In situ characterization of optoelectronic nanostructures and nanodevices

One-dimensional (1-D) semiconductor nanostructures can effectively transport electrons and photons, and are considered to be promising building blocks for future optoelectronic nanodevices. In this review, we present our recent efforts to integrate optical techniques and in situ electron microscopy for comprehensively characterizing individual 1-D optoelectronic nanostructures and nanodevices. The technical strategies and their applications in “green” emission and optical confinement in 1-D ZnO nanostructures will be introduced. We also show in situ assembly and characterization of nanostructures for optoelectronic device purposes. Using these examples, we demonstrate that the combination of optical techniques and in situ electron microscopy can be powerful for the studies of optoelectronic nanomaterials and nanodevices.     

纳米材料及HfO_2基存储器件的原位电子显微学研究

总结了我们将原位技术和透射电子显微学分析方法相结合,针对纳米材料和器件的结构、形貌、成分以及电势分布等物理性质的动态行为所开展的综合物性表征和分析工作.主要成果有:揭示了C_(60)纳米晶须在焦耳热作用下的结构相变路径;观察到了电荷俘获存储器中的电荷存储位置以及栅极电压诱导的氧空位缺陷;研究了阻变存储器中氧空位通道的形成过程以及导电通道的开关机理.这些成果不但有助于深入理解纳米材料和器件相关功能的物理机理,改善其工作性能,更展示了透射电子显微学在微电子领域强大的研究能力.     

Optical waveguide behavior of Se-doped and undoped CdS one-dimensional nanostructures using near-field optical microscopy

The optical waveguide behaviors of CdS and CdS _x Se_1−x nanostructures are studied using near-field optical microscopy. Optical measurements demonstrate that light may be guided on sub-wavelength scales along CdS nanoribbons in straight or bent structures. The photoluminescence (PL) spectra from nanoribbon emission using scanning near-field optical microscopy are analyzed under different incident laser intensities. The PL spectra along Se-doped and undoped CdS nanoribbons at different propagation distances are investigated. Both the guided PL spectra of Se-doped and undoped CdS nanoribbons show red-shifts because of the band-edge absorption. Our results are useful for the development of new kinds of functional nano devices. Supported by the National Natural Science Foundation of China (Grant Nos. 10574002, 90406007, and 50602015) and the National Basic Research Program of China (Grant No. 2007CB936800)     

In situ TEM observations of dislocation/anti-phase boundary interactions

L2₁-ordered Fe₅₉Mn₁₇Al₂₄ (in at%) single crystals were in situ strained at either 300?K or 700?K in a transmission electron microscope. At 300?K, the strain was accommodated by the glide of four-fold dissociated super-dislocations, whereas, at 700?K, the strain was accommodated by the glide of a/2?111? partials. Dislocation pile-ups occurred at a/4?111? thermal anti-phase boundaries (APBs). Screw super-dislocations frequently cross-slipped when they encountered the thermal APBs, while mixed dislocations tended to be pinned at them. This impediment is attributed to the creation of new APB segments when dislocations pass through the curvy thermal APBs.     

通过不同烷基链取代调控喹吖啶酮分子在Ag(110)表面上的自组织结构

采用低能电子衍射、扫描隧道显微镜、第一性原理密度泛函理论计算以及分子力学计算，分别对不同烷基链取代的喹吖啶酮（QA）分子在Ag（110）基底上的吸附和生长进行了研究．QA和Ag基底的相互作用主要来自分子中0原子和Ag基底的共价键，它决定了分子的取向和最优吸附位置；而烷基链决定了分子吸附层的取向，QA分子间的排列可以通过烷基链的长度来调节．由此借助调节烷基链的长度，能够可控地制备具有不同物理性质的单层分子薄膜．     

Structural characterization of Ga-doped Mg0.1Zn0.9O layers grown on ZnO/α-Al2O3 templates by P-MBE

In this study, structural properties of epitaxial Ga-doped Mg_0.1Zn_0.9O layers grown on ZnO/α-Al₂O₃ templates by plasma-assisted molecular beam epitaxy have been investigated by high-resolution transmission electron microscopy (HRTEM), and high resolution X-ray diffraction (HRXRD). From analysis of the diffraction pattern, the monocrystallinity of the Mg_0.1Zn_0.9O layer with hexagonal structure is confirmed. The orientation relationship between Mg_0.1Zn_0.9O and the template is determined as (0 0 0 1)_Mg0.1Zn0.9O(0 0 0 1)_ZnO(0 0 0 1)_Al2O3 and [ [ ]_ZnO[ . The density of dislocations near the top surface layers measured by plan-view TEM is about 3.610¹⁰ cm⁻², one order of magnitude higher than the value obtained for ZnO layers on α-Al₂O₃ with a MgO buffer. Cross-sectional observation revealed that the majority of threading dislocations are in the [0 0 0 1] line direction, i.e. they lie along the surface normal and consist of edge, screw, and mixed dislocations. Cross- sectional TEM and X-ray rocking curve experiments reveal that most of dislocations are edge dislocations. The interface of Mg_0.1Zn_0.9O and ZnO layers and the effect of excess Ga-doping in these layers have been also studied.     

