硅纳米孔柱阵列的结构和光学特性研究

采用水热腐蚀技术在单晶硅衬底上制备出一种新的硅微米／纳米结构复合体系——硅纳米孔柱阵列(Si-NPA)，并对其表面形貌、结构及光学特性进行研究.Si-NPA的结构复合性体现为 在微米和纳米两个尺度上形成了三个分明的结构层次，即微米尺度的硅柱阵列结构、硅柱上 的纳米多孔结构以及组成孔壁的硅纳米晶粒.积分光反射谱和荧光光谱测试表明，Si-NPA具 有良好的光吸收和光致发光特性.依据Si－NPA积分反射谱的实验数据，采用Kramers-Kronig 变换关系计算得到了Si-NPA的复折射率和复介电函数、吸收系数等光学常数，并由此讨论了 Si-NPA相对于单晶硅的光学特性发生显著变化的原因.最后，通过分析Si-NPA的光吸收系数 与入射光子能量之间的关系，揭示出Si-NPA具有直接带隙半导体的电子结构特征，而且理论 计算得到的Si-NPA的带隙能与其光致发光谱的峰位能很好符合. 关键词： 硅纳米孔柱阵列 光学特性 电子结构 水热腐蚀     

氧化锌/硅纳米孔柱阵列的结构和光致发光特性研究

以硅纳米孔柱阵列(Si-NPA)为衬底、用化学气相沉积法制备了具有规则阵列结构特征的ZnO/Si-NPA纳米复合体系，并对其结构和光致发光性质进行了表征. 实验结果显示，组成ZnO/Si-NPA表面阵列的每个柱子均呈现层壳结构. 不同于衬底Si-NPA的红光和蓝光发射，ZnO/Si-NPA在紫外光区和蓝绿光区呈现出两个强的宽发光峰. 分析表明，紫外光发射应归因于ZnO晶体的带边激子跃迁；而蓝绿光发射则来自于ZnO晶体本征缺陷所形成的两类深能级复合中心上载流子的辐射跃迁.     

Electronic band structure and optical properties of silicon nanoporous pillar array

Silicon nanoporous pillar array (Si-NPA) is fabricated by hydrothermally etching single crystal silicon (c-Si) wafers in hydrofluoric acid containing ferric nitrate. Microstructure studies disclosed that it is a typical micron/nanometer structural composite system with clear hierarchical structures. The optical parameters of Si-NPA were calculated by general light-absorption theory and Kramers–Kronig relations based on the experimental data of reflectance and the variations compared with the counterparts of c-Si were analyzed. The features of the electronic band structure deduced from the optical measurements strongly indicate that Si-NPA material is a direct-band-gap semiconductor and possesses separated conduction sub-bands which accords with conduction band splitting caused by silicon nanocrystallites several nanometers in size. All these electronic and optical results are due to the quantum confinement effect of the carriers in silicon nanocrystallites.     

Growth process and mechanism of a multi-walled carbon nanotube nest deposited on a silicon nanoporous pillar array

A large scale nest array of multi-walled carbon nanotubes (NACNTs) was grown on silicon nanoporous pillar array (Si-NPA) by thermal chemical vapor deposition. Through observing its macro/micromorphology and structure, ascertaining the catalyst component and its locations at different growth time by hiring field emission scanning electron microscopy, transmission electron microscopy (TEM), high-resolution TEM, and selected area electron diffraction, the growth process was deduced. Its thermal properties were also investigated by using a thermogravimetric analyzer. Our experiments demonstrated that the CNTs growth by means of root-growth mechanism at the initial growth stage, then a continuous growth process with its tip open is suggested, finally, a schematic growth model of NACNT/Si-NPA was presented.     

Forward and reverse electron transport properties across a CdS/Si multi-interface nanoheterojunction

The electron transport behavior across the interface plays an important role in determining the performance of op- toelectronic devices based on heterojunctions. Here through growing CdS thin film on silicon nanoporous pillar array, an untraditional, nonplanar, and multi-interface CdS/Si nanoheterojunction is prepared. The current density versus voltage curve is measured and an obvious rectification effect is observed. Based on the fitting results and model analyses on the forward and reverse conduction characteristics, the electron transport mechanism under low forward bias, high forward bias, and reverse bias are attributed to the Ohmic regime, space-charge-limited current regime, and modified Poole-Frenkel regime respectively. The forward and reverse electrical behaviors are found to be highly related to the distribution of inter- facial trap states and the existence of localized electric field respectively. These results might be helpful for optimizing the preparing procedures to realize high-performance silicon-based CdS optoelectronic devices.     

