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Synthetic two-dimensional (2D) mono-elemental crystals, namely X-enes, have recently emerged as a new frontier for atomically thin nanomaterials with on-demand properties. Among X-enes, antimonene, the β-phase allotrope of antimony, is formed by atoms arranged in buckled hexagonal rings bearing a comparatively higher environmental stability with respect to other players of this kind. However, the exploitation of monolayer or few-layer antimonene and other 2D materials in novel opto-electronic devices is still hurdled by the lack of scalable processes. Here, we demonstrated the viability of a bottom-up process for the epitaxial growth of antimonene-like nanocrystals (ANCs), based on a Metal-Organic Chemical Vapor Deposition (MOCVD) process, assisted by gold nanoparticles (Au NPs) on commensurate (1 1 1)-terminated Ge surfaces. The growth mechanism was investigated by large- and local-area microstructural analysis, revealing that the etching of germanium, catalyzed by the Au NPs, led to the ANCs growth on the exposed Ge (1 1 1) planes. As a supportive picture, ab-initio calculations rationalized this epitaxial relationship in terms of compressively strained β-phase ANCs. Our process could pave the way to the realization of large-area antimonene layers by a deposition process compatible with the current semiconductor manufacturing technology.

In recent years, the process requirements of nano-devices have led to the gradual reduction in the scale of semiconductor devices, and the consequent non-negligible sidewall defects caused by etching. Since plasma-enhanced chemical vapor deposition can no longer provide sufficient step coverage, the characteristics of atomic layer deposition ALD technology are used to solve this problem. ALD utilizes self-limiting interactions between the precursor gas and the substrate surface. When the reactive gas forms a single layer of chemical adsorbed on the substrate surface, no reaction occurs between them and the growth thickness can be controlled. At the Å level, it can provide good step coverage. In this study, recent research on the ALD passivation on micro-light-emitting diodes and vertical cavity surface emitting lasers was reviewed and compared. Several passivation methods were demonstrated to lead to enhanced light efficiency, reduced leakage, and improved reliability.

Background This study aimed to assess the possibility of benzene exposure in workers of a Korean semiconductor manufacturing company by reviewing the issued patents. Methods A systematic patent search was conducted with the Google “Advanced Patent Search” engine using the keywords “semiconductor” and “benzene” combined with all of the words accessed on January 24, 2016. Results As a result of the search, we reviewed 75 patent documents filed by a Korean semiconductor manufacturing company from 1994 to 2010. From 22 patents, we found that benzene could have been used as one of the carbon sources in chemical vapor deposition (CVD) for capacitor; as diamond-like carbon for solar cell, graphene formation, or etching for transition metal thin film; and as a solvent for dielectric film, silicon oxide layer, nanomaterials, photoresist, rise for immersion lithography, electrophotography, and quantum dot ink. Conclusion Considering the date of patent filing, it is possible that workers in the CVD, immersion lithography, and graphene formation processes could be exposed to benzene from 1996 to 2010.

Single crystal diamond particles were heated with liquid phase alkali metals (Li, Na, K) in an argon atmosphere. It was found that Li reacts with the diamond above 600 degrees C, Na makes the surface rougher on a nm scale at 800 degrees C, and K did not change the surface morphology. The etching speed by the reaction with Li is the fastest on the (001) surface. Photoluminescence of the NV- (negatively charged nitrogen vacancy) center decreased only after the annealing with K. DFT calculations explained the strong chemical interaction between Li and the diamond (001) surfaces, and upward band bending at the interfaces with Na and K. The behavior of the NV-center photoluminescence is consistent with the extent of band bending. (C) 2021 Elsevier Ltd. All rights reserved.

The realization of hybrid superconductor–semiconductor quantum devices, in particular a topological qubit, calls for advanced techniques to readily and reproducibly engineer induced superconductivity in semiconductor nanowires. Here, we introduce an on-chip fabrication paradigm based on shadow walls that offers substantial advances in device quality and reproducibility. It allows for the implementation of hybrid quantum devices and ultimately topological qubits while eliminating fabrication steps such as lithography and etching. This is critical to preserve the integrity and homogeneity of the fragile hybrid interfaces. The approach simplifies the reproducible fabrication of devices with a hard induced superconducting gap and ballistic normal-/superconductor junctions. Large gate-tunable supercurrents and high-order multiple Andreev reflections manifest the exceptional coherence of the resulting nanowire Josephson junctions. Our approach enables the realization of 3-terminal devices, where zero-bias conductance peaks emerge in a magnetic field concurrently at both boundaries of the one-dimensional hybrids., Advanced fabrication techniques enable a wide range of quantum devices, such as the realization of a topological qubit. Here, the authors introduce an on-chip fabrication technique based on shadow walls to implement topological qubits in an InSb nanowire without fabrication steps such as lithography and etching.

Purpose The aim of this study was to evaluate in vitro, the shear bond strength (SBS) and adhesive remnant index (ARI) of pit and fissure sealants (PFS) after enamel conditioning with different new-generation self-etching (SE) agents; additionally, enamel etching patterns were assessed. Methods Healthy unerupted third molars surgically removed for therapeutic reasons (n = 25p/g), were randomly assigned to six groups. Conventional etching (CE) or SE was applied prior to pit and fissure sealants bonding. Enamel conditioned surfaces were evaluated by SEM at × 500, × 1000, and × 2000 magnification to determine etching patterns. Subsequently, 25 PFS blocks (3 × 2 × 1.5 mm) p/g were bonded to enamel surface. Samples were stored in water at 37 °C for 24 h, previous to SBS and ARI test. One-way ANOVA and Tamhane statistic tests were used for SBS; while Mann–Whitney U and Kruskal–Wallis were employed for ARI (p ≤ 0.05). Results For SBS test, CE_PFS_3M and SE1_PFS_Shofu groups showed the lowest values (8.74 ± 4.02 and 8.75 ± 3.90, respectively). The highest scores were observed in SE_PFS_Kuraray group (13.46 ± 5.83). Significant differences in SBS and ARI assessments were found. All experimental groups showed type 1 etching pattern. Conclusion The etching pattern was less pronounced in self-etching groups, which showed an equal or superior in vitro performance compared to conventional etching agents. The clinical use of self-etching agents could be recommended before pit and fissure sealants application in new dental protocols. The best in vitro performance was observed when both applied materials, self-etching agent and pit and fissure sealant have 10-methacryloyloxydecyl dihydrogen phosphate in their chemical composition.