In situ scanning electron microscope electrical characterization of GaN nanowire nanodiodes using tungsten and tungsten/gallium nanoprobes

A lithography-free technique for measuring the electrical properties of n-type GaN nanowires has been investigated using nanoprobes mounted in a scanning electron microscope (SEM). Schottky contacts were made to the nanowires using tungsten nanoprobes, while gallium droplets placed in situ at the end of tungsten nanoprobes were found to be capable of providing Ohmic contacts to GaN nanowires. Schottky nanodiodes were fabricated based on single n-type nanowires, and measured current–voltage (I–V) results suggest that the Schottky nanodiodes deviate from ideal diodes mainly due to their nanoscopic contact area. Additionally, the effect of the SEM electron beam on the I–V characteristics was investigated and was found to impact the transport properties of the Schottky nanodiodes, possibly due to an increase in carrier density in the nanodiodes.     

Initial oxidation of Ni(1 1 1) observed by electron emission microscopy: PEEM and MEEM

The initial oxidation of Ni(1 1 1) in the temperature range of 550-700 K has been monitored by photoelectron emission microscopy (PEEM) and metastable-atom electron emission microscopy (MEEM). The PEEM and MEEM images show uniform patterns for the chemisorbed overlayer, reflecting the electronic homogeneity as seen at the μm scale. During the nucleation and lateral growth of oxide, however, the μm-scale pattern due to the formation of oxide domains appears and its evolution depends strongly on the substrate temperature and dose pressure of gaseous O₂. Our data indicate that the high-temperature oxidation is regarded as a successive multi-nucleation process in a reaction-diffusion field.     

通过不同烷基链取代调控喹吖啶酮分子在Ag(110)表面上的自组织结构

采用低能电子衍射、扫描隧道显微镜、第一性原理密度泛函理论计算以及分子力学计算,分别对不同烷基链取代的喹吖啶酮(QA)分子在Ag(110)基底上的吸附和生长进行了研究.QA和Ag基底的相互作用主要来自分子中O原子和Ag基底的共价键,它决定了分子的取向和最优吸附位置;而烷基链决定了分子吸附层的取向,QA分子间的排列可以通过烷基链的长度来调节.由此借助调节烷基链的长度,能够可控地制备具有不同物理性质的单层分子薄膜.     

Diagnostics of Tin Plasma Produced by Visible and IR Nanosecond Laser Ablation

We present the optical emission spectroscopic studies of the Tin (Sn) plasma, produced by the fundamental (1064 nm) and second (532 nm) harmonics of a Q switched Nd: YAG pulsed laser having pulse duration of 5 ns and 10 Hz repetition rate which is capable of delivering 400 mJ at 1064 nm, and 200 mJ at 532 nm using Laser Induced Breakdown Spectroscopy (LIBS). The laser beam was focused on target material by placing it in air at atmospheric pressure. The experimentally observed line profiles of four neutral tin (Sn I) lines at 231.72, 248.34, 257.15 and 266.12 nm were used to extract the electron temperature (T_e) using the Boltzmann plot method and determined its value 6360 and 5970 K respectively for fundamental and second harmonics of the laser. Whereas, the electron number density (N_e) has been determined from the Stark broadening profile of neutral tin (Sn I) line at 286.33 nm and determined its value 5.85 x 10¹⁶ and 6.80 x 10¹⁶cm^–3 for fundamental and second harmonics of the laser respectively. Both plasma parameters (T_e and N_e) have also been calculated by varying distance from the target surface along the line of propagation of plasma plume and also by varying the laser irradiance. (© 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of Cr doped CdS nanoparticles stabilized with polyvinylpyrrolidone

Undoped and Cr (2 and 4 at.%) doped CdS nanoparticles were synthesized in aqueous solution by simple chemical co-precipitation method using polyvinylpyrrolidone (PVP) as stabilizer. The prepared nanoparticles were examined using X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDAX), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DRS) and Fourier transform infrared spectroscopy (FTIR). XRD pattern of the nanoparticles showed cubic zincblende phase with the particle size of the order of 3-4 nm, which was in good agreement with the results obtained from TEM studies. The EDAX analysis confirmed that Cd, Cr and S elements were present in the samples and the variations between the target and actual compositions were microscopic. UV-vis DRS spectra of the samples exhibited decrease in the band gap which further attests the incorporation of Cr into CdS nanoparticles. FTIR studies revealed that the undoped as well as Cr doped CdS nanoparticles were capped by polyvinylpyrrolidone.     

