comparison of Direct and Indirect Laser Ablation of Metallized Paper for Inexpensive Paper-Based Sensors.

In this work, we present a systematic study of laser processing of metallized papers (MPs) as a simple and scalable alternative to conventional photolithography-based processes and printing technologies. Two laser-processing methods are examined in terms of selectivity for the removal of the conductive aluminum film (25 nm) of an MP substrate; these processes, namely direct and indirect laser ablation (DLA and ILA), operate at wavelengths of 1.06 μm (neodymium-doped yttrium aluminum garnet) and 10.6 μm (CO2), respectively. The required threshold energy for each laser processing method was systematically measured using electrical, optical, and mechanical characterization techniques. The results of these investigations show that the removal of the metal coating using ILA is only achieved through partial etching of the paper substrate. The ILA process shows a narrow effective set of laser settings capable of removing the metal film while not completely burning through the paper substrate. By contrast, DLA shows a more defined and selective removal of the aluminum layer without damaging the mechanical and natural fibular structure of the paper substrate. Finally, as a proof of concept, interdigitated capacitive moisture sensors were fabricated by means of DLA and ILA onto the MP substrate, and their performance was assessed in the humidity range of 2-85%. The humidity sensitivity results show that the DLA sensors have a superior humidity sensing performance compared to the ILA sensors. The observed behavior is attributed to the higher water molecule absorption and induced capillary condensation within the intact cellulose network resulting from the DLA process (compared to the damaged one from the ILA process). The DLA process of MP should enable scalable production of low-cost, paper-based physical and chemical sensing systems for potential use in point-of-care diagnostics and food packaging.

Elliptically polarized exciton-polariton condensate in a semiconductor microcavity with a chiral photonic crystal slab

We demonstrate a method for controling polarization of exciton-polariton condensate emission in a planar semiconductor microcavity based on modification of the electromagnetic mode structure in the microcavity. The modification is realized by fabrication of a chiral photonic crystal slab with partial etching of the upper Bragg mirror lowering the microcavity symmetry to C4. A degree of circular polarization as high as 70% has been demonstrated experimentally in the structure with optimized parameters without the use of a static magnetic field or birefringent wave plates.

The effects of ICP dry etching and HF wet etching on the morphology of SiO2 surface

Both dry etching and wet etching are an integral part for the fabrication of semiconductor devices. However, both types of etching can cause problems such as surface degradation, uncontrollability of etching depth and undercut. For instance, aqueous HF (wet etching) and dry etching are used to etch SiO2 films. During HF partial etch (SiO2 is not fully removed), it introduces some interesting phenomena such as adhesion degradation on SiO2 surface morphology which is not present when SiO2 is fully etched. This paper reports the first study of systematical characterization of the SiO2 surface morphology after partial dry and HF wet etching and compares their different effects on the strength of adhesion on polaric and nonpolar liquids. To study the strength of adhesion, this experiment utilized two different types of resist such as PMMA resist and PMGI based LOR resist. Atomic Force Microscopy (AFM) was used to determine the surface morphology before and after dry etching and HF wet etching process. Telescope-Goniometer was used to measure the contact angles as an indicator of liquid-solid adhesion. From the comparison study it’s evident that partial wet etching by HF changes the surface morphology of the SiO2 significantly and degrades the adhesion between the resist and the surface. On the other hand, dry etching does not alter the SiO2 surface morphology significantly and it is recommended to use dry etching instead of HF wet etching to avoid the degradation in adhesion strength on SiO2 surface whenever possible. Next, as a more general approach, adhesion promoter was used to restore the adhesion between the resist and SiO2 surface.

Three-dimensional long-period waveguide gratings for mode-division-multiplexing applications.

We propose a three-dimensional (3D) long-period grating structure that has a controllable grating width and depth and can be formed at any chosen position on the surface of a waveguide core with a single photolithography process. The process relies on the partial etching of small structures on the surface of a polymer waveguide through a waveguide mask with narrow apertures that define the grating pattern. The 3D grating structure allows the design of mode converters for any nondegenerate guided modes of a waveguide, regardless of their symmetry properties, and thus relaxes the design constraint of conventional two-dimensional waveguide gratings. To show the flexibility of the 3D grating structure, we present several mode converters fabricated with this structure. The mode-conversion efficiencies achieved are higher than 90% at the resonance wavelengths. In addition, we demonstrate a three-mode multiplexer by integrating a grating-based mode converter with two asymmetric directional couplers. The proposed grating structure together with the fabrication process can greatly facilitate the development of grating-based devices, especially for MDM applications.

Air-clad suspended nanocrystalline diamond ridge waveguides.

