Anisotropic etching mechanisms of 4H-SiC:Experimental and first-principles insights

Molten-alkali etching has been widely used to reveal dislocations in 4H silicon carbide(4H-SiC),which has promoted the identification and statistics of dislocation density in 4H-SiC single crystals.However,the etching mechanism of 4H-SiC is limited misunderstood.In this letter,we reveal the anisotropic etching mechanism of the Si face and C face of 4H-SiC by combining molten-KOH etching,X-ray photoelectron spectroscopy(XPS)and first-principles investigations.The activation energies for the molten-KOH etching of the C face and Si face of 4H-SiC are calculated to be 25.09 and 35.75 kcal/mol,respectively.The molten-KOH etching rate of the C face is higher than the Si face.Combining XPS analysis and first-principles calculations,we find that the molten-KOH etching of 4H-SiC is proceeded by the cycling of the oxidation of 4H-SiC by the dissolved oxygen and the removal of oxides by molten KOH.The faster etching rate of the C face is caused by the fact that the oxides on the C face are unstable,and easier to be removed with molten alkali,rather than the C face being easier to be oxidized.

The etching strategy of zinc anode to enable high performance zinc-ion batteries

Zinc-ion batteries(ZIBs)are considered to be one of the most promising candidates to replace lithium-ion batteries(LIBs)due to the high theoretical capacity,low cost and intrinsic safety.However,zinc dendrites,hydrogen evolution reaction,surface passivation and other side reactions will inevitably occur during the charging and discharging process of Zn anode,which will seriously affect the cycle stability of the battery and hinder its practical application.The etching strategy of Zn anode has attracted wide attention because of its simple operation and broad commercial prospects,and the etched Zn anode can effectively improve its electrochemical performance.However,there is no comprehensive review of the etching strategy of Zn anode.This review first summarizes the challenges faced by Zn anode,then puts forward the etching mechanisms and properties of acid,salt and other etchants.Finally,based on the above discussion,the challenges and opportunities of Zn anode etching strategy are proposed.

Etching‑Induced Surface Reconstruction of NiMoO_(4) for Oxygen Evolution Reaction

Rational reconstruction of oxygen evolution reaction(OER)precatalysts and performance index of OER catalysts are crucial but still challenging for universal water electrolysis.Herein,we develop a double-cation etching strategy to tailor the electronic structure of NiMoO_(4),where the prepared NiMoO_(4) nanorods etched by H_(2)O_(2) reconstruct their surface with abundant cation deficiencies and lattice distortion.Calculation results reveal that the double cation deficiencies can make the upshift of d-band center for Ni atoms and the active sites with better oxygen adsorption capacity.As a result,the optimized sample(NMO-30M)possesses an overpotential of 260 mV at 10 mA cm−2 and excellent long-term durability of 162 h.Importantly,in situ Raman test reveals the rapid formation of high-oxidation-state transition metal hydroxide species,which can further help to improve the catalytic activity of NiMoO_(4) in OER.This work highlights the influence of surface remodification and shed some light on activating catalysts.

Recent Advances and Perspectives of Lewis Acidic Etching Route:An Emerging Preparation Strategy for MXenes

Since the discovery in 2011,MXenes have become the rising star in the field of two-dimensional materials.Benefiting from the metallic-level conductivity,large and adjustable gallery spacing,low ion diffusion barrier,rich surface chemistry,superior mechanical strength,MXenes exhibit great application prospects in energy storage and conversion,sensors,optoelectronics,electromagnetic interference shielding and biomedicine.Nevertheless,two issues seriously deteriorate the further development of MXenes.One is the high experimental risk of common preparation methods such as HF etching,and the other is the difficulty in obtaining MXenes with controllable surface groups.Recently,Lewis acidic etching,as a brand-new preparation strategy for MXenes,has attracted intensive attention due to its high safety and the ability to endow MXenes with uniform terminations.However,a comprehensive review of Lewis acidic etching method has not been reported yet.Herein,we first introduce the Lewis acidic etching from the following four aspects:etching mechanism,terminations regulation,in-situ formed metals and delamination of multi-layered MXenes.Further,the applications of MXenes and MXene-based hybrids obtained by Lewis acidic etching route in energy storage and conversion,sensors and microwave absorption are carefully summarized.Finally,some challenges and opportunities of Lewis acidic etching strategy are also presented.