Conventional neuronal network pattern formation techniques cannot control the arrangement of axons and dendrites because network structures must be fixed before neurite differentiation. To overcome this limitation, we developed a non-destructive stepwise microfabrication technique that can be used to alter microchannels within agarose to guide neurites during elongation. Micropatterns were formed in thin agarose layer coating of a cultivation dish using the tip of a 0.7 $$\upmu \mathrm{m}$$ μ m -diameter platinum-coated glass microneedle heated by a focused 1064-nm wavelength infrared laser, which has no absorbance of water. As the size of the heat source was 0.7 $$\upmu \mathrm{m}$$ μ m , which is smaller than the laser wavelength, the temperature fell to 45 $$^\circ \hbox {C}$$ ∘ C within a distance of 7.0 $$\upmu \mathrm{m}$$ μ m from the edge of the etched agarose microchannel. We exploited the fast temperature decay property to guide cell-to-cell connection during neuronal network cultivation. The first neurite of a hippocampal cell from a microchamber was guided to a microchannel leading to the target neuron with stepwise etching of the micrometer resolution microchannel in the agarose layer, and the elongated neurites were not damaged by the heat of etching. The results indicate the potential of this new technique for fully direction-controlled on-chip neuronal network studies.

In this study, we develop a reactive force field (ReaxFF) for a Si/O/H/F system to perform etching simulations of SiO2 with an HF etchant. Quantum mechanical (QM) training sets from density functional theory calculations, which contain structures of reactant/product and energies with bond dissociation, valence angle distortions, and reactions between SiO2 clusters and SiO2 slab with HF gases, are used to optimize the ReaxFF parameters. Structures and energies calculated using the ReaxFF match well with the QM training sets. Using the optimized ReaxFF, we conduct molecular dynamics simulations of the etching process of SiO2 substrates with active HF molecules. The etching yield and number of reaction products with different incident energies of the HF etchant are investigated. These simulations show that the developed ReaxFF offers insights into the atomistic surface reaction of the SiO2 etching process.

In order to effectively utilize the photovoltaic properties of gallium arsenide, its surface/interface needs to be properly prepared. In the experiments described here we examined eight different paths of GaAs surface treatment (cleaning, etching, passivation) which resulted in different external quantum efficiency (EQE) values of the tested photovoltaic (PV) cells. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) examinations were conducted to obtain structural details of the devices. X-ray photoelectron spectroscopy (XPS) with depth profiling was used to examine interface structure and changes in the elemental content and chemical bonds. The photoluminescence (PL) properties and bandgap measurements of the deposited layers were also reported. The highest EQE value was obtained for the samples initially etched with a citric acid-based etchant and, in the last preparation step, either passivated with ammonium sulfide aqueous solution or treated with ammonium hydroxide solution with no final passivation. Subsequent I–V measurements, however, confirmed that from these samples, only the sulfur-passivated ones provided the highest current density. The tested devices were fabricated by using the ALD method.

The integration of gallium nitride (GaN) nanowire light-emitting diodes (nanoLEDs) on flexible substrates offers opportunities for applications beyond rigid solid-state lighting (e.g., for wearable optoelectronics and bendable inorganic displays). Here, we report on a fast physical transfer route based on femtosecond laser lift-off (fs-LLO) to realize wafer-scale top–down GaN nanoLED arrays on unconventional platforms. Combined with photolithography and hybrid etching processes, we successfully transferred GaN blue nanoLEDs from a full two-inch sapphire substrate onto a flexible copper (Cu) foil with a high nanowire density (~107 wires/cm2), transfer yield (~99.5%), and reproducibility. Various nanoanalytical measurements were conducted to evaluate the performance and limitations of the fs-LLO technique as well as to gain insights into physical material properties such as strain relaxation and assess the maturity of the transfer process. This work could enable the easy recycling of native growth substrates and inspire the development of large-scale hybrid GaN nanowire optoelectronic devices by solely employing standard epitaxial LED wafers (i.e., customized LED wafers with additional embedded sacrificial materials and a complicated growth process are not required).

Both multilayered (ML) and few-layered (FL) Ti3C2Tx nanosheets have been prepared through a typical etching and delaminating procedure. Various characterizations confirm that the dominant terminal groups on ML-Ti3C2Tx and FL-Ti3C2Tx are different, which have been assigned to O-related and hydroxyl groups, respectively. Such deviation of the dominant terminals results in the different physical and chemical performance and eventually makes the nanosheets have different potential applications. In particular, before coupling to Ag nanoparticles, ML-Ti3C2Tx can present stronger near-field enhancement effect; however, Ag/FL-Ti3C2Tx hybrid structure can confine stronger near-field due to the electron injection, which can be offered by the terminated hydroxyl groups.

To investigate the effects of their surface recovery and optical properties, extremely small sized (12 µm × 12 µm mesa area) red AlGaInP micro light emitting diodes ($$\upmu$$ μ LED) were fabricated using a diluted hydrofluoric acid (HF) surface etch treatment. After the chemical treatment, the external quantum efficiencies (EQEs) of $$\upmu$$ μ -LED at low and high injection current regions have been improved by 35.48% and 12.86%, respectively. The different phenomena of EQEs have a complex relationship between the suppression of non-radiative recombination originating from the etching damage of the surface and the improvement of light extraction of the sidewalls. The constant enhancement of EQE at a high injection current it is attributed to the expansion of the active region’s sidewall surface area by the selective etching of AlInP layers. The improved EQE at a low injection current is related to the minimization of the surface recombination caused by plasma damage from the surface. High-resolution transmission electron microscopy (HR-TEM) revealed physical defects on the sidewall surface, such as plasma-induced lattice disorder and impurity contamination damage, were eliminated using chemical treatment. This study suggests that chemical surface treatment using diluted HF acid can be an effective method for enhancing the $$\upmu$$ μ -LED performance.

An ultra-wideband, compact planar antenna with defected ground structure (DGS) has been presented in this article for future 5G millimeter-wave applications. The proposed antenna overcomes the limitation of bandwidth of the conventional microstrip patch antenna (typically < 5%). The antenna exhibits an ultra-wideband characteristic covering frequency band from 21.3 GHz to 40.6 GHz which makes the fractional bandwidth of 62.36%. The antenna performance is enhanced by etching slots on the patch and incorporating defect on the ground plane. The antenna achieves gain greater than 4.01 dBi and radiation efficiency greater than 95% throughout the operating band. In the given band it also exhibits very low cross-polarization level as well as stable radiation performance. This antenna is designed to operate in n257, n258, n260 and n261 5G millimeter-wave spectrum.

Background/purpose: Increasing the bond strength between the orthodontic brackets and all-ceramic materials is one of the challenges facing orthodontists. The purpose of this study is to assess the shear bond strength (SBS) of metal brackets to two types of all ceramic materials using various surface mechanical and chemical conditioning methods. Materials and methods: Sixty ceramic blocks were prepared using two types of all ceramic materials (IPS e.max and VITA Suprinity® PC) and treated with 3 surface treatments; surface etching with 9.6% hydrofluoric acid (HFA) for 2 mins; surface roughening with Sof-Lex finishing discs; and surface roughening with Sof-Lex finishing discs and etching with HFA. Metal brackets were attached to the surface of the ceramic blocks using light cure orthodontic adhesive. Samples were subjected to 2000 thermo-cycles (5–50 °C) and the SBS was assessed using Instron machine. The adhesive remnant index (ARI) was evaluated under light microscope. Descriptive and group comparison were calculated using Two-way ANOVA, Post-hoc Tukey's and Chi-square tests and significance level set at (P

