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 of quartz crystals in liquid phase environment:A review

Quartz crystals are the most widely used material in resonant sensors,owing to their excellent piezoelectric and mechanical properties.With the development of portable and wearable devices,higher processing efficiency and geometrical precision are required.Wet etching has been proven to be the most efficient etching method for large-scale production of quartz devices,and many wet etching approaches have been developed over the years.However,until now,there has been no systematic review of quartz crystal etching in liquid phase environments.Therefore,this article provides a comprehensive review of the development of wet etching processes and the achievements of the latest research in thisfield,covering conventional wet etching,additive etching,laser-induced backside wet etching,electrochemical etching,and electrochemical discharge machining.For each technique,a brief overview of its characteristics is provided,associated problems are described,and possible solutions are discussed.This review should provide an essential reference and guidance for the future development of processing strategies for the manufacture of quartz crystal devices.

Etching Mechanism of Ti_(3)C_(2)Cl_(2) MXene Phases by CuCl_(2)-Lewis Molten Salt Method

We described a method for obtaining fluorine-free Ti_(3)C_(2)Cl_(2)MXene phases by melting copper in CuCl_(2)instead of aluminum in Ti_(3)AlC_(2).XRD results show that when molten salt CuCl_(2)etches Ti_(3)AlC_(2),it forms an intermediate product Ti_(3)CuC_(2),and then reacts with Ti_(3)CuC_(2)to obtain Ti_(3)C_(2)Cl_(2).The reaction of Ti_(3)AlC_(2)and CuCl_(2)at a temperature of 800℃for 2 h to obtain Ti_(3)C_(2)Cl_(2)with an optimal lamellar structure is shown in SEM results.The pseudopotential plane-wave(PP-PW)method is used to calculate on the electronic structure.The etching mechanism is investigated by the total energies of each substance.The chemical reaction of Ti_(3)AlC_(2)and CuCl_(2)will first become Ti_(3)CuC_(2)and Cu,and then become Ti_(3)C_(2)Cl_(2)during the Lewis acid etching process,which are consistent with the experimental results.

Remote plasma enhanced cyclic etching of a cyclosiloxane polymer thin film

The continuous evolution of chip manufacturing demands the development of materials with ultra-low dielectric constants.With advantageous dielectric and mechanical properties,initiated chemical vapor deposited(iCVD)poly(1,3,5-trimethyl-1,3,5-trivinyl cyclotrisiloxane)(pV3D3)emerges as a promising candidate.However,previous works have not explored etching for this cyclosiloxane polymer thin film,which is indispensable for potential applications to the back-end-of-line fabrication.Here,we developed an etching process utilizing O2/Ar remote plasma for cyclic removal of iCVD pV3D3 thin film at sub-nanometer scale.We employed in-situ quartz crystal microbalance to investigate the process parameters including the plasma power,plasma duration and O2 flow rate.X-ray photoelectron spectroscopy and cross-sectional microscopy reveal the formation of an oxidized skin layer during the etching process.This skin layer further substantiates an etching mechanism driven by surface oxidation and sputtering.Additionally,this oxidized skin layer leads to improved elastic modulus and hardness and acts as a barrier layer for protecting the bottom cyclosiloxane polymer from further oxidation.

Mechanism of K/Ni Etching for Biochar-H_(2)O Gasification

Biomass-H_(2)O gasification is a complex thermochemical reaction,including three processes of volatile removal:homogeneous/heterogeneous reforming,biochar gasification and etching.The rate-determining step is biochar-H_(2)O gasification and etching so the DFT is carried out to see the catalytic role of different metal elements(K/Ni)in the zigzag biochar model.The calculation results show that the gasification of biochar-H_(2)O needs to go through four processes:dissociative adsorption of water,hydrogen transfer(hydrogen desorption,hydrogen atom transfer),carbon dissolution and CO desorption.The energy barrier indicated that the most significant step in reducing the activation energy of K is reflected in the hydrogen transfer step,which is reduced from 374.14 kJ/mol to 152.41 kJ/mol;the catalytic effect of Ni is mainly reflected in the carbon dissolution step,which is reduced from 122.34 kJ/mol to 84.8 kJ/mol.The existence of K causes the edge to have a stronger attraction to H and does not destroy theπbonds of biochar molecules.The destruction ofπbonds is mainly due to the role of H free radicals,while the destruction ofπbonds will lead to easier C-C bond rupture.Ni shows a strong attraction to O in OH,which forms strong Ni-O chemical bonds.Ni can also destroy the aromatic structure directly,making the gasification easier to happen.This study explored the catalytic mechanism of K/Ni on the biochar-H_(2)O gasification at the molecular level and looked forward to the potential synergy of K/Ni,laying a foundation for experimental research and catalyst design.

In situ synthesis of SnPS_(3)/Ti_(3)C_(2)T_(x) hybrid anode via molten salt etching method for superior sodium-ion batteries

Recently,SnPS_(3) has gained attention as an impressive sodium-ion battery anode material because of its significant theoretical specific capacity derived from the conversion-alloying reaction mechanism.Nevertheless,its practical applicability is restricted by insufficient rate ability,and severe capacity loss due to inadequate electrical conductivity and dramatic volume expansion.Inspired by the electrochemical enhancement effect of MXene substrates and the innovative Lewis acidic etching for MXene preparation,SnPS_(3)/Ti_(3)C_(2)T_(x) MXene(T=-Cl and-O) is constructed by synchronously phospho-sulfurizing Sn/Ti_(3)C_(2)T_(x) precursor.Benefiting from the boosted Na^(+) diffusion and electron transfer rates,as well as the mitigated stress expansion,the synthesized SnPS_(3/)Ti_(3)C_(2)T_(x) composite demonstrates enhanced rate capability(647 mA h g^(-1) at 10 A g^(-1)) alongside satisfactory long-term cycling stability(capacity retention of 94.6% after 2000 cycles at 5 A g^(-1)).Importantly,the assembled sodium-ion full cell delivers an impressive capacity retention of 97.7% after undergoing 1500 cycles at 2 A g^(-1).Moreover,the sodium storage mechanism of the SnPS_(3/)Ti_(3)C_(2)T_(x) electrode is elucidated through in-situ and ex-situ characterizations.This work proposes a novel approach to ameliorate the energy storage performance of thiophosphites by facile in-situ construction of composites with MXene.