A hybrid group IV ridge waveguide platform is demonstrated, with potential application across the optical spectrum from ultraviolet to the far infrared wavelengths. The waveguides are fabricated by partial etching of sub-micron ridges in a nanocrystalline diamond thin film grown on top of a silicon wafer. To create vertical confinement, the diamond film is locally undercut by exposing the chip to an isotropic fluorine plasma etch via etch holes surrounding the waveguides, resulting in a mechanically stable suspended air-clad waveguide platform. Optical characterization of the waveguides at 1550 nm yields an average optical loss of 4.67 ± 0.47 dB/mm. Further improvement to the fabrication process is expected to significantly reduce this waveguide loss.

Direct observation of grain boundaries in graphene through vapor hydrofluoric acid (VHF) exposure.

The shape and density of grain boundary defects in graphene strongly influence its electrical, mechanical, and chemical properties. However, it is difficult and elaborate to gain information about the large-area distribution of grain boundary defects in graphene. An approach is presented that allows fast visualization of the large-area distribution of grain boundary-based line defects in chemical vapor deposition graphene after transferring graphene from the original copper substrate to a silicon dioxide surface. The approach is based on exposing graphene to vapor hydrofluoric acid (VHF), causing partial etching of the silicon dioxide underneath the graphene as VHF diffuses through graphene defects. The defects can then be identified using optical microscopy, scanning electron microscopy, or Raman spectroscopy. The methodology enables simple evaluation of the grain sizes in polycrystalline graphene and can therefore be a valuable procedure for optimizing graphene synthesis processes.

Design and Novel Synthesis of Tailored Si@Void@C Nanostructures with Long Cycle Life for Next-Generation Li-Ion Batteries

A facile and low cost method has been investigated in this study to prepare silicon nanoparticles with a conductive carbon shell and engineered voids as anode materials for lithium ion batteries. Several carbon-coating methods have been tried to form a hard and dense carbon shell, while partial etching of Si has been investigated with various etching chemicals and conditions to create engineered voids inside the carbon coated Si nanoparticles. It is demonstrated that the electrochemical performance and cycle stability of Si@void@C depends strongly on synthesis conditions, especially the engineered voids in their structure and composition control in the final product. The higher the Si-to-carbon ratio, the higher discharge capacity it could achieve. Further, as the volume of the engineered void increases, the cycle stability improves. The best properties obtained from these tailored Si@void@C nanostructures are about 3100 mAh/g of specific discharge capacity at the first cycle, and 2500 mAh/g after 300 cycles at the current density of 0.5 A/g. The cycling experiment is still on-going and thus one can expect longer cycle life from these tailored Si@void@C nanostructures.

Electrodeposition of well-defined gold nanowires with uniform ends for developing 3D nanoelectrode ensembles with enhanced sensitivity

Fabrication of well-defined gold nanowires (GNWs) is of significant importance in many fields such as sensing applications. In this study, the electrodeposition of well-defined GNWs inside polycarbonate (PC) template has been discussed in detail. GNWs were potentiostatically electrodeposited at different filling rates. The growth of GNWs at different stages of pore filling was monitored by electrochemical measurements and field-emission scanning electron microscopy (FE-SEM). It was confirmed that under growth rates between 2.5 and 4 nm/s, GNWs with smooth ends grew uniformly inside the template without any imperfections or corrugations. The length of GNWs was electrochemically controlled to be as same as the template thickness (6 μm) for sensing aims. Ensembles of three dimensional gold nanoelectrodes (3D GNEs) were then developed by partial etching of the PC template, thus making a brush-like structure out of GNWs. The sensitivity of the 3D GNEs was investigated in the presence of [Fe(CN)6]4-/3- redox couple. The results indicated that the response of the prepared 3D GNEs effectively improved as the number of etching cycles increased. The introduced 3D GNEs show promising results for the future sensing applications.

Design of a broadband reciprocal optical diode in multimode silicon waveguide by partial depth etching

We propose a design of reciprocal optical diode based on asymmetric spatial mode conversion in multimode silicon waveguide on the silicon-on-insulator platform. The design possesses large bandwidth, high contrast ratio and high fabrication tolerance. The forward even-to-odd mode conversion and backward blockade of even mode are achieved by partial depth etching in the functional region. Simulated by three-dimension finite-difference time-domain method, the forward transmission efficiency is about −2.05 dB while the backward transmission efficiency is only −22.68 dB, reaching a highest contrast ratio of 0.983 at the wavelength of 1550 nm. The operational bandwidth is up to 200 nm (from 1450 nm to 1650 nm) with contrast ratio higher than 0.911. The numerical analysis also demonstrates that the proposed optical diode possesses high tolerance for geometry parameter errors which may be introduced in fabrication. The design based on partial depth etching is compatible with CMOS process and is expected to contribute to the silicon-based all-optical circuits.

Thermally Driven Self-Limiting Atomic Layer Etching of Metallic Tungsten Using WF6 and O2.