Recent advances in preparation of metallic superhydrophobic surface by chemical etching and its applications

In the past few decades,inspired by the superhydrophobic surfaces(SHPS)of animals and plants such as lotus leaves,rose petals,legs of water striders,and wings of butterflies,preparing metal materials with metallic SHPS(MSHPS)have attracted great research interest,due to the great prospect in practical applications.To obtain SHPS on conventional metal materials,it is necessary to construct rough surface,followed by modification with low surface energy substances.In this paper,the action mechanism and the current research status of MSHPS were reviewed through the following aspects.Firstly,the model of wetting theory was presented,and then the progress in MSHPS preparation through chemical etching method was discussed.Secondly,the applications of MSHPS in self-cleaning,anti-icing,corrosion resistance,drag reduction,oil-water separation,and other aspects were introduced.Finally,the challenges encountered in the present application of MSHPS were summarized,and the future research interests were discussed.

RDX crystals with high sphericity prepared by resonance acoustic mixing assisted solvent etching technology

In order to obtain high-quality spherical RDX crystal particles,the RDX crystals were suspended in a mixed solvent of cyclohexanone and cyclohexane,subsequently a solvent etching study was carried out under the action of vibration/acoustic flow coupled flow field,which generated by resonance acoustic mixing.The effects of solvent ratio,temperature,acceleration and experiment time on morphology as well as particle size of RDX crystals were studied.Not only were the morphology,particle size distribution and crystal form of RDX crystals determined,but also the thermal decomposition performance and mechanical sensitivity of spherical RDX were examined and discussed.Results indicated that under the process of solvent/non-solvent volume ratio at 1:2,temperature of 40℃,acceleration of 40 g and experiment time of 4 h,α-type RDX crystal with sphericity of 0.92 can be obtained.Furthermore,the median particle size(D_(50))of spherical RDX crystals is 215.8 μm with a unimodal particle size distribution(size span 1.34).For one thing,the thermal decomposition peak temperature of spherical RDX is about 2.5℃ higher than that of raw RDX,and apparent activation energy reaches 444.68 kJ/mol.For another thing,impact sensitivity and friction sensitivity of spherical RDX are 18.18% and 33.33% lower than that of raw RDX,respectively.It demonstrates that safety of spherical RDX under thermal,impact and friction stimuli has been improved.

Etching characteristics and surface modification of InGaSnO thin films under Cl_(2)/Ar plasma

Indium gallium tin oxide(IGTO)thin films have the potential for high mobility and lowtemperature processing,which makes them suitable for applications such as display backplanes and high-voltage switching devices.However,very few studies have investigated the plasmaetching characteristics of IGTO and changes in its properties after etching.In this study,the etching characteristics of IGTO were investigated using Cl_(2)/Ar plasma,and changes in surface properties were analyzed.Results showed that the etch rate increased with an increase in the proportion of Cl_(2),with the highest etch rate observed at 69 nm min^(-1)in pure Cl_(2)plasma with a gas flow rate of 100 sccm.Furthermore,increased radio-frequency power caused a rise in the etch rate,while a process pressure of 15 m Torr was optimal.The primary etching mechanism for IGTO thin films under Cl_(2)plasma was a chemical reaction,and an increased work function indicated the occurrence of defects on the surface.In addition,the etching process reduced the surface roughness of Cl_(2)-containing plasma,whereas the etching process in pure Ar plasma increased surface roughness.This study contributes to a better understanding of the plasmaetching characteristics of IGTO and changes in its properties after etching,providing valuable insights for IGTO-based applications.

