Electro-chemical mechanical polishing of silicon carbide

In an effort to improve the silicon carbide (SiC) substrate surface, a new electro-chemical mechanical polishing (ECMP) technique was developed. This work focused on the Si-terminated 4H-SiC (0001) substrates cut 8° off-axis toward 〈1120〉. Hydrogen peroxide (H₂O₂) and potassium nitrate (KNO₃) were used as the electrolytes while using colloidal silica slurry as the polishing medium for removal of the oxide. The current density during the polishing was varied from 10 μA/cm² to over 20 mA/cm². Even though a high polishing rate can be achieved using high current density, the oxidation rate and the oxide removal rate need to be properly balanced to get a smooth surface after polishing. A two-step ECMP process was developed, which allows us to separately control the anodic oxidation and removal of formed oxide. The optimum surface can be achieved by properly controlling the anodic oxidation current as well as the polishing rate. At higher current flow (>20 mA/cm²), the final surface was rough, whereas a smoother surface was obtained when the current density was in the vicinity of 1 mA/cm². The surface morphology of the as-received wafer, fine diamond slurry (0.1 μm) polished wafer, and EMCP polished wafer were studied by high-resolution atomic force microscopy (AFM).     

Relay Catalysis of Multi-Sites Promotes Oxygen Reduction Reaction

The two-electron pathway to form hydrogen peroxide (H₂O₂) is undesirable for the oxygen reduction reaction (ORR) in iron and nitrogen doped carbon (Fe–N–C) material as it not only lowers the catalytic efficiency but also impairs the catalyst durability. In this study, a relay catalysis pathway is designed to minimize the two-electron selectivity of Fe–N–C catalyst. Such a design is achieved by introducing two other sites, that is, MnN₄ site and α-Fe(110) face. A combination of transmission electron microscopy image and X-ray absorption spectra verify the three site formation. Electrochemical test coupled with post-treatment confirm the improvement of MnN₄ site and α-Fe(110) face on catalyst performance. Theoretical calculation proposes a relay catalysis pathway of three sites, that is, H₂O₂ released from the FeN₄ site migrates to the MnN₄ site or α-Fe(110) face, on which the captive H₂O₂ is further reduced to H₂O. The relay catalysis pathway positioned the as-prepared catalyst among the best ORR catalysts in both aqueous electrode and alkaline direct methanol fuel cell test. This study examples an interesting relay catalysis pathway of multi-sites for the ORR, which offers insights into the design of efficient electrocatalysts for fuel cells or beyond.     

Carbon Black-Supported Single-Atom Co?N?C as an Efficient Oxygen Reduction Electrocatalyst for H2O2 Production in Acidic Media and Microbial Fuel Cell in Neutral Media

Single metal atom isolated in nitrogen-doped carbon materials (M N C) are effective electrocatalysts for oxygen reduction reaction (ORR), which produces H₂O₂ or H₂O via 2-electron or 4-electron process. However, most of M N C catalysts can only present high selectivity for one product, and the selectivity is usually regulated by complicated structure design. Herein, a carbon black-supported Co N C catalyst (CB@Co N C) is synthesized. Tunable 2-electron/4-electron behavior is realized on CB@Co-N-C by utilizing its H₂O₂ yield dependence on electrolyte pH and catalyst loading. In acidic media with low catalyst loading, CB@Co N C presents excellent mass activity and high selectivity for H₂O₂ production. In flow cell with gas diffusion electrode, a H₂O₂ production rate of 5.04 mol h⁻¹ g⁻¹ is achieved by CB@Co N C on electrolyte circulation mode, and a long-term H₂O₂ production of 200 h is demonstrated on electrolyte non-circulation mode. Meanwhile, CB@Co N C exhibits a dominant 4-electron ORR pathway with high activity and durability in pH neutral media with high catalyst loading. The microbial fuel cell using CB@Co N C as the cathode catalyst shows a peak power density close to that of benchmark Pt/C catalyst.     

Selective chemical etching of polycrystalline SiGe alloys with respect to Si and SiO2

Polycrystalline SiGe etches that are selective to silicon dioxide as well as silicon are needed for flexibility in device fabrication. A solution of NH₄OH, H₂O₂, and H₂O has been found to selectivity etch polycrystalline silicon-germanium alloys over both silicon and silicon dioxide. Optimum composition of the solution was determined by maximizing etch rates for SiGe films with several germanium compositions. The dependence of etch rates on germanium content, etching temperature, and doping concentration are reported. The etch rate and selectivity are approximately exponentially proportional to the germanium content. Etching was found to be insensitive to deposition method, doping method, and annealing conditions of the SiGe films. In addition, etching leaves a smooth silicon substrate surface after removal of SiGe films.     