The semiconductor industry faces a tremendous challenge in the development of a transistor device with sub-10 nm complex features. Self-limiting atomic layer etching (ALE) is essential for enabling the manufacturing of complex transistor structures. In this study, we demonstrated a thermally driven ALE process for tungsten (W) using sequential exposures of O2 and WF6. Based on the insight gained from the previous study on TiO2 thermal ALE, we proposed that etching of W could proceed in two sequential reaction steps at 300 °C: (1) oxidation of metallic tungsten using O2 or O3 to form WO3(s) and (2) formation and removal of volatile WO2F2(g) during the reaction between WO3(s) and WF6(g). The O2/WF6 etch process was experimentally studied using a quartz crystal microbalance (QCM). We find that both the O2 and WF6 ALE half reactions are self-limiting, with an estimated steady-state etch rate of ∼6.3 Å/cycle at 300 °C. We also find that etching of W proceeds readily at 300 °C, but not at temperatures lower than 275 °C. Thermodynamic modeling reveals that the observed temperature dependence is likely due to the limited volatility of WO2F2. The use of WF6 with O3 in place of O2 also allows W etching, where the stronger oxidant leads to a larger mass removal rate per cycle. However, we find O2 to be more controllable for precise metal removal per cycle. In addition, etched W films were examined with ex situ analytical tools. Using spectroscopic ellipsometry (SE) and scanning electron microscopy (SEM), we confirm etching of tungsten film on silicon substrates. Surface analysis by X-ray photoelectron spectroscopy (XPS) revealed a minimal fluorine content on the W film after partial etching and on the silicon surface after full etching. This suggests that W ALE does not significantly alter the chemical composition of W films. This work serves to increase the understanding of ALE reactions and expand the base of available ALE processes for advanced material processing.

Controlled growth and optical response of a semi-hollow plasmonic nanocavity and ultrathin sulfide nanosheets on Au/Ag platelets.

Herein, we report a strategy to construct a semi-hollow plasmonic nanocavity and grow ultrathin sulfide nanosheets inside. The competition and cooperation of Au deposition with Ag etching based on flat Ag nanoplates are proposed. For the establishment of the semi-hollow nanocavity, Au shells are grown on Ag nanoplates, which serve as a stable frame, followed by partial etching of the Ag nanoplates. By controlling the thickness of the initial Ag nanoplates or the injected amount of etchant, the nanocavity size is fine-tuned. Significantly, the remaining unetched Ag layers provide a flat platform for the growth of 2D ultrathin sulfides of Ag2S and CdS inside the semi-hollow plasmonic nanocavity. Strong plasmon resonance and large local field enhancement are exhibited inside the plasmonic cavity where the ultrathin semiconductor sulfides are grown, indicating strong plasmon-exciton interactions in the hybrids. Furthermore, this synthetic approach is extended to grow other metal sulfides such as Bi2S3 and PbS. The combination of a flat plasmonic cavity with ultrathin semiconductor nanosheets in this study provides a new strategy for the development of unique plasmon-based hybrids with excellent optical properties.

Formation of yttria-stabilized zirconia nanotubes by atomic layer deposition toward efficient solid electrolytes

We describe a fabrication strategy for preparing yttria-stabilized zirconia nanotube (YSZ-NT) arrays embedded in porous alumina membranes by means of template-directed atomic layer deposition (ALD) technique. The individual YSZ-NTs have a high aspect-ratio of well over 120, about ~ 110 nm in diameter, and ~ 14 µm in length. Interfacing the tube arrays with porous Pt was also introduced on the basis of partial etching technique in order to construct Pt/YSZ-NTs/Pt membrane electrode assembly (MEA) structures. The resulting YSZ-NTs MEAs show a 7 mm in diameter with a roughness factor of ~ 2. Area specific resistance was measured up to 1.84 Ω cm2 at 400 °C using H2 as fuel.

Synthesis and performance of nanostructured silicon/graphite composites with a thin carbon shell and engineered voids

Utilizing silicon as an anode material for Li-ion batteries has been the subject of many studies. However, due to the huge volume change of silicon during lithiation, the electrochemical performance of silicon is poor. Here, we have investigated a novel yet simple approach to synthesize nanostructured silicon/graphite composites with a carbon coating and engineered voids. High-energy ball mill is employed to convert micrometer-sized silicon and graphite to nanostructured silicon/graphite composite building blocks, while a thin carbon coating is applied to encapsulate these composite agglomerates, followed by partial etching of silicon to create engineered voids inside the composite agglomerates. The batteries made with this tailored nanostructure exhibit improved electrochemical performance over the counterparts made with silicon nanoparticles and exhibited a specific capacity of ∼1800 mA h g−1 discharge capacity at the first cycle, 580 mA h g−1 after 40 cycles, and 350 mA h g−1 after 300 cycles. This study has established a novel method scalable at industry environment and capable of producing low cost Si anodes and clearly shown that the cycle stability of the tailored nanostructure improves with increasing engineered voids in the range we have investigated.