多孔硅成核的电化学研究

将p型单晶硅在HF溶液中进行阳极电化学腐蚀制备出孔隙率约为30%~85%、直径为2~30nm不等的多孔硅,用原子力显微镜(AFM)观察其表面形貌。采用电化学工作站(CHI660A)监测p型硅电极在不同浓度HF溶液中的电流-电压特性,记录恒电流情况下硅电极的电压变化。这些曲线可从精确反映多孔硅形成的早期成核过程。将这些电化学特性曲线在同一坐标轴下显示,得出多孔硅的电化学成核机理。     

碱性水溶液中甲醛在硅电极表面的电化学行为及其对硅化学刻蚀的影响

研究了KOH水溶液中氧化剂甲醛在p-Si和n-Si(100)单晶半导体电极表面的电化学行为及其对硅化学刻蚀表面形貌的影响．实验结果表明,甲醛不仅影响p-和n-型半导体电极在碱性溶液中的阳极氧化峰电流,而且在负电位区能在Si(100)电极上发生还原．在光照条件下,p-Si(100)电极上也观测到了HCHO的电化学还原及光电流倍增效应．甲醛在硅电极表面的电化学还原反应分两步进行,反应终产物为甲醇．此外,HCHO能有效抑制碱性溶液中Si表面“金字塔”型表面粗糙颗粒的形成。     

光照强度和掺杂浓度对n-PS形貌和电化学行为影响

测试分析了光照强度和掺杂浓度对n型硅电极电化学特性的影响。采用电化学阳极腐蚀法在光照辅助下制备多孔硅(PS),通过扫描电镜研究掺杂浓度对PS表面微观形貌的影响,通过积分球测试仪测试研究了PS对光的反射率。结果表明,对于n型硅,光照是激发空穴的必要手段,光照强度越强,硅/电解液界面的电荷转移阻抗越小,更利于反应的进行;掺杂浓度越高,电化学极化阻力越小,促进PS孔密度增加。本实验条件下,形成的PS是微米级孔,随着掺杂浓度的增加,形成的PS孔径越小,孔深存在一个极值;电阻率为0.35Ω·cm的硅片拥有最大的孔深13μm;PS的孔结构大大提升了硅基对光子的捕获能力,相比于单晶硅,在可见-近红外范围,电阻率为0.0047Ω·cm的硅片制备的n-PS对光的反射率已经从30%降低到了5%。     

光照强度和掺杂浓度对多孔硅形貌和电化学行为的影响

测试分析了光照强度和掺杂浓度对n型硅电极电化学特性的影响。采用电化学阳极腐蚀法在光照辅助下制备多孔硅(PS),通过扫描电镜研究掺杂浓度对PS表面微观形貌的影响,通过积分球测试仪测试研究了PS对光的反射率。结果表明,对于n型硅,光照是激发空穴的必要手段,光照强度越强,硅/电解液界面的电荷转移阻抗越小,更利于反应的进行;掺杂浓度越高,电化学极化阻力越小,促进PS孔密度增加。本实验条件下,形成的PS是微米级孔,随着掺杂浓度的增加,形成的PS孔径越小,孔深存在一个极值;电阻率为0.35Ω·cm的硅片拥有最大的孔深13μm;PS的孔结构大大提升了硅基对光子的捕获能力,相比于单晶硅,在可见-近红外范围,电阻率为0.0047Ω·cm的硅片制备的n-PS对光的反射率已经从30%降低到了5%。     

硅片表面多金属污染的交流阻抗表征

在接近氢氟酸实际应用浓度条件下, 利用交流阻抗技术研究了硅片表面金属微观污染行为, 在氢氟酸溶液中分别加入0.5和1 mg/g的铜、铁、镍、钙四种金属离子, 获得了硅片在单金属溶液中的特征交流阻抗谱, 并在此基础上研究了三种金属及四种金属共存时的特征交流阻抗谱, 通过等效电路的拟合估算了硅/氢氟酸界面电化学反应的动力学参数, 并结合扫描电镜形貌图探讨了不同类型的单金属和多金属对硅电化学行为的影响. 结果表明, 多金属微观污染是各种单金属协同作用的结果, 铜在硅片上发生电化学沉积, 直接导致硅片表面粗糙化. 铁对硅片表面的破坏严重, 同时影响铜的沉积. 镍的存在使硅片表面更容易氧化. 而钙通过在硅片表面形成氟化钙沉淀物可以钝化表面, 减缓铜在硅片表面的沉积.     