AlGaN/GaN-Si based MIS-HEMTs are considered as the popular candidates for application in the 5G communication system due to their competitive characteristics and low cost. Ohmic contact, as an important fabrication process, significantly affects the performance of the device. In this study, the ohmic contact process, including the SiN passivation layer etching, surface treatment, and barrier layer etching, was studied in detail in order to effectively optimize the device performance. It is observed that the sample with the SiN passivation layer etched by the magnetic neutral loop discharge (NLD) resulted in a lower contact resistance as compared to the reaction ion etching (RIE). The sample surface treated with the O plasma and pickled in the HCl:H2O = 1:10 liquid could effectively remove the pollutants and oxides from the surface, thus, correspondingly presenting a lower ohmic contact resistance as compared to the N2 plasma. Meanwhile, an optimum etching depth was developed with the ICP process for 6 min with an etching speed of 1.6 nm/min. A contact resistance of $0.76~\Omega \cdot \text {mm}$ and square resistance of 274.63 ohm/sq were observed under the above-mentioned optimized ohmic contact process. The AlGaN/GaN-Si MIS-HEMT with gate length of $0.5~\mu \text{m}$ , gate-source space of $1~\mu \text{m}$ , gate-drain space of $2.5~\mu \text{m}$ , and gate width of $100~\mu \text{m}$ was fabricated using the optimized process. A saturation current density of 794.30 mA/mm and the maximum transconductance of 16.86 mS were observed. The findings in this study provide the experimental basis for the manufacturing of AlGaN/GaN-Si based MIS-HEMTs for RF applications.

We propose and numerically verify a design approach to a grating coupler (GC) for in-plane generation and propagation of quasi-TE vortex modes with azimuthal order $\pm$1 within photonic integrated circuits (PICs). In the considered GC design example, silicon nitride waveguides with silica substrate and cladding are used. The shallowly etched grating is illuminated by the incident optical beam from a standard single-mode fiber. We optimize the GC design parameters to maximize the purity of orbital angular momentum (OAM) mode first for the case of a theoretical ideally fabricated grating, and then consider a more practical case of GC design, when the etching resolution is limited. The numerical modeling results show possibility of the vortex mode generation with >96% purity of the target OAM state $\pm$1 at the wavelength 1550 nm. The proposed design, compatible with the standard nanofabrication process, provides a simple, compact and robust solution for various potential PIC-based applications of OAM beams.

To fully understand the kinetics of graphene growth, large-scale atomic simulations of graphene islands evolution up to macro sizes (i.e., graphene islands of a few micrometers or with billions of carbon atoms) during growth and etching is essential, but remains a great challenge. In this paper, we developed a low computational cost large-scale kinetic Monte Carlo (KMC) algorithm, which includes all possible events of carbon attachments and detachments on various edge sites of graphene islands. Such a method allows us to simulate the evolution of graphene islands with sizes up to tens of micrometers during either growth or etching with a single CPU core. With this approach and the carefully fitted parameters, we have reproduced the experimentally observed evolution of graphene islands during both growth or etching on Pt(111) surface, and revealed more atomic details of graphene growth and etching. Based on the atomic simulations, we discovered a complementary relationship of graphene growth and etching—the route of graphene island shape evolution during growth is exactly the same as that of the etching of a hole in graphene and that of graphene island etching is exactly same as that of hole growth. The complementary relation brings us a basic principle to understand the growth and etching of graphene, and other 2D materials from atomic scale to macro size and the KMC algorithm is expected to be further developed into a standard simulation package for investigating the growth mechanism of 2D materials on various substrates.

Atmospheric-pressure (AP) plasma etching provides an alternative method for mechanical grinding to realize wafer thinning of Si wafer. It can avoid the damages and micro-cracks that would be introduced by mechanical stress during the grinding process. In this study, the material removal characteristics of Si (100) wafer processed by linear field AP plasma generated using carbon tetrafluoride (CF4) as the reactive source were analyzed. This linear field plasma etching tool has a typical removal profile and the depth removal rate that can reach up to 1.082 μm/min. The effect of O2 concentration on the removal rate was discussed and the surface morphology during the process was characterized using scanning electron microscopy. It is shown that the subsurface damage layer was gradually removed during the etching process and the surface was observed to be smoothened with the increase of the etching depth. This present work contributes a basic understanding of the linear field AP plasma etching performance with different gas composition and the typical characteristics would be further applied to damage-free precision removal of Si.

Thermoelectric generators made by large arrays of nanowires perpendicular to a silicon substrate, that is, so-called silicon nanowire forests are fabricated on large areas by an inexpensive metal-assisted etching technique. After fabrication, a thermal diffusion process is used for doping the nanowire forest with phosphorous. A suitable experimental technique has been developed for the measurement of the Seebeck coefficient under static conditions, and results are reported for different doping parameters. These results are in good agreement with numerical simulations of the doping process applied to silicon nanowires. These devices, based on doped nanowire forests, offer a possible route for the exploitation of the high power factor of silicon, which, combined with the very low thermal conductivity of nanostructures, will yield a high efficiency of the conversion of thermal to electrical energy.

The combination of metal-assisted chemical etching (MACE) with colloidal lithography has emerged as a simple and cost-effective approach to nanostructure silicon. It is especially efficient at synthesizing Si micro- and nanowire arrays using a catalytic metal mesh, which sinks into the silicon substrate during the etching process. The approach provides a precise control over the array geometry, without requiring expensive nanopatterning techniques. Although MACE is a high-throughput solution-based approach, achieving large-scale homogeneity can be challenging because of the instability of the metal catalyst when the experimental parameters are not set appropriately. Such instabilities can lead to metal film fracture, significantly damaging the substrate and thus compromising the nanowire array quality. Here, we report on the critical parameters that influence the stability of the metal catalyst layer for achieving large-scale homogeneous MACE: etchant composition, metal film thickness, adhesion layer thickness, nanowire diameter and pitch, metal film coverage, Si/Au/etchant interface length, and crystalline quality of the colloidal template (grain size and defects). Our results investigate the origin of the catalyst film fracture and reveal that MACE experiments should be optimized for each Si wire array geometry by keeping the etch rate below a certain threshold. We show that the Si/Au/etchant interface length also affects the etch rate and should thus be considered when optimizing the MACE experimental parameters. Finally, our results demonstrate that colloidal templates with small grain sizes (i.e.

