UHV-MOCVD growth of TiO2 on SiOx/Si(1 1 1): Interfacial properties reflected in the Si 2p photoemission spectra

Metal–organic chemical vapour deposition growth of titanium oxide on moderately pre-oxidised Si(1 1 1) using the titanium(IV) isopropoxide precursor has been studied for two different growth modes, reaction-limited growth at 300 °C and flux-limited growth at 500 °C. The interfacial properties have been characterized by monitoring synchrotron radiation excited Si 2p photoemission spectra. The cross-linking from oxidised Si to bulk Si after TTIP exposure has been found to be very similar to that of SiO_x/Si(1 1 1). However, the results show that the additional oxidation of Si most probably causes a corrugation of the SiO_x/Si interface. Those conclusions are valid for both growth modes. A model is introduced in which the amorphous interface region is described as (TiO₂)_x(SiO₂)_y where x and y changes linearly and continuously over the interface. The model quantifies how (TiO₂)_x(SiO₂)_y mixing changes the relative intensities of the signals from silicon oxide and silicon. The method can be generalised and used for the analyses of other metal-oxides on silicon.     

Formation of luminescent (NH4)2SiF6 phase from vapour etching-based porous silicon

In this paper we describe the formation of a luminescent (NH₄)₂SiF₆ via porous silicon (PS) obtained from HNO₃/HF vapour etching (VE) silicon (Si) substrates. It was found that at specific conditions, PS transforms in a luminescent thick white powder (WP) layer. Scanning electron microscopy (SEM) revealed that the WP has a coral-like structure. It was also found that PS persists as an intermediate layer between the Si substrate and the WP, and seems to be the seed that transforms into the WP. SEM microanalysis show that the WP is essentially composed of silicon (Si), nitrogen (N) and fluorine (F). Fourier transform infrared (FTIR) spectroscopy investigations show that this WP contains SiF₆²⁻ and NH₄⁺ ions and N---H chemical bonds. X-ray diffraction (XRD) patterns of the WP confirm that a (NH₄)₂SiF₆ cubic phase is concerned. SEM microanalyses show an excess of Si in the WP matrix. FTIR spectroscopy and XRD analysis reveal the presence of crystalline Si particles and SiO_x, both originating from the excess of Si. The (NH₄)₂SiF₆ WP phase emits an intense photoluminescence (PL) band, shifted towards higher energies as compared to the starting PS layer. The possible origin and mechanism of the luminescence emission was discussed taking into account the ability of small SiO_x-surrounded Si particles to emit PL at rather high energy. The wide range variation of the thickness of the (NH₄)₂SiF₆ WP may be easily used for the grooving of Si wafers.     

In situ X-ray photoelectron spectroscopy study of the oxidation of CuGaSe2

The thermal and native oxidation of CuGaSe₂ thin films was studied by in situ X-ray photoelectron spectroscopy (XPS). The special design of the XPS chamber allowed to measure XP-spectra under oxidizing gas atmospheres at pressures of up to 5 mbar (in situ) or in ultra high vacuum (UHV). During thermal oxidation, the formation of predominantly Ga₂O₃ and some amount of SeO₂ were observed, but no copper oxides could be detected in the near surface region of the thin films. The same oxides were found after native oxidation in air under ambient conditions. Only after long term native oxidation for longer than 4 months Cu(OH)₂ was detected. An additional sodium oxide compound formed at the thin film surface, Na_xO and Na₂CO₃ after thermal and native oxidation, respectively. The amount of these sodium oxide compounds depends on the Na content on the as prepared surface. The formation of SeO₂ under humid conditions at 100 °C was found to depend on the surface composition of the thin film.     