Effect of Different Etching Time on Fabrication of an Optoelectronic Device Based on GaN/Psi

Gallium nitride(GaN)/porous silicon(PSi)film was prepared using a pulsed laser deposition method and 1064 nm Nd:YAG laser for optoelectronic applications and a series of Psi substrates were fabricated using a photoelectrochemical etching method assisted by laser at different etching times for 2.5–15 min at 2.5 min intervals.X-ray diffraction,room-temperature photoluminescence,atomic force microscopy and field emission scanning electron microscopy images,and electrical characteristics in the prepared GaN on the Psi film were investigated.The optimum Psi substrate was obtained under the following conditions:10 min,10 mA/cm^(2),and 24%hydrofluoric acid.The substrate exhibited two highly cubic crystalline structures at(200)and(400)orientations and yellow visible band photoluminescence,and homogeneous pores formed over the entire surface.The pores had steep oval shapes and were accompanied by small dark pores that appeared topographically and morphologically.The GaN/Psi film fabricated through PLD exhibited a high and hexagonal crystallographic texture in the(002)plane.Spectroscopic properties results revealed that the photoluminescence emission of the deposited nano-GaN films was in the ultraviolet band(374 nm)related to GaN material and in the near-infrared band(730 nm)related to the Psi substrate.The topographical and morphological results of the GaN films confirmed that the deposited film contained spherical grains with an average diameter of 51.8 nm and surface roughness of 4.8 nm.The GaN/Psi surface showed a cauliflower-like morphology,and the built-in voltage decreased from 3.4 to 2.7 eV after deposition.The fabricated GaN/Psi film exhibited good electrical characteristics.

Tuning active sites in MoS_(2)-based catalysts via H_(2)O_(2)etching to enhance hydrodesulfurization performance

A H_(2)O_(2)etching strategy was adopted to introduce coordinatively unsaturated sites(CUS)on MoS_(2)-based catalysts for dibenzothiophene(DBT)hydrodesulfurization(HDS).The CUS concentrations on MoS_(2) slabs were finely regulated by changing the concentrations of H_(2)O_(2)solution.With the increasing H_(2)O_(2)concentrations(0.1–0.3 mol/L),The CUS concentrations on MoS_(2) slabs increased gradually.However,the high-concentration H_(2)O_(2)etching(0.5 mol/L)increased the MoOxSy and MoO_(3) contents on MoS_(2) slabs compared to etching with the H_(2)O_(2)concentration of 0.3 mol/L,which led to the less CUS concentration in the sulfided Mo–H-0.5 catalyst than in the sulfided Mo–H-0.3 catalyst.A microstructure-activity correlation indicated that the CUS introduced by H_(2)O_(2)etching on MoS_(2) slabs significantly enhanced DBT HDS.Different Co loadings were further introduced into Mo–H-0.3,which had the most CUS concentration,and the corresponding 0.2-CoMo catalyst with the highest CoMoS content(3.853 wt%)exhibited the highest reaction rate constant of 6.95×10^(−6)mol g^(−1)s^(−1)among these CoMo catalysts.

NH_(3)‑Induced In Situ Etching Strategy Derived 3D‑Interconnected Porous MXene/Carbon Dots Films for High Performance Flexible Supercapacitors

2D MXene(Ti_(3)CNT_(x))has been considered as the most promising electrode material for flexible supercapacitors owing to its metallic conductivity,ultra-high capacitance,and excellent flexibility.However,it suffers from a severe restacking problem during the electrode fabrication process,limiting the ion transport kinetics and the accessibility of ions in the electrodes,especially in the direction normal to the electrode surface.Herein,we report a NH_(3)-induced in situ etching strategy to fabricate 3D-interconnected porous MXene/carbon dots(p-MC)films for high-performance flexible supercapacitor.The pre-intercalated carbon dots(CDs)first prevent the restacking of MXene to expose more inner electrochemical active sites.The partially decomposed CDs generate NH_(3)for in situ etching of MXene nanosheets toward 3D-interconnected p-MC films.Benefiting from the structural merits and the 3D-interconnected ionic transmission channels,p-MC film electrodes achieve excellent gravimetric capacitance(688.9 F g^(-1)at 2 A g^(-1))and superior rate capability.Moreover,the optimized p-MC electrode is assembled into an asymmetric solid-state flexible supercapacitor with high energy density and superior cycling stability,demonstrating the great promise of p-MC electrode for practical applications.