Metal–Organic Framework as a Simple and General Inert Nanocarrier for Photosensitizers to Implement Activatable Photodynamic Therapy

There has been a surging interest in the synthesis of activatable photosensitizers (PSs) as they can be selectively activated with minimum nonspecific phototoxic damages for photodynamic therapy (PDT). Conventional strategies to realize activatable PSs are only applicable to a limited number of molecules. Herein, a simple and general strategy to yield activatable PSs by coupling MIL‐100 (Fe) (MIL: Materials Institute Lavoisier) with different kinds of PSs is presented. Specifically, when PSs are encapsulated into MIL‐100 (Fe), the photosensitization capability is suppressed due to their isolation from O₂. After the reaction between iron(III) in MIL‐100 (Fe) and H₂O₂ occurs, the framework of MIL‐100 (Fe) collapses and the encapsulated PSs regain contact with O₂, leading to activation of photosensitization. In addition, the decomposition of H₂O₂ can generate O₂ to relieve tumor hypoxia and enhance PDT effect. As O₂ is an indispensable factor for PDT, the activation strategy should be generally applicable to different PSs for activatable PDT.     

Abrasive-Free Chemical Mechanical Polishing of Hard Disk Substrate with Cumene Hydroperoxide-H2O2 Slurry

With magnetic heads operating closer to hard disks, the hard disks must be ultra-smooth. The abrasive-free polishing (AFP) performance of cumene hydroperoxide (CHP) as the initiator in H₂O₂-based slurry for hard disk substrate was investigated in our work, and the results showed that the slurry including CHP could improve the material removal rate (MRR) and also reduce surface roughness. Electron spin-resonance spectroscopy (EPR), electrochemical measurement and Auger electron spectroscopy (AES) were conducted to investigate the acting mechanism with CHP during the polishing process. Compared with the H₂O₂ slurry, the EPR analysis shows that the CHP–H₂O₂ slurry provides a higher concentration of the HO^O free radical. In addition, the AES analysis shows the oxidization reaction occurs in the external layer of the substrate surface. Furthermore, electrochemical measurements reveal that CHP can promote the electrochemical effect in AFP and lead to the increase of MRR.     

An efficient titanium‐based photoanode for dye‐sensitized solar cell under back‐side illumination

Pretreatment of H₂O₂ is performed on titanium (Ti) foil as an efficient photoanode substrate for dye‐sensitized solar cell (DSSC). The H₂O₂‐treated Ti shows high surface area because of the formation of networked TiO₂ nanosheets, which enhances electrical contact between screen‐printed TiO₂ nanoparticles and Ti foil. Electron transfer on the photoanode is improved, as identified by reduced charge transfer resistance and improved electron transport properties. Compared with DSSC based on non‐treated Ti photoanode, DSSC with this H₂O₂‐treated Ti photoanode exhibits remarkable increases in short‐circuit current density (from 8.55 to 14.38 mA/cm²) and energy conversion efficiency (from 4.68 to 7.10%) under AM1.5 back‐side illumination. Copyright © 2011 John Wiley & Sons, Ltd.     

Dealloyed AuNi Dendrite Anchored on a Functionalized Conducting Polymer for Improved Catalytic Oxygen Reduction and Hydrogen Peroxide Sensing in Living Cells

Dealloyed‐AuNi dendrite anchored on carboxylic acid groups of a conducting polymer is prepared and demonstrated for the catalysis of the oxygen reduction reaction (ORR) and detection of hydrogen peroxide (H₂O₂) released from living cells. The dendrite formation is initiated on a poly(benzoic acid‐2,2′:5′,2′′‐terthiophene) (pTBA) layer, where the polymer layer acts as a stable substrate to improve the long‐term stability and catalytic activity of the alloy electrode. A co‐deposition of Au and Ni is performed to produce a Ni‐rich Au surface at first; subsequent removal of the surface Ni atoms through electrochemical dealloying enhances the performance of the catalyst because of an increase in the electrochemically active area by 12 times. The hydrodynamic voltammetry of dealloyed‐AuNi@pTBA shows a half‐wave potential at –0.08 V, which is a large shift towards more positive potential when compared to those on AuNi@pTBA (?0.14 V) and commercial Pt/C (–0.12 V) electrodes. The proposed catalytic electrode achieved a superior analytical performance for the detection of trace H₂O₂ (at –0.15 V) released from cancer and normal cells with a very low detection limit (ca. 5 nM). In addition, the in vitro studies suggest no significant cytotoxicity effect for the dealloyed sample and the viability of the cells are more than 85% even after 48 h of incubation.     