Structural phase transitions in Au thin films on Si (1 1 0): An in situ temperature dependent transmission electron microscopy study

We present a review on the formation of gold silicide nanostructures using in situ temperature dependent transmission electron microscopy (TEM) measurements. Thin Au films of two thicknesses (2.0 nm and 5.0 nm) were deposited on Si (1 1 0) substrate under ultra-high vacuum (UHV) conditions in a molecular beam epitaxy (MBE) system. Also a 2.0 nm thick Au film was deposited under high vacuum condition (with the native oxide at the interface of Au and Si) using thermal evaporation. In situ TEM measurements (for planar samples) were made at various temperatures (from room temperature, RT to 950 °C). We show that, in the presence of native oxide (UHV-MBE) at the interface, high aspect ratio (≈15.0) aligned gold silicide nanorods were observed. For the films that were grown with UHV conditions, a small aspect ratio (∼1.38) nanogold silicide was observed. For 5.0 nm thick gold thin film, thicker and lesser aspect ratio silicides were observed. Selected area diffraction pattern taken at RT after the sample for the case of 5.0 nm Au on Si (1 1 0)-MBE was annealed at 475 °C show the signature of gold silicide formation.     

Near-field optical characterization of GaN and InxGa1−xN/GaN heterostructures grown on freestanding GaN substrates

Using near-field scanning optical microscopy (NSOM), we report the spatial distribution of photoluminescence (PL) intensity in III-nitride-based semiconductor layers grown on GaN substrates. Undoped GaN, In_0.11Ga_0.89N, and In_0.13Ga_0.87N/GaN multi-quantum wells (MQWs) were grown by metal organic chemical vapor deposition (MOCVD) on freestanding GaN substrates. Micro-Raman spectroscopy has been used to evaluate the crystalline properties of the GaN homoepitaxial layers. The variation of the PL intensity from the NSOM imaging indicates that the external PL efficiency fluctuates from 20% to 40% in the 200 nm InGaN single layer on freestanding GaN, whereas it fluctuates from 20% to 60% in InGaN/GaN MQWs. In the NSOM-PL images, bright island-like features are observed. After deconvolution with the spatial resolution of the NSOM, the size of these features is estimated to be in the range of 150–250 nm.     

Structural characterization of Rh/pumice SMAD catalysts

The structure of Rh/pumice catalysts prepared by the SMAD (Solvated Metal Atoms Dispersion) technique at different metal loadings has been investigated by EXAFS (Extended X-ray Absorption Fine Structure Spectroscopy), XPS (X-ray Photoelectron Spectroscopy), SAXS (Small-Angle X-ray Scattering), WAXS (Wide-Angle X-ray Scattering) and TEM (Transmission Electron Microscopy). According to EXAFS and XPS, a fraction of the Rh atoms is oxidised, but a noticeable part is also present as Rh ⁰. The Rh oxidation is attributed to the interaction of the Rh atoms with the hydroxyls of the support; after the formation of the oxide, the nucleation of metallic rhodium becomes possible. The WAXS data do not show evidence of rhodium fcc crystallites; the metal-bearing particles are probably amorphous and/or very small, as results from the SAXS and TEM data analysis. The disagreement between the latter two techniques, resulting in a small-angle determination of the average size of the particles that is about half that of TEM in the catalyst with the higher Rh loading, is acknowledged and discussed. Preliminary catalytic tests are described, demonstrating the suitability of using a low surface area support for the preparation of SMAD catalysts. Received 2 February 1999     

Electronic, chemical and structural characterization of CNTs grown by acetylene decomposition over MgO supported Fe-Co bimetallic catalysts

The electronic and chemical structure of carbon nanotubes synthesized by decomposition of acetylene over Fe-Co bimetallic catalysts in different growth conditions, were analyzed by valence band photoelectron spectroscopy and scanning electron microscopy. A clear relationship between the bonding features and the growth condition allowed us to determine the key parameters in terms of temperature, growth time and catalyst content. Furthermore, the analysis allowed a determination of the byproducts.     