蛋氨酸衍生物缓蚀剂的合成与性能研究

以蛋氨酸为基础通过酰胺化反应合成一种新型的蛋氨酸衍生物缓蚀剂,应用极化曲线、电化学阻抗谱图研究蛋氨酸及其衍生物在3(wt)%Na Cl溶液中对N80碳钢的缓蚀作用,利用SEM观察添加缓蚀剂过后钢片表面的腐蚀形貌,并从分子结构上探讨了缓蚀剂在碳钢表面的作用机理。结果表明,蛋氨酸及其衍生物都属于阳极型缓蚀剂,且缓蚀率随着添加浓度增加而增加,添加250mg/L蛋氨酸衍生物在3(wt)%Na Cl溶液中对N80碳钢的缓蚀率达到86.94%。相同浓度条件下蛋氨酸衍生物的缓蚀率要高于蛋氨酸,其原因是蛋氨酸衍生物分子结构中增加了吸附位点和疏水长链。     

液膜分离富集、测定痕量钼

用乳状液膜体系对钼进行富集。该体系包括载体 ( 5,8-二乙基 - 7-羟基十二烷 - 6-单肟 ,简称LIX63)、表面活性剂 (N1 1 3C)、溶剂(煤油 )以及内相 ( 0 .1 5mol/LNaOH溶液 )。研究了乳状液膜的稳定性、温度、钼的浓度、外相的HNO3溶液浓度及乳水比等因素对分离富集钼的影响。实验表明 ,在适宜的条件下 ,钼的迁移率可达 99.5%～1 0 0 .2 %。该法已应用于富集、测定纯钨和钢铁中的痕量钼 ,结果相当满意     

硫酸根离子对铁在弱碱性溶液中阳极溶解和钝化行为的影响

采用浸泡实验, 电化学测试和表面分析技术研究了硫酸根离子浓度对铁在稀碳酸氢钠溶液中开路状态和阳极极化行为的影响. 在无硫酸根离子及含有少量硫酸根离子的碳酸氢钠溶液中, 铁的开路电位约为(-0.225±0.005) V, 并呈现钝化状态, 其电化学阻抗很大, 腐蚀速率较低. 在含有较高浓度硫酸根离子的碳酸氢钠溶液中, 铁的开路电位为(-0.790±0.010) V并呈现活性溶解状态, 其电化学阻抗较小, 腐蚀速率较高, 同时阳极极化曲线上能观察到活化-钝化转变现象. 由于铁在含有较高浓度硫酸根离子的碳酸氢钠溶液中处于活化状态, 阳极极化曲线上存在数个电流峰. 足够高的硫酸根离子浓度会导致铁表面预先形成或转变而成的氧化膜失效. 相比于自然曝氧状态, 在除氧条件下较低的硫酸根离子浓度即可引起铁在碳酸氢钠溶液中由钝态向活性溶解态的转变.     

两步法制备多孔硅及其表征I:恒电流法(英文)

本工作通过采用电化学极 -化学氧化两步法在 1:1氢氟酸和乙醇溶液中制备出孔径约为 1～ 2 μm ,厚度大经为 6～ 10 μm的多孔硅样品 .首先将 0 .0 3A/cm2 的恒电流施加到p( 10 0 )硅片一段时间 ,然后将该硅片浸到 2 0 %的硝酸溶液中氧化一段时间 .通过此方法获得的多孔硅结构再进一步用扫描电子显微镜和拉曼光谱仪进行表面形貌和光学性质的考察 .所有制备出的多孔硅结构均有光致发光现象 .老化的多孔硅样品 (在干燥器放置一年 )的光致发光谱峰强度明显增强 ,但分别经过苯乙烯和十六碳烯 ( 1)两种有机溶剂处理 1h后的老化多孔硅样品的光致发光强度却没有显著改变 .     

碳量子点@纳米Co_3O_4生物传感器检测人血清中尿酸

通过静电纺丝法合成了纳米四氧化三钴(C_3O_4),使用滴涂法将碳量子点(CDs)和纳米C_3O_4的混合溶液修饰到玻碳电极(GCE)表面,制备了CDs@C_3O_4/GCE,研究了该修饰电极的电化学性质以及尿酸在CDs@C_3O_4/GCE上的电化学行为。结果表明,CDs@C_3O_4/GCE对尿酸的氧化反应具有催化作用。在最优条件下,尿酸的氧化峰电流与尿酸浓度在1. 0×10~(-8)～1. 0×10~(-4)mol/L范围内呈现线性关系,检出限为3. 3 nmol/L,对实际样品进行加标回收试验,加标回收率为98. 0%～106. 5%,该传感器可用于人血清中尿酸含量的测定。     

SWELLING BEHAVIOR OF ACRYLAMIDE HYDROGEL IN DIFFERENT SOLVENTS AND pHs

Swelling property of acrylamide hydrogels, prepared from aqueous solutions of acrylamide monomer having concentrations in the range of 10-60 wt% by γ-ray irradiation method using a Co-60 gamma radiation source at doses ranging 1-30.0 kGy, has been investigated under various swelling media. These swelling media were basically solvents (solutions), produced by dissolving methanol, ethanol, glucose, sucrose, sodium chloride and sodium persulfate individually with distilled water, and solutions prepared with pHs = 3, 7 and 10. The investigation was performed in order to observe the effect of these solvents and pHs as well as the influence of monomer concentrations, radiation doses and times on swelling behavior of hydrogels. Swelling values were found higher for hydrogels prepared with lower monomer concentrations (ca.20 wt%) and radiation doses (ca. 5 kGy) and showed a leveling off tendency within 24 h. The glucose solvent and the buffer solution of pH = 10 revealed significant increase of swelling of hydrogels as compared to other solutions. Results are explained based on crosslinking density in hydrogel, polymer-solvent/polymer-polymer interactions in solutions,permeability of molecules in solutions and ionization capacity of hydrogel in pH.     

Analysis of high purity graphite and silicon carbide by direct solid sampling electrothermal atomic absorption spectrometry

Solid sampling electrothermal atomic absorption spectrometry using the boat technique and a transversely heated graphite tube was applied to direct analysis of graphite and silicon carbide powders for 14 and 12 impurity elements, respectively. With graphite, for all analytes under investigation, a very effective in-situ analyte/matrix separation was achieved. That was the case also for analytes in silicon carbide requiring atomization temperatures below 2400 degrees C. At higher atomization temperatures, the decomposition products of silicon carbide give rise to significant background, which can still be corrected. Sample amounts of up to 4 mg graphite and 8 mg silicon carbide per analysis cycle were applied. For all analytes in both materials, limits of detection at the lower ng g(-1) and sub-ng g(-1) level were achieved, excluding arsenic for which they were 50 ng g(-1) and 23 ng g(-1) for graphite and silicon carbide, respectively. Quantification was performed using calibration curves measured with aqueous standard solutions. The accuracy was checked by comparison of the results with those obtained by instrumental neutron activation analysis and by other independent methods.     

Dynamic Surface Properties of Poly(vinylpyrrolidone) Solutions

The dynamic surface tension and the complex dynamic surface elasticity of poly(vinylpyrrolidone) (PVP) solutions were measured in the concentration range 10(-5) wt% up to about 1 wt%. The surface tension changed slowly with time at low (<10(-4) wt%) and high concentrations (>0.1 wt%). At low concentrations this is a consequence of the slow transport by diffusion of PVP molecules from the depth of the bulk phase to the surface. At high concentrations the time effect is unexpected and probably the result of PVP contamination of high surface activity. The dynamic surface elasticity of PVP solutions gradually decreases with increasing concentration up to the range of high concentrations (>0.1 wt%) where an abrupt increase in the elasticity caused by the adsorbed impurity is observed. At low and medium concentrations the viscoelastic behavior of PVP adsorbed films is similar to that of the previously investigated poly(ethylene oxide) and poly(ethylene glycol) films and is determined by the number of loops and tails protruding into the bulk phase.     

Hybrid silica-organic material with immobilized amino groups: surface probing and use for electrochemical determination of nitrite ions

A sol–gel based hybrid process was developed by manipulating different techniques in sol–gel process to synthesize γ-alumina and (CuO, CuO + ZnO) doped γ-alumina spherical particles. Catalysts having spherical geometry have an important advantage over powders or pellets which are impervious to fluids, when packed in a reactor. Boehmite sol was used as alumina precursor for synthesizing porous γ-alumina and doped materials. γ-alumina particles having 5 wt% CuO, 4 wt% CuO + 1 wt% ZnO, 3 wt% CuO + 2 wt% ZnO and 2 wt% CuO + 3 wt% ZnO were prepared by adding required amounts of Cu(NO₃)₂ and Zn(NO₃)₂ solutions prior to gelation of the sol. Methanol dehydration studies were carried out by employing these synthesized catalysts. Hundred percent conversion of methanol to dimethyl ether was observed with (4 wt% CuO + 1 wt% ZnO)-γ-alumina and (5 wt% CuO)-γ-alumina microspheres at 325 and 350 °C, respectively.     

Determination of antimony dopant and some ultra-trace elements in semiconductor silicon by atomic absorption spectrometry with introduction of solid samples into the furnace

Antimony as a dopant at a level of ca. 35 atom/10⁶ atoms (ppm, atomic) and ultra-trace concentrations of lead and manganese (<0.02 ppm, atomic) are determined in semiconductor silicon by atomic absorption spectrometry after introduction of milligram samples of silicon to a pyrolytically-coated graphite furnace. Calibration was done with standard aqueous solutions. Iron, silver, zinc and cadmium were sought but were at concentrations below the limits of detection. The graphite microboats used for sample introduction were useful for only 3–10 samples because of silicon carbide formation.     

ALL-trans RETINAL PHOTOISOMERIZATION AND PHOTOOXIDATION FROM UV LASER RADIATION. VIBRATIONAL ASSIGNMENTS OF ALL-trans 5,8-PEROXYRETINAL

Abstract— Photoisomerization and photooxygenation of all- trans retinal in acetonitrile, illuminated by laser radiations (λ_act, = 333.6 or 350.7 nm), were investigated under various experimental conditions. In deoxygenated solutions, the major photoproducts are 13- cis and 9- cis retinal. All- trans and 13- cis 5,8-peroxyretinal are obtained in large amounts in oxygenated solutions. 11-cis derivatives have not been detected in any of these solutions. The photoproducts were identified by UV, NMR, mass and vibrational spectroscopies and HPLC chromatography. All- trans and 13- cis 5,8-peroxyretinal were isolated. Their vibrational spectra (IR and Raman) are analyzed. Most of the bands are assigned by comparison with previous studies on all- trans and 13- cis retinal, ( E,E,E )-3-methyl-2,4,6-octatrienal and peroxides.     

Silicon nitride synthesis in an atmospheric pressure convection—Stabilized arc

Submicron -, -, and amorphous-phase silicon nitride particles have been synthesized in an experimental plasma reactor, using metallic silicon and ammonia as reactants. Injection of ammonia at different locations of the reactor results in different yields. A maximum yield of 85 wt% has been achieved by injecting NH₃ at both downstream and upstream locations of the reactor. The powders synthesized in this way contained approximately 60 wt% silicon nitride in crystal form with equal amounts of and phases. The remainder consisted of the amorphous phase. The average size of the particles ranged from 50 to 90 nm, with a standard deviation of 1.47–1.87 depending on the location of ammonia injection. Seeding with 1 and 10 wt% of preexisting silicon nitride particles for fostering heterogeneous nucleation did not improve the yield, but it changed the particle size distribution.     

Potential induced tuning of the luminescence of porous silicon: A simultaneous study of electroluminescence and photoluminescence emission

The voltage dependence of light emission from illuminated porous silicon samples immersed in solutions containing persulfate anions was studied. It is reported that the signal obtained is not simply the sum of the individual photoluminescence and electroluminescence signals. The ‘cross-talk’ observed is discussed in terms of a previously proposed mechanism of photoluminescence and electroluminescence potential tuning. It is shown that a mechanism involving radiative quenching by an Auger process is consistent with the results obtained.     

Preparation of Poly(acrylic acid) Nano-films by In-situ Polymerization of Acrylic Acid Macroclusters on Silicon Oxide Surfaces

A new method for preparing poly(acrylic acid) (PAA) films on silicon oxide surfaces with smooth morphology has been developed. Acrylic acid (AA) was preferably adsorbed on silicon oxide surfaces in AA/ chloroform binary liquids and formed a hydrogen-bonded organized structure, which was called molecular macrocluster. AA macroclusters on silicon oxide surfaces were in-situ polymerized to obtain molecularly flat polymer films with thickness up to 10 nm. In-situ polymerizations were conducted by photo-irradiation in the presence of a photo initiator, 2,2-dimethoxy-2-phenylacetophenone (DPA). As a reference, the adsorption of PAA polymerized in the bulk solution was examined on silicon oxide surfaces. A series of techniques such as attenuated total reflection–FTIR (ATR-FTIR) spectroscopy, ellipsometry and atomic force microscopy (AFM) was utilized for characterizing two types of films. It was found that flat PAA films with linear hydrogen-bonded COOH could only be obtained by in-situ polymerization, which demonstrated this method was an effective way for preparing molecularly uniform polymer films. The surface morphology and thickness of obtained PAA films were found to be dependent on the monomer concentration, initiator amount and photoirradiation time. Molecularly uniform and flat PAA films were obtained after 5 min irradiation at 0.8 mol% AA in the presence of 5 wt% DPA.     

Determination of silicon in organic matrices with grazing-emission X-ray fluorescence spectrometry

The potential of a prototype grazing-emission X-ray fluorescence spectrometer for reliable analysis of sample solutions, obtained by pressurized microwave oven digestion of Si-spiked organic and biological materials, was investigated as part of an inter-laboratory study. The fact that this grazing-emission technique is based on the total reflection phenomenon and wavelength-dispersive detection, gives it the benefit to determine light elements in a sensitive way. Results of the determination of silicon in pork liver, cellulose, urine, serum, spinach, beer, mineral water and horsetail (dry plant extract) samples are presented. Some of the results are compared with those obtained with other analytical techniques. The study proved that determination of silicon traces in biological matrices represents an extremely difficult task, however, measurements of silicon are achieved with acceptable precision. The most important problems still arise when sample pre-treatment is needed prior to analysis.