Structure characteristics and valence state study for La1-xNaxTiO3 synthesized under high-pressure and high-temperature conditions

By using a novel high-pressure, high-temperature method, perovskite oxides of La1-xNaxTiO3 (x = 0.05, 0.1-0.8) with mixed valence state were synthesized. XRD analysis shows a cubic cell for the samples. Cell volumes of the samples with 0.1 less than or equal to x less than or equal to 0.5 decreases as x increases, and the cell Volume for x = 0.05 is smaller than that for x = 0.1. XPS of surface and EPR measurements indicate that Ti ions are of mixed valence of +3 and +4 and that A-cations vacancies exist in the samples. As x increases, the amount of Ti3+ ions decreases and the amount of A-cations vacancies increases. The valence state of Ti ions can be altered by changing both pressure and temperature. (C) 2000 Elsevier Science B.V. All rights reserved.

Unidirectional current flow of reversible redox couples on a MoO3 film-modified microelectrode

In this paper, we have investigated the reactivity of the molybdenum oxide film toward some standard redox systems (e.g., ferrocene (Fc) and its derivatives) and observed a few interesting phenomena. The results demonstrate that the electrochemical behaviour of Fc and its derivatives at the oxide-modified carbon fiber (CF) microelectrode differs from that at a bare CF microelectrode, The conductivity of the molybdenum oxide film is seriously affected by the range and the direction of the potential scan, which influences the electrochemical behaviour of these redox systems at the film electrode. If the cycling potential is more positive than the reduction potential of the molybdenum oxide film, the reduction and oxidation peak currents of Fc and its derivatives could not be observed. The result indicates that the molybdenum oxide film on a microelectrode surface cannot transfer electrons between the surface of the electrode and Fc or its derivatives due to the existence of a high resistance between the interface in these potential ranges. On the other hand, if the lower limit of the scan potential was extended to a potential more negative than the reduction peak potential of the film, the oxidation peak of Fc or its derivatives appeared at about the potential relative to E-0 of Fc or its derivatives on the bare electrode, and the peak current is proportional to the concentration of these couples in the electrolyte. To our surprise, the peak height on the modified electrode is much larger than that on the bare CF microelectrode under the same conditions in the range of low concentration of these couples, and the oxidation peak potential of these couples is more negative than that on the bare CF microelectrode. On the basis of the experimental observation, we propose that these redox couples may undergo an interaction with the reduction state of the molybdenum oxide film. The new phenomena that we observed have been explained by using this interaction. (C) 1997 Elsevier Science S.A.

Studies on the PTC/NTC effect of carbon black filled low density polyethylene composites

The positive temperature coefficient (PTC) and negative temperature coefficient (NTC) effect of carbon black (CB) filled low density polyethylene (LDPE) composites was studied using electrical resistivity spectra, DSC, tensile mechanical analysis (TMA) and small-angle X-ray scattering (SAXS) techniques. The three LDPEs used have a similar crystallinity and different melting index (MI). The experimental results indicate that the CB has no significant effect on the crystallinity and the long spacing of crystalline domains of LDPE. Based upon the TMA and dynamic elastic modulus spectra, it can be concluded that the PTC effect is related to the thermal expansion of the polymer matrix, and the NTC effect is caused by a decrease of the elastic modulus of the polymer at high temperatures. The NTC effect can be reduced by enhancing either the elastic modulus or the interaction between carbon black and matrix. (C) 1997 Elsevier Science Ltd.

SEMICONDUCTOR TO METAL TRANSITION IN LN(2)MO(3)O(9) COMPOUNDS

Ln(2)Mo(3)O(12) and Ce2Mo3O12.25 are reduced by hydrogen yielding Mo4+ oxides of the formula Ln(2)Mo(3)O(9) (Ln = La, Ce, Pr, Nd, Sm, Gd and Dy). The new compound Ce2Mo3O9 has the same structure as other Ln(2)Mo(3)O(9) compounds. All of the products are single phase materials and crystallize in a tetragonal scheelite type structure with Mo2O6 clusters. The IR spectra of the Ln(2)Mo(3)O(9) oxides show two absorption bands. These compounds are black n-type semiconductors, and exhibit Curie-Weiss Law behavior from 100K to 250K. Temperature dependence of the electrical properties of these compounds were measured for the first time, and a semiconductor-metal transition was found at about 250 degrees C.

