Stress-induced platelet formation in silicon:a molecular dynamics study

The effect of stress on vacancy cluster configurations in silicon is examined using molecular dynamics. At zero pressure, the shape and stability of the vacancy clusters agrees with previous atomistic results. When stress is applied the orientation of small planar clusters changes to reduce the strain energy. The preferred orientation for the vacancy clusters under stress agrees with the experimentally observed orientations of hydrogen platelets in the high stress regions of hydrogen implanted silicon. These results suggest a theory for hydrogen platelet formation. © 2005 The American Physical Society.

Heavy ion irradiation effects in zirconium nitride

Polycrystalline zirconium nitride (ZrN) samples were irradiated with He +, Kr ++, and Xe ++ ions to high (>1·10 16 ions/cm 2) fluences at ∼100 K. Following ion irradiation, transmission electron microscopy (TEM) and grazing incidence X-ray diffraction (GIXRD) were used to analyze the microstructure and crystal structure of the post-irradiated material. For ion doses equivalent to approximately 200 displacements per atom (dpa), ZrN was found to resist any amorphization transformation, based on TEM observations. At very high displacement damage doses, GIXRD measurements revealed tetragonal splitting of some of the diffraction maxima (maxima which are associated with cubic ZrN prior to irradiation). In addition to TEM and GIXRD, mechanical property changes were characterized using nanoindentation. Nanoindentation revealed no change in elastic modulus of ZrN with increasing ion dose, while the hardness of the irradiated ZrN was found to increase significantly with ion dose. Finally, He + ion implanted ZrN samples were annealed to examine He gas retention properties of ZrN as a function of annealing temperature. He gas release was measured using a residual gas analysis (RGA) spectrometer. RGA measurements were performed on He-implanted ZrN samples and on ZrN samples that had also been irradiated with Xe ++ ions, in order to introduce high levels of displacive radiation damage into the matrix. He evolution studies revealed that ZrN samples with high levels of displacement damage due to Xe implantation, show a lower temperature threshold for He release than do pristine ZrN samples.

Mechanical properties of thin sol-gel films

This thesis presents a study of the mechanical properties of thin films. The main aim was to determine the properties of sol-gel derived coatings. These films are used in a range of different applications and are known to be quite porous. Very little work has been carried out in this area and in order to study the mechanical properties of sol-gel films, some of the work was carried out on magnetron sputtered metal coatings in order to validate the techniques developed in this work. The main part of the work has concentrated on the development of various bending techniques to study the elastic modulus of the thin films, including both a small scale three-point bending, as well as a novel bi-axial bending technique based on a disk resting on three supporting balls. The bending techniques involve a load being applied to the sample being tested and the bending response to this force being recorded. These experiments were carried out using an ultra micro indentation system with very sensitive force and depth recording capabilities. By analysing the result of these forces and deflections using existing theories of elasticity, the elastic modulus may be determined. In addition to the bi-axial bending study, a finite element analysis of the stress distribution in a disk during bending was carried out. The results from the bi-axial bending tests of the magnetron sputtered films was confirmed by ultra micro indentation tests, giving information of the hardness and elastic modulus of the films. It was found that while the three point bending method gave acceptable results for uncoated steel substrates, it was very susceptible to slight deformations of the substrate. Improvements were made by more careful preparation of the substrates in order to avoid deformation. However the technique still failed to give reasonable results for coated specimens. In contrast, biaxial bending gave very reliable results even for very thin films and this technique was also found to be useful for determination of the properties of sol-gel coatings. In addition, an ultra micro indentation study of the hardness and elastic modulus of sol-gel films was conducted. This study included conventionally fired films as well as films ion implanted in a range of doses. The indentation tests showed that for implantation of H⁺ ions at doses exceeding 3x10¹⁶ ions/cm², the mechanical properties closely resembled those of films that were conventionally fired to 450°C.