第一原理研究Sn(O1-xNx)2材料的光电磁性质

基于第一原理的密度泛函理论, 以量子化学从头计算软件 为平台研究了Sn(O_1-xN_x)₂材料的光电磁性能, 分析了体系的态密度、 能带结构、 磁性、 介电虚部及折射率. 计算结果表明, N替代O后, 随着掺杂浓度的增加, 体系的带隙先减小后增大, 掺杂量为12.50%时带隙最窄. 由于N 2p轨道电子的贡献, 在0.55-1.05 eV范围内产生了浅受主能级, 价带和导带处的能级均出现了劈裂及轨道的重叠现象, Sn-O键的键强大于N-O键的键强. 从磁性来看, N原子决定了磁矩的大小. 从介电虚部可知, 掺杂后体系的光学吸收边增宽, 主跃迁峰发生红移, 反射率和介电谱相对应, 各峰值与电子的跃迁吸收有关.     

ZnO/p-Si异质结的深能级及其对发光的影响

利用深能级瞬态谱(DLTS)和光致发光谱(PL),研究了ZnO/pSi异质结的两种不同温度(850℃,1000℃)退火下的深能级中心。发现850℃退火的样品存在3个明显的深中心,分别为E₁=E_v+0.21eV,E₂=E_v+0.44eV,E₃=E_v+071eV;而1000℃退火样品仅存在一个E₁=E_v+021eV的中心,且其隙态密度要比850℃退火的大。同时,测量了两个样品的PL谱。发现1000℃退火可消除一些影响发光强度的深能级,对改善晶格结构,提高样品的发光强度有利。     

Atomic and Electronic Structure of V/MgO Interface

Thin films of vanadium were deposited on the (001) surface of a MgOsubstrate by molecular beam epitaxy (MBE) and the V/MgO interface wasinvestigated by cross-sectional high resolution electron microscopy(HREM) and electron energy loss spectroscopy (EELS). In order todetermine the location of atoms at the interface, computersimulations were performed for four possible models, and bestmatching between the experimental and simulated images was obtainedfor the model where the V atoms are located directly on top of the Mgatoms at the interface. Interface bonding mechanism was investigatedby a first principles molecular-orbital (MO) calculation using thediscrete-variational (DV)-X method for a modelcluster of the interface, i.e., (Mg₉O₉V₅).The V-3d band was located in between the band-gap of MgO, and nearly empty Mg-3sp orbitals werefound to overlap with the V-3d band. The Mg-3sp and V-3d hybridizedin a bonding manner, thereby generates strong covalent bondingbetween V and Mg. Nearly filled O-2p orbitals were also found tohybridize with the V-3d orbitals in an antibonding manner. The bondoverlap population of the V–O bond was approximately four timessmaller than that of the V–Mg bond when the bond-length was thesame. The near edge structure of EELS specific to the interface wasobtained using a V/MgO multilayer specimen at both Mg-K and O-Kedges. Comparison between the experimental and theoretical spectra bythe present MO calculation clearly found the presence of hybridizedorbitals of V-3d with Mg-3p.     

晶体PZCST:VO2+的EPR谱及光吸收谱的理论研究

采用双旋-轨耦合参量模型和3d¹电子组态在四角对称下的能级公式,计算了KZnClSO₄·3H₂O(PZCST): VO²⁺的EPR谱和光吸收谱,所得EPR谱和光吸收谱的理论结果与实验发现符合得很好. 研究发现,该晶体沿C₄轴局域对称结构呈压缩的四角畸变,其大小为0.47 nm;大的κ值表明VO²⁺的未配对电子的自旋极化对超精细结构常数有着较大的贡献.     

Effect of Maleated Styrene/Ethylene-co-Butylene/Styrene on the Dispersed Particles Size and Mechanical Properties of Polyamide 6/Poly(styrene-co-acrylonitrile)/Poly(styrene-b-(ethylene-co-butylene)-b-styrene) Ternary Blends

In this study, the effect of several parameters, including composition, order of mixing, viscosity, and interfacial tension, on the phase structure and size of dispersed particles of polyamide 6 (PA6)/poly(styrene-co-acrylonitrile) SAN/poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) ternary blends was investigated. Moreover, the effect of addition of different ratios of reactive SEBS (maleic anhydride grafted-SEBS) and non-reactive SEBS at a fixed order of mixing and composition of 70/15/15 (PA6/SAN/SEBS + SEBS-g-MAH) on the mechanical properties of ternary blends was examined. Scanning electron microscopy (SEM) micrographs showed that among the studied parameters, interfacial tension and viscosity of dispersed phases were the leading factors in the formation of morphology and size of dispersed droplets. Mechanical results revealed that in contrast to the expectation, formation of core/shell structure of PA6/SAN/SEBS ternary blends did not result in a significant increasing of impact strength. The highest impact strength was achieved when a 50/50 weight ratio of SEBS/SEBS-g-MAH was used.