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1
Lewis, R. R. "Mechanisms of copper vapour lasers." Thesis, University of Oxford, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.233563.
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2
Marshall, Graham David. "Kinetically enhanced copper vapour lasers." Thesis, University of Oxford, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.270222.
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3
Wadsworth, W. J. "Copper vapour laser pumped TI:sapphire lasers." Thesis, University of Oxford, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.389029.
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4
Kapitan, Daniel. "Laser ablation with copper vapour lasers." Thesis, University of Oxford, 1999. https://ora.ox.ac.uk/objects/uuid:a1dc1a3b-602a-4ebb-abe2-734e8e11f15a.
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The use of copper vapour lasers for laser ablation in laser materials processing applications is studied. To this purpose, the generation of near diffraction-limited beam quality output from a single medium-scale oscillator is demonstrated via matching the total buffer gas pressure to the specific electrical input power loading and the degree of insulation of the plasma tube. The design and characterisation of a Master-Oscillator Power-Amplifier system based on a smallbore oscillator is also described, focusing on pulse stretching techniques to provide efficient seeding required for producing 20-50 W high beam-quality output for laser materials processing purposes. Various experimental studies on the fundamental processes of laser ablation of metals are presented. The effect of the background gas properties on shock-wave formation in laser generated plasmas is studied using a ballistic pendulum. The experimental findings are found to be accurately described by a modified Sedov-Taylor-Von Neumann theory which accounts for the effect of the piston-mass. The theory is applied to characterise the fluorination process in the shock-wave, in view of oxygen isotope analysis in geochemistry. Atomic emission spectroscopy is shown to provide some measure of the electron temperature and electron density at the plasma core. The experimental results are discussed in view of existing models to describe the extreme Stark-broadening and self-absorption in dense, cool plasmas. A comparative study of the use of femtosecond and nanosecond pulsed lasers for laser ablation of metals is presented to assess the relative importance of thermal diffusion. Measurement of the recoil momentum due to ejection of molten particulates during ablation in vacuum provides insight into the effect of material properties. Diffusion-limited surface texturing of metals via direct transfer of an optical interference patterns is demonstrated.
5
Clark, Graeme Lawrence. "Studies of copper and gold vapour lasers." Thesis, University of St Andrews, 1988. http://hdl.handle.net/10023/13803.
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The work described in this thesis covers various aspects of pulsed copper and gold vapour lasers. The work is divided into four main parts : a computer model of the kinetics of the copper vapour laser discharge; construction and characterization of a copper vapour laser and a gold vapour laser system (to be used for photodynamic cancer treatment); analysis of the thermal processes occurring in the various forms of thermal insulation used in these lasers; and studies of the use of metal walls to confine a discharge plasma. The results of this work were combined in the design of the first copper vapour laser to use metal rather than an electrically insulating ceramic material for confinement of the discharge plasma. Laser action in copper vapour has been achieved in a number of metal-walled designs, with continuous lengths of metal ranging from 30 mm, in a segmented design, to 400 mm, where the discharge plasma was confined by two molybdenum tubes of this length. A theoretical explanation of the behaviour of plasmas in metal-walled discharge vessels is described.
6
Hogan, Geoff P. "A study of the kinetics of copper vapour lasers." Thesis, University of Oxford, 1993. https://ora.ox.ac.uk/objects/uuid:174eb6ce-3576-49c1-add4-5e1b0d2e1571.
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A 42 mm bore, 40 W copper vapour laser (CVL) has been set up in a test rig in order to measure the values of many of the parameters of the laser as a function of time in the laser pulse-delay cycle, and of radial position in the plasma tube, while at all times running under standard operating conditions. In this way it has been possible to obtain the world's first truly comprehensive parameter map of the CVL in which all of the measurements have been performed upon the same device, operating under identical conditions and with all times accurately referenced to a datum. It is intended that this set of data is primarily for the benefit of those involved in the computer modelling of the CVL plasma, however initial analysis of the results obtained has been undertaken. All diagnostic techniques have been carefully selected as offering the highest possible level of accuracy and freedom from assumptions, and each one employed has been described in detail in terms of both theory and practical application. The hook method has been used for the measurement of the population density in the copper ground state, the upper and lower laser levels, one of the copper quartet levels, and one of the neon metastable levels, each with a time resolution of 5 ns, and a radial resolution of 2 mm. The electron density has been measured, also with a radial resolution of 2 mm and with nanosecond time resolution using a two colour interferometric technique employing the measurement of the refractive index of the plasma at 10.6 μm and 670 nm. Measurement has been made of the voltage on the laser electrodes and the current flowing in the laser during the discharge. Ancillary experiments have been performed to study the CVL discharge which have yielded some unexpected results, and measurements have been performed on a 60 mm bore CVL to determine fully the mechanism of the time delay between the onset of lasing at the plasma tube wall and on axis, and novel observations have been made.