Implantation Induced Hardening of Nanocrystalline Titanium Thin Films

Formation of nanocrystalline TiN at low temperatures was demonstrated by combining Pulsed Laser Deposition (PLD) and ion implantation techniques. The Ti films of nominal thickness similar to 250 nm were deposited at a substrate temperature of 200 degrees C by ablating a high pure titanium target in UHV conditions using a nanosecond pulsed Nd:YAG laser operating at 1064 nm. These films were implanted with 100 keV N+ ions with fluence ranging from 1.0 x 10(16) ions/cm(2) to 1.0 x 10(17) ions/cm(2). The structural, compositional and morphological evolutions were tracked using Transmission Electron Microscopy (TEM), Secondary Ion Mass Spectrometry (SIMS) and Atomic Force Microscopy (AFM), respectively. TEM analysis revealed that the as-deposited titanium film is an fcc phase. With increasing ion fluence, its structure becomes amorphous phase before precipitation of nanocrystalline fcc TiN phase. Compositional depth profiles obtained from SIMS have shown the extent of nitrogen concentration gradient in the implantation zone. Both as-deposited and ion implanted films showed much higher hardness as compared to the bulk titanium. AFM studies revealed a gradual increase in surface roughness leading to surface patterning with increase in ion fluence.

The intrinsic temperature effect of the Raman spectra of graphite

The Raman spectra of ion-implanted highly oriented pyrolytic graphite (HOPG) are reported, in which an additional mode at 1083 cm(-1) and three doublet structures in the positions of similar to 1350, similar to 2450, and similar to 2710 cm(-1) are revealed. Noticeable frequency shifts are observed for all the Raman bands between the spectra excited with different laser powers, which are interpreted as the pure temperature effect and a downshift in the C-C stretching frequency induced by the thermal expansion. Moreover, the pure temperature effect (d omega/dT)(V) without anharmonic contribution is achieved in pristine HOPG. The results suggest that the pure temperature effect without anharmonic contribution plays an important role in the frequency shifts with temperature. (C) 1999 American Institute of Physics. [S0003-6951(99)01313-3].

Gas source molecular beam epitaxy and thermal stability of Si1-xGex/Si superlattice materials

Gas source molecular beam epitaxy has been used to grow Si1-xGex alloys and Si1-xGex/Si multi-quantum wells (MQWs) on (100) Si substrates with Si2H6 and GeH4 as sources. Heterostructures and MQWs with mirror-like surface morphology, good crystalline qualify, and abrupt interfaces have been studied by a variety of in situ and ex situ techniques. The structural stability and strain relaxation in Si1-xGex/Si heterostructures have been investigated, and compared to that in the As ion-implanted Si1-xGex epilayers. The results show that the strain relaxation mechanism of the non-implanted Si1-xGex epilayers is different from that of the As ion-implanted Si1-xGex epilayers.

Influence of the semi-insulating GaAs Schottky pad on the Schottky barrier in the active layer

The influence of the sidegate voltage on the Schottky barrier in the ion-implanted active layer via the Schottky pad on the semi-insulating GaAs substrate was observed, and the mechanism for such an influence was proposed. (C) 1996 American Institute of Physics.

A novel high sensitivity CE-PTHPT for optical fiber communication

Planar punch through heterojunction phototransistors with a novel emitter control electrode and ion- implanted isolation (CE-PTHPT) are investigated. The phototransistors have a working voltage of 3-10V and high sensitivity at low input power. The base of the transistor is completely depleted under operating condition. Base current is zero. The CE-PTHPT has an increased speed and a decreased noise. The novel CE-PTHPT has been fabricated in this paper. The optical gain of GaAlAs/GaAs CE-PTHPT for the incident light power 1.3 and 43nw with the wavelength of 0.8 mu m reached 1260 and 8108. The input noise current calculated is 5.46 x 10(-16) A/H-z(1/2). For polysilicon emitter CE-PTHPT, the optical gain is 3083 at the input power of 0.174 mu w. The optical gain of InGaAs/InP CE-PTHPT reaches 350 for an incident power of 0.3 mu w at the wavelength of 1.55 mu m. The CE-PTHPT detectors is promising as photo detectors for optical fiber communication system.

