Plasma etching of refractory metals (W,Mo, Ta) and silicon in SF6 and SF6-O2. An analysis of the reaction products

The etching rates and reaction products of refractory metals (W, Mo, and Ta) and silicon have been studied in a SF₆-O₂ r.f. plasma at 0.2 torr. The relative concentrations of WF₆ and WOF₄ and the intensities of the WF _n ⁺ (n=3–5), WOF _m ⁺ (m=1–3), MoF _n ⁺ , and MoF _m ⁺ ions have been measured by mass spectroscopy. An analysis of the neutral composition of the plasma during etching of these metals and a comparison with the results obtained for silicon show that at least two species are involved for W and Mo etching: fluorine and oxygen atoms. A reaction scheme is proposed.     

Iodine- and Bromine-Based Dry Etching of LaCaMnO3

Two novel plasma chemistries, BI ₃ and BBr ₃ , have been employed for dry etching of LaCaMnO ₃ thin films. For both mixtures there is some chemical enhancement of etch rates at low halide compositions in the discharge, and the rates are a strong function of ion/neutral ratio. Maximum rates are obtained at ratios near 0.02. Etch yields are typically low (<0.3) under inductively-coupled plasma (CICP) conditions. Smooth _d surface morphologies are obtained over a wide range of conditions, with high-fidelity pattern transfer using SiO ₂ or SiN _x masks.     

Optical Diagnostics of the Effect of Oxygen on Bi-Level Contact Etch

The effect of oxygen flow rate on bi-level contact etch was studied by observing uv-visible emission from the plasma, during CHF₃/CO/O₂ etching of di-electric layers consisting of SiO₂ and SiN_x. The emission intensity of CN at 387 nm drifted progressively from wafer to wafer during plasma etch. Such a phenomenon became more obvious when using low or high oxygen flow rate, whereas for intermediate flow rates, no significant drift of emission intensity was observed. The critical dimension (CD) bias of each wafer showed a strong correlation with CN emission intensity. Possible mechanisms for such an intensity drift phenomenon are proposed. The drift of emission intensity indicates that the contribution of chamber wall polymers in wafer etching is non-negligible. The CN emission intensity is an indication of the magnitude of etching rate. Our results suggest that the variation of plasma emission intensity might be used as an index for in-line monitoring of CD bias fluctuation.     

Etching Efficiency for Si and SiO2 by CF+x,F+, and C+ Ion Beams Extracted from CF4 Plasmas

Fluorocarbon (CF⁺ _x), fluorine (F⁺), and carbon (C⁺) ion beams with highcurrent density (50i<800 A/cm²) were irradiated to Si and SiO₂surfaces to investigate the influence of the ion species on the etchingefficiency. The ion beams were extracted from magnetized helicon-wave CF₄plasmas operated in pulsed modes. The CF⁺ ₃ beam had the largest etchingefficiency for Si at the same beam energy. When the same data weresummarized as a function of the momentum of the incident ion beam, thedifference in the etching efficiency became small, although the CF⁺ ₃ beamstill had a slightly larger etching efficiency. On the other hand, theetching efficiency for SiO₂ by the CF⁺ ₃ beam was larger than that by theother ion beams in the low-momentum region. In addition, in the low-momentumregion, the etching efficiency for SiO₂ by CF⁺ ₃ was larger than that forSi. These results suggest the high chemical reactivity of CF⁺ ₃ with SiO₂,leading to the high etching selectivity of SiO₂ over underlying Si in thefabrication of semiconductor devices.     

Study of reactive ion etching of Si and SiO2 for CFxCl4−x gases

A parametric study of the etching of Si and SiO₂ by reactive ion etching (RIE) was carried out to gain a better understanding of the etching mechanisms. The following fluorocarbons (FCs) were used in order to study the effect of the F-to-Cl atom ratio in the parent molecule to the plasma and the etching properties: CF₄, CF₃Cl, CF₂Cl₂, and CFCl₃ (FC-14, FC-13, FC-12, and FC-11 respectively). The Si etch rate uniformity across the wafer as a function of the temperature of the wafer and the Si load, the optical emission as a function of the temperature of the load, the etch rate of SiO₂ as a function of the sheath voltage, and the mass spectra for each of the FCs were measured. The temperature of the wafer and that of the surrounding Si load strongly influence the etch rate of Si, the uniformity of etching, and the optical emission of F, Cl, and CF₂. The activation energy for the etching reaction of Si during CF₄ RIE was measured. The etch rate of Si depends more strongly on the gas composition than on the sheath voltage; it seems to be dominated by ion-assisted chemical etching. The etching of photoresist shifted from chemical etching to ion-assisted chemical etching as a function of the F-to-Cl ratio and the sheath voltage. The etch rate of SiO₂ depended more strongly on the sheath voltage than on the F-to-Cl ratio.     