A General Carboxylate-Assisted Approach to Boost the ORR Performance of ZIF-Derived Fe/N/C Catalysts for Proton Exchange Membrane Fuel Cells

An Fe/N/C catalyst derived from the pyrolysis of metal–organic frameworks, for example, a zeolitic-imidazolate-framework-8 (ZIF-8), has been regarded as one of the most promising non-precious metal catalysts toward oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). However, its ORR mass activity is still much inferior to that of Pt, partly because of the lack of general and efficient synthetic strategies. Herein, a general carboxylate-assisted strategy that dramatically enhances the ORR mass activity of ZIF-derived Fe/N/C catalysts is reported. The carboxylate is found to promote the formation of Fe/N/C catalysts with denser accessible active sites and entangled carbon nanotubes, as well as a higher mesoporosity. These structural advantages make the carboxylate-assisted Fe/N/C catalysts show a 2–10 fold higher ORR mass activity than the common carboxylate-free one in various cases. When applied in H₂–O₂ PEMFCs, the active acetate-assisted Fe/N/C catalyst generates a peak power density of 1.33 W cm⁻², a new record of peak power density for a H₂–O₂ PEMFC with non-Pt ORR catalysts.     

Al-oxynitrides as a buffer layer for Pr2O3/SiC interfaces

We elaborate the possibility of combining high-k dielectrics with wide band gap semiconductors, i.e. Pr₂O₃ on SiC. The thermal stability of interfacial aluminum oxynitride (AlON) layers between Pr-oxide and SiC has been investigated by synchrotron radiation photoemission spectroscopy (SRPES). The interface of Pr₂O₃ with SiC is reactive. Such reaction is successfully prevented by utilizing a stable interlayer derived from AlON. No elemental carbon is observed in detectable amount after Pr-Oxide deposition on AlON covered 3C-SiC and subsequent vacuum annealing. After vacuum annealing at 500 °C AlON transformed to AlN and Pr-aluminate with a small amount of CN close to the SiC surface which were thermally stable even at 900 °C. AlON hence provides a good diffusion barrier between Pr-oxide dielectric and 3C-SiC.     

Carbon Free and Noble Metal Free Ni2Mo6S8 Electrocatalyst for Selective Electrosynthesis of H2O2

Electrocatalytic two-electron reduction of oxygen is a promising method for producing sustainable H₂O₂ but lacks low-cost and selective electrocatalysts. Here, the Chevrel phase chalcogenide Ni₂Mo₆S₈ is presented as a novel active motif for reducing oxygen to H₂O₂ in an aqueous electrolyte. Although it has a low surface area, the Ni₂Mo₆S₈ catalyst exhibits exceptional activity for H₂O₂ synthesis with >90% H₂O₂ molar selectivity across a wide potential range. Chemical titration verified successful generation of H₂O₂ and confirmed rates as high as 90 mmol H₂O₂ g_cat⁻¹ h⁻¹. The outstanding activities are attributed to the ligand and ensemble effects of Ni that promote H₂O dissociation and proton-coupled reduction of O₂ to HOO*, and the spatial effect of the Chevrel phase structure that isolates Ni active sites to inhibit O O cleavage. The synergy of these effects delivers fast and selective production of H₂O₂ with high turn-over frequencies of ≈30 s⁻¹. In addition, the Ni₂Mo₆S₈ catalyst has a stable crystal structure that is resistive for oxidation and delivers good catalyst stability for continuous H₂O₂ production. The described Ni-Mo₆S₈ active motif can unlock new opportunities for designing Earth-abundant electrocatalysts to tune oxygen reduction for practical H₂O₂ production.     

The role of oxygen in electron cyclotron resonance etching of silicon carbide

The electron cyclotron resonance (ECR) etching of silicon carbide (SiC) was studied using SF₆ + O₂ based plasma. The role of O₂ was studied by varying the O₂ flow rate while keeping the total gas flow constant. It was found that oxygen enhances the etch rate at low O₂ fraction through releasing more fluorine atoms, while lowers the etch rate at high O₂ fraction by diluting fluorine atoms and forming an oxide-like layer. The etched surface roughness was found to be affected by the surface oxidation and oxygen ion related physical ion bombardment. The role of oxygen in chemical etching of carbon was found to be insignificant. In general, the etched surface is smooth and free of micromasking effect that can arise from Al contamination and C rich layer.     