Gas source molecular beam epitaxy and thermal stability of Si1-xGex/Si superlattice materials

Gas source molecular beam epitaxy has been used to grow Si1-xGex alloys and Si1-xGex/Si multi-quantum wells (MQWs) on (100) Si substrates with Si2H6 and GeH4 as sources. Heterostructures and MQWs with mirror-like surface morphology, good crystalline qualify, and abrupt interfaces have been studied by a variety of in situ and ex situ techniques. The structural stability and strain relaxation in Si1-xGex/Si heterostructures have been investigated, and compared to that in the As ion-implanted Si1-xGex epilayers. The results show that the strain relaxation mechanism of the non-implanted Si1-xGex epilayers is different from that of the As ion-implanted Si1-xGex epilayers.

碳化硅中氦离子辐照缺陷演化及SiCOI薄膜合成的研究

碳化硅是一种宽带隙半导体材料,具有禁带宽度大、击穿电压高、热导率高、电子饱和漂移速度大、介电常数小、抗辐射能力强、化学稳定性好等优良特性,使其在越来越多的领域如航空航天、太空探测、人造卫星、地热勘探、核能仪器、雷达通讯等, 所需要高温、高速、高频、大功率的微电子器件方面倍受青睐,并和氮化镓、金刚石一起被誉为发展前景十分广阔的第三代半导体材料。本论文采用He+离子注入,在SiC衬底一定深度引入纳米气泡/空腔的方法,来增强对氧原子的俘获以增加O原子在RP处局域浓度,使得更利于O与Si的反应,从而促进氧化埋层的形成,以达到降低注入O的剂量而形成优良的氧化物电绝缘层的目的。由于高剂量的O注入会引起表层SiC材料的损伤，该方法有望缓解目前SIMOX技术中O离子高剂量注入引起表层材料的损伤问题，以期获得低成本、低缺陷密度的SiCOI材料。论文主要开展了如下研究：（1）对He+离子高温（600 K）注入6H-SiC中产生的辐照缺陷,以及缺陷在阶梯温度退火的演化行为的特征进行了分析。实验采用100 keV的He+,辐照剂量范围为3.0×1015～3.0×1016 He+/cm2。利用拉曼光谱、室温光致发光谱、红外吸收光谱、沟道卢瑟福背散射谱的特征进行了分析。实验结果表明,离子注入所产生晶格损伤的程度与He+离子注入剂量有关；高温退火使得损伤得到恢复,不同注入剂量造成的晶格损伤需要不同的退火温度才可恢复。高剂量注入的样品在阶梯温度退火条件下呈现出了点缺陷的复合、氦-空位团的产生、氦泡的形核、长大等特性。与室温注入相比,高温注入引入的自退火作用使大部分简单缺陷发生复合,限制了损伤的积累,从而在材料中产生相对较小的损伤。在一定剂量范围内是避免注入层非晶化的一个重要方法,为后续利用氦离子注入空腔掩埋层吸杂或者制备低成本、低缺陷密度的绝缘层上碳化硅(SiCOI)材料提供了可能。 （2）对He的预注入引入的辐照缺陷与随后注入的氧原子的相互作用机理进行了初步分析。实验采用先He后O注入的方法，采用的离子能量为30 keV (He+)，100 keV (O+)；剂量分别为3.0×1016 (He+)、1.0×1017 (O+) ions/cm2。拉曼散射谱结果表明,空腔对氧的吸收主要是通过捕获简单缺陷释放出来的间隙氧原子实现的,进而促进了对氧的吸附,形成硅氧化合物,有利于氧化埋层的形成。紫外-可见吸收谱中的干涉带表明在材料表面下大概198 nm处是损伤层与晶体层的分界面，接近于SRIM2006估算得到的30 keV He+和100 keV O+辐照损伤的深度（He+辐照损伤的深度为195 nm；O+辐照损伤的深度为165 nm）。沟道卢瑟福背散射谱表明，在特定深度（约150 nm）处,样品中形成了接近非晶的埋层。He离子预注入的碳化硅基体由于含有较多的空位,注入的氧在退火过程中从简单缺陷中释放,向空腔层扩散并捕获在空腔层内,使得He离子预先注入形成的空腔层限制了随后O离子注入造成的损伤层的厚度