STUDY ON POLYANILINE FILM WITH HIGH-DENSITY AND HIGH MECHANICAL STRENGTH

Free-standing film of polyaniline with excellent mechanical and electrical properties has been successfully prepared by using the solution-casting method. The results show that its tensile strength, Young's modulus and elongation at break are about 87.9 MPa, 1563.9 MPa and 10.2%, respectively. It is essential that the soluble polyaniline should be appropriately treated in some suitable organic solvents before making a free-standing film. Films having lustrous, smooth surface, high density and good flexibili...

面向CNT基纳米器件的DEP装配实验研究

碳纳米管(Carbon nanotube,CNT)由于独特的纳米结构以及优异的物理、化学特性,在纳米器件领域具有广阔的应用前景。有效的CNT的操控与装配方法对于其在上述领域的研究应用是至关重要的。为此,本文在分析非均匀电场条件下CNT所受介电泳(Dielectrophoresis,DEP)力模型的基础上,构建了基于DEP力的CNT装配实验系统。本文进行了多壁碳纳米管(MWNTs)的装配实验;并测试了MWCNTs束的电特性。

控制热力学条件下的矿物、岩石电学性质研究

电导率是重要的地球物理参数。模拟地球内部条件下的矿物、岩石电导率测量是了解地球内部物质组成及物理化学性质的有效手段，同时，还可以为野外大地电磁测量结果的解释提供依据。在YJ-紧装式六面顶压机上，对原有的矿物、岩石电性测量系统进行了进一步的改进；建立了一套以Solartron 1260阻抗／增益一相位分析仪为测试仪器，使用Mo电极和Mo盾来控制样品氧逸度的测量系统，该系统的氧逸度环境为Mo-MoO2，接近Iw缓冲对。石英（人造水晶）、橄榄石、纯橄榄岩、辉石岩、二辉橄榄岩、巨晶辉石的电导率测量是在新的测量系统下获得的，而辉长岩的电导率测量是基于LCR仪为测量仪器的测试系统下获得的。在压力为1-3GPa、温度为675K-160OK、频率为106-0.1Hz、氧逸度为Mo-MoO2的条件下，对不同方向石英（人造水晶）的电学性质进行了研究。复阻抗平面上出现了反映样品本身性质的阻抗弧和反映样品与电极之间扩散的直线。石英的电导率随温度增加而增加，随压力的变化比较微弱。石英的导电机制主要为离子导电，载流子可能为碱金属离子和氢离子，这些碱金属离子和氢离子主要在平行于光轴的通道中运动。