SERS activity of Au nanoparticles coated on an array of carbon nanotube nested into silicon nanoporous pillar

A novel composite structure, Au nanoparticles coated on a nest-shaped array of carbon nanotube nested into a silicon nanoporous pillar array (Au/NACNT/Si-NPA), was fabricated for surface-enhanced Raman scattering (SERS). The morphology of the Au/NACNT/Si-NPA composite structure was characterized with the aid of scanning electron microscopy, X-ray diffraction instrumentation and Transmission electron microscopy. Compared with SERS of rhodamine 6G (R6G) adsorbed on SERS-active Au substrate reported, the SERS signals of R6G adsorbed on these gold nanoparticles were obviously improved. This was attributed to the enlarged specific surface area for adsorption of target molecules brought by the nest-shaped CNTs structure.     

Structure transition and photoluminescence of CdS/Si nanoheterostructure array on thermal annealing

CdS/Si heterojunctions have been prepared through growing CdS nanocrystallites (nc-CdS) on the silicon nanoporous pillar array (Si-NPA) by the chemical bath deposition method. Cadmium nanocrystallites (nc-Cd) have been observed and ascribed to the reducibility of Si-NPA. The reason for the appearance of CdO is indistinct and the related work will be done in the future. The blue, green and red emissions are ascribed to the silicon oxide layer, band gap of nc-CdS and the sulphur vacancies, respectively. Redshift and blueshift with the annealing temperature about green emissions are contributed to quantum size effect and the structure transition from nc-Cd to CdO. It is beneficial for investigating the structures and defects to the application of CdS/Si in the optoelectronic field.     

Improved surface-enhanced Raman scattering of patterned gold nanoparticles deposited on silicon nanoporous pillar arrays

Large-area silicon nanoporous pillar arrays (Si-NPA) uniformly coated with gold nanoparticles was synthesized, and surface-enhanced Raman scattering of rhodamine 6G adsorbed on these gold nanoparticles were studied and compared. It's found that Au/Si-NPA substrate has a significantly high Raman signal sensitivity and good homogeneity. These are attributed to gold nanoparticles with narrow particle-size distribution uniformly coated on the surface and to the enlarged specific surface area for adsorption of target molecules brought by the porous silicon pillars.     

一种自支撑金纳米薄膜的制备、结构和氮吸附特性

以一种新的硅微米/纳米结构复合体系——硅纳米孔柱阵列作为还原性衬底，采用浸渍技术制备出一种自支撑的金纳米薄膜，并对其表面形貌和结构进行了表征.实验表明，金纳米薄膜的制备过程是一个自终止过程.当硅纳米孔柱阵列被耗尽后，浸渍溶液中Au³⁺的还原反应将自行终止；同时，所形成的金纳米薄膜自动与衬底脱离并成为一种自支撑薄膜.薄膜的形成机理被归因于硅纳米孔柱阵列所具有的高的表面活性和还原性.用能量弥散x射线谱对薄膜表面化学成分分析的结果表明，如此制备的金纳米薄膜具有很强的氮吸附和氮储存能力.这一特性有可能在气体传感器、空气分离和氮纯化以及氮化合物的膜合成器等技术领域得到应用. 关键词： 自支撑金纳米薄膜 硅纳米孔柱阵列 浸渍技术     

Microstructure and blue photoluminescence enhancement of silicon nanoporous pillar array embedded in ferroelectric barium strontium titanate

A silicon nanoporous pillar array (Si-NPA) with micrometer/nanometer hierarchical structure was fabricated by hydrothermal etching, followed by spin-coating barium strontium titanate (BST) on Si-NPA substrate. The photoluminescence (PL) spectra of the Si-NPA and BST/Si-NPA thin film were investigated. The emission band of freshly prepared Si-NPA located at 630 nm, and a blueshift at 425 nm as well as degradation in intensity after annealing at 600 °C for 1 h was observed, which might be explained by a quantum confinement effect model. BST ferroelectric material provided a static-electric field and induced the excited carriers in Si-NPA to migrate toward the opposite direction and recombine in an interfacial oxide layer. Therefore, BST enhanced blue emission of Si-NPA as well as passivated Si-NPA.     

Influence of growth time on field emission properties from carbon nanotubes deposited on arrayed nanoporous silicon pillars

We investigated the influence of growth time on field emission properties of multi-walled carbon nanotubes deposited on silicon nanoporous pillar array (MWCNTs/Si-NPA), which were fabricated by thermal chemical vapour deposition at 800 °C for 5, 15 and 25 min respectively, to better understand the origins of good field emission properties. The results showed that the MWCNTs/Si-NPA grown for 15 min had the highest field emission efficiency of the three types of samples. Morphologies of the products were examined by field-emission scanning electron microscope, and the excellent field emission performance was attributed not only to the formation of a nest array of multi-walled carbon nanotubes, which would largely reduce the electrostatic shielding among the emitters and resulted in a great enhancement factor, but also to the medium MWCNTs density films, there was an ideal compromise between the emitter density and the intertube distance, which also could effectively avoid electrostatic shielding effects, along with a high emitter density.     