Design and fabrication of a photothermal spectrometer and investigations of multilayer thin films"

In this work we present the results of our attempt to build a compact photothermal spectrometer capable of both manual and automated mode of operation.The salient features of the system include the ability to analyse thin film, powder and polymer samples. The tool has been in use to investigate thermal, optical and transport properties. Binary and ternary semiconducting thin films were analysed for their thermal diffusivities. The system could perform thickness measurements nondestructively. Ion implanted semiconductors are widely studied for the effect of radiation induced defects. We could perform nondestructive imaging of defects using our spectrometer.The results reported in his thesis on the above in addition to studies on In2S3 and transparent conducting oxide ZnO have been achieved with this spectrometer. Various polymer samples have been easily analysed for their thermal diffusivities. The technique provided ease of analysis not achieved with conventional techniques like TGA and DSC. Industrial application of the tool has also been proved by analyzing defects of welded joints and adhesion of paints. Indigenization of the expensive lock-in-amplifier and automation has been the significant achievement in the course of this dissertation. We are on our way to prove the noise rejection capabilities of our PC LIA.

Preconcentration and determination of metal ions from fuel ethanol with a new 2,2'-dipyridylamine bonded silica

A silica surface chemically modified with [3-(2,2'-dipyridylamine) propyl] groups was prepared, characterized, and evaluated for its metal ion preconcentration in fuel ethanol. To our knowledge, we are the first authors who have reported the present modification on silica gel surface. The material was characterized using infrared spectra, scanning electronic microscopy, and 13C and 29Si solid-state NMR spectra. Batch and column experiments were conducted to investigate for metal ion removal from fuel ethanol. The results showed that the Langmuir model describes the sorption equilibrium data of the metal ions in a satisfactory way. From the Langmuir isotherms, the following maximum adsorption capacities (in mmolg -1) were determined: 1.81 for Fe(III), 1.75 for Cr(III), 1.30 for Cu(II), 1.25 for Co(II), 1.15 for Pb(II), 0.95 for Ni(II), and 0.87 for Zn(II). Thermodynamic functions, the change of free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) showed that the adsorption of metal ions onto Si-Pr-DPA was feasible, spontaneous, and endothermic. The sorption-desorption of the metal ions made possible the development of a preconcentration and quantification method of metal ions in fuel ethanol. © 2012 Elsevier Inc.

Dispositifs optoélectroniques à base de semi-conducteurs organiques en couches minces

Les petites molécules de type p à bandes interdites étroites sont de plus en plus perçues comme des remplaçantes possibles aux polymères semi-conducteurs actuellement utilisés conjointement avec des dérivés de fullerènes de type n, dans les cellules photovoltaïques organiques (OPV). Par contre, ces petites molécules tendent à cristalliser facilement lors de leur application en couches minces et forment difficilement des films homogènes appropriés. Des dispositifs OPV de type hétérojonction de masse ont été réalisés en ajoutant différentes espèces de polymères semi-conducteurs ou isolants, agissant comme matrices permettant de rectifier les inhomogénéités des films actifs et d’augmenter les performances des cellules photovoltaïques. Des polymères aux masses molaires spécifiques ont été synthétisés par réaction de Wittig en contrôlant précisément les ratios molaires des monomères et de la base utilisée. L’effet de la variation des masses molaires en fonction des morphologies de films minces obtenus et des performances des diodes organiques électroluminescentes reliées, a également été étudié. La microscopie électronique en transmission (MET) ou à balayage (MEB) a été employée en complément de la microscopie à force atomique (AFM) pour suivre l’évolution de la morphologie des films organiques minces. Une nouvelle méthode rapide de préparation des films pour l’imagerie MET sur substrats de silicium est également présentée et comparée à d’autres méthodes d’extraction. Motivé par le prix élevé et la rareté des métaux utilisés dans les substrats d’oxyde d’indium dopé à l’étain (ITO), le développement d’une nouvelle méthode de recyclage eco-responsable des substrats utilisés dans ces études est également présenté.