Aim: This study assessed the effect of postetch cleansing on the surface microstructure, surface topography, and microshear bond strength (μSBS) of lithium disilicate and the resin cement. Setting and Design: In Vitro analytical study. Materials and Methods: Fifteen discs (10 mm diameter and 2 mm thickness) were fabricated from highly translucent lithium disilicate IPS Emax 2 ceramic (Ivoclar Vivadent, Schaan, Liechtenstein). Four resin cement (RelyX Ultimate, 3M ESPE) cylinders (0.9 mm diameter and 4 mm high) were placed on each ceramic disc (total n = 60). The samples were divided into three groups based on the surface treatment of the ceramic discs (20 resin cement cylinders on 5 discs in each group). Group I (HF) (control) etched with 9.6% HF with no postetch cleansing, Group II (HFP) etched with 9.6% HF for 20 s followed by rinsing with water and postetching cleansing with 37% phosphoric acid, and Group III (HFPU) etched with 9.6% HF followed by active application of 37% phosphoric acid followed by postetch cleansing in ultrasonic bath for 5 min. μSBS of resin cement to ceramic surfaces was tested following a standard protocol. Surface roughness was evaluated using an atomic force microscope. Surface topography and elemental analysis were analyzed using SEM/EDX. Mode of failure was also assessed. Statistical Analysis Used: The data were analysed using one way analysis of variance and post hoc tukeys test. Results: The μSBS were found to be highest for Group III (HFPU), followed by Group II (HFP) followed by Group I (HF) and were statistically significant. There was a difference in the surface topography and surface microstructure between the three groups. Mode of failure was predominantly adhesive. Conclusion: The μSBS, surface topography, and surface microstructure were found to be superior in the groups, in which postetch cleansing was done as compared to the control in which no postetch cleansing was done.

The integration of quantum well infrared photodetectors with plasmonic cavities has allowed for demonstration of sensitive photodetectors in the mid-infrared up to room-temperature operating conditions. However, clear guidelines for optimizing device structure for these detectors have not been developed. Using simple stripe cavity detectors as a model system, we clarify the fundamental factors that improve photodetector performance. By etching semiconductor material between the stripes, the cavity resonance wavelength was expected to blue-shift, and the electric field was predicted to strongly increase, resulting in higher responsivity than unetched stripe detectors. Contrary to our predictions, etched stripe detectors showed lower responsivities, indicating surface effects at the sidewalls and reduced absorption. Nevertheless, etching led to higher detectivity due to significantly reduced detector dark current. These results suggest that etched structures are the superior photodetector design, and that appropriate sidewall surface treatments could further improve device performance. Finally, through polarization and incidence angle dependence measurements of the stripe detectors, we clarify how the design of previously demonstrated wired patch antennas led to improved device performance. These results are widely applicable for cavity designs over a broad range of wavelengths within the infrared, and can serve as a roadmap for improving next-generation infrared photodetectors.

High-chi (where chi is the Flory-Huggins interaction parameter) block copolymers (BCPs) have great potential to achieve ultra-small microphase-separated structures with domain spacings (d) of

Vanadium sulfide (VS2) nanomaterials have been deposited on surface-modified stainless steel mesh (SMSSM) by facial hydrothermal method and subsequent effects of acidic etching on surface morphology and supercapacitive performance of the electrode were studied. The acid etching process improves the coupling interaction between the stainless steel mesh and active materials. The optimized 1% etched SMSSM with VS2 (1%/VS2) loaded electrode reveals the porous fine nanoparticles composed surface nanostructure. The prepared 1%/VS2 electrode exhibited an excellent areal capacitance of 45.83 mF/cm2, which is two times higher than that of a non-etched VS2 loaded electrode. These results showed that the acidic etching process significantly improved the surface nanostructure of the VS2 material that improved the capacitance of the SMSSM substrate.

Liquation cracks are generally regarded as thermal defects in various materials, e.g. in steels and nickel-based alloys. However, direct observation of microstructure with crack-like morphology that may be revealed by chemical etching or electrochemical etching methods, might lead to the misinterpretation of liquation cracks. To avoid the possible misinterpretation, comparative etching was employed to reveal the effect of various etching processes on the determination of liquation cracks. As a result, the formation process and mechanism of the false liquation crack in 9% Cr/CrMoV welded joint were clarified. The results obtained by optical microscope (OM) and scanning electron microscope (SEM) in the heat treatment zone of 9% Cr steel (9% Cr-HAZ) after chemical etching clearly demonstrate the existence of crack-like morphology, and the disappearance of element segregation zone after regrinding and re-polishing. Besides, laser scanning confocal microscope (LSCM) was applied to further exhibit the microstructure evolution experiencing high temperature to confirm the possibility of the liquation crack. The results showed that the element segregation and subsequent chemical etching process were the crucial factors to cause the formation of false liquation crack.

Subwavelength-scale nanorods were implemented on the hexagonal pyramid of photochemically etched light-emitting diodes (LEDs) to improve light extraction efficiency (LEE). Sequential processes of Ag deposition and inductively coupled plasma etching successfully produce nanorods on both locally unetched flat surface and sidewall of hexagonal pyramids. The subwavelength-scale structures on flat surface offer gradually changed refractive index, and the structures on side wall of hexagonal pyramid reduce backward reflection, thereby enhancing further enhancement of the light extraction efficiency. Consequently, the nanorods implemented LED shows a remarkable enhancement in the light output power by 14% compared with that of the photochemically etched LEDs which is known to exhibit the highest light output power. Theoretical calculations using a rigorous coupled wave analysis method reveal that the subwavelength-scale nanorods are very effective in the elimination of TIR as well as backward reflections, thereby further enhancing LEE of the LEDs.

In this study, we report a metal-ion-assisted precipitation etching strategy that can be used to manipulate the optical properties associated with the assembling of sulfur quantum dots (S dots) using copper ions. Transmission electron microscopy confirmed that the S dots were mainly distributed within 50–80 nm and that they exhibited an ambiguous boundary. After the post-synthetic Cu2+-assisted modification was completed, the assisted precipitation-etching S dots (APE-S dots) were observed to exhibit a relatively clear boundary with a high fluorescence (FL) quantum yield (QY) of 32.8%. Simultaneously, the Fourier transform infrared radiation, X-ray photoelectron spectra, and time-resolved FL decay spectra were used to illustrate the improvement in the FL QY of the APE-S dots.

In this study, high-purity V2CTx MXene was successfully synthesized by etching V2AlC with fluoride and hydrochloric acid mixed solution using a hydrothermal-assisted method. This method is more concise and effective and has a low level of danger. The morphology and structure of the V2CTx MXene was characterized by X-ray diffraction, field emission scanning electron microscopy, and X-ray photoelectron spectroscopy. The electrochemical properties were investigated as an anode material for lithium ion batteries. The results show that the prepared V2CTx had a higher purity and showed excellent electrochemical properties as an anode of lithium-ion batteries. And V2CTx prepared with different etching system can he obtained with high yield and excellent purity by changing the reactive conditions of the system. However, electrochemical performance of V2CTx MXene obtained at different etching system is quite different. V2CTx synthesized in the mixed solution of ammonium fluoride and hydrochloric acid has the best performance, which originates from more accessible active sites for ion in the enlarged interlayer distance, and the smaller impedance of V2CTx. Keywords: MXene, V2CTx, Hydrothermal, Lithium ion battery

We fabricated a highly water-repellent quartz nanopillar (NP) structure to investigate the effect of varying the contact angle (CA) by using 10-nm-order gaps and 10-nm-diameter NPs. Gaps from 15 to 30 nm led to CAs of more than 100°, showing hydrophobicity, to a maximum of 105°. The mechanism of repelling water on quartz could be explained by the Cassie-Baxter model with a filling factor. A gap of more than 30 nm fills with water due to capillarity, but a gap of less than 30 nm causes water to be repelled by air. We were able to repeatedly fabricate a quartz NP structure with a controllable gap by using a combination of a bio-template and neutral-beam etching and found this structure to be highly water-repellent. The structure has high durability and optical transparency. As a result, we conclude that it can be used in sensors and lenses on various devices such as cameras and radars.