7
Fallberg, Anna. "Chemical Vapour Deposition of Undoped and Oxygen Doped Copper (I) Nitride." Doctoral thesis, Uppsala universitet, Institutionen för materialkemi, 2010. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-110533.
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In science and technology there is a steadily increased demand of new materials and new materials production processes since they create new application areas as well as improved production technology and economy. This thesis includes development and studies of a chemical vapour deposition (CVD) process for growth of thin films of the metastable material copper nitride, Cu3N, which is a semiconductor and decomposes at around 300 oC. The combination of these properties opens for a variety of applications ranging from solar cells to sensor and information technology. The CVD process developed is based on a metal-organic compound copper hexafluoroacetylacetonate, Cu(hfac)2 , ammonia and water and was working at about 300 oC and 5 Torr. It was found that a small amount of water in the vapour increased the growth rate considerably and that the phase content, film texture, chemical composition and morphology were strongly dependent on the deposition conditions. In-situ oxygen doping during the CVD of Cu3N to an amount of 9 atomic % could also be accomplished by increasing the water concentration in the vapour. Oxygen doping increases the band gap of the material as well as the electrical resistivity and changes the stability. The crystal structure of Cu3N is very open and contains several sites which can be used for doping. Different spectroscopic techniques like X-ray photoelectron spectroscopy, Raman spectroscopy and near edge X-ray absorption fine structure spectroscopy were used to identify the oxygen doping site(s) in Cu3N. Besides the properties, the oxygen doping also affected the morphology and texture of the films. By combining thin layers of different materials several properties can be optimized at the same time. It has been demonstrated in this thesis that multilayers, composed of alternating Cu3N and Cu2O layers, i.e. a metastable and a stable material, could be grown by CVD technique. However, the stacking sequence affected the texture, morphology and chemical composition. The interfaces between the different layers were sharp and no signs of decomposition of the initially deposited metastable Cu3N layer could be detected.
8
Lewis, Amanda. "Fundamental studies of the chemical vapour deposition of graphene on copper." Thesis, University of Manchester, 2014. https://www.research.manchester.ac.uk/portal/en/theses/fundamental-studies-of-the-chemical-vapour-deposition-of-graphene-on-copper(f85feb54-5994-4201-b400-c622f4d7b216).html.
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The chemical vapour deposition (CVD) of graphene is the most promising route for production of large-area graphene films. However there are still major challenges faced by the field, including control of the graphene coverage, quality, and the number of layers. These challenges can be overcome by developing a fundamental understanding of the graphene growth process. This thesis contributes to the growing body of work on graphene CVD by uniquely exploring the gas phase chemistry and fluid flow in the hot-wall graphene CVD reactor. Firstly the reported parameter space for the hot-wall CVD of graphene on copper was mapped, informing the subsequent work and providing a resource for the wider community. A CVD reactor was constructed to extend this parameter space to lower pressures using methane as a carbon source, and the films were categorised using scanning electron microscopy, Raman spectroscopy and optical dark field microscopy. The latter showed particular promise as a rapid and non-destructive characterization technique for identifying graphene films on the deposition substrate. The gas phase equilibrium compositions were calculated across the parameter space, and correlations between the stabilities of various chemical species and the types of deposition were drawn. This laid a foundation for the remainder of the experimental work, which explored the effect of diluent gases and different feedstocks on the growth to understand the importance of the identified correlations. Diluent gases (argon and nitrogen) were added to the experimental conditions and the thermodynamic model, and were found to reduce the degree of coverage of the graphene films. This result shows that the CVD of graphene is sensitive to factors other than the thermodynamic state parameters, such as the fluid flow profile in the reactor and inelastic collisions between the higher mass diluent gases and the methane/hydrogen/copper system. Using a nitrogen diluent raises the equilibrium carbon vapour pressure and seems to allow larger graphene grains to form. This suggests that thermodynamic factors can contribute to the nucleation of graphene films. Varying the hydrocarbon feedstock and the process conditions indicated that the structure of the deposited carbon is closely related to the nucleation kinetics. Three nucleation regimes are associated with different types of deposition: homogeneous nucleation with amorphous carbon or soot; uncatalysed nucleation with multilayer deposition; and nucleation processes controlled by the copper substrate withpredominantly monolayer deposition. Changing the feedstock from methane to acetylene resulted in poorer graphene coverage, showing that thermodynamic control does not apply in the portion of the parameter space at the high temperatures and lowpressures most successfully used for the deposition of continuous graphene monolayers.