Dispositifs optoélectroniques à base de semi-conducteurs organiques en couches minces

Les petites molécules de type p à bandes interdites étroites sont de plus en plus perçues comme des remplaçantes possibles aux polymères semi-conducteurs actuellement utilisés conjointement avec des dérivés de fullerènes de type n, dans les cellules photovoltaïques organiques (OPV). Par contre, ces petites molécules tendent à cristalliser facilement lors de leur application en couches minces et forment difficilement des films homogènes appropriés. Des dispositifs OPV de type hétérojonction de masse ont été réalisés en ajoutant différentes espèces de polymères semi-conducteurs ou isolants, agissant comme matrices permettant de rectifier les inhomogénéités des films actifs et d’augmenter les performances des cellules photovoltaïques. Des polymères aux masses molaires spécifiques ont été synthétisés par réaction de Wittig en contrôlant précisément les ratios molaires des monomères et de la base utilisée. L’effet de la variation des masses molaires en fonction des morphologies de films minces obtenus et des performances des diodes organiques électroluminescentes reliées, a également été étudié. La microscopie électronique en transmission (MET) ou à balayage (MEB) a été employée en complément de la microscopie à force atomique (AFM) pour suivre l’évolution de la morphologie des films organiques minces. Une nouvelle méthode rapide de préparation des films pour l’imagerie MET sur substrats de silicium est également présentée et comparée à d’autres méthodes d’extraction. Motivé par le prix élevé et la rareté des métaux utilisés dans les substrats d’oxyde d’indium dopé à l’étain (ITO), le développement d’une nouvelle méthode de recyclage eco-responsable des substrats utilisés dans ces études est également présenté.

Advanced Analytical Microscopy at the Nanoscale: Applications in Wide Bandgap and Solid Oxide Fuel Cell Materials

The atomic-level structure and chemistry of materials ultimately dictate their observed macroscopic properties and behavior. As such, an intimate understanding of these characteristics allows for better materials engineering and improvements in the resulting devices. In our work, two material systems were investigated using advanced electron and ion microscopy techniques, relating the measured nanoscale traits to overall device performance. First, transmission electron microscopy and electron energy loss spectroscopy (TEM-EELS) were used to analyze interfacial states at the semiconductor/oxide interface in wide bandgap SiC microelectronics. This interface contains defects that significantly diminish SiC device performance, and their fundamental nature remains generally unresolved. The impacts of various microfabrication techniques were explored, examining both current commercial and next-generation processing strategies. In further investigations, machine learning techniques were applied to the EELS data, revealing previously hidden Si, C, and O bonding states at the interface, which help explain the origins of mobility enhancement in SiC devices. Finally, the impacts of SiC bias temperature stressing on the interfacial region were explored. In the second system, focused ion beam/scanning electron microscopy (FIB/SEM) was used to reconstruct 3D models of solid oxide fuel cell (SOFC) cathodes. Since the specific degradation mechanisms of SOFC cathodes are poorly understood, FIB/SEM and TEM were used to analyze and quantify changes in the microstructure during performance degradation. Novel strategies for microstructure calculation from FIB-nanotomography data were developed and applied to LSM-YSZ and LSCF-GDC composite cathodes, aged with environmental contaminants to promote degradation. In LSM-YSZ, migration of both La and Mn cations to the grain boundaries of YSZ was observed using TEM-EELS. Few substantial changes however, were observed in the overall microstructure of the cells, correlating with a lack of performance degradation induced by the H2O. Using similar strategies, a series of LSCF-GDC cathodes were analyzed, aged in H2O, CO2, and Cr-vapor environments. FIB/SEM observation revealed considerable formation of secondary phases within these cathodes, and quantifiable modifications of the microstructure. In particular, Cr-poisoning was observed to cause substantial byproduct formation, which was correlated with drastic reductions in cell performance.