Etching Fused Quartz With CHF_3/Ar

报道了用氟利昂ＣＨＦ３和氩气Ａｒ作工作气体的反应离子刻蚀融石英的技术，研究了气体流速、腔压和射频等离子体功率对刻蚀速度的影响，并分析了刻蚀工艺对样品表面的污染，同时也考察了刻蚀工艺的均匀性和重复性。为了优化刻蚀工艺，采用Ｒｓ１／Ｄｉｓｃｏｖｅｒ软件工具设计优化实验。实验中射频等离子体功率在１２０～１６０Ｗ范围，氩气和氟利昂流速分别在１５～３５ｓｃｍ和２０～５０ｓｃｃｍ范围，腔压在１００～１４０ｍＴｏｒ范围，相应的刻蚀速度为１５～２５ｎｍ／ｍｉｎ。

Morphological evolution of tunnel tips for aluminum foils during DC etching

The morphologies of tunnel tips in different stages for aluminum foils during DC etching in 1.5 mol/L HC1 solution at 90℃ were observed by field emission scanning electron microscopy （FE-SEM）. A novel model was proposed to describe the morphological evolution of tunnel tips throughout the growth processes. In the pit nucleation stage, the pits vary from the hemispherical to half-cubic shapes due to the activation of pit tips from the center to the edge. During the tunnel growth stage, the pits dissolve toward the depth direction and develop into the tunnels, and their tips remain flat. In the tip passivation stage, as the passivation of tunnel tips speeds up from the edge to the center＇s the tunnel tips change from flat shapes to three-dimensional protrusions. The mechanism may be attributed to the order of activation or passivation on the tunnel tips changed in different stages.

Experimental Study of the Influence of Process Pressure and Gas Composition on GaAs Etching Characteristics in Cl_2/BCl_3-Based Inductively Coupled Plasma

A study of Cl2/BCl3-based inductively coupled plasma （ICP） was conducted using thick photoresist mask for anisotropic etching of 50μm diameter holes in a GaAs wafer at a relatively high average etching rate for etching depths of more than 150μm. Plasma etch characteristics with ICP process pressure and the percentage of BCI3 were studied in greater detail at a constant ICP coil/bias power. The measured peak-to-peak voltage as a function of pressure was used to estimate the minimum energy of the ions bombarding the substrate. The process pressure was found to have a substantial influence on the energy of heavy ions. Various ion species in plasma showed minimum energy variation from 1.85 eV to 7.5 eV in the pressure range of 20 mTorr to 50 mTorr. The effect of pressure and the percentage of BCl3 on the etching rate and surface smoothness of the bottom surface of the etched hole were studied for a fixed total flow rate. The etching rate was found to decrease with the percentage of BCl3, whereas the addition of BCl3 resulted in anisotropic holes with a smooth veil free bottom surface at a pressure of 30 mTorr and 42% BC13. In addition, variation of the etching yield with pressure and etching depth were also investigated.