在相同的温度和压力条件下，a石英的电导率和c轴的夹角有关，石英的电导率随着夹角的增大而减小，表现出了强烈的各向异性。对“各个方向石英在发生了相变前后的电导率进行了研究，发现Q石英转变为p石英后，电导率并没有突变，仍然随着温度的增加而增加。在压力为1-2GP。、温度为563-1173K、频率为12-105Hz的条件下研究了辉长岩的阻抗。结果发现辉长岩复阻抗的实部随频率的增加而减小，而虚部随频率增加先增大后减小；相角随频率增加而减小。在复阻抗平面上出现了反映颗粒内部的阻抗弧，该阻抗弧出现在高频段。实验室获得辉长岩在地壳的压力和温度（1.0GP。和893K）条件下的电导率值为1.77×-4S／m，而高导层的电导率值为0-01-0-15S／m，二者相差了2-3个数量级，推断辉长岩不能在下地壳形成高导层。在压力为3.0GPa、温度为1299-1600K、频率为106-0.1Hz、氧逸度为Mo-MoO2条件下，对不同颗粒粒度的橄榄石电导率进行了测量。在复阻抗平面上均出现了反映颗粒内部电响应的阻抗弧，这些阻抗弧随着温度的增加而减小。而反映颗粒边界导电机制的阻抗弧并不明显，两种阻抗弧出现在不同的频率范围内，反映颗粒内部导电机制的阻抗弧出现在频率较高的范围内，而反映颗粒边界导电机制的阻抗弧出现在频率相对低的范围内。不同粒度橄榄石在3.0GPa条件下的电导率随着温度的增加而增加，它们的激化烩介于1.03-2.11ev之间。在压力为1-3GPa、温度为1282-1544K、频率为0.1-106Hz、氧逸度为MO-MoO2的条件下，对纯橄榄岩的电导率进行了测量。在复阻抗平面上出现了反映颗粒内部电响应和颗粒边界电响应的阻抗弧。反映颗粒内部导电的阻抗弧出现在较高的频率段，随着温度的增加，这些阻抗弧逐渐收缩。颗粒边界的阻抗弧出现在相对低的频率段。纯橄榄岩的电导率随着温度增加而增加，随压力变化比较微弱。对颗粒边界的电导率研究表明，颗粒边界的电导率高于颗粒内部的电导率，总电导率则小于颗粒内部和颗粒边界的电导率，颗粒边界并没有增强总电导率。纯橄榄岩的激化能为1，62eV，而激化体积为0.67cm3／mol，指前因子为5125加。利用实验所获得的拟合参数，建立了地球内部200-40Okm处的电导率模型，并同地球物理模型进行了对比，在温度和氧逸度的合理波动范围内，实验室电导率模型和地球物理模型吻合的很好。在压力为1-2GPa、温度为1228-1584K、频率为0.1-106Hz、氧逸度为MO-MoO2条件下，测量了天然和热压辉石岩、热压巨晶辉石、二辉橄榄岩的电导率。结果发现，在复阻抗平面上出现了反映颗粒内部电响应和颗粒边界电响应的阻抗弧，反映颗粒内部导电的阻抗弧出现在较高的频率段，随着温度的增加，这些阻抗弧逐渐收缩。颗粒边界的阻抗弧出现在相对低的频率段。辉石岩、二辉橄榄岩、巨晶辉石电导率随着温度增加而增加，随压力变化比较微弱。天然辉石岩和热压辉石岩颗粒边界的电导率高于它们各自颗粒内部的电导率，而总电导率则小于颗粒内部和颗粒边界的电导率，颗粒边界并没有增强总电导率。辉石岩一二辉橄榄岩一纯橄榄岩的电导率依次减小，这可能是与它们的铁含量有关。天然辉石岩的电导率与热压辉石岩的电导率的差异可能与样品中的水（氢）含量的不同有关。