In this paper, we proposed a novel Fabry-Perot cavity antenna with high-gain radiation over two wide bands based on a partially reflective metasurface. To satisfy the resonance condition of the dual-wideband Fabry-Perot cavity, we constructed the unit cell of the partial reflection metasurface by loading magnetic coupling enhancement layers and etching the bottom patches. The partial reflection metasurface composed of the above unit cells can generate reflection phases of positive gradient with almost the same slope over two wide bands, where the partial reflection amplitude is close to 1. Subsequently, a normal dual-band microstrip antenna has also been designed for excitation. Finally, the Fabry-Perot cavity antenna consists of the proposed partial reflection metasurface and the dual-band antenna has been simulated, fabricated, and measured in a microwave anechoic chamber. Both simulation and experimental results demonstrate that the designed Fabry-Perot cavity antenna achieves 3-dB gain bandwidths of 20.7% and 10.1% with peak gains of 12.07dBi and 13.5dBi over two wide bands of 5.7-6.9GHz and 11.7-12.95GHz, respectively.

Optical bound states in the continuum (BICs) have recently been studied in a wide range of material systems, where light is perfectly confined in the continuous spectrum of radiating modes. In this paper, we reported periodic nonlinear metasurfaces on the etchless LiNbO3 platform, realizing the enhancement of second-order generation (SHG). All-dielectric heterogeneous metasurfaces are constructed by patterning a low-refractive-index polymer on a high refractive-index LiNbO3 film without etching. Due to BICs, light is localized in the LiNbO3 film where the excellent optical second-order nonlinearity is exploited. We demonstrated that with normal incident waves, symmetry-protected BICs are formed at near-infrared wavelength showing a vanishing linewidth in the transmission spectrum. In addition, to manifest the invisible BICs to detectable supercavity resonances at normal incidence, asymmetry is introduced into the system, degrading the symmetry-protected BICs to sharp resonances with a high Q factor. Furthermore, the second harmonic generation (SHG) of the etchless lithium niobate metasurface is studied, predicting that the SHG efficiency can exceed 10-3 with 30 MW/cm2 of the pump intensity. The proposed strategy without facing the fabrication challenge of etching single-crystal LiNbO3 film opens a new avenue for the utilization of BIC in nonlinear optics of all-dielectric heterogeneous metasurfaces.

GeSn is a promising material for the fabrication of on-chip photonic and nanoelectronic devices. Processing techniques dedicated to GeSn have thus been developed, including epitaxy, annealing, ion implantation, and etching. In this work, suspended, strain-relaxed, and high-quality GeSn microdisks are realized by a new approach without any etching to GeSn alloy. The GeSn alloy was grown on pre-patterned Ge (001) substrate by molecular beam epitaxy at low temperatures. The transmission electron microscopy and scanning electron microscopy were carried out to determine the microstructures of the GeSn samples. The microdisks with different diameters of Ge pedestals were fabricated by controlling the selective wet etching time, and micro-Raman results show that the microdisks with different dimensions of the remaining Ge pedestals have different extents of strain relaxation. The compressive strain of microdisks is almost completely relaxed under suitable conditions. The semiconductor processing technology presented in this work can be an alternative method to fabricate innovative GeSn and other materials based micro/nano-structures for a range of Si-compatible photonics, 3D-MOSFETs, and microelectromechanical device applications.

Introduction: Composite resins have developed in past years, however, failures may occur which needs whole restoration repairing. this study aimed to evaluate the effect of different surface treatments on shear bond strength of new to old composite restorations. Materials and Methods: A total of 60 blocks of Z250 composite resin were divided to four groups 1) no surface preparation (control group), 2) abrasion through aerosols using 50-micron aluminum oxide particles, 3) abrasion through diamond milling with 125-micrometer particles, 4) surface preparation using hydrofluoric acid. Shear bond strength in different methods such as etching with hydrofluoric acids (with and without silanization), air abrasion, and diamond milling was compared with the control group. All data were analyzed using the Kolmogorov-Smirnov test and one-way analyses of variance (ANOVA) and Tukey’s post hoc test. Results: In comparing the groups with each other, it was found that shear bond strength in Hydrofluoric acid and silanization group was significantly higher than control (P = 0.017). Conclusion: The effects of etching with hydrofluoric acid and silanization in increasing shear bond strength between aged and new composite resins are superior to control, which could be a suitable repair protocol to obtain optimal repair bond strength.

Monolayers of self-assembled quasi-spherical colloidal particles are essential building blocks in the field of materials science and engineering. More typically, they are used as a template for the fabrication of nanostructures if they serve, for instance, as a mask for deposition of new material on the surface on which particles are assembled or for etching of the material underneath; in this case, they are removed afterwards. This is what occurs in colloidal or nanosphere lithography. In some other cases, they are not used as a sacrificial material but they are incorporated in the final structure because they are inherently interesting for their properties. Independently of their specific use and application, different strategies have been devised in order to modify size and shape of colloidal particles, so as to enrich the variety of attainable patterns and to tailor the properties of the final structures and materials. In this review, we will focus on one of the most widespread methods to shape spherical colloidal particles, i.e. dry etching techniques. We will follow the development of such approaches until recent days, so as to trace an extensive panorama of the diverse parameters that can be harnessed to achieve specific morphological changes and highlight the characteristic features of the variants of this method. We will finally discuss how particles modified via dry etching can be used for patterning or can be resuspended in solvents for very diverse applications., Advances in Colloid and Interface Science, 299, ISSN:0001-8686, ISSN:1873-3727