9
Boreland, Matt School of Electrical Engineering UNSW. "Laser Crystallisation of Silicon for Photovoltaic Applications using Copper Vapour Lasers." Awarded by:University of New South Wales. School of Electrical Engineering, 1999. http://handle.unsw.edu.au/1959.4/17190.
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Thin film silicon on low temperature glass substrates is currently seen as the best path toreduce the $/W cost of photovoltaic (PV) modules. However, producing thin film polysilicon, on glass, is an ongoing research challenge. Laser crystallisation of a-Si is one of the possible methods. Typically excimer (XMR) lasers are used for laser crystallisation. This thesis introduces the copper vapour laser (CVL) as a viable alternative for thin film photovoltaic applications. The CVL, like the XMR, is a high powered, pulsed laser. However, the CVL has higher pulse rates (4-20kHz), better beam quality and a visible wavelength output (578 & 511nm). Preliminary experiments, using 600K-heated silicon-on-quartz samples, confirmed that CVL crystallisation can produce area weighted average grain size of 0.1-0.15??m, which is comparable to results reported for XMR??? s. Importantly, the CVL results used thicker films (1??m), which is more applicable to thin photovoltaic devices that need 1-10??m of silicon to be viable. The CVL??? s longer wavelength and therefore longer penetration depth (1/alpha) are proffered as the main reason for this result. Extensive laser-thermal modelling highlighted further opportunities specific to CVL crystallisation. Through-the-glass doublesided irradiation was shown in simulations to reduce thermal gradients, which would enhance crystal growth. The simulations also produced deeper melts at lower surface temperatures, reducing the thermal stress on the sample. Subsequent experiments, using silicon-on-glass, confirmed the benefit of through-the-glass doublesided irradiation by maintaining grain sizes without the usual need for substrate heating. Furthermore, Raman analysis showed that doublesided crystallisation achieved full depth crystallisation, unlike single side irradiation which produced partial crystallisation. A new mode of crystallisation, stepwise crystallisation, was also postulated whereby a series of CVL pulses could be used to incrementally increase the crystallisation depth into the silicon. Simulations confirmed the theoretical basis of the concept, with HeNe Raman spectroscopy and analysis of surface grain sizes providing indirect experimental support. The CVL??? s ability to crystallise thicker films more directly applicable to photovoltaic devices secures its viability as an alternative laser for photovoltaic applications. The through-the-glass doublesided irradiation and the stepwise crystallisation provide additional potential for increased process flexibility over XMR???s.
10
Boreland, Matt. "Laser crystallisation of silicon for photovoltaic applications using copper vapour lasers." [Sydney : University of New South Wales], 1999. http://www.library.unsw.edu.au/~thesis/adt-NUN/public/adt-NUN1999.0055/index.html.
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Knowles, Martyn R. H. "Solid state devices for frequency conversion of Copper Vapour Laser radiation." Thesis, University of Oxford, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.240635.
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Rosenberg, Chico L. "Novel precursors for chemical vapour deposition of the metals copper, nickel and cobalt." Thesis, Imperial College London, 2003. http://hdl.handle.net/10044/1/11893.
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McGonigle, A. J. S. "Tunable UV lasers." Thesis, University of Oxford, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.343230.
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Perkins, Neil. "Reactivity of Pd single crystal, alloy and model catalyst surfaces." Thesis, University of Reading, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.369758.
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Cox, Jennifer Jane. "Structure of organic molecular thin films vapour deposited on III-V semiconductor surfaces." Thesis, Imperial College London, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.327025.
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Nuesca, Guillermo M. "Surface and Interfacial Studies of Metal-Organic Chemical Vapor Deposition of Copper." Thesis, University of North Texas, 1997. https://digital.library.unt.edu/ark:/67531/metadc278058/.
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The nucleation and successful growth of copper (Cu) thin films on diffusion barrier/adhesion promoter substrates during metal-organic chemical vapor deposition (MOCVD) are strongly dependent on the initial Cu precursor-substrate chemistry and surface conditions such as organic contamination and oxidation. This research focuses on the interactions of bis(1,1,1,5,5,5-hexafluoroacetylacetonato)copper(II), [Cu(hfac)2], with polycrystalline tantalum (Ta) and polycrystalline as well as epitaxial titanium nitride (TiN) substrates during Cu MOCVD, under ultra-high vacuum (UHV) conditions and low substrate temperatures (T < 500 K). The results obtained from X-ray photoelectron
spectroscopy (XPS), Auger Electron Spectroscopy (AES) and Temperature Programmed Desorption (TPD) measurements indicate substantial differences in the chemical reaction pathways of metallic Cu formation from Cu(hfac)2 on TiN versus Ta surfaces.
17
Procházka, Pavel. "Příprava grafenu metodou CVD." Master's thesis, Vysoké učení technické v Brně. Fakulta strojního inženýrství, 2012. http://www.nusl.cz/ntk/nusl-230205.
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This diploma thesis is mainly focused on the fabrication of graphene layers on the copper foil by the Chemical Vapor Deposition (CVD). For this purpose the high-temperature chamber for the production of the graphene was completed and fully automated. The production of the high area graphene on the copper foil was experimentally achieved. The Raman microscopy and X-ray photoelectron spectroscopy measurements proved that the produced graphene is mostly a monolayer. Graphene layer was transferred on non-conductive substrate.
18
Welton, Theresa E. (Theresa Eilene). "The Metal-Organic Chemical Vapor Deposition of Cu(II)-bishexafluoroacetylacetonate on a Tungsten Substrate." Thesis, University of North Texas, 1992. https://digital.library.unt.edu/ark:/67531/metadc500726/.
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Evidence is reported for the formation of carbon-containing contamination products at the copper-tungsten (Cu-W) interface during the metal organic chemical vapor deposition (MOCVD) of copper on tungsten. Cu(II)bishexafluoroacetylacetonate [Cu(hfac)_2] was physisorbed onto lightly oxidized tungsten (WO_x) at 115K, under ultra-high vacuum conditions, and then annealed sequentially to higher temperatures. Copper reduction was observed by 320K. Carbonaceous and carbidic contamination of the WO_x surface was observed, even after sample warming to 625K in UHV. The results indicate that low temperature MOCVD of Cu may be possible, but interfacial contamination from the organic ligand fragmentation is a major concern.
19
Smith, Thomas. "Studies of p-type semiconductor photoelectrodes for tandem solar cells." Thesis, Loughborough University, 2014. https://dspace.lboro.ac.uk/2134/14522.
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Photoelectrodes and photovoltaic devices have been prepared via multiple thin film deposition methods. Aerosol assisted chemical vapour deposition (AACVD), electrodeposition (ED), chemical bath deposition (CBD) and doctor blade technique (DB) have been used to deposit binary and ternary metal oxide films on FTO glass substrates. The prepared thin films were characterised by a combination of SEM (Scanning Electron Microscopy), powder X-ray diffraction, mechanical strength tests and photochemical measurements. Nickel oxide (NiO) thin films prepared by AACVD were determined to have good mechanical strength . with a photocurrent of 7.6 μA cm-2 at 0 V and an onset potential of about 0.10 V. This contrasted with the dark current density of 0.3 μA cm-2 at 0 V. These NiO samples have very high porosity with crystalline columns evidenced by SEM. In comparison with the AACVD methodology, NiO films prepared using a combination of ED and DB show good mechanical strength but a higher photocurrent of 24 μA cm-2 at 0 V and an onset potential of about 0.10 V with a significantly greater dark current density of 7 μA cm-2 at 0 V. The characteristic features shown in the SEM are smaller pores compared to the AACVD method. Copper (II) oxide (CuO) and copper (I) oxide (Cu2O) films were fabricated by AACVD by varying the annealing temperature between 100-325°C in air using a fixed annealing time of 30 min. It was shown by photocurrent density (J-V) measurements that CuO produced at 325 °C was most stable and provided the highest photocurrent of 173 μA cm-2 at 0 V with an onset potential of about 0.23 V. The alignment of zinc oxide (ZnO) nano-rods and nano-tubes fabricated by CBD have been shown to be strongly affected by the seed layer on the FTO substrate. SEM images showed that AACVD provided the best seed layer for aligning the growth of the nano-rods perpendicular to the surface. Nano-rods were successfully altered into nano-tubes using a potassium chloride bath etching method. NiO prepared by both AACVD and the combined ED/DB method were sensitized to absorb more of the solar spectrum using AACVD to deposit CuO over the NiO. A large increase in the photocurrent was observed for the p-type photoelectrode. These p-type photoelectrode showed a photocurrent density of approximately 100 μA cm-2 at 0 V and an onset potential of 0.3 V. This photocathode was then used as a base to produce a solid state p-type solar cell. For the construction of the solid state solar cells several n-type semiconductors were used, these were ZnO, WO3 and BiVO4. WO3 and BiVO4 were successfully produced with BiVO4 proving to be the optimum choice. This cell was then studied more in depth and optimised by controlling the thickness of each layer and annealing temperatures. The best solid state solar cell produced had a Jsc of 0.541 μA cm-2 (541 nA) and a Voc of 0.14 V, TX146 made up of NiO 20 min, CuFe2O4 50 min, CuO 10 min, BiVO4 27 min, using AACVD and then annealed for 30 min at 600°C.
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Krishnan, Vidya. "Electroless deposition of copper for microelectronic applications." Thesis, Georgia Institute of Technology, 2000. http://hdl.handle.net/1853/11752.
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Stephens, Alan Thomas. "Chemical vapor deposition reactor design and process optimization for the deposition of copper thin films /." Online version of thesis, 1994. http://hdl.handle.net/1850/11578.
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Grant, Ann W. "Surface studies of model catalysts using metal atoms and particles on ZnO(0001)-Zn and -O and TiO₂(110) /." Thesis, Connect to this title online; UW restricted, 2001. http://hdl.handle.net/1773/8499.
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Young, Valerie Lynne Vandigrifft. "The chemistry of metalorganic chemical vapor deposition from a copper alkoxide precursor." Diss., This resource online, 1992. http://scholar.lib.vt.edu/theses/available/etd-06062008-170227/.
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Mohsin, Ali. "Graphene synthesis and characterization on copper." Thesis, University of Iowa, 2012. https://ir.uiowa.edu/etd/3354.
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Graphene, two dimensional sheet of carbon atoms has recently gained attention as some of its properties are promising for electronics applications e.g. higher mobility that translates to higher operating frequency for devices geared towards radio frequency applications. Excellent optical transmittance combined with its semi metallic behavior makes it an important material for transparent contacts in solar cells. To bring graphene to the production level, synthesis methods are needed for its growth on wafer scale. It has been shown that chemical vapor deposition (CVD) is one of the techniques that can potentially synthesize wafer scale graphene. Recently copper has gained popularity as an important substrate material for graphene growth due to its lower carbon solubility, which allows better control over number of graphene layers. Here we report optimization of graphene growth on copper foils with our home made atmospheric pressure chemical vapor deposition (APCVD) setup. Graphene growth on copper under APCVD was non self-limiting similar to other reports. It was found that apart from growth parameters surface texture plays a very important role in graphene growth. In fact, few layer and bilayer graphene were obtained on the regions where copper surface was not uniform, confirmed by Raman spectroscopy. To improve copper surface texture thin layer of copper film was evaporated by electron beam evaporation before the graphene growth process. After this modification, monolayer graphene was obtained on areas as large as 300 um × 300 um confirmed by Raman area maps. Graphene transfer procedure was also optimized so that graphene on metal surface could be transferred to insulating substrate
25
Chiang, Tony Ping-chen. "Surface kinetic study of ion induced chemical vapor deposition of copper." Thesis, Massachusetts Institute of Technology, 1996. http://hdl.handle.net/1721.1/9869.
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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1996.Includes bibliographical references (leaves 158-162).
by Tony Ping-chen Chiang.
Ph.D.
26
Sutcliffe, Ronald David. "Aluminum and Copper Chemical Vapor Deposition on Fluoropolymer Dielectrics and Subsequent Interfacial Interactions." Thesis, University of North Texas, 1997. https://digital.library.unt.edu/ark:/67531/metadc279304/.
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Au, Yeung Billy. "Chemical Vapor Deposition of Thin Film Materials for Copper Interconnects in Microelectronics." Thesis, Harvard University, 2012. http://dissertations.umi.com/gsas.harvard:10227.
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The packing density of microelectronic devices has increased exponentially over the past four decades. Continuous enhancements in device performance and functionality have been achieved by the introduction of new materials and fabrication techniques. This thesis summarizes the thin film materials and metallization processes by chemical vapor deposition (CVD) developed during my graduate study with Professor Gordon at Harvard University. These materials and processes have the potential to build future generations of microelectronic devices with higher speeds and longer lifetimes. Manganese Silicate Diffusion Barrier: Highly conformal, amorphous and insulating manganese silicate \((MnSi_xO_y)\) layers are formed along the walls of trenches in interconnects by CVD using a manganese amidinate precursor vapor that reacts with the surfaces of the insulators. These \((MnSi_xO_y)\) layers are excellent barriers to diffusion of copper, oxygen and water.
Manganese Capping Layer: A selective CVD manganese capping process strengthens the interface between copper and dielectric insulators to improve the electromigration reliability of the interconnects. High selectivity is achieved by deactivating the insulator surfaces using vapors containing reactive methylsilyl groups. Manganese at the Cu/insulator interface greatly increases the strength of adhesion between the copper and the insulator. Bottom-up Filling of Copper and Alloy in Narrow Features: Narrow trenches, with widths narrow than 30 nm and aspect ratios up to 9:1, can be filled with copper or copper-manganese alloy in a bottom-up fashion using a surfactant-catalyzed CVD process. A conformal manganese nitride \((Mn_4N)\) layer serves as a diffusion barrier and adhesion layer. Iodine atoms chemisorb on the \(Mn_4N\) layer and are then released to act as a catalytic surfactant on the surface of the growing copper layer to achieve void-free, bottom-up filling. Upon post-annealing, manganese in the alloy diffuses out from the copper and forms a self-aligned barrier in the surface of the insulator. Conformal Seed Layers for Plating Through-Silicon Vias: Through-silicon vias (TSV) will speed up interconnections between chips. Conformal, smooth and continuous seed layers in TSV holes with aspect ratios greater than 25:1 can be prepared using vapor deposition techniques. \(Mn_4N\) is deposited conformally on the silica surface by CVD to provide strong adhesion at Cu/insulator interface. Conformal copper or Cu-Mn alloy seed layers are then deposited by an iodine-catalyzed direct-liquid-injection (DLI) CVD process.Chemistry and Chemical Biology
28
Fang, Wenjing Ph D. Massachusetts Institute of Technology. "Bilayer graphene growth by low pressure chemical vapor deposition on copper foil." Thesis, Massachusetts Institute of Technology, 2012. http://hdl.handle.net/1721.1/75656.
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Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Electrical Engineering and Computer Science, 2012.Cataloged from PDF version of thesis.
Includes bibliographical references (p. 49-51).
Successfully integrating graphene in standard processes for applications in electronics relies on the synthesis of high-quality films. In this work we study Low Pressure Chemical Vapor Deposition (LPCVD) growth of bilayer graphene on the outside surface of copper enclosures. The effect of several parameters on bilayer growth rate and domain size was investigated and high-coverage bilayers films were successfully grown. Furthermore, the quality of the bilayer was confirmed using Raman spectroscopy. Finally, we consider future studies that may reveal the underlying mechanisms behind bilayer growth.
by Wenjing Fang.
S.M.
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Waechtler, Thomas, Yingzhong Shen, Alexander Jakob, Ramona Ecke, Stefan E. Schulz, Lars Wittenbecher, Hans-Josef Sterzel, et al. "Evaluation of Phosphite and Phosphane Stabilized Copper(I) Trifluoroacetates as Precursors for the Metal-Organic Chemical Vapor Deposition of Copper." Universitätsbibliothek Chemnitz, 2006. http://nbn-resolving.de/urn:nbn:de:swb:ch1-200600315.
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Copper has become the material of choice
for metallization of high-performance
ultra-large scale integrated circuits.
As the feature size is
continuously decreasing, metal-organic
chemical vapor deposition (MOCVD) appears
promising for depositing the Cu seed
layer required for electroplating, as well
as for filling entire interconnect structures.
In this work, four novel organophosphane
and organophosphite Cu(I) trifluoroacetates
were
studied as precursors for Cu MOCVD. Details
are reported on CVD results obtained with
Tris(tri-n-butylphosphane)copper(I)trifluoroacetate,
(nBu3P)3CuO2CCF3.
Solutions of this
precursor with acetonitrile and isopropanol
were used for deposition experiments
on 100 mm Si wafers sputter-coated with Cu,
Cu/TiN, and Al(2 % Si)/W. Experiments
were carried out in a cold-wall reactor at
a pressure of 0.7 mbar, using a
liquid delivery approach for precursor dosage.
On Cu seed layers, continuous films were
obtained at low deposition rates (0.5 to
1 nm/min). At temperatures above 320°C,
hole formation in the Cu films was observed.
Deposition on TiN led to the formation of
single copper particles and etching of the
TiN, whereas isolating aluminum oxyfluoride
was formed after deposition on Al(Si)/W. It
is concluded that the formation of CF3
radicals during decarboxylation has a
negative effect on the deposition results.
Furthermore, the precursor chemistry needs
to be improved for a higher volatility of
the complex.
30
Kim, Dojun. "Chemical vapor deposition of tungsten-based diffusion barrier thin films for copper metallization." [Gainesville, Fla.] : University of Florida, 2009. http://purl.fcla.edu/fcla/etd/UFE0041042.
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Norman, John A. T., Melanie Perez, Stefan E. Schulz, and Thomas Waechtler. "New Precursors for CVD Copper Metallization." Universitätsbibliothek Chemnitz, 2008. http://nbn-resolving.de/urn:nbn:de:bsz:ch1-200801346.
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A novel CVD copper process is described using
two new copper CVD precursors, KI3 and KI5, for
the fabrication of IC or TSV (Through Silicon Via)
copper interconnects. The highly conformal CVD
copper can provide seed layers for subsequent
copper electroplating or can be used to directly
fabricate the interconnect in one step. These
new precursors are thermally stable yet chemically
reactive under CVD conditions, growing copper
films of exceptionally high purity at high growth
rates. Their thermal stability can allow for
elevated evaporation temperatures to generate
the high precursor vapor pressures needed for
deep penetration into high aspect ratio TSV vias.
Using formic acid vapor as a reducing gas with
KI5, copper films of > 99.99 atomic % purity
were grown at 250°C on titanium nitride at a
growth rate of > 1500 Å/min. Using
tantalum
nitride coated TSV type wafers, ~ 1700 Å of
highly conformal copper was grown at 225°C into
32 μm × 5 μm trenches with good adhesion. With
ruthenium barriers we were able to grow copper
at 125°C at a rate of 20 Å/min to give a
continuous ~ 300 Å copper film. In this respect,
rapid low temperature CVD copper growth offers
an alternative to the long cycle times associated
with copper ALD which can contribute to copper
agglomeration occurring.
© 2008 Elsevier B.V.
32
Ross, Francis L. (Francis LaFayette) 1968. "Nano-cellular microstructure evolution in ion-induced chemical vapor deposition (II-CVD) of copper." Thesis, Massachusetts Institute of Technology, 2003. http://hdl.handle.net/1721.1/29971.
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Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2003.Includes bibliographical references (p. 179-181).
A systematic investigation of the microstructure produced in ion-induced chemical vapor deposition (11-CVD) of copper from copper(I)hexafluoroacetylacetonatevinyltrimethylsilane (Cu(I)hfacVTMS) gas precursor is reported. II-CVD involves the ion-driven decomposition of Cu(l)hfacVTMS and subsequent deposition of copper films at ambient temperature. The thin films were grown with the aid of a broad beam Kaufman source in a "multibeam apparatus", which allowed monitoring of experimental conditions - growth rate, temperature, ion beam flux, ion beam energy and gas precursor flux. Deposition temperatures ranged from room temperature to 100⁰C. The desirable operation range is the "ion-flux-limited regime", in which sufficient precursor flux allows the growth rate to scale with the ion flux. Plan-view TEM and cross-sectional TEM (XTEM) show that the film develops a characteristic cellular microstructure of continuous crystalline copper columns (15 nm diameter) surrounded by an amorphous phase containing both carbon impurity and copper. The column diameter increases with temperature but is not affected by the growth rate for temperatures up to 60⁰C. At higher temperatures, the growth mechanism is not purely ion driven due to the onset of thermal CVD. However, quantitative XPS (x-ray photoelectron spectroscopy) shows that the film purity not only increases with substrate temperature, but also increases with decreasing growth rate due to the kinetics of byproduct desorption. STEM-EDS (scanning transmission electron microscopy - energy dispersive x-ray spectroscopy) shows that the intercolumnar spaces contain more copper at lower growth rates for a given substrate temperature. Hydrogen-atom-assisted II-CVD effectively removed all carbonaceous impurity to within the detection limit of XPS. The cellular microstructure is not observed in these films; however, deposition at 100⁰C produces films that still retain a columnar structure even though the atomic fraction of carbon is only [approximately] 0.5%. This high temperature growth process has a mixed mechanism where the ion beam flux also enhances the kinetics of the thermal CVD process. The microstructure evolution is modeled as a cellular growth process that is controlled by surface transport of carbon impurity. The cellular mechanism is corroborated by the sharp transitions
(cont.) observed in XTEM for a change in deposition conditions. The surface diffusion is not only a function of temperature but also the ion flux. This explains why the column diameter remains independent of growth rate at constant temperature. The model assumes an approximately linear dependence of the diffusion constant's pre-exponential factor with ion the flux. The model predicts column diameters that are in good agreement with experimental data. The model was designed to integrate with Chiang's kinetic model to provide a foundation for depositing controlled microstructures using I-CVD. The work presented here demonstrates the possibility of growing controlled nano-cellular microstructures using a low voltage broad ion beam at or near ambient temperature. Films with such nano-cellular structures are expected to have highly anisotropic properties that could be used in a variety of applications, including magnetics ...
by Francis L. Ross, III.
Ph.D.
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Chaitoglou, Stefanos. "Growth Study and Characterization of Single Layer Graphene Structures Deposited on Copper Substrate by Chemical Vapor Deposition." Doctoral thesis, Universitat de Barcelona, 2016. http://hdl.handle.net/10803/400402.
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Graphene was first isolated from graphite using the method called the tape by scientists at the University of Manchester (Andre Geim, Konstantin Novoselov); such work was later awarded the Nobel Prize in Physics (2010) highlighting its innovative contribution. Still, the method of the tape or mechanical exfoliation can not provide larger domains graphene some hundred micrometers. different technologies that could promote the synthesis of continuous layers of graphene large area in order to boost the potential for large-scale applications were needed. Synthesis chemical vapor deposition (CVD) on various metal substrates is probably the method that meets the above requirements.
In the CVD technique, a precursor gas is introduced into a carbon furnace where the metal substrate is placed. The gas molecule decomposes and the carbon atoms are deposited on the metal surface. There are different factors that affect the growth of graphene: the selection of the metal substrate and the thickness thereof; the growth temperature, pressure and partial pressures of the precursor gas carbon / hydrogen / argon; and finally, the growth time.
Considering the synthesis of graphene, the aim of the thesis lies present new experiments and results that demonstrate the effect of H2 partial pressure, through PCH4 / PH2 ratio between gas flows, on the growth of crystals dimensional graphene and morphology. To do this, we have designed an experimental methodology consisting of three experiments:
1) Application of a hydrogen plasma to reduce the copper substrate, rather than the regular process in the presence of hydrogen.
2) In relation to the growth of graphene, we propose an optimization experiment to determine control factors for a single continuous layer of graphene and graphene large single crystal domains.
3) intended to identify the role of partial pressure ratio, El grafeno fue aislado por primera vez a partir del grafito mediante el llamado método de la cinta adhesiva por científicos de la Universidad de Manchester (Andre Geim, Konstantin Novoselov); dicho trabajo fue posteriormente reconocido con el Premio Nobel en Física (2010) destacando su aportación innovadora. Aún así, el método de la cinta adhesiva o exfoliación mecánica no puede proporcionar dominios de grafeno mayores que algunos cientos de micrómetros. Eran necesarias diferentes tecnologías que pudieran promover la síntesis de capas de grafeno continuas de area grande con el fin de impulsar el potencial para aplicaciones a gran escala. La síntesis de deposición química en fase vapor (CVD) sobre diferentes sustratos metálicos es probablemente el método que cumple con los requisitos anteriores. En la técnica CVD, se introduce un gas precursor de carbono en un horno donde se coloca el sustrato metálico. La molécula de gas se descompone y los átomos de carbono se depositan sobre la superficie metálica. Existen diferentes factores que afectan el crecimiento del grafeno: la selección del sustrato del metal y el espesor de la misma; la temperatura de crecimiento, la presión, así como las presiones parciales del gas precursor del carbono / hidrógeno / argón; y, por último, el tiempo de crecimiento. Teniendo en cuenta la síntesis de grafeno, el objetivo de la tesis recae en presentar nuevos experimentos y resultados que evidencien el efecto de la presión parcial de H2, a través de la relación PCH4/PH2 entre los flujos de gas, sobre el crecimiento de cristales bidimensionales de grafeno y en su morfología. Para ello, hemos diseñado una metodología experimental que consiste en tres experimentos: 1)La aplicación de un plasma de hidrógeno para reducir el sustrato de cobre, en lugar del proceso regular en presencia de hidrógeno. 2)En relación con el crecimiento de grafeno, proponemos un experimento de optimización que determinen los factores de control para obtener una sola capa continua de grafeno y grandes dominios monocristalinos de grafeno. 3)Con la intención de identificar el papel de la relación de presiones parciales,
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Han, Jaesung. "Combined experimental and modelling studies of laser assisted chemical vapor deposition of copper and aluminum." Thesis, Massachusetts Institute of Technology, 1993. http://hdl.handle.net/1721.1/12494.
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Mukati, Kapil. "An alternative structure for next generation regulatory controllers and scale-up of copper(indium gallium)selenide thin film co-evaporative physical vapor deposition process." Access to citation, abstract and download form provided by ProQuest Information and Learning Company; downloadable PDF file, 311 p, 2007. http://proquest.umi.com/pqdweb?did=1397912441&sid=12&Fmt=2&clientId=8331&RQT=309&VName=PQD.
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Thesis (Ph.D.)--University of Delaware, 2007.Principal faculty advisor: Babatunde Ogunnaike, Dept. of Chemical Engineering, and Robert W. Birkmire, Dept. of Materials Science & Engineering. Includes bibliographical references.
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Fiuza, Junior Raildo Alves. "Hidrogenólise do glicerol sobre catalisