Copper Diffusion Barrier Deposition on Integrated Circuit Devices by Atomic Layer Deposition Technique

Transfer from aluminum to copper metallization and decreasing feature size of integrated circuit devices generated a need for new diffusion barrier process. Copper metallization comprised entirely new process flow with new materials such as low-k insulators and etch stoppers, which made the diffusion barrier integration demanding. Atomic Layer Deposition technique was seen as one of the most promising techniques to deposit copper diffusion barrier for future devices. Atomic Layer Deposition technique was utilized to deposit titanium nitride, tungsten nitride, and tungsten nitride carbide diffusion barriers. Titanium nitride was deposited with a conventional process, and also with new in situ reduction process where titanium metal was used as a reducing agent. Tungsten nitride was deposited with a well-known process from tungsten hexafluoride and ammonia, but tungsten nitride carbide as a new material required a new process chemistry. In addition to material properties, the process integration for the copper metallization was studied making compatibility experiments on different surface materials. Based on these studies, titanium nitride and tungsten nitride processes were found to be incompatible with copper metal. However, tungsten nitride carbide film was compatible with copper and exhibited the most promising properties to be integrated for the copper metallization scheme. The process scale-up on 300 mm wafer comprised extensive film uniformity studies, which improved understanding of non-uniformity sources of the ALD growth and the process-specific requirements for the ALD reactor design. Based on these studies, it was discovered that the TiN process from titanium tetrachloride and ammonia required the reactor design of perpendicular flow for successful scale-up. The copper metallization scheme also includes process steps of the copper oxide reduction prior to the barrier deposition and the copper seed deposition prior to the copper metal deposition. Easy and simple copper oxide reduction process was developed, where the substrate was exposed gaseous reducing agent under vacuum and at elevated temperature. Because the reduction was observed efficient enough to reduce thick copper oxide film, the process was considered also as an alternative method to make the copper seed film via copper oxide reduction.

Grazing impacts on the susceptibility of rangelands to wind erosion: The effects of stocking rate, stocking strategy and land condition

An estimated 110 Mt of dust is eroded by wind from the Australian land surface each year, most of which originates from the arid and semi-arid rangelands. Livestock production is thought to increase the susceptibility of the rangelands to wind erosion by reducing vegetation cover and modifying surface soil stability. However, research is yet to quantify the impacts of grazing land management on the erodibility of the Australian rangelands, or determine how these impacts vary among land types and over time. We present a simulation analysis that links a pasture growth and animal production model (GRASP) to the Australian Land Erodibility Model (AUSLEM) to evaluate the impacts of stocking rate, stocking strategy and land condition on the erodibility of four land types in western Queensland, Australia. Our results show that declining land condition, over stocking, and using inflexible stocking strategies have potential to increase land erodibility and amplify accelerated soil erosion. However, land erodibility responses to grazing are complex and influenced by land type sensitivities to different grazing strategies and local climate characteristics. Our simulations show that land types which are more resilient to livestock grazing tend to be least susceptible to accelerated wind erosion. Increases in land erodibility are found to occur most often during climatic transitions when vegetation cover is most sensitive to grazing pressure. However, grazing effects are limited during extreme wet and dry periods when the influence of climate on vegetation cover is strongest. Our research provides the opportunity to estimate the effects of different land management practices across a range of land types, and provides a better understanding of the mechanisms of accelerated erosion resulting from pastoral activities. The approach could help further assessment of land erodibility at a broader scale notably if combined with wind erosion models.

Essays on Banking Crises

This thesis aims at finding the role of deposit insurance scheme and central bank (CB) in keeping the banking system safe. The thesis also studies the factors associated with long-lasting banking crises. The first essay analyzes the effect of using explicit deposit insurance scheme (EDIS), instead of using implicit deposit insurance scheme (IDIS), on banking crises. The panel data for the period of 1980-2003 includes all countries for which the data on EDIS or IDIS exist. 70% of the countries in the sample are less developed countries (LDCs). About 55% of the countries adopting EDIS also come from LDCs. The major finding is that the using of EDIS increases the crisis probability at a strong significance level. This probability is greater if the EDIS is inefficiently designed allowing higher scope of moral hazard problem. Specifically, the probability is greater if the EDIS provides higher coverage to deposits and if it is less powerful from the legal point of view. This study also finds that the less developed a country is to handle EDIS, the higher the chance of banking crisis. Once the underdevelopment of an economy handling the EDIS is controlled, the EDIS separately is no longer a significant factor of banking crises. The second essay aims at determining whether a country s powerful CB can lessen the instability of the banking sector by minimizing the likelihood of a banking crisis. The data used include indicators of the CB s autonomy for a set of countries over the period of 1980-89. The study finds that in aggregate a more powerful CB lessens the probability of banking crisis. When the CB s authority is disentangled with respect to its responsibilities, the study finds that the longer tenure of CB s chief executive officer and the greater power of CB in assigning interest rate on government loans are necessary for reducing the probability of banking crisis. The study also finds that the probability of crisis reduces more if an autonomous CB can perform its duties in a country with stronger law and order tradition. The costs of long-lasting banking crises are high because both the depositors and the investors lose confidence in the banking system. For a rapid recovery of a crisis, the government very often undertakes one or more crisis resolution policy (CRP) measures. The third essay examines the CRP and other explanatory variables correlated with the durations of banking crises. The major finding is that the CRP measure allowing the regulation forbearance to keep the insolvent banks operative and the public debt relief program are respectively strongly and weakly significant to increase the durations of crises. Some other explanatory variables, which were found by previous studies to be related with the probability of crises to occur, are also correlated with the durations of crises.

Corporate Governance in European Banks: Essays on Bank Ownership

Banks are important as they have a central role in the financial system, where funds are channelled either through financial intermediaries, such as banks, or through financial markets, hence promoting growth in any economy. Recently, we have been reminded of the drawbacks of the central role of banks. The current financial crisis, which started out as a sub-prime mortgage crisis in the US, has become a global financial crisis with substantial impact on the real economy in many countries. Some of the roots to the current financial crisis can be sought in the changing role of banks and in bank corporate governance. Moreover, the substantial revitalising measures taken have been justified by the central role of banks. Not only are banks important, they are also very special. The fact that banks are regulated in conjunction with greater opacity, make bank corporate governance different from corporate governance in non-bank companies. Surprisingly little is, however, known about bank corporate governance, in particularly, in a European setting. Hence, the objective of this doctoral thesis is to provide new insights in this research area by examining banks from 37 different European countries. Each of the three essays included in the doctoral thesis examines a particular aspect of bank corporate governance. In the first essay the interaction between the regulatory environment a bank operates in and its ownership structure is explored. Indicators of the severity of the moral hazard problem induced by the deposit insurance system and implicit too-big-to-fail government guarantee, particular features of deposit insurance systems as well as legal protection of shareholders, legal origin of a country and level of integration to the European community are used in the analysis. The empirical findings confirm previous findings on the link between legal protection of shareholders and ownership structure. Moreover, they show that differences in deposit insurance system features can explain some of the differences in ownership structure across European banks. In the second essay the impact of management and board ownership on the profitability of banks with different strategy is examined. The empirical findings suggest that the efficiency of these two particular corporate governance mechanisms varies with the characteristics of the agency problem faced by the bank. More specifically, management ownership is important in opaque non-traditional banks, whereas board ownership is important in traditional banks, where deposit insurance reduces the monitoring incentives of outsiders. The higher profitability does, however, go together with higher risk. In the third essay the profitability and risk of commercial, savings and cooperative banks are compared. The empirical findings suggest that distinct operational and ownership characteristics rather than only the mere fact that a bank is a commercial, savings or cooperative bank explain the profitability and risk differences. The main insight from the three essays is that a number of different aspects should be addressed simultaneously in order to give the complexity of bank corporate governance justice.

Bank Run Risk and Optimal Reserves

We characterize the optimal reserves, and the generated probability of a bank run, as a function of the penalty imposed by the central bank, the probability of depositors’ liquidity needs, and the return on outside investment opportunities.

As-deposited near-single crystalline high Tc and Jc superconducting thin films by a pulsed lased deposition process

As-deposited high Tc superconducting Y1Ba2Cu3O7−x films with zero resistance temperatures of similar, equals89 K and critical current densities about 0.7×106 A/cm2 at 77 K have been reproducibly fabricated at a substrate holder temperature at 650°C, using pulsed laser deposition, without post-annealing. One key to these results is the injection of gaseous oxygen into laser produced plume just in front of the target. In this way, the correct amount of oxygen is incorporated into the as-grown film so that post-deposition treatment becomes unnecessary. Axial ion channeling in these as-deposit high Tc superconducting films on (100) SrTiO3 and X-ray photoelectron spectroscopy (XPS) on the film surfaces were performed. Angular yield profile near the film surface for Ba, and the surface peak intensity were measured using 3 MeV He ions. For channeling normal to the substrate a minimum yield of 7%, compared to similar, equals3% for single crystals, was obtained. The results of ion channeling and XPS studies indicate that the as-deposited films have good crystallinity as well as toichiometry to within similar, equals1 nm of the film surface. The in-situ growth of such high Tc and Jc films is an important step in the use of the laser deposition technique to fabricate multilayer structures and the surface perfection is of importance in tunneling devices such as Josephson junctions.

The Amenability Studies on Beneficiation of Low Grade Phyllite Deposits of Tungsten From Degana, Rajasthan

The phyllite deposit of Degana, Rajasthan, containing tungsten values in the form of wolframite, (Fe, MnWO sub 4 ) finely dispersed in the quartz groundmass, has been quantitatively analysed to give 0.063% WO sub 3 , 6.66% Fe sub 2 O sub 3 , 14.30% Al sub 2 O sub 3 and 67.4% SiO sub 2 . The major gangue minerals identified are quartz, iron oxides and mica along with minor amounts of graphite, fluorite and sulphides. The amenability of the ore to gravity concentration, magnetic separation and a combination of the processes has been studied. A combination of tabling on --100 mesh ground ore and dry magnetic separation of the tabled concentrate gave a final concentrate containing 1.834% WO sub 3 with an overall recovery of only 4.6%. The complex mineralogy combined with fine dispersion of very low W values have contributed to the low recoveries and grades. Graph, photomicrographs. 10 ref.--AA

Microstructure and Properties of the Spray-Formed and Extruded 7075 Al Alloy

In the present investigation, a very good combination of strength and ductility, 630MPa 0.2% proof stress and 14.8% elongation to fracture in tensile test, has been obtained for the 7075 Al alloy after optimizing the processing parameters for spray forming, hot extruding the spray deposit, and peak aging the samples taken from the extruded rod. The spray deposits contained some porosity but it was almost eliminated on hot extrusion. Electron probe microanalysis revealed that even though spray forming was carried out in an open atmosphere, it did not affect the oxygen content and its distribution in the material on spray forming, because the atomizing argon gas provided a protective cover to molten droplets and prevented their oxidation. The chemical composition of the spray-formed material was found to be almost the same as the raw material, and the major alloying elements were found to be uniformly distributed in the extruded rod.

Precursor Dependent Microstructure Evolution and Nonstoichiometry in Nanostructured Cerium Oxide Coatings Using the Solution Precursor Plasma Spray Technique

A solution precursor plasma spray (SPPS) technique has been used for direct deposition of cerium oxide nanoparticles (CNPs) from various cerium salt solutions as precursors. Solution precursors were injected into the hot zone of a plasma plume to deposit CNP coatings. A numerical study of the droplet injection model has been employed for microstructure development during SPPS. The decomposition of each precursor to cerium oxide was analyzed by thermogravimetric-differential thermal analysis and validated by thermodynamic calculations. The presence of the cerium oxide phase in the coatings was confirmed by X-ray diffraction studies. Transmission electron microscopy studies confirmed nanocrystalline (grain size <14 nm) characteristic of the coatings. X-ray photoelectron spectroscopy studies indicated the presence of a high concentration of Ce3+ (up to 0.32) in the coating prepared by SPPS. The processing and microstructure evolution of cerium oxide coatings with high nonstoichiometry are reported.

Selective-Area Atomic Layer Deposition

Atomic layer deposition (ALD) is a method to deposit thin films from gaseous precursors to the substrate layer-by-layer so that the film thickness can be tailored with atomic layer accuracy. Film tailoring is even further emphasized with selective-area ALD which enables the film growth to be controlled also on the substrate surface. Selective-area ALD allows the decrease of a process steps in preparing thin film devices. This can be of a great technological importance when the ALD films become into wider use in different applications. Selective-area ALD can be achieved by passivation or activation of a surface. In this work ALD growth was prevented by octadecyltrimethoxysilane, octadecyltrichlorosilane and 1-dodecanethiol SAMs, and by PMMA (polymethyl methacrylate) and PVP (poly(vinyl pyrrolidone) polymer films. SAMs were prepared from vapor phase and by microcontact printing, and polymer films were spin coated. Microcontact printing created patterned SAMs at once. The SAMs prepared from vapor phase and the polymer mask layers were patterned by UV lithography or lift-off process so that after preparation of a continuous mask layer selected areas of them were removed. On these areas the ALD film was deposited selectively. SAMs and polymer films prevented the growth in several ALD processes such as iridium, ruthenium, platinum, TiO2 and polyimide so that the ALD films did grow only on areas without SAM or polymer mask layer. PMMA and PVP films also protected the surface against Al2O3 and ZrO2 growth. Activation of the surface for ALD of ruthenium was achieved by preparing a RuOX layer by microcontact printing. At low temperatures the RuCp2-O2 process nucleated only on this oxidative activation layer but not on bare silicon.

A novel laser direct write technique for fabrication of thin film MICs

A technique for fabrication of thin-film circuits for microwave integrated circuit (MIC) application is presented. This low-cost fabrication technique utilizes laser direct write of copper patterns on alumina substrates. The method obviates the need for photomasks and photolithography. The film deposition mechanism, deposit film analysis, and MIC fabrication sequence are presented. Performance evaluation of MICs fabricated using this technique is also included

FIN-CLARIN: A Framework for Depositing and Disseminating Language Resources for R&D

Researchers and developers in academia and industry would benefit from a facility that enables them to easily locate, licence and use the kind of empirical data they need for testing and refining their hypotheses and to deposit and disseminate their data e.g. to support replication and validation of reported scientific experiments. To answer these needs initially in Finland, there is an ongoing project at University of Helsinki and its collaborators to create a user-friendly web service for researchers and developers in Finland and other countries. In our talk, we describe ongoing work to create a palette of extensive but easily available Finnish language resources and technologies for the research community, including lexical resources, wordnets, morphologically tagged corpora, dependency syntactic treebanks and parsebanks, open-source finite state toolkits and libraries and language models to support text analysis and processing at customer site. Also first publicly available results are presented.

Nano structured carbon nitrides prepared by chemical vapour deposition

Nanostructured carbon nitride films were prepared by pyrolysis assisted chemical vapour deposition(CVD). A two zone furnace with a temperature profile having a uniform temperature over a length of 20 cm length has been designed and developed. The precursor Azabenzimidazole was taken in a quartz tube and evaporated at 400 degrees C. The dense vapours enter the pyrolysis zone kept at a desired temperature and deposit on the quartz substrates. The FTIR spectrum of the prepared samples shows peaks at 1272 cm(-1) (C-N stretching) and 1600 cm(-1) (C=N) confirms the bonding of nitrogen with carbon. Raman D and G peaks, are observed at 1360 cm(-1) and 1576 cm(-1) respectively. XPS core level spectra of C 1s and N 1s show the formation of pi bonding between carbon and nitrogen atoms. The size of the nano crystals estimated from the SEM images and XRD is similar to 100 nm. In some regions of the sample a maximum of 57 atom % of nitrogen has been observed.

Ultrasonic spray pyrolysis of CZTS solar cell absorber layers and characterization studies

CZTS (Copper Zinc Tin Sulphide) is a wide band gap quartnery chalcopyrite which has a band gap of about 1.45 eV and an absorption coefficient of 10(4) cm(-1); thus making it an ideal material to be used as an absorber layer in solar cells. Ultrasonic Spray Pyrolysis is a deposition technique, where the solution is atomized ultrasonically, thereby giving a fine mist having a narrow size distribution which can be used for uniform coatings on substrates. An Ultrasonic Spray Pyrolysis equipment was developed and CZTS absorber layers were successfully grown with this technique on soda lime glass substrates using aqueous solutions. Substrate temperatures ranging from 523 K to 723 K were used to deposit the CZTS layers and these films were characterized using SEM, EDAX and XRD. It was observed that the film crystallized in the kesterite structure and the best crystallites were obtained at 613 K. It was observed that the grain size progressively increased with temperature. The optical band gap of the material was obtained as 1.54 eV.

Thermodynamic modeling to analyse composition of carbonaceous coatings of MnO and other oxides of manganese grown by MOCVD

Equilibrium thermodynamic analysis has been applied to the low-pressure MOCVD process using manganese acetylacetonate as the precursor. ``CVD phase stability diagrams'' have been constructed separately for the processes carried out in argon and oxygen ambient, depicting the compositions of the resulting films as functions of CVD parameters. For the process conduced in argon ambient, the analysis predicts the simultaneous deposition of MnO and elemental carbon in 1: 3 molar proportion, over a range of temperatures. The analysis predicts also that, if CVD is carried out in oxygen ambient, even a very low flow of oxygen leads to the complete absence of carbon in the film deposited oxygen, with greater oxygen flow resulting in the simultaneous deposition of two different manganese oxides under certain conditions. The results of thermodynamic modeling have been verified quantitatively for low-pressure CVD conducted in argon ambient. Indeed, the large excess of carbon in the deposit is found to constitute a MnO/C nanocomposite, the associated cauliflower-like morphology making it a promising candidate for electrode material in supercapacitors. CVD carried out in oxygen flow, under specific conditions, leads to the deposition of more than one manganese oxide, as expected from thermodynamic analysis ( and forming an oxide-oxide nanocomposite). These results together demonstrate that thermodynamic analysis of the MOCVD process can be employed to synthesize thin films in a predictive manner, thus avoiding the inefficient trial-and-error method usually associated with MOCVD process development. The prospect of developing thin films of novel compositions and characteristics in a predictive manner, through the appropriate choice of CVD precursors and process conditions, emerges from the present work.