HfO2 is a high-k material that is used in semiconductor devices. Atomic-level control of material processing is required for the fabrication of thin films of high-k materials at nanoscale device sizes. Thermal atomic layer etching (ALE) of metal oxides, in which up to one monolayer of material can be removed, can be achieved by sequential self-limiting fluorination and ligand-exchange reactions at elevated temperatures. First-principles-based atomic-level simulations using density functional theory can give deep insights into the precursor chemistry and the reactions that drive the etching of metal oxides. A previous study examined the hydrogen fluoride (HF) pulse in the first step in the thermal ALE process of crystalline HfO2 and ZrO2. This study examines the HF pulse on amorphous HfO2 using first-principles simulations. The Natarajan–Elliott analysis, a thermodynamic methodology, is used to compare reaction models representing the self-limiting and spontaneous etch processes taking place during an ALE pulse. For the HF pulse on amorphous HfO2, we found that thermodynamic barriers impeding spontaneous etching are present at ALE relevant temperatures. HF adsorption calculations on the amorphous oxide surface are studied to understand the mechanistic details of the HF pulse. An HF molecule adsorbs dissociatively by forming Hf–F and O–H bonds. HF coverages ranging from 1.1 ± 0.3 to 18.0 ± 0.3 HF/nm2 are investigated, and a mixture of molecularly and dissociatively adsorbed HF molecules is present at higher coverages. A theoretical etch rate of −0.82 ± 0.02 Å/cycle for amorphous HfO2 was calculated using a maximum coverage of 9.0 ± 0.3 Hf–F/nm2. This theoretical etch rate is greater than the theoretical etch rate for crystalline HfO2 that we previously calculated at −0.61 ± 0.02 Å/cycle. Undercoordinated atoms and void regions in amorphous HfO2 allow for more binding sites during fluorination, whereas crystalline HfO2 has a limited number of adsorption sites. We acknowledge support for this work from the LAM Research and the Science Foundation Ireland–NSF China Partnership Program, NITRALD Grant No. 17/NSFC/5279. We are grateful for access to Tyndall computing facilities supported by SFI and the Irish Centre for High-End Computing, www.ichec.ie. J.J.G.M. acknowledges financial support from the FusionCAT project (No. 001-P-001722) co-financed by the European Union Regional Development Fund within the framework of the ERDF Operational Program of Catalonia 2014–2020 with a grant of 50% of total cost eligible, and the access to HPC resources at the National Supercomputing Center in Shenzhen, acquired with funding from the Postdoctoral Science Foundation of China (Grant No. 2018M643152).

Silicon nanowires combine a high electrical conductivity with low thermal conductivity due to the small cross section offering a good template for sensing. Silicon p-type (100) substrate was used in this work to present a comparative study from a morphological point of view as well as for the electrical properties of silicon nanowires (SiNWs) etched by Ag-assisted chemical method in one-step and two-step process. The comparison between both techniques for SiNWs samples’ elaborated with Metal-Assisted Chemical Technique (MACE) was investigated by Scanning Electron Microscopy images that clearly show the presence of nanowires and the existence of porous silicon structure especially by Transmission Electron Microscopy technique. Several particles on the SiNWs surface such as oxygen and hydrogen elements were identified by Fourier-Transformed Infrared Spectroscopy measurements. The results indicate that the MACE’s steps influence the nucleation and motility of Ag particles, which leads to a different length and density structure within the nanowires. These parameters influence the electrochemical properties of the surface that was studied using electrochemical measurements. Impedance analysis revealed that the charge transfer resistance decreases with the length of the SiNWs dissimilar to the capacitance based on the cyclic voltammetry analysis. In this paper, we studied the electrochemical parameters which indicate that two-step MACE procedure presents a resistance nearly the half of the value of SiNWs produced using one-step MACE technique; as for the capacitance, it increases by 28.5%. We can notice that SiNWs produced using two-step MACE show better results for biosensing application. For that reason, we decide to functionalize the two-step MACE SiNWs to prove the ease of the surface modification. Deposition of nickel nanoparticles was analysed manifesting a good amelioration of the resistance with a factor of 2.5.

This paper presents prime results on process development and optimization of dry etching of silicon carbide (SiC) for via formation and deep etching for SiC-based microsystems. The investigations and corresponding results of the process developments enable the first realization of a full SiC-based technological demonstrator composed of a SiC-interposer with a flip chip mounted deep etched MEMS SiC Device. By optimizing the process, etch depth of 200μm with an etch rate of up to 2μm/min can be achieved for via etching. In addition, a Design Of Experiments (DOE) with a total of 29 experiments with seven factors was done to characterize the deep etching of large areas into the silicon carbide. Hereby, vertical sidewalls with low micro masking, low micro trenching and an etch rate of up to 4 μm / min could be achieved. The findings and optimized processes were implemented to develop on the one hand a 200 μm thick SiC interposer with copper metallization. On the other hand, a SiC-MEMS Device was manufactured with a deep etched cavity in SiC bulk wafer forming by the end a 50 μm thin membrane. The results demonstrate the ability of etching monocrystalline SiC with a high etch rate, enabling new fundamental topologies/structures and packaging concepts for harsh environments micro electromechanical systems (MEMS) and high-power electronics. The developed etching technologies demonstrate and enable various applications for 3D Integration with wide bandgap substrates taking advantage of the superior electrical and mechanical properties of SiC.

A temperature-responsive photonic coating on a flexible substrate was prepared by a photoinduced phase-separation process. In this coating a low molecular weight cholesteric liquid crystal (Ch-LC) mixture was encapsulated between the substrate and an in situ formed protective polymer top layer. The photonic coating showed a blue-shift of the photonic reflection band of 100 nm by heating from 22 to 23 °C due to the close proximity to the smectic to cholesteric phase transition and an overall 330 nm blue-shift while heating from 22 to 45 °C. Hence, the red coating turned green upon contact with skin within seconds. Furthermore, the coating structure and composition were investigated in detail, revealing a thick top coat. The adhesion of the coating was improved by providing trays on the substrate (by etching or 3D printing), resulting in a link between arbitrary-shaped substrates and the protective polymer top layer. These bendable coatings could be of interest for sensors, anticounterfeit labels, or customizable aesthetic applications.

We report high efficiency cell processing technologies for the ultra-thin Si solar cells based on crystalline Si thin foils (below a 50 µm thickness) produced by the proton implant exfoliation (PIE) technique. Shallow textures of submicrometer scale is essential for effective light trapping in crystalline Si thin foil based solar cells. In this study, we report the fabrication process of random Si nanohole arrays of ellipsoids by a facile way using low melting point metal nanoparticles of indium which were vacuum-deposited and dewetted spontaneously at room temperature. Combination of dry and wet etch processes with indium nanoparticles as etch masks enables the fabrication of random Si nanohole arrays of an ellipsoidal shape. The optimized etching processes led to effective light trapping nanostructures comparable to conventional micro-pyramids. We also developed the laser fired contact (LFC) process especially suitable for crystalline Si thin foil based PERC solar cells. The laser processing parameters were optimized to obtain a shallow LFC contact in conjunction with a low contact resistance. Lastly, we applied the random Si nanohole arrays and the LFC process to the crystalline Si thin foils (a 48 µm thickness) produced by the PIE technique and achieved the best efficiency of 17.1% while the planar PERC solar cell without the Si nanohole arrays exhibit 15.6%. Also, we demonstrate the ultra-thin wafer is bendable to have a 16 mm critical bending radius.