以非晶硅为硬掩膜的TaN金属栅的选择性湿法腐蚀

提出了一种在HfSiON介质上,采用非晶硅为硬掩膜的选择性去除TaN的湿法腐蚀工艺。由于SC1(NH4OH:H2O2:H2O)对金属栅具有合适的腐蚀速率且对硬掩膜和高K材料的选择比很高,所以选择它作为TaN的腐蚀溶液。与光刻胶掩膜和TEOS硬掩膜相比,因非晶硅硬掩膜不受SC1溶液的影响且很容易用NH4OH溶液去除（NH4OH溶液对TaN和HfSiON薄膜无损伤）,所以对于在HfSiON介质上实现TaN的选择性去除来说非晶硅硬掩膜是更好的选择。另外,在TaN金属栅湿法腐蚀和硬掩膜去除后, 高K介质的表面是光滑的,这可防止器件性能退化。因此,采用非晶硅为硬掩膜的TaN湿法腐蚀工艺可以应用于双金属栅集成,实现先淀积的TaN金属栅的选择性去除。     

Pb‐Based Halide Perovskites: Recent Advances in Photo(electro)catalytic Applications and Looking Beyond

Photo(electro)catalysis has triggered ripples of excitement in environmental protection and energy conversion due to its potential applications in the degradation of organic pollutants, evolution of H₂ and O₂ from H₂O splitting, and reduction of CO₂ by utilizing solar energy. Over the past three years, halide perovskites, which render extraordinary charge transport capability in solar cells, have witnessed a burgeoning development in photocatalysis over the conventional oxide perovskites. This type of perovskite demonstrates a small surface area, limited light utilization, and high carrier recombination, resulting in inadequate reactant contact on catalyst surfaces and decreased catalytic activity. In this review, the progress of halide perovskites is presented starting from fundamental properties (i.e., synthesis and structure) to applications in light‐driven reactions with the focus on crystal dimensions, toxicity, and stability. In addition, computational studies on halide perovskites from electronic properties to catalytic mechanisms are presented to lay a foundation for future research and advancement in this field. Last, critical insights are provided into the existing limitations and favorable prospects for halide perovskites.     

Biodegradable Fe(III)@WS2‐PVP Nanocapsules for Redox Reaction and TME‐Enhanced Nanocatalytic,Photothermal, and Chemotherapy

In this study, biocompatible Fe(III) species‐WS₂‐polyvinylpyrrolidone (Fe(III) @ WS₂‐PVP) nanocapsules with enhanced biodegradability and doxorubicin (DOX) loading capacity are one‐pot synthesized. In this nanocapsule, there exists a redox reaction between Fe(III) species and WS₂ to form Fe²⁺ and WO₄^2?. The formed Fe²⁺ could be oxidized to Fe³⁺, which reacts with Fe(III) @ WS₂‐PVP again to continuously produce Fe²⁺ and WO₄^2?. Such a repeated endogenous redox reaction leads to an enhanced biodegradation and DOX release of DOX @ Fe(III) @ WS₂‐PVP. More strikingly, the Fe²⁺ generation and DOX release are further accelerated by the overexpressed H₂O₂ and the mild acidic tumor microenvironment (TME), since H₂O₂ and H⁺ can accelerate the oxidation of Fe²⁺. The continuously generated Fe²⁺ catalyzes a fast Fenton reaction with the innate H₂O₂ in tumor cells and produces abundant highly toxic hydroxyl radicals for nanocatalytic tumor therapy. Together with the high photothermal transforming capability, the DOX @ Fe(III) @WS₂‐PVP nanocapsules successfully achieve the endogenous redox reaction and exogenous TME‐augmented tumor photothermal therapy, chemo and nanocatalytic therapy outcome. The concept of material design can be innovatively extended to the synthesis of biodegradable Fe(III) @ MoS₂‐PVP nanocomposite, thus paving a promising novel way for the rational design of intelligent theranostic agents for highly efficient treatment of cancer.     

Electrochemical corrosion effects and chemical mechanical polishing characteristics of tungsten film using mixed oxidizers

In this paper, the effects of mixed oxidizers on tungsten-chemical mechanical polishing (W-CMP) process were studied using three different kinds of oxidizers such as Fe(NO₃)₃, KIO₃ and H₂O₂. Moreover, the interaction between the tungsten film and the oxidizer was discussed by potentiodynamic polarization test, in order to compare the CMP performances and electrochemical behavior of the tungsten film as a function of mixed oxidizers. The potentiodynamic polarization results indicated that the corrosion current densities of the 5 wt% H₂O₂ and 5 wt% H₂O₂ + 5 wt% Fe(NO₃)₃ were higher than the other mixed oxidizers. Such an electrochemical corrosion effect implies that slurries with the highest removal rate have a high dissolution rate at lower pH. Therefore, we conclude that W-CMP performances are strongly dependent on the kind of oxidizers and the amounts of oxidizer additive.     