飞秒脉冲激光辐照对硅发光性能的影响

利用飞秒脉冲激光对单晶硅进行辐照,研究了在不同环境(纯水和空气)和能量密度条件下激光刻蚀过后硅片的光致荧光特性.对于辐照后的硅片,利用了场发射扫描电子显微镜(FESEM)、能谱仪(EDS)、傅里叶红外光谱仪(FT-IR)、光致荧光光谱仪(PL)进行表征.结果显示:在空气中样品表面形成了条纹状微结构,纯水中硅片表面生成了尺寸更小的珊瑚状微结构;激光刻蚀后在硅片表面的生成物主要是SiOx(x2),在纯水中处理后硅片氧元素的含量接近是空气中的4倍;傅里叶变换红外透射谱中主要为Si—Si键(610 cm-1)和Si—O—Si键(1105 cm-1)的振动;在空气和纯水中激发出的荧光均为蓝光(420—470 nm),在各自最佳激发波长下,纯水中荧光强度比空气中强2到3倍,但是在可见光范围内荧光峰的位置和形状都基本没有发生变化.研究表明:氧元素在光致发光增强上起着重要作用,光致发光最主要是由形成的氧缺陷SiOx(x2)导致的,生成低值氧化物SiOx的多少决定了发光的强弱.     

Room temperature NO_2 gas sensing of Au-loaded tungsten oxide nanowires/porous silicon hybrid structure

In this work, we report an enhanced nitrogen dioxide(NO_2) gas sensor based on tungsten oxide(WO_3)nanowires/porous silicon(PS) decorated with gold(Au) nanoparticles. Au-loaded WO_3 nanowires with diameters of 10 nm–25 nm and lengths of 300 nm–500 nm are fabricated by the sputtering method on a porous silicon substrate. The high-resolution transmission electron microscopy(HRTEM) micrographs show that Au nanoparticles are uniformly distributed on the surfaces of WO_3 nanowires. The effect of the Au nanoparticles on the NO_2-sensing performance of WO_3 nanowires/porous silicon is investigated over a low concentration range of 0.2 ppm–5 ppm of NO_2 at room temperature(25℃). It is found that the 10-? Au-loaded WO_3 nanowires/porous silicon-based sensor possesses the highest gas response characteristic. The underlying mechanism of the enhanced sensing properties of the Au-loaded WO_3 nanowires/porous silicon is also discussed.     

Density functional theory study of formaldehyde adsorption and decomposition on Co-doped defective CeO_2(110) surface

Formaldehyde as an air pollutant to adverse health effects for humanity has been getting attention. The adsorption and dissociation of formaldehyde(HCHO) on the Co_xCe_(1-x_O_(2-δ)(110) surface were investigated by the density functional theory(DFT) calculations. We calculated the oxygen vacancy formation energy as the function of its site around dopant Co in detail. The results showed that Co doping was accompanied by compensating oxygen hole spontaneous formation.The adsorption configurations and bindings of HCHO at different locations on the Co_xCe_(1-x)O_2(110) were presented.Four possible pathways of oxidation of formaldehyde on the catalytic surface were explored. The results suggested that formaldehyde dissociation at different adsorption sites on the doped CeO_2(110) — first forming dioxymethylene(CH_2O_2)intermediate, and then decomposing into H_2O, H_2, CO_2, and CO molecules. It was found that the presence of cobalt and oxygen vacancy significantly prompted the surface activity of CeO_2.     

Impurity levels of iron-group ions in TiO2(II)

Photocurrent measurements on oxidized, single-crystal TiO₂ undoped and doped with V, Cr, Mn or Fe were made both before and after exposure to white light from a tungsten lamp; they revealed a band of states centered at 2.0 eV below the conduction-band edge E_c that appears to be the band of surface states active in the photoelectrolysis of water. They also revealed a band of bulk states extending from near the valence-band edge E_v to about 1.9 eV below E_c. The ESR signals from V⁴⁺, Cr³⁺ and Fe³⁺ ions in oxidized samples and from Mn³⁺ ions in reduced samples were measured before and after exposure to white and monochromatic light; changes in the ESR signal intensities allow placement of the V⁴⁺: d¹ level about 2.1 eV below E_c, the Cr³⁺: d³ level about 2.7 eV belo E_c, the Fe³⁺ level at or just below the valence band edge E_v which is 3.0 eV below E_c, the Fe²⁺ level approximately at E_c, the Mn³⁺ level about 1.9 eV below E_c. Comparison of experiments on oxidized and reduced samples suggests that the bulk states are associated with cation vacancies, and measurements with polarized light gave anisotropies that are qualitatively interpretable with a cation-vacancy model for the oxidized samples.     