Atomic layer deposition of copper for CMOS interconnects

This work concerns the atomic layer deposition (ALD) of copper. ALD is a technique that allows conformal coating of difficult topographies such as narrow trenches and holes or even shadowed regions. However, the deposition of pure metals has so far been less successful than the deposition of oxides except for a few exceptions. Challenges include difficulties associated with the reduction of the metal centre of the precursor at reasonable temperatures and the tendency of metals to agglomerate during the growth process. Cu is a metal of special technical interest as it is widely used for interconnects on CMOS devices. These interconnects are usually fabricated by electroplating, which requires the deposition of thin Cu seed layers onto the trenches and vias. Here, ALD is regarded as potential candidate for replacing the current PVD technique, which is expected to reach its limitations as the critical dimensions continue to shrink. This work is separated into two parts. In the first part, a laboratory-scale ALD reactor was constructed and used for the thermal ALD of Cu. In the second part, the potentials of the application of Cu ALD on industry scale fabrication were examined in a joint project with Applied Materials and Intel. Within this project precursors developed by industrial partners were evaluated on a 300 mm Applied Materials metal-ALD chamber modified with a direct RF-plasma source. A feature that makes ALD a popular technique among researchers is the possibility to produce high- level thin film coatings for micro-electronics and nano-technology with relatively simple laboratory- scale reactors. The advanced materials and surfaces group (AMSG) at Tyndall National Institute operates a range of home-built ALD reactors. In order to carry out Cu ALD experiments, modifications to the normal reactor design had to be made. For example a carrier gas mechanism was necessary to facilitate the transport of the low-volatile Cu precursors. Precursors evaluated included the readily available Cu(II)-diketonates Cu-bis(acetylacetonate), Cu-bis(2,2,6,6-tetramethyl-hepta-3,5-dionate) and Cu-bis(1,1,1,5,5,5-hexafluoacetylacetonate) as well as the Cu-ketoiminate Cu-bis(4N-ethylamino- pent-3-en-2-onate), which is also known under the trade name AbaCus (Air Liquide), and the Cu(I)- silylamide 1,3-diisopropyl-imidazolin-2-ylidene Cu(I) hexamethyldisilazide ([NHC]Cu(hmds)), which was developed at Carleton University Ottawa. Forming gas (10 % H2 in Ar) was used as reducing agent except in early experiments where formalin was used. With all precursors an extreme surface selectivity of the deposition process was observed and significant growth was only achieved on platinum-group metals. Improvements in the Cu deposition process were obtained with [NHC]Cu(hmds) compared with the Cu(II) complexes. A possible reason is the reduced oxidation state of the metal centre. Continuous Cu films were obtained on Pd and indications for saturated growth with a rate of about 0.4 Å/cycle were found for deposition at 220 °C. Deposits obtained on Ru consisted of separated islands. Although no continuous films could be obtained in this work the relatively high density of Cu islands obtained was a clear improvement as compared to the deposits grown with Cu(II) complexes. When ultra-thin Pd films were used as substrates, island growth was also observed. A likely reason for this extreme difference to the Cu films obtained on thicker Pd films is the lack of stress compensation within the thin films. The most likely source of stress compensation in the thicker Pd films is the formation of a graded interlayer between Pd and Cu by inter-diffusion. To obtain continuous Cu films on more materials, reduction of the growth temperature was required. This was achieved in the plasma assisted ALD experiments discussed in the second part of this work. The precursors evaluated included the AbaCus compound and CTA-1, an aliphatic Cu-bis(aminoalkoxide), which was supplied by Adeka Corp.. Depositions could be carried out at very low temperatures (60 °C Abacus, 30 °C CTA-1). Metallic Cu could be obtained on all substrate materials investigated, but the shape of the deposits varied significantly between the substrate materials. On most materials (Si, TaN, Al2O3, CDO) Cu grew in isolated nearly spherical islands even at temperatures as low as 30 °C. It was observed that the reason for the island formation is the coalescence of the initial islands to larger, spherical islands instead of forming a continuous film. On the other hand, the formation of nearly two-dimensional islands was observed on Ru. These islands grew together forming a conductive film after a reasonably small number of cycles. The resulting Cu films were of excellent crystal quality and had good electrical properties; e.g. a resistivity of 2.39 µΩ cm was measured for a 47 nm thick film. Moreover, conformal coating of narrow trenches (1 µm deep 100/1 aspect ratio) was demonstrated showing the feasibility of the ALD process.

Atomic layer deposition of interface control layers for the fabrication of III/V MOS devices