Investigation of electrical and optoelectronic properties of zinc oxide nanowires

Zinc oxide (ZnO) nanowires have been synthesized by using tubular furnace chemical vapor deposition technique. The morphology, chemical composition and crystal structure of as-synthesized ZnO nanowires were examined by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) techniques. Four-terminal current-voltage (I-V) measurements were employed to study the electrical conductance of ZnO nanowires under various testing gas environments for gas sensing purpose. The I-V curves at temperature ranging from 150 to 300 K were recorded in the testing chamber under vacuum. The Arrhenius plot shows perfect linear relationship between the logarithm of the current I and inverse temperature 1/T. The donor level of the semiconducting nanowires is about 326 meV. The I-V behaviors were found to be reversible and repeatable with testing gases. The electrical conductivity was enhanced by a factor of four with ambient CO gas compared to that in vacuum and other testing gases. The optoelectronic properties of the ZnO nanowires were obtained by two-terminal I-V measurement method while the nanowires were illuminated by a ruby laser. The electrical conductivity was increased by 60% when the laser was present in comparison to that when the laser was off. Those significant changes suggest that nano-devices constructed by the ZnO nanowires could be used in gas sensing and optical switching applications.     

Improvement in the electrical performance and bias-stress stability of dual-active-layered silicon zinc oxide/zinc oxide thin-film transistor

Si-doped zinc oxide(SZO) thin films are deposited by using a co-sputtering method,and used as the channel active layers of ZnO-based TFTs with single and dual active layer structures.The effects of silicon content on the optical transmittance of the SZO thin film and electrical properties of the SZO TFT are investigated.Moreover,the electrical performances and bias-stress stabilities of the single- and dual-active-layer TFTs are investigated and compared to reveal the effects of the Si doping and dual-active-layer structure.The average transmittances of all the SZO films are about 90% in the visible light region of 400 nm-800 nm,and the optical band gap of the SZO film gradually increases with increasing Si content.The Si-doping can effectively suppress the grain growth of ZnO,revealed by atomic force microscope analysis.Compared with that of the undoped ZnO TFT,the off-state current of the SZO TFT is reduced by more than two orders of magnitude and it is 1.5 × 10~(-12) A,and thus the on/off current ratio is increased by more than two orders of magnitude.In summary,the SZO/ZnO TFT with dual-active-layer structure exhibits a high on/off current ratio of 4.0 × 10~6 and superior stability under gate-bias and drain-bias stress.     

Theoretical study of structural, optical and electrical properties of zirconium-doped zinc oxide

The structural, optical and electrical properties of zirconium-doped zinc oxide have been investigated by first principle calculations. Three possible structures including substitutional Zr for Zn (Zr_Zn), interstitial Zr (Zr_i) and substitutional Zr for O (Zr_O) are considered. The results show that the formation energy of Zr_Zn defect is the lowest, which indicates that Zr_Zn defect forms easier and its concentration may be the highest in the samples. It is also found that as the proportion of Zr increases, the lattice constants increase while the optical band gap first becomes larger and then smaller, which are consistent with our recently experimental results. The electronic structure calculations display that as Zr_Zn defect is introduced into ZnO, the Fermi-level shifts to the conduction band, and there are excess electrons in the conduction band, which may be a possible reason of the good conductivity of Zr doped ZnO film.     

New surface-modified zinc oxide nanoparticles with aminotriethylene oxide chains linked by 1,2,3-triazole ring: Preparation, and visible light-emitting and noncytotoxic properties

Novel surface-modified, visible light-emitting and noncytotoxic ZnO nanoparticles (NPs) (ZPAZ) having aminotriethylene oxide chains linked by 1,4- and/or 1,5-disubstituted 1,2,3-triazole rings were prepared from ZnO NPs (ZPA) with ethynyl groups on the surfaces and an azide derivative of triethylene oxide chain linking terminal amino group (ATA) via 1,3-dipolar azide/alkyne click reaction by heating without Cu(I) catalyst. FTIR spectroscopy, elemental analysis, XRD analysis and TEM observation suggested that the resulting ZPA and ZPAZ NPs have the particle sizes below 10 nm in diameters, triethylene oxide chains linking the terminal amino groups and wurtzite crystal structure. UV-vis absorption spectrum of the ZPAZ NPs in methanol showed maximum absorption band at 346.5 nm, supporting the TEM observation. PL spectra depicted that the ZPA and ZPAZ NPs display broad light green and lightly greenish yellow visible light emitting bands in methanol. Zeta potentials measured in distilled water suggested that the ZPAZ NPs have a low tendency to aggregate and possess better stability than the ZPA NPs. Cytotoxicity assay revealed that the ZPAZ NPs, having water-dispersion properties, are noncytotoxic at low concentrations and almost all RAW264.7 cells are alive after 24 h of treatment.     