On the role of interface properties in the degradation of metalorganic vapor phase epitaxially grown Fe profiles in InP

Fe doping profiles in InP layers grown by low-pressure metalorganic vapor phase epitaxy (LP-MOVPE) were investigated by secondary ion mass spectroscopy. Different pre-treatments of the InP substrates proved to have substantially different effects on the Fe profiles which strongly indicate the relevance of underlying interfaces to dopant diffusion in subsequent layers, at least in the case of dopants occupying the group-III sublattice. We attribute the degradation of Fe profiles observed for some kinds of treatment to the emission of In interstitials from surfaces covered by oxides or other residues which are incompletely removed during the MOVPE preheat cycle. A favorable substrate preparation method for avoiding Fe profile degradation relies on etching by 5:1:1 H₂SO₄:H₂O₂:H₂O at room temperature followed by 30 min deionized water rinsing.     

碱性Cu抛光液中非离子表面活性剂和氧化剂作用的研究

化学机械抛光是集成电路制造工艺中十分精密的技术。在本文中,为了改善抛光效果,分表讨论了非离子表面活性剂和氧化剂在CMP过程中作用。我们主要分析了非离子表面活性剂对片内非均匀性和表面粗糙度的影响。同时,我们从静态腐蚀速率、电化学曲线和剩余高低差的角度,讨论了在不加BTA条件下,不同氧化剂浓度的抛光液的钝化特性。实验结果明显地表明：加入了非离子表面活性剂的抛光液,更有利于改善抛光后的片内非均匀性和表面粗糙度,并确定2vol%体积分数是比较合适的浓度。当抛光液中氧化剂浓度超过3vol%,抛光液拥有较好的钝化能力,能够有效减小高低差,并有助于获得平整和光滑的表面。根据这些实验结果,非离子表面活性剂和氧化剂的作用进一步被了解,将有助于抛光液性能的改善。     

Inductively coupled plasma reactive ion etching of SiC single crystals using NF<Subscript>3</Subscript>-based gas mixtures

Inductively coupled plasma reactive ion etching of SiC single crystals using NF₃-based gas mixtures was investigated. Mesas with smooth surfaces and vertical sidewalls were obtained, with a maximum etch rate of about 400 nm/min. Effects of CH₄ and O₂ addition to the NF₃ gas and the crystalline quality of substrates were studied during the SiC dry etching using various masks. Selectivity of the photoresist (PR) mask improved from about 0.2 to about 0.4 by the addition of 30% CH₄ during the RIE, although the etch rate decreased by 50–70%. Results also indicated that the substrate quality does not significantly affect the etch results.     

Synthesis of Pt Hollow Nanodendrites with Enhanced Peroxidase‐Like Activity against Bacterial Infections: Implication for Wound Healing

Improving the antibacterial activity of H₂O₂ and reducing its usage are requirements for wound disinfection. Nanomaterials with intrinsic peroxidase‐like properties are developed to enhance the antibacterial performance of H₂O₂ and avoid the toxicity seen with high H₂O₂ levels. Here, Pd–Pt core–frame nanodendrites consist of a dense array of platinum (Pt) branches on a Pd core are synthesized, and subsequently converted to Pt hollow nanodendrites by selective removal of the Pd cores by wet etching. The fabricated Pt hollow nanodendrites exert striking peroxidase‐like activity due to the maximized utilization efficiency of the Pt atoms and the presence of high‐index facets on their surfaces. By catalyzing the decomposition of H₂O₂ into more toxic hydroxyl radicals (?OH), Pt hollow nanodendrites exhibit excellent bactericidal activity against both Gram‐negative and Gram‐positive bacteria with the assistance of low concentrations of H₂O₂. Furthermore, Pt hollow nanodendrites accelerate wound healing in the presence of low doses of H₂O₂. In addition, no obvious adverse effects are observed at the given dose of nanodendrites. These findings can be used to guide the design of noble metal‐based nanomaterials as potential enzyme‐mimetic systems and advance the development of nanoenzymes to potentiate the antibacterial activity of H₂O₂.