The continued advancement of metal oxide semiconductor field effect transistor (MOSFET) technology has shifted the focus from Si/SiO2 transistors towards high-κ/III-V transistors for high performance, faster devices. This has been necessary due to the limitations associated with the scaling of the SiO2 thickness below ~1 nm and the associated increased leakage current due to direct electron tunnelling through the gate oxide. The use of these materials exhibiting lower effective charge carrier mass in conjunction with the use of a high-κ gate oxide allows for the continuation of device scaling and increases in the associated MOSFET device performance. The high-κ/III-V interface is a critical challenge to the integration of high-κ dielectrics on III-V channels. The interfacial chemistry of the high-κ/III-V system is more complex than Si, due to the nature of the multitude of potential native oxide chemistries at the surface with the resultant interfacial layer showing poor electrical insulating properties when high-κ dielectrics are deposited directly on these oxides. It is necessary to ensure that a good quality interface is formed in order to reduce leakage and interface state defect density to maximise channel mobility and reduce variability and power dissipation. In this work, the ALD growth of aluminium oxide (Al2O3) and hafnium oxide (HfO2) after various surface pre-treatments was carried out, with the aim of improving the high-κ/III-V interface by reducing the Dit – the density of interface defects caused by imperfections such as dangling bonds, dimers and other unsatisfied bonds at the interfaces of materials. A brief investigation was performed into the structural and electrical properties of Al2O3 films deposited on In0.53Ga0.47As at 200 and 300oC via a novel amidinate precursor. Samples were determined to experience a severe nucleation delay when deposited directly on native oxides, leading to diminished functionality as a gate insulator due to largely reduced growth per cycle. Aluminium oxide MOS capacitors were prepared by ALD and the electrical characteristics of GaAs, In0.53Ga0.47As and InP capacitors which had been exposed to pre-pulse treatments from triethyl gallium and trimethyl indium were examined, to determine if self-cleaning reactions similar to those of trimethyl aluminium occur for other alkyl precursors. An improved C-V characteristic was observed for GaAs devices indicating an improved interface possibly indicating an improvement of the surface upon pre-pulsing with TEG, conversely degraded electrical characteristics observed for In0.53Ga0.47As and InP MOS devices after pre-treatment with triethyl gallium and trimethyl indium respectively. The electrical characteristics of Al2O3/In0.53Ga0.47As MOS capacitors after in-situ H2/Ar plasma treatment or in-situ ammonium sulphide passivation were investigated and estimates of interface Dit calculated. The use of plasma reduced the amount of interface defects as evidenced in the improved C-V characteristics. Samples treated with ammonium sulphide in the ALD chamber were found to display no significant improvement of the high-κ/III-V interface. HfO2 MOS capacitors were fabricated using two different precursors comparing the industry standard hafnium chloride process with deposition from amide precursors incorporating a ~1nm interface control layer of aluminium oxide and the structural and electrical properties investigated. Capacitors furnished from the chloride process exhibited lower hysteresis and improved C-V characteristics as compared to that of hafnium dioxide grown from an amide precursor, an indication that no etching of the film takes place using the chloride precursor in conjunction with a 1nm interlayer. Optimisation of the amide process was carried out and scaled samples electrically characterised in order to determine if reduced bilayer structures display improved electrical characteristics. Samples were determined to exhibit good electrical characteristics with a low midgap Dit indicative of an unpinned Fermi level

Synthesis, functionalisation and characterisation of germanium nanocrystals & their applications

In the last two decades, semiconductor nanocrystals have been the focus of intense research due to their size dependant optical and electrical properties. Much is now known about how to control their size, shape, composition and surface chemistry, allowing fine control of their photophysical and electronic properties. However, genuine concerns have been raised regarding the heavy metal content of these materials, which is toxic even at relatively low concentrations and may limit their wide scale use. These concerns have driven the development of heavy metal free alternatives. In recent years, germanium nanocrystals (Ge NCs) have emerged as environmentally friendlier alternatives to II-VI and IV-VI semiconductor materials as they are nontoxic, biocompatible and electrochemically stable. This thesis reports the synthesis and characterisation of Ge NCs and their application as fluorescence probes for the detection of metal ions. A room-temperature method for the synthesis of size monodisperse Ge NCs within inverse micelles is reported, with well-defined core diameters that may be tuned from 3.5 to 4.5 nm. The Ge NCs are chemically passivated with amine ligands, minimising surface oxidation while rendering the NCs dispersible in a range of polar solvents. Regulation of the Ge NCs size is achieved by variation of the ammonium salts used to form the micelles. A maximum quantum yield of 20% is shown for the nanocrystals, and a transition from primarily blue to green emission is observed as the NC diameter increases from 3.5 to 4.5 nm. A polydisperse sample with a mixed emission profile is prepared and separated by centrifugation into individual sized NCs which each showed blue and green emission only, with total suppression of other emission colours. A new, efficient one step synthesis of Ge NCs with in situ passivation and straightforward purification steps is also reported. Ge NCs are formed by co-reduction of a mixture of GeCl4 and n-butyltrichlorogermane; the latter is used both as a capping ligand and a germanium source. The surface-bound layer of butyl chains both chemically passivates and stabilises the Ge NCs. Optical spectroscopy confirmed that these NCs are in the strong quantum confinement regime, with significant involvement of surface species in exciton recombination processes. The PL QY is determined to be 37 %, one of the highest values reported for organically terminated Ge NCs. A synthetic method is developed to produce size monodisperse Ge NCs with modified surface chemistries bearing carboxylic acid, acetate, amine and epoxy functional groups. The effect of these different surface terminations on the optical properties of the NCs is also studied. Comparison of the emission properties of these Ge NCs showed that the wavelength position of the PL maxima could be moved from the UV to the blue/green by choice of the appropriate surface group. We also report the application of water-soluble Ge NCs as a fluorescent sensing platform for the fast, highly selective and sensitive detection of Fe3+ ions. The luminescence quenching mechanism is confirmed by lifetime and absorbance spectroscopies, while the applicability of this assay for detection of Fe3+ in real water samples is investigated and found to satisfy the US Environmental Protection Agency requirements for Fe3+ levels in drinkable water supplies.