The influence of Fermi energy on structural and electrical properties of laser crystallized P-doped amorphous silicon

A series of phosphorous-doped hydrogenated amorphous silicon films (a-Si:H) were crystallized using step-by-step laser crystallization process. The structural changes during the sequential crystallization process were detected by Raman measurements. The dehydrogenation was monitored by measuring the Si-H local vibrational modes using Raman spectroscopy and hydrogen effusion measurements. Interestingly, hydrogen bonding is affected by doping of the amorphous material. The influence of doping concentrations, thus the Fermi energy on electronic properties has been investigated employing secondary ion mass spectroscopy (SIMS), dark-conductivity- and Hall-effect measurements. The results from hydrogen effusion are consistent with the results obtained from Raman spectroscopy, Hall-effect- and dark-conductivity measurements.     

Effect of doping on structural,optical and electrical properties of nanostructure ZnO films deposited onto a-Si:H/Si heterojunction

We investigated the structural; optical and electrical properties of ZnO thin films as the n-type semiconductor for silicon a-Si:H/Si heterojunction photodiodes. The ZnO film forms the front contact of the super-strata solar cell and has to exhibit good electrical (high conductivity) and optical (high transmittance) properties. In this paper we focused our attention on the influence of doping on device performance. The results show that the X-ray diffraction (XRD) spectra revealed a preferred orientation of the crystallites along c-axis. SEM images show that all films display a granular, polycrystalline morphology and the ZnO:Al exhibits a better grain uniformity. The transmittance of the doped films was found to be higher when compared to undoped ZnO. A low resistivity of the order of 2.8 × 10⁻⁴ Ω cm is obtained for ZnO:Al using 0.4 M concentration of zinc acetate. The photoluminescence (PL) spectra exhibit a blue band with two peaks centered at 442 nm (2.80 eV) and 490 nm (2.53 eV). It is noted that after doping the ZnO films a shift of the band by 22 nm (0.15 eV) is recorded and a high luminescence occurs when using Al as a dopant. Dark I–V curves of ZnO/a-Si:H/Si structure showed large difference, which means there is a kind of barrier to current flow between ZnO and a-Si:H layer. Doping films was applied and the turn-on voltages are around 0.6 V. Under reverse bias, the current of the ZnO/a-Si:H/Si heterojunction is larger than that of ZnO:Al/a-Si:H/Si. The improvement with ZnO:Al is attributed to a higher number of generated carriers in the nanostructure (due to the higher transmittance and a higher luminescence) that increases the probability of collisions.     

水热法制备In2O3/ZnO异质结及其高的光催化性能

采用简单的两步水热法合成了不同In₂O₃质量比的In₂O₃/ZnO异质结复合材料．通过X射线衍射仪(XRD)、紫外-可见分光光度计(UV-vis)和扫描电子显微镜(SEM)对复合材料的结构、形貌和性能进行了表征．同时还使用UV-vis分光光度计测试了异质结降解罗丹明B(RhB)的光催化活性．实验结果表明,与纯ZnO和In₂O₃相比,In₂O₃的引入将ZnO的吸收光谱扩展到可见光区域,从而提高了其光生电子和空穴的分离．此外,In₂O₃/ZnO异质结在可见光照射对RhB具有较高的光催化活性．5 wt%-In₂O₃/ZnO异质结对RhB的降解率为84.3%,且具有良好的光催化稳定性．In₂O₃/ZnO异质结复合材料在有机染料废水的降解中有更广阔的应用前景．     

ZnO/ZnMgO异质结场效应管的制备与性能研究

利用等离子体增强化学气相沉积(PECVD)技术,在ZnO/ZnMgO异质结构上制备SiO₂作为栅绝缘层,采用光刻与腐蚀工艺制备ZnO/ZnMgO异质结场效应管。电学性能测试及计算结果表明器件栅压调控作用明显。发现栅端漏电流对器件性能造成一定影响。在低温条件下,栅绝缘层产生钝化,从而能够改善器件的性能。     

Effects of electron-beam irradiation on structural,electrical, and optical properties of amorphous indium gallium zinc oxide thin films

High-energy electron-beam irradiation of indium gallium zinc oxide (IGZO) films improved the short-range arrangement. The increase in band gap was used as an indication of such improvement. X-ray diffraction confirmed that the films treated with a DC voltage of 2–4.5 kV for duration of up to 35 min are in the amorphous state or nanocrystalline phase. Higher energy electron-beam irradiation led to increased conductivity, which mainly comes from the drastic increase in electron concentration. Electron-beam treatment could be a viable route to improve the contact resistance between the source/drain and channel layer in thin-film transistor devices.