Transparent solar cells (TSCs) are emerging devices that combine the advantages of visible transparency and light-to-electricity conversion. Currently, existing TSCs are based predominantly on organics, dyes, and perovskites; however, the rigidity and color-tinted transparent nature of those devices strongly limit the utility of the resulting TSCs for real-world applications. Here, we demonstrate a flexible, color-neutral, and high-efficiency TSC based on a freestanding form of n-silicon microwires (SiMWs). Flat-tip SiMWs with controllable spacing are fabricated via deep-reactive ion etching and embedded in a freestanding transparent polymer matrix. The light transmittance can be tuned from ~10 to 55% by adjusting the spacing between the microwires. For TSCs, a heterojunction is formed with a p-type polymer in the top portion of the n-type flat-tip SiMWs. Ohmic contact with an indium-doped ZnO film occurs at the bottom, and the side surface has an Al2O3 passivation layer. Furthermore, slanted-tip SiMWs are developed by a novel solvent-assisted wet etching method to manipulate light absorption. Finite-difference time-domain simulation revealed that the reflected light from slanted-tip SiMWs helps light-matter interactions in adjacent microwires. The TSC based on the slanted-tip SiMWs demonstrates 8% efficiency at a visible transparency of 10% with flexibility. This efficiency is the highest among Si-based TSCs and comparable with that of state-of-the-art neutral-color TSCs based on organic–inorganic hybrid perovskite and organics. Moreover, unlike others, the stretchable and transparent platform in this study is promising for future TSCs., Transparent solar cells: Microwire-array shows potential A flexible, stretchable and fully transparent solar cell shows promise for harvesting sunlight as it hits windows. In designing transparent solar cells, there is a trade-off between efficiency and transparency – many existing cells are rigid and tinted because of the way they absorb certain wavelengths of light, and this limits their use in electronic devices and windows. Now, Kyoung Jin Choi at the Ulsan National Institute of Science and Technology, Ulsan, Korea, and co-workers have used a freestanding form of microwire-arrays to create a flexible, fully transparent solar cell. Their design comprises a crystalline silicon microwire array embedded in a transparent polymer matrix. The conducting junction occurs where the n-type-Si microwire tips meet the p-type polymer. The team also manipulated the shape of the microwire tips so that this enhances efficiency whilst maintaining transparency.

Dry etching is a prevalent technique for pattern transfer and material removal in microelectronics, optics and photonics due to its high precision material removal with low surface and subsurface damage. These processes, including reactive ion etching (RIE) and plasma etching (PE), are performed at vacuum conditions and provide high selectivity and vertical side wall etched patterns but create high costs and efforts in maintenance due to the required machinery. In contrast to electrically generated plasmas, laser-induced micro plasmas are controllable sources of reactive species in gases at atmospheric pressure that can be used for dry etching of materials. In the present study, we have demonstrated the laser-induced plasma etching of monocrystalline silicon. A Ti:Sapphire laser has been used for igniting an optically pumped plasma in a CF4/O2 gas mixture near atmospheric pressure. The influence of process parameters, like substrate temperature, O2 concentration, plasma-surface distance, etching duration, pulse energy and crystal orientation on etching rate and surface morphology has been investigated. Typical etching rates of 2–12 µm x min−1 can be achieved by varying mentioned parameters with a decreasing etching rate during the process. Different morphologies can be observed due to the parameters set, smooth as well as rough surfaces or even inverted pyramids. The presented etching method provides an approach for precise machining of silicon surfaces with good surface qualities near atmospheric pressure and sufficiently high material removal rates for ultraprecise surface machining.

In the current study, we investigated the partial decomposition of GaN layers grown on SiN-treated sapphire substrate in an atmospheric pressure metal organic vapor phase epitaxy (AP-MOVPE) vertical reactor under N2 ambient at 1200 °C. Under these experimental conditions, we studied the decomposition of different coalescence degrees GaN layers and the early thermal decomposition stages of GaN films. By the help of the scanning electron microscope (SEM), the surface morphology of the decomposed GaN epilayers was examined. We demonstrated that the thermal decomposition leads to an irregular etching process, which was carried out step by step. The optical properties of the decomposed films were then studied by using the photoreflectance (PR) technique at room temperature and at 11 K. We determined a logarithmic relation between the built-in electric field in the surface of GaN layers and the stress value. A model is also proposed to extract the stress value from PR spectra. It should be noted also that by using the thermal decomposition process, the stress inside GaN layers can be reduced by a factor of 6.

Graphene nanoribbons are a greatly intriguing form of nanomaterials owing to their unique properties that overcome the limitations associated with a zero bandgap of two-dimensional graphene at room temperature. Thus, the fabrication of graphene nanoribbons has garnered much attention for building high-performance field-effect transistors. Consequently, various methodologies reported previously have brought significant progress in the development of highly ordered graphene nanoribbons. Nonetheless, easy control in spatial arrangement and alignment of graphene nanoribbons on a large scale is still limited. In this study, we explored a facile, yet effective method for the fabrication of graphene nanoribbons by employing orientationally controlled electrospun polymeric nanowire etch-mask. We started with a thermal chemical vapor deposition process to prepare graphene monolayer, which was conveniently transferred onto a receiving substrate for electrospun polymer nanowires. The polymeric nanowires act as a robust etching barrier underlying graphene sheets to harvest arrays of the graphene nanoribbons. On varying the parametric control in the process, the size, morphology, and width of electrospun polymer nanowires were easily manipulated. Upon O2 plasma etching, highly aligned arrays of graphene nanoribbons were produced, and the sacrificial polymeric nanowires were completely removed. The graphene nanoribbons were used to implement field-effect transistors in a bottom-gated configuration. Such approaches could realistically yield a relatively improved current on&ndash, off ratio of ~30 higher than those associated with the usual micro-ribbon strategy, with the clear potential to realize reproducible high-performance devices.

In this paper, an all-fiber Mach-Zehnder interferometer (MZI) sensor for refractive index (RI) measuring is presented, which is based on Multimode–Single-mode–Multimode (MSM) fiber. The effects of both reducing the radius of the sensing part and the surface plasmon resonance (SPR) on its efficiency are investigated. Increasing the interaction of high-order modes with external media, caused by etching the cladding layer of the single-mode fiber part, significantly improves the sensitivity. Both wavelength and intensity interrogation approaches are employed to study the Multimode–etched Single-mode–Multimode (MESM) fiber sensor. The intensity and the wavelength sensitivities for the RI measurement in the range of 1.428-1.458 are obtained as -2308.92 %/RIU and 1313.14 nm/RIU, respectively. Finally, the MESM-SPR sensor is proposed and characterized. Results exhibit high performance in the RI range of 1.333 to 1.357, in which the sensitivity of 1433 nm/RIU is achieved. The advantages like low cost, high sensitivity, and simple fabrication methods make these sensors promising devices for chemical, food industry, and biosensing applications.

In this study, an efficient nanofabrication process of metal microdisk arrays using direct imprinting was developed. This process was comprised of three steps; sputter etching on the quartz glass substrate, gold thin film deposition on an etched surface of a substrate, and transfer imprinting using a polyethylene terephthalate (PET) film mold on the Au thin film. A new idea to utilize a PET film mold for disk patterning by the nano transfer imprinting was examined. The PET film mold was prepared by thermally embossing the pillar pattern of a master mold on the PET film. The master mold was prepared from a silicon wafer. The PET film mold was used for transfer imprinting on a metal film deposited on a quartz substrate. The experimental results revealed that the PET film mold can effectively form gold micro-disk arrays on the Au film despite the PET film mold being softer than the Au film. This method can control the distribution and orientation of the nano-arrays on the disk. The plasmonic properties of the gold micro-disk arrays are studied and the absorbance spectrum exhibit depends on the distribution and orientation of gold micro-disk patterns. The nano-transfer imprinting technique is useful for fabricating metallic microdisk arrays on substrate as a plasmonic device.