Orthogonal orientation control of carbon nanotube growth.

Carbon nanotubes (CNTs) have attracted attention for their remarkable electrical properties and have being explored as one of the best building blocks in nano-electronics. A key challenge to realize such potential is the control of the nanotube growth directions. Even though both vertical growth and controlled horizontal growth of carbon nanotubes have been realized before, the growth of complex nanotube structures with both vertical and horizontal orientation control on the same substrate has never been achieved. Here, we report a method to grow three-dimensional (3D) complex nanotube structures made of vertical nanotube forests and horizontal nanotube arrays on a single substrate and from the same catalyst pattern by an orthogonally directed nanotube growth method using chemical vapor deposition (CVD). More importantly, such a capability represents a major advance in controlled growth of carbon nanotubes. It enables researchers to control the growth directions of nanotubes by simply changing the reaction conditions. The high degree of control represented in these experiments will surely make the fabrication of complex nanotube devices a possibility.

Low temperature surface nitridation processes for dielectric-Ge interfaces

Germanium MOS capacitors have been fabricated with a high-? HfO dielectric using ALD. An in-situ low temperature (250°C) nitrogen plasma treatment on the germanium surface prior to the deposition of HfO was found to be beneficial to the electrical properties of the devices. Germanium MOS capacitors have also been fabricated with a SiO dielectric deposited by an atmospheric pressure CVD 'silox' process. The same low temperature plasma nitridation was found to degrade the electrical properties of the silox devices. The effect of a post-metal anneal in H and N on both types of capacitor structure was also found to degrade device electrical properties. copyright The Electrochemical Society.

Phase agile reflectarray cells based on liquid crystals

Experimental results at X-band are used to compare the electromagnetic scattering from a printed reflectarray cell, which is constructed on 500 mu m thick layers of three different nematic state liquid crystals. It is shown that a small voltage can be used to vary the permittivity of the tunable substrate and thereby control the phase of the reflected signals. Numerical results using Ansoft HFSS are compared with the measured phase, resonant frequencies and signal attenuation for two orientations of the liquid crystal molecules. Data fitting is employed to quantify the loss tangent and the permittivity values of the three anisotropic specimens. The performance trade-offs that are imposed by the use of commercially available materials are discussed, and the computer model is used to specify the electrical properties of a liquid crystal mixture, which can provide a signal loss of <1 dB and a dynamic phase range of 300 degrees from the patch elements at 10 GHz.

Tunable liquid crystal reflectarray patch element

Numerical and measured results are employed at X-band to demonstrate that the electrical properties ofnematic state liquid crystal can be exploited to produce phase shifters for beam scanning printed reflectarray antennas with a tunable range greater than 180'.

Asymptotic layer-type model of high pressure direct current glow discharge in electronegative gases

Here a self-consistent one-dimensional continuum model is presented for a narrow gap plane-parallel dc glow discharge. The governing equations consist of continuity and momentum equations for positive and negative ions and electrons coupled with Poisson's equation. A singular perturbation method is developed for the analysis of high pressure dc glow discharge. The kinetic processes of the ionization, electron attachment, and ion-ion recombination are included in the model. Explicit results are obtained for the asymptotic limits: delta=(r(D)/L)(2)--> 0, omega=(r(S)/L)(2)--> 0, where r(D) is the Debye radius, r(S) is recombination length, and L is the gap length. The discharge gap divides naturally into four layers with multiple space scales: anode fall region, positive column, transitional region, cathode fall region and diffusion layer adjacent to the cathode surface, its formation is discussed. The effects of the gas pressure, gap spacing and dc voltage on the electrical properties of the layers and its dimension are investigated. (C) 2000 American Institute of Physics. [S0021-8979(00)00813-6].