Mass spectrometric study of SF6-N2 plasma during etching of silicon and tungsten

The reaction products in the SF₆-N₂ mixture rf plasma during reactive ion etching of Si and W have been measured by a mass spectrometric method. Two kinds of cathode materials were used in this work; they were stainless steel for the Si etching, and SiO₂ for the W etching. The main products detected in the etching experiments of Si and W included SF₄, SF₂, SO₂, SOF₂, SOF₄, SO₂F₂, NSF, NF₃, N₂F₄, N_xS_y, NO₂, and SiF₄. In the W etching with the SiO₂ cathode, additional S₂F₂, N₂O, and WF₆ molecules were also obtained. The formation reactions about the novel NSF compound and the sulfur oxyfuorides were discussed.     

Chemical analysis of acidic silicon etch solutions: II. Determination of HNO3, HF, and H2SiF6 by ion chromatography

The processing of silicon in microelectronics and photovoltaics involves the isotropic chemical etching using HF-HNO₃ mixtures to clean the surface from contaminations, to remove the saw damage, as well as to polish or to texture the wafer surface. Key element of an effective etch process control is the knowledge of the actual etch bath composition in order to maintain a certain etch rate by replenishment of the consumed acids. The present paper describes a methods for the total analysis of the etch bath constituents HF, HNO₃, and H₂SiF₆ by ion chromatography. First step is the measurement of the total fluoride and nitrate content in the analyte. In a second step, H₂SiF₆ is precipitated as K₂SiF₆. After careful filtration of the precipitate, the fluoride concentration in the filtrate is measured and the content of free HF is calculated therefrom. The K₂SiF₆ is dissolved again and the fluoride content measured and recalculated as H₂SiF₆. The results obtained with the presented method are discussed with respect to the results from two other, previously published methods, based on a titration using methanolic cyclohexylamine solution as titrant and based on a method using a fluoride ion selective electrode (F-ISE). An evaluation with respect to the needs for an industrial application is given.     

Chemically assisted ion beam etching of silicon and silicon dioxide using SF6

A chemical flux of sulfur hexafluoride (SF₆) in conjunction with low-energy Ar-ion bombardment has been used for chemically assisted ion beam etching (CAIBE) of silicon and silicon dioxide. The study has shown a large degree of independent control over the selectivity and anisotropy in dry etching. The total etch rate could be controlled by varying either the Ar-ion milling parameters or the chemical flux of SF₆. Etch rate enhancement of 7–8 for silicon and 3–4 for silicon dioxide have been obtained over pure physical etching.     

多孔SiO_2·xH_2O负载RuB纳米粒子催化喹啉加氢反应

通过水解,聚乙烯吡咯烷酮(PVP)保护,NaOH刻蚀等方法制备了多孔及富含表面羟基的SiO2·xH2O负载的RuB催化剂RuB/SiO2·xH2O,并用X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、傅里叶变换红外(FT-IR)光谱和BET(Brunauer-Emmett-Teller)等手段对该催化剂进行了表征.结果表明该催化剂具有良好的抗中毒能力,在3.0MPa的H2压力和80℃的温和反应条件下,喹啉的转化率高于95%,生成1,2,3,4-四氢喹啉的选择性高于97%.并系统研究了表面羟基和溶剂对催化剂性能的影响,发现以水为溶剂时,RuB/SiO2·xH2O对喹啉加氢反应展示出较高的活性和对1,2,3,4-四氢喹啉较高的选择性,催化剂能够多次循环使用.这一体系的优异催化性能归属于载体表面羟基和水的协同作用.     