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.

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 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.

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 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.

Maskless fabrication of quasi-omnidirectional V-groove solar cells using an alkaline solution-based method

Silicon passivated emitter and rear contact(PERC) solar cells with V-groove texture were fabricated using maskless alkaline solution etching with in-house developed additive. Compared with the traditional pyramid texture, the V-groove texture possesses superior effective minority carrier lifetime, enhanced p–n junction quality and better applied filling factor(FF). In addition, a V-groove texture can greatly reduce the shading area and edge damage of front Ag electrodes when the V-groove direction is parallel to the gridline electrodes. Due to these factors, the V-groove solar cells have a higher efficiency(21.78%) than pyramid solar cells(21.62%). Interestingly, external quantum efficiency(EQE) and reflectance of the V-groove solar cells exhibit a slight decrease when the incident light angle(θ) is increased from 0° to 75°, which confirms the excellent quasi omnidirectionality of the V-groove solar cells. The proposed V-groove solar cell design shows a 2.84% relative enhancement of energy output over traditional pyramid solar cells.

Effect of internal structure of a batch-processing wet-etch reactor on fluid flow and heat transfer

Batch-processing wet-etch reactors are the key equipment widely used in chip fabrication,and their performance is largely affected by the internal structure.This work develops a three-dimensional computational fluid dynamics(CFD)model considering heat generation of wet-etching reactions to investigate the fluid flow and heat transfer in the wet-etch reactor.The backflow is observed below and above the wafer region,as the flow resistance in this region is high.The temperature on the upper part of a wafer is higher due to the accumulation of reaction heat,and the average temperature of the side wafer is highest as its convective heat transfer is weakest.Narrowing the gap between wafer and reactor wall can force the etchant to flow in the wafer region and then facilitate the convective heat transfer,leading to better within-wafer and wafer-to-wafer etch uniformities.An inlet angle of 60°balances fluid by-pass and mechanical energy loss,and it yields the best temperature and etch uniformities.The batch with 25wafers has much wider flow channels and much lower flow resistance compared with that with 50wafers,and thus it shows better temperature and etch uniformities.These results and the CFD model should serve to guide the optimal design of batch-processing wet-etch reactors.

Effect of chemical plating Zn on DC-etching behavior of Al foil in HCl-H_2SO_4

The Al foil for high voltage Al electrolytic capacitor usage was immersed in 5.0%NaOH solution containing trace amount of Zn2＋and Zn was chemically plated on its surface through an immersion-reduction reaction. Such Zn-deposited Al foil was quickly transferred into HCl-H 2 SO 4 solution for DC-etching. The effects of Zn impurity on the surface and cross-section etching morphologies and electrochemical behavior of Al foil were investigated by SEM, polarization curve （PC） and electrochemical impedance spectroscopy （EIS）. The special capacitance of 100 V formation voltage of etched foil was measured. The results show that the chemical plating Zn on Al substrate in alkali solution can reduce the pitting corrosion resistance, enhance the pitting current density and improve the density and uniform distribution of pits and tunnels due to formation of the micro Zn-Al galvanic local cells. The special capacitance of etched foil grows with the increase of Zn2＋concentration.

Effect of pretreatment on electrochemical etching behavior of Al foil in HCl-H_2SO_4

The aluminum foil for high voltage aluminum electrolytic capacitor was immersed in 0.5 mol/L H3PO4 or 0.125 mol/L NaOH solution at 40 ℃ for different time and then DC electro-etched in 1 mol/L HC1＋2.5 mol/L H2SO4 electrolyte at 80 ℃. The pitting potential and self corrosion potential of A1 foil were measured with polarization curves （PC）. The potentiostatic current--time curve was recorded and the surface and cross section images of etched A1 foil were observed with SEM. The electrochemical impedance spectroscopy （EIS） of etched A1 foil and potential transient curves （PTC） during initial etching stage were measured. The results show the chemical pretreatments can activate A1 foil surface, facilitate the absorption, diffusion and migration of C1- onto the A1 foil during etching, and improve the initiation rate of meta-stable pits and density of stable pits and tunnels, leading to much increase in the real surface area and special capacitance of etched A1 foil.

Chemical etching process of copper electrode for bioelectrical impedance technology

In order to obtain bioelectrical impedance electrodes with high stability, the chemical etching process was used to fabricate the copper electrode with a series of surface microstructures. By changing the etching processing parameters, some comparison experiments were performed to reveal the influence of etching time, etching temperature, etching liquid concentration, and sample sizes on the etching rate and surface microstructures of copper electrode. The result shows that the etching rate is decreased with increasing etching time, and is increased with increasing etching temperature. Moreover, it is found that the sample size has little influence on the etching rate. After choosing the reasonable etching liquid composition （formulation 3）, the copper electrode with many surface microstructures can be obtained by chemical etching process at room temperature for 20 rain. In addition, using the alternating current impedance test of electrode-electrode for 24 h, the copper electrode with a series of surface microstructures fabricated by the etching process presents a more stable impedance value compared with the electrocardiograph （ECG） electrode, resulting from the reliable surface contact of copper electrode-electrode.