TREATMENT OF METALS, POLYMER FILMS, AND FABRICS WITHA ONE ATMOSPHERE UNIFORM GLOW DISCHARGE PLASMA(OAUGDP) FOR INCREASED SURFACE ENERGY AND DIRECTIONAL ETCHING

Direct exposure of samples to the active species of air generated by a One Atmosphere Uniform Glow Discharge Plasma (OAUGDP) has been used to etch and to increase the surface energy of metallic surfaces, photoresist, polymer films, and nonwoven fab- rics. The OAUGDP is a non-thermal plasma with the classical characteristics of a DC normal glow discharge that operates in air (and other gases) at atmospheric pres- sure. Neither a vacuum system nor batch processing is necessary. A wide range of applications to metals, photoresist, films, fabrics, and polymeric webs can be accom- modated by direct exposure of the workpiece to the plasma in parallel-plate reactors. This technolopy is simple, it produces effects that can be obtained in no other way at one atmosphere; it generates minimal pollutants or unwanted by-products; and it is suitable for individual sample or online treatment of metallic surfaces, wafers, films, and fabrics. Early exposures of solid materials to the OAUGDP required minutes to produce rela- tively small increases of surface energy. These durations appeared too long for com- mercial application to fast-moving webs. Recent improvements in OAUGDP gas com- position, power density, plasma quality, recireulating gas flow, and impedance match- ing of the power supply to the parallel plate plasma reactor have made it possible to raise the surface energy of a variety of polymeric webs (PP, PET PE etc.) to levels of 60 to 70 dynes/cm with one second of exposure. In air plasmas, the high surface ener- gies are not durable, and fall to 50 dynes/cm after periods of weeks to months. Here, we report the exposure of metallic surfaces, photoresist, polymeric films, and nonwo- ven fabrics made of PP and PET to an impedance matched parallel plate OAUGDP for durations ranging from one second to several tens of seconds. Data will be re- ported on the surface energy, wettability, wickability, and aging effect of polymeric films and fabrics as functions of time of exposure, and time after exposure; the rate and uniformity of photoresist etching; and the production of sub-micron structures by OAUGDP etching at one atmosphere.

Fabrication and Optical Properties of Silicon Nanowires Arrays by Electroless Ag-catalyzed Etching

In order to realize ultralow surface reflectance and broadband antireflection effects which common pyramidal textures and antireflection coatings can't achieve in photovoltaic industry,we used low-cost and easy-made Ag-catalyzed etching techniques to synthesize silicon nanowires(Si NWs) arrays on the substrate of single-crystalline silicon.The dense vertically-aligned Si NWs arrays are fabricated by local oxidation and selective dissolution of Si in etching solution containing Ag catalyst.The Si NWs arrays with 3 μm in depth make reflectance reduce to less than 3% in the range of 400 to 1000 nm while reflectance gradually reached the optimum value with the increasing of etching time.The antireflection of Si NWs arrays are based on indexgraded mechanism:Si NWs arrays on a subwavelength scale strongly scatter incident light and have graded refractive index that enhance the incidence of light in usable wavelength range.However,surface recombination of Si NWs arrays are deteriorated due to numerous dangling bonds and residual Ag particles.

Effect of acid etching on marginal adaptation of mineral trioxide aggregate to apical dentin:microcomputed tomography and scanning electron microscopy analysis

The present investigation assessed the effect of acid etching on marginal adaptation of white- and gray-colored mineral trioxide aggregate （MTA） to apical dentin using microcomputed tomography （micro-CT） and scanning electron microscopy （SEM）. Sixty-four extracted single-rooted human maxillary teeth were used. Following root-end resection and apical preparation, the teeth were equally divided into four groups according to the following root end filling materials： （i） white-colored MTA （WMTA）, （ii） etched WMTA （EWMTA）, （iii） gray-colored MTA （GMTA） and （iv） etched GMTA （EGMTA）. After 48 h, the interface between root-end filling materials and the dentinal walls was assessed using micro-CT and SEM. Data were statistically analyzed using the KruskaI-Wallis and Dunn tests. Micro-CT analysis revealed gap volumes between the apical cavity dentin walls and EGMTA, GMTA, EWMTA and WMTA of （0.007 1±0.004） mm3, （0.053±0.002） mm3, （0.003 6±0.001） mm3 and （0.005 9±0.002） mm3 respectively. SEM analysis revealed gap sizes for EGMTA, WMTA, EWMTA and GMTA to be （492.3±13.8） μm, （594.5±17.12）μm, （543.1±15.33） μm and （910.7±26.2）μm respectively. A significant difference in gap size between root end preparations filled with GMTA and EGMTA was found （P〈O.05）. No significance difference in gap size between WMTA and EWMTA were found in either SEM or micro-CT analysis. In conclusion, pre-etching of apical dentin can provide a better seal for GMTA but not for WMTA.