Mass spectrometer-wall probe diagnostic of Ar discharges containing SF6 and/or O2: Reactive ions in etching plasmas

Positive and negative ions of Ar/SF₆ and Ar/SF₆/O₂ plasmas (etching plasmas) and of Ar/O₂ plasmas (cleaning plasmas) in Pyrex tubes have been investigated using a mass spectrometer-wall probe diagnostic technique. The measurement of negative ions proved to be a very sensitive method for the detection of wall material. In etching plasmas with small admixtures of SF₆, oxygen was found as the only representative of wall material. At larger amounts of SF₆, silicon could be detected. In cleaning plasmas with small admixtures of O₂ applied to a previously etched Pyrex surface, fluorine was found, indicating the reversal of fluoridation by oxygenation.     

Highly Selective and Low Damage Etching of GaAs/AlGaAs Heterostructure using Cl2/O2 Neutral Beam

Highly selective and low damage etching of the GaAs cap layer on AlGaAs is essential in fabricating GaAs/AlGaAs high electron mobility transistors. The GaAs on AlGaAs was etched using a low energy Cl₂/O₂ neutral beam and the Schottky device characteristics fabricated on the exposed AlGaAs were compared with those fabricated after the etching using wet etching and a Cl₂/O₂ ion beam. Using a low energy Cl₂/O₂ ion beam or a Cl₂/O₂ neutral beam, highly selective etching of the GaAs cap layer to AlGaAs similar to wet etching could be achieved through the formation of Al₂O₃ on the exposed AlGaAs during the etching. When the electrical characteristics of the Schottky devices were compared, the devices fabricated after the etching using the neutral beam showed the best electrical characteristics such as electrical stability, low leakage current, higher barrier height, etc. by showing low damage to the exposed AlGaAs surface.     

Titrimetric determination of silicon dissolved in concentrated HF-HNO3-etching solutions

The wet chemical etching of silicon by concentrated HF-HNO₃ mixtures in solar and semiconductor wafer fabrication requires the strict control of the etching conditions. Surface morphology and etch rates are mainly affected by the amount of dissolved silicon, that is continuously enriched in the etching solution with each etching run. A fast and robust method for the titrimetric determination of the total dissolved silicon content out of the concentrated etching solution is presented. This method is based on the difference between the two equivalence points of the total amount of acid and the hydrolysis of the hexafluorosilicic anion. This approach allows a silicon determination directly from the etching process in spite of the presence of dissolved nitric oxides in the etching solution. The influences of different acid mixing ratios and of the etching solution density depending on the silicon content is considered and discussed in detail.     

氢氟酸腐蚀对α-Fe2O3薄膜光解水电极光电化学性质的影响

使用溶胶-凝胶法制备了α-Fe₂O₃薄膜,研究了氢氟酸腐蚀薄膜表面对其光电化学性质的影响. 实验发现,薄膜表面的孔洞和间隙随着氢氟酸浸蚀时间的增长而发生变化. 氢氟酸浸蚀5 min,α-Fe₂O₃电极的光电流降低;随后随浸蚀时间增加而迅速增加;当浸蚀时间大于15 min时,其光电流再次下降,但对浸蚀过的样品再次退火可以使光电流大幅增加. 通过电化学交流阻抗谱、拉曼和X射线光电子能谱分析,提出了两个影响光电流的因素：氢氟酸表面浸蚀造成薄膜表面的多孔性和结晶度降低. 为此,通过示意图解释了结合浸蚀和退火后处理两个步骤来增强α-Fe₂O₃薄膜光解水电极光电活性的原理. 相对于初始的α-Fe₂O₃电极,浸蚀并且再退火处理后,其光电性质更加稳定.     

Role of etch products in polysilicon etching in a high-density chlorine discharge

For low-pressure, high-density plasma systems, etch products can play a significant role in affecting plasma parameters such a.s species concentration and electron temperature. The residence time of etch products in the chamber can he long, hence depleting the concentration of the reactants, and leading to a decrease in etch rate. We use a spatially averaged global model including both gas phase and surface chemistry to study Cl₂ etching of polvsilicon. Etch products leaving the wafer surface are assioned to he SiCL₂ and SiCl₄. These species can be fragmented and ionized by collisions with energetic electrons, generating neutral and charged SiCl, products (x=0–4). Two limiting cases of the etch mechanism are found. an ion flux-limited regime and a neutral reactant-limited regime. The high degree of dissociation in high-density plasmas leads to the formation of elemental silicon, which can deposit on the chamber walls and wafer surface. We include surface models for both the wall and the wafer to better understand the role of etch products as a function of flowrate, pressure, and input pwer. A phenomenological model for the surface chemistry is based on available experimental data. We consider the two limiting conditions of nonreactive and reactive walls. These models are perfectly reflective walls, where all silicon-containing species are reflected; and reactive walls, which act as reactive sites for the formation of SiCl₂ and SiCl₄ etch products. The two limiting conditions give significantly different results. A decrease in the absolute atomic silicon density and a weaker dependence of etch rate on flowrate are observed for the reactive wall.     