Superhydrophobic surfaces on 6082 aluminum alloy substrates are tailored by low-cost chemical surface treatments coupled to a fluorine-free alkyl-silane coating deposition. In particular, three different surface treatments are investigated: boiling water, HF/HCl, and HNO3/HCl etching. The results show that the micro-nano structure and the wetting behavior are greatly influenced by the applied surface texturing treatment. After silanization, all the textured surfaces exhibit a superhydrophobic behavior. The highest water contact angle (WCA, ≈180°) is obtained by HF/HCl etching. Interestingly, the water sliding angle (WSA) is affected by the anisotropic surface characteristics. Indeed, for the HF/HCl and the HNO3/HCl samples, the WSA in the longitudinal direction is lower than the transversal one, which slightly affects the self-cleaning capacity. The results point out that the superhydrophobic behavior of the aluminum alloys surface can be easily tailored by performing a two-step procedure: (i) roughening treatment and (ii) surface chemical silanization. Considering these promising results, the aim of further studies will be to improve the knowledge and optimize the process parameters in order to tailor a superhydrophobic surface with an effective performance in terms of stability and durability.

Funding Information: The authors thank Eurofins EAG Materials Science, LLC (California, USA) for the TEM analysis. S.K.N. thanks ICHEC and the Science Foundation Ireland funded computing center of Tyndall National Institute for computer time. S.K.N. thanks Rita Mullins for help with reaction free energy calculations. Publisher Copyright: © 2021 Wiley-VCH GmbH Thermally activated chemical vapor-phase etching of titanium nitride (TiN) is studied by utilizing either alternate exposures of niobium pentafluoride (NbF5) and carbon tetrachloride (CCl4) or by using CCl4 alone. Nitrogen (N2) gas purge steps are carried out in between every reactant exposure. Titanium nitride is etched in a non-self-limiting way by NbF5–CCl4 based binary chemistry or by CCl4 at temperatures between 370 and 460 °C. Spectroscopic ellipsometry and a weight balance are used to calculate the etch per cycle. For the binary chemistry, an etch per cycle of ≈0.8 Å is obtained for 0.5 and 3 s long exposures of NbF5 and CCl4, respectively at 460 °C. On the contrary, under the same conditions, the etch process with CCl4 alone gives an etch per cycle of about 0.5 Å. In the CCl4-only etch process, the thickness of TiN films removed at 460 °C varies linearly with the number of etch cycles. Furthermore, CCl4 alone is able to etch TiN selectively over other materials such as Al2O3, SiO2, and Si3N4. X-ray photoelectron spectroscopy and bright field transmission electron microscopy are used for studying the post-etch surfaces. To understand possible reaction products and energetics, first-principles calculations are carried out with density functional theory. From thermochemical analysis of possible reaction models, it is found that NbF5 alone cannot etch TiN while CCl4 alone can etch it at high temperatures. The predicted byproducts of the reaction between the CCl4 gas molecules and TiN surface are TiCl3 and ClCN. Similarly, TiF4, NbFCl3, and ClCN are predicted to be the likely products when TiN is exposed to both NbF5 and CCl4. A more favorable etch reaction is predicted when TiN is exposed to both NbF5 and CCl4 (ΔG = −2.7 eV at 640 K) as compared to exposure to CCl4 only (ΔG = −2 eV at 640 K) process. This indicates that an enhanced etch rate is possible when TiN is exposed alternately to both NbF5 and CCl4, which is in close agreement with the experimental results.

International audience; MXenes are two-dimensional metal carbides or nitrides that are currently proposed in many applications thanks to their unique attributes including high conductivity and accessible surface. Recently, a synthetic route was proposed to prepare MXenes from the molten salt etching of precursors allowing for the preparation of MXene (denoted as MS-MXenes, for molten salt MXene) with tuned surface termination groups, resulting in improved electrochemical properties. However, further delamination of as-prepared multilayer MS-MXenes still remains a major challenge. Here, we report on the successful exfoliation of MS-Ti 3 C 2 T x via the intercalation of the organic molecule TBAOH (tetrabutylammonium hydroxide), followed by sonication to separate the layers. The treatment time could be adapted to tune the wetting behavior of the MS-Ti 3 C 2 T x. As a result, a self-supported Clterminated MXene film could be prepared by filtration. Finally, MS-Ti 3 C 2 T x used as a Li-ion battery anode could achieve a high specific capacity of 225 mAh g −1 at a 1C rate together with an excellent rate capability of 95 mAh g −1 at 167C. These results also show that tuning of the surface chemistry of MXene is of key importance to this field with the likely result being increased electrochemical performance.

Sub-micrometre single crystal diamond membranes are of huge importance for next generation optical, quantum and electronic device applications. Electrochemical etching has proven a critical step in the production of such membranes. Etching is used to selectively remove a very thin layer of sub-surface sp2 carbon, prepared by ion implantation in bulk diamond, releasing the diamond membrane. Due to the nanosized dimensions, etching is typically carried out using non-contact electrochemistry in low conductivity solutions (bipolar arrangement) which whilst effective, results in extremely slow etch rates. In this work, a new method of non-contact electrochemical etching is presented which uses high conductivity, high concentration, fully dissociated aqueous electrolytes. Careful choice of the electrolyte anion results in significant improvements in the sp2 carbon etch rate. In particular, we show both chloride and sulfate electrolytes increase etch rates significantly (up to × 40 for sulfate) compared to our measurements using the current state-of-the-art solutions and methodologies. Electron paramagnetic resonance experiments, recorded after the electrode potential has been switched off, reveal sizeable hydroxyl radical concentrations at timescales > 107 longer than their lifetime (≤μs). These measurements highlight the importance of electrochemically initiated, solution chemistry radical generation and regeneration pathways in high concentration sulfate and chloride solutions for nano-etching applications.

There is an increasing interest in atomic layer deposition (ALD) on polymers for the development of membranes, electronics, (3D) nanostructures and specially for the development of hermetic packaging of the new generation of flexible implantable micro-devices. This evolution demands a better understanding of the ALD nucleation process on polymers, which has not been reported in a visual way. Herein, a visual study of ALD nucleation on polymers is presented, based on the different dry etching speeds between polymers (fast) and metal oxides (slow). An etching process removes the polyimide with the nucleating ALD acting as a mask, making the nucleation features visible through secondary electron microscopy analyses. The nucleation of both Al2O3 and HfO2 on polyimide was investigated. Both materials followed an island-coalescence nucleation. First, local islands formed, progressively coalescing into filaments, which connected and formed meshes. These meshes evolved into porous layers that eventually grew to a full layer, marking the end of the nucleation. Cross-sections were analyzed, observing no sub-surface growth. This approach was used to evaluate the influence of plasma-activating polyimide on the nucleation. Plasma-induced oxygen functionalities provided additional surface reactive sites for the ALD precursors to adsorb and start the nucleation. The presented nucleation study proved to be a straightforward and simple way to evaluate ALD nucleation on polymers.