Fabrication of Nanoscale Step Height Structure Using Atomic Layer Deposition Combined with Wet Etching

The current techniques used for the fabrication of nanosteps are normally done by layer growth and then ion beam thinning. There are also extra films grown on the step surfaces in order to reduce the roughness. So the whole process is time consuming. In this paper, a nanoscale step height structure is fabricated by atomic layer deposition （ALD） and wet etching techniques. According to the traceable of the step height value, the fabrication process is controllable. Because ALD technology can grow a variety of materials, aluminum oxide （Al2O3） is used to fabricate the nanostep. There are three steps of Al2O3 in this structure including 8 nm, 18 nm and 44 inn. The thickness of Al2O3 film and the height of the step are measured by anellipsometer. The experimental results show that the thickness of Al2O3 film is consistent with the height of the step. The height of the step is measured by AFM. The measurement results show that the height is related to the number of cycles of ALD and the wet etching time. The bottom and the sidewall surface roughness are related to the wet etching time. The step height is calibrated by Physikaliseh-Technische Bundesanstalt （PTB） and the results were 7.5±1.5 nm, 15.5±2.0 nm and 41.8±2.1 nm, respectively. This research provides a method for the fabrication of step height at nanoscale and the nanostep fabricated is potential used for standard references.

Effect of Pd ions in the chemical etching solution

The acrylonitrile-butadiene-styrene （ABS） surface was etched by dipping it into chromic acid-sulfuric acid containing a trace amount of palladium. The surface roughness, activity, and valence bond were characterized by atomic force microscopy （AFM） and X-ray photoelectron spectroscopy （XPS）. The results showed that with the increase of Pd concentration in the etching solution the ABS surface roughness reduced. The ratio of O to C increases and forms a large amount of O=C？O functional groups by dipping into Pd contained etching solution, thus the amount of colloids palladium adsorption increases. The carboxyl group acts as the ad- sorption site for the Pd/Sn catalyst.

Etching‐assisted femtosecond laser modification of hard materials

With high hardness, high thermal and chemical stability and excellent optical performance, hard materials exhibit great potential applications in various fields, especially in harsh conditions. Femtosecond laser ablation has the capability to fabricate three-dimensional micro/nanostructures in hard materials. However, the low efficiency, low precision and high surface roughness are the main stumbling blocks for femtosecond laser processing of hard materials. So far, etching- assisted femtosecond laser modification has demonstrated to be the efficient strategy to solve the above problems when processing hard materials, including wet etching and dry etching. In this review, femtosecond laser modification that would influence the etching selectivity is introduced. The fundamental and recent applications of the two kinds of etching assisted femtosecond laser modification technologies are summarized. In addition, the challenges and application prospects of these technologies are discussed.

A Multi-Scale Study on Silicon-Oxide Etching Processes in C_4F_8/Ar Plasmas

A multi-scale numerical method coupled with the reactor,sheath and trench model is constructed to simulate dry etching of SiO_2 in inductively coupled C_4F_8 plasmas.Firstly,ion and neutral particle densities in the reactor are decided using the CFD-ACE＋ commercial software.Then,the ion energy and angular distributions（IEDs and IADs） are obtained in the sheath model with the sheath boundary conditions provided with CFD-ACE＋.Finally,the trench profile evolution is simulated in the trench model.What we principally focus on is the effects of the discharge parameters on the etching results.It is found that the discharge parameters,including discharge pressure,radio-frequency（rf） power,gas mixture ratios,bias voltage and frequency,have synergistic effects on IEDs and IADs on the etched material surface,thus further affecting the trench profiles evolution.