泡沫镍负载Fe2O3@Ni3S2纳米线网状结构电极的制备及其电催化析氧性能

通过两步水热法制备泡沫镍(NF)负载Fe_2O_3纳米粒子@Ni_3S_2纳米线网状结构电极(Fe_2O_3@Ni_3S_2/NF)。运用X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、N_2吸附-脱附测试等方法对电极材料的物相和微观结构特征等进行了表征。水热条件下原位表面化学刻蚀生成的Ni_3S_2纳米线与三维多孔NF基体间拥有强结合力和低界面电阻,Fe_2O_3粒子均匀分布在纳米线的表面。在1 mol·L~(-1)的KOH溶液中,运用线性扫描伏安测试(LSV)、计时电位法、电化学交流阻抗测试(EIS)等对电极的电催化析氧(OER)性能进行了测试。结果表明:在100 mA·cm~(-2)的超高电流密度下,Fe_2O_3@Ni_3S_2/NF电极的OER过电势仅为223 mV,比Ni_3S_2/NF材料的过电势降低了285 mV;经过10 h计时电位测试,性能保持率高达80%。     

Li3V2(PO4)3/C的P123辅助流变相法制备及电化学性能

以V₂O₅、NH₄H₂PO₄、LiOH、柠檬酸、三嵌段聚合物表面活性剂P123为原料, 用流变相(RPR)法制备了Li₃V₂(PO₄)₃/C正极材料. 用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)等方法表征, 结果表明: 材料为单一纯相的单斜晶体结构, 颗粒均匀并呈现珊瑚结构; 恒流充放电, 循环伏安(CV)及电化学交流阻抗(EIS)等电化学性能测试表明, 采用P123 辅助合成材料电化学性能明显优于未采用P123 辅助合成材料. 3.0-4.3 V放电区间, 0.1C充放电下P123 辅助合成Li₃V₂(PO₄)₃/C材料首次放电比容量为129.8 mAh·g^-1, 经过50 次循环后容量只衰减0.9%; 倍率性能及循环性能优异, 1C、10C、25C的首次放电比容量分别为128.2、121.3、109.1 mAh·g^-1, 50次循环后容量保持率分别为99.1%, 96.9%, 90.7%. 这归因于三嵌段聚合物P123 作为分散剂的同时也作为有机碳源在颗粒表面及间隙形成碳网络, 有利于材料导电率的改善, 降低了其电荷转移阻抗, 减小了电极充放电过程的极化现象.     

Structural characterization of Th-doped TiO2 photocatalyst and its extension of response to solar light for photocatalytic oxidation of oryzalin pesticide: a comparative study

The degradation efficiency of Th-doped TiO₂ / TiO₂ photocatalysts were investigated under UV and solar light illumination. The model compound chosen for the study was Oryzalin (OZ). Doping of inner transition metal ion Th was intended to modify the electronic properties of TiO₂. The Th-doped TiO₂ were synthesized by incorporating 0.02, 0.04, 0.06, and 0.1 atom percentage of Th into the TiO₂ lattice by solid-state reaction. The stochiometry of the prepared samples is Ti_1−xTh_xO₂, where ‘x’ is the percentage of Th. The samples were characterized by UV-Visible absorption, UV-Visible -Diffused reflectance spectra, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX) and X-ray Diffraction (XRD). The pore size and surface area of these samples were studied by Brunauer, Emmett and Teller (BET) adsorption method. It was found that metal ion doping at various percentage compositions enables a large shift in the absorption band of the TiO₂ towards visible light region. This is due to the formation of various mid band gaps at 2.84 eV, 2.804 eV, 2.66 eV, and 2.55 eV. The extent of degradation of the pesticide was followed by UV-Visible spectroscopy and GC-MS methods. Based on the spectral analysis, the probable degradation reaction mechanism for OZ is proposed. These results indicate that Th-doped TiO₂ with the modified electronic properties is a good catalyst under solar light irradiation. But these particles show marginal variation in rates under UV-illumination. All the photodegradation reactions follow the first order kinetics.      

Roles of Oxygen Vacancies of CeO2 and Mn-Doped CeO2 with the Same Morphology in Benzene Catalytic Oxidation

Mn-doped CeO₂ and CeO₂ with the same morphology (nanofiber and nanocube) have been synthesized through hydrothermal method. When applied to benzene oxidation, the catalytic performance of Mn-doped CeO₂ is better than that of CeO₂, due to the difference of the concentration of O vacancy. Compared to CeO₂ with the same morphology, more oxygen vacancies were generated on the surface of Mn-doped CeO₂, due to the replacement of Ce ion with Mn ion. The lattice replacement has been analyzed through XRD, Raman, electron energy loss spectroscopy and electron paramagnetic resonance technology. The formation energies of oxygen vacancy on the different exposed crystal planes such as (110) and (100) for Mn-doped CeO₂ were calculated by the density functional theory (DFT). The results show that the oxygen vacancy is easier to be formed on the (110) plane. Other factors influencing catalytic behavior have also been investigated, indicating that the surface oxygen vacancy plays a crucial role in catalytic reaction.     

Reactivity investigations of some chosen peroxo-vanadium(V), manganese(III) and chromium(VI) compounds

An interpretative account of the results of reactions in aqueous medium of a highly peroxygenated vanadium(V) complex, K [V(O_{2 3}]·3H₂O, with different organic and inorganic substrates is presented. The reactions were monitored by solution EPR spectroscopy and isolation of products at different stages of the reactions. Redox reactions between diperoxide, K[VO(O₂)₂(H₂O)] and VOSO₄ were conducted. The results of the investigation suggest that secondary oxygen exchange-reaction occurs which not only depends on but also utilises the intermediates in the primary reaction during diperoxovanadate-dependent oxidation of VOSO₄. In an interesting reactiontris(acetylacetonato)-manganese(III), Mn(acac)₃, on being reacted with a hydrogen peroxide adduct, KF·H₂O₂, and bpy and phen afforded crystalline [Mn(acac)₂(bpy)] and [Mn(acac)₂(phen)], respectively. The X-ray structural analysis of [Mn(acac)₂(phen)] showed that the compound crystallised in orthorhombic space groupPbcn. The structure consists of a pseudooctahedral Mn(II) ion being bound to two acac⁻(C₅H₅O ₂ ⁻ ) and a phen ligand with the molecule lying on two-fold axis. Reactivity profiles of two new chromium(VI) reagents viz., pyridinium fluorochromate, C₅H₅NH[CrO₃F] (PFC), and quinolinium fluorochromate C₉H₇NH [CrO₃F] (QFC), have been presented. The compounds are capable of acting as both electron-transfer and oxygen-atom-transfer agents. The X-ray analysis of PFC crystals reveals that the compound crystallises in the orthorhombic space group CmcZ₁. The structure consists of discrete pyridinium cations and CrO₃ F anions with no significant hydrogen bonding. This results in total disorder of the pyridinium cation. The tetrahedral [CrO₃ F]⁻ ion lies on a crystallographic mirror plane.     

多孔超薄g-C3N4纳米片负载Pt复合材料的制备及其光催化性能

以三聚氰胺为前驱体,通过热氧化刻蚀法制备多孔超薄g-C₃N₄纳米片（CNHS）,将其与氯铂酸钾溶液混合后采用原位光化学还原法成功制备了CNHS负载Pt光催化剂（Pt-CNHS）。使用粉末X射线衍射、场发射扫描电子显微镜、X射线光电子能谱、透射电子显微镜、紫外可见漫反射光谱和N₂吸附-脱附测试等技术对所制备样品的结构、形貌、光吸收特性、光电化学性能和比表面积等进行系统分析。并以气相甲苯为目标降解物,研究其光催化性能。结果表明,相对于体相g-C₃N₄（CNB）和CNHS,Pt的引入可以有效增强催化剂对可见光的吸收能力、响应范围及载流子分离效率。与纯g-C₃N₄和CNHS相比,Pt-CNHS在紫外和可见光照射下均表现出更高的光催化降解气相甲苯的活性。此外,也对Pt-CNHS光催化剂在可见光照射下降解气相甲苯的反应历程做了初步研究。