The crystallization kinetics of sodalites grown by the hydrothermal transformation of kaolinite studied by Si MAS NMR

The hydrothermal transformation of kaolinite to basic sodalite Na₈[AlSiO₄]₆ (OH · H₂O)₂ and hydroxoborate sodalite Na₈[AlSiO₄]₆ [B(OH)₄]₂ has been investigated at different temperatures (353 and 473 K). In the early stage of the reactions, the crystallization kinetics was studied by X-ray powder diffraction, thermogravimetry, IR spectroscopy and ²⁹Si MAS NMR spectroscopy. Besides the crystallization of the sodalites, no further intermediate phases were formed. MAS NMR of the ²⁹Si nucleus has been found to be a versatile tool to follow the progress of reactions from the signal ratio of the initial material and the crystallization product because the differences in chemical shifts result in well-separated signals. From these measurements, the growth rates of the sodalites could be determined quantitatively even for the very early stages of crystallization. It was found that sodium carbonate impurities in the NaOH solution used for the synthesis has an important influence on the reaction kinetics.     

薄膜硅/晶体硅异质结电池中本征硅薄膜钝化层的性质及光发射谱研究

本文采用甚高频等离子体化学气相沉积技术 (VHF-PECVD) 制备薄膜硅/晶体硅异质结电池中的本征硅薄膜钝化层, 光发射谱 (OES) 测量技术研究了硅薄膜沉积过程中等离子体发光谱随时间的变化. 结果表明: 在实验优化条件下等离子体发光谱很快达到稳定 (大约25 s), 并且SiH^*/H_α^* 的比值随时间变化较小, 避免了生长过程中硅薄膜结构的不均匀性, 这主要是SiH₄没有完全耗尽避免了SiH₄的反向扩散. 进一步研究了沉积参数对稳态发光谱和硅薄膜性质的影响, 结果表明: 随着硅烷浓度增加, H_α^*峰强度减小, SiH^*峰强度增加, 薄膜从微晶转变成非晶, 非晶硅薄膜钝化效果好; 随着沉积气压增大, H_α^*和 SiH^*峰强度先增加后减小, 高气压下H_α^*和 SiH^*峰强度下降主要是反应前驱物的聚合形成高聚合物, 不利于形成高质量的硅薄膜, 因此钝化效果下降; 随着反应功率密度增加, H_α^*和 SiH^*峰强度增大, 当功率密度为150 mW/cm² 趋于饱和, 硅薄膜的致密度和钝化效果也开始下降, 50 mW/cm²的低功率密度下硅薄膜钝化效果差可能是由于原子H 浓度低, 不能完全钝化单晶硅表面的悬挂键. 关键词： 薄膜硅 异质结 光发射谱 钝化     

Ln1−xSrxCoO3(Ln = Sm, Dy) for the electrode of solid oxide fuel cells

The perovskite-type oxides were synthesized in the series of Ln_1−xSr_xCoO₃(Ln = Sm, Dy). The formation of solid solutions in Dy_{1 − x}Sr_xCoO₃ was limited, compared with that in Sm_{1 − x}Sr_xCoO₃. The electrical conductivities of the sintered samples were measured as a function of x in the temperature range 30 to 1000 °C. The highest conductivity of around 500 S/cm at 1000 °C was found in Sm_0.7Sr_0.3CoO₃. The reactivity of all the samples with YSZ was examined at 800–1000 °C for 96 h. The Sr-doped perovskite oxides were more reactive with YSZ and produced SrZrO₃ at 900 °C after 96 h. However, no reaction product between SmCoO₃ and YSZ was observed at 1000 °C for 96 h. The cathodic polarization of the oxide electrodes, sputtered on yttria stabilized zirconia (YSZ), was studied at 800–1000 °C in air. SmCoO₃ shows no degradation of the electrode performance at higher temperatures. The thermal expansion measurements on the sintered samples were carried out from room temperature to 1000 °C. Large thermal expansion coefficients were found in these samples.     

Synthesis and investigation of the complex copper oxides Bi2Sr2R2−xCexCu2O10+δ (R=rare earth)

Bi-2222 phases were prepared by solid state reactions and were studied using X-ray diffraction, chemical and EDS-analysis. Compounds with composition Bi₂Sr₂R_1.33Ce_0.67Cu₂O_10+δ were obtained for R=Pr, Nd, Sm-Er. The phases Bi₂Sr₂Cu₂O_10+δ with similar structure but without Ce were prepared for R = Pr, Sm-Dy. For Bi₂Sr₂Eu_2−xCe_xCu₂O_10+δ the solubility limit was determined and the effect of treatment under different oxygen pressures was investigated. Weak diamagnetic signals (<3%) were detected for some of these samples.     

Time-resolved photoluminescence study of the red emission in nanoporous SiGe alloys

Porous Si_1−xGe_x (PSiGe) layers with efficient room temperature visible photoluminescence (PL) were elaborated by anodical etching from p-type doped epitaxial layers with Ge contents from 5 to 30%. The luminescence is characterised by a broad PL band centred at 1.8 eV. Time resolved photoluminescence decay is studied in porous silicon germanium as a function of germanium content, temperature, emission energies and surface passivation. The PL decay line shape is well described by a stretched exponential in all cases. The effective lifetime at low temperature in as prepared porous Si_1−xGe_x is 400 μs, i.e. an order of magnitude less than in porous silicon. After the formation of a 20 Å thick oxide surface layer we observe a decrease of the effective lifetime to 20 μs at T=4 K.     

便携式FTIR的机动车尾气检测方法

随着汽车排放标准的提高,相关VOC标准从总烃检测变为非甲烷碳氢化合物(NMHC)检测;随着含氧燃料的增加,增加了非甲烷有机气体(NMOG)测量.针对国内汽车尾气分析仪分析组分单一、精度有限、VOCs检测过程复杂等问题,提出了基于便携式FTIR的机动车尾气检测方法,基于立体角镜优化FTIR光学系统结构,提高动镜扫描速度,...     

Preparation and room temperature NO_2-sensing performances of porous silicon/V_2O_5nanorods

In this paper, porous silicon/V₂O₅ nanorod composites are prepared by a heating process of as-sputtered V film on porous silicon (PS) at 600 ℃ for different times (15, 30, and 45 min) in air. The morphologies and crystal structures of the samples are investigated by field emission scanning electron microscope (FESEM), x-ray diffractometer (XRD), x-ray photoelectron spectroscopy (XPS), and Raman spectrum (RS). An improved understanding of the growth process of V₂O₅ nanorods on PS is presented. The gas sensing properties of samples are measured for NO₂ gas of 0.25 ppm～3 ppm at 25 ℃. We investigate the effects of the annealing time on the NO₂-sensing performances of the samples. The sample obtained at 600 ℃ for 30 min exhibits a very strong response and fast response-recovery rate to ppm level NO₂, indicating a p-type semiconducting behavior. The XPS analysis reveals that the heating process for 30 min produces the biggest number of oxygen vacancies in the nanorods, which is highly beneficial to gas sensing. The significant NO₂ sensing performance of the sample obtained at 600 ℃ for 30 min probably is due to the strong amplification effect of the heterojunction between PS and V₂O₅ and a large number of oxygen vacancies in the nanorods.     

Improvement of electrochemical properties of the spinel LiMn2O4 using a Cr dopant effect

A series of LiCr_xMn_2−xO₄ spinels were synthesised by the Pechini method which enables dopant Cr ions to distribute at Mn sites homogeneously. Neutron diffraction and EDS analysis confirmed that Cr ions do occupy 16d sites (octahedral intestial) evenly in the spinel structure. The Cr dopant effect improves the cyclability of spinel LiMn₂O₄ electrodes and decreases the self-discharge rate substantially. Cyclic voltammetry and AC impedance spectroscopy were employed to characterise the reactions of lithium insertion into and extraction from LiCr_xMn_2−xO₄ electrodes. It was found that a thicker surface layer was formed on the surface of the pure LiMn₂O₄ electrode than on the LiMn₂O₄ electrode.     

Stray-field imaging of quadrupolar nuclei of half integer spin in solids

A report is presented on the observation of Hahn echoes from the following quadrupolar nuclei of half integer spin (I) in polycrystalline solids in the large static magnetic field gradient (37.5 T/m) which exists in the fringe field of a superconducting solenoid: ⁷Li, ²³Na, ¹¹B, ⁶⁵Cu (I = 3/2); ²⁷Al (I = 5/2); ⁵¹V, ⁵⁹Co (I = 7/2); and ¹¹⁵In (I = 9/2). ²³Na echo-trains from NaCl (with non-selective excitation) and from Na₂SO₄ (with selective excitation) are compared quantitatively for two different RF pulse sequences: 90_x-(τ-90_y-τ-echo-)_n and 90_x-(τ-90_x-τ-echo-)_n. The signals obtained from RF pulses corresponding to non-selective 90 ° pulses were shown to be quantitative, whereas in the selective case smaller signals were obtained since only the central transition contributed. The loss of signal from this cause can be distinguished from small signals resulting from low density of nuclei by use of the second sequence. A ⁷Li image obtained from LiF in a cylindrical glass-vial is shown.     

PECVD分层结构对提高氢化非晶硅TFT迁移率的影响

为了进一步提高氢化非晶硅薄膜晶体管 (a-Si:H TFT) 的场效应电子迁移率, 研究了批量生产条件下对欧姆接触层和栅极绝缘层进行多层 制备, 不同的工艺参数对a-Si:H TFT场效应电子迁移率的影响. 研究表明随着对欧姆接触层 (n⁺层) 分层数的增加, 以及低速生长的栅极绝缘层 (GL层) 和高速生长的栅极绝缘层 (GH 层) 厚度比值提高, a-Si:H TFT的场效应迁移率得到提升. 当n⁺层分层数达到 3层, GL层和GH层厚度比值为4:11 时, 器件的场效应电子迁移率达到0.66 cm²/V·s, 比传统工艺提高了约一倍, 显著改善了a-Si:H TFT 的电学特性, 并在量产线上得到了验证. 关键词： 非晶硅薄膜晶体管 电子迁移率 欧姆接触层 栅极绝缘层     

31P NMR表面线圈探头射频场B1的空间分布特性研究

对本实验室自制的³¹P表面线圈探头的射频场B₁强度的空间分布和脉冲宽度进行了初步研究.结果表明该表面线圈中心的90°脉冲约为10μs.得到的信号主要是线圈圆周内射频场B₁作用的结果,在垂直线圈平面的方向上随距离增加,信号迅速减弱.因此该表面线圈射频场B₁有效的作用范围在一个近半圆球体内,底面积半径约为线圈外半径,有效作用深度约为线圈半径.     

银纳米颗粒/多孔硅复合材料的制备与气敏性能研究

采用双槽电化学腐蚀法以电阻率为10-15 Ω·cm的p型<100>晶向的单晶硅片制备了孔径约为1.5 μm, 孔深约为15-20 μm的p型多孔硅, 并以此多孔硅作为基底采用无电沉积法通过调控沉积时间在其表面沉积了不同厚度的银纳米颗粒薄膜. 采用扫描电子显微镜和X 射线衍射仪表征了银纳米颗粒/多孔硅复合材料的形貌和微观结构, 结果表明银纳米颗粒较均匀的分布于多孔硅的表面上且沉积时间对产物的形貌有重要影响. 采用静态配气法在室温下研究了银纳米颗粒/多孔硅复合材料对NH₃的气敏性能. 气敏测试结果表明沉积时间对产物的气敏性能影响较大. 当沉积时间较短时, 适量银纳米颗粒掺杂的多孔硅复合材料由于其较高的比表面积以及特殊的形貌和结构, 对NH₃气体表现出较高的灵敏度、优良的响应/恢复性能. 室温下, 其对50 ppm 的NH₃气体的气敏灵敏度可以达到5.8左右.     

C掺杂Mn3Ge的电子结构和磁性

采用第一性原理计算方法研究C掺杂对Mn₃Ge的影响.对Mn_3-xGeC_x的晶体结构进行几何优化,发现C原子最稳定的掺杂位置在正八面体的中心位置.研究其电子结构和总磁矩随C掺杂量的变化,发现总磁矩随着C浓度的增加先减小后增大,其中Mn₃GeC_0.4总磁矩接近零,可以实现完全的磁性补偿.研究Mn₃GeC_0.4多层膜的磁性,给出总磁矩接近零的Mn₃GeC_0.4多层膜结构,为Mn₃Ge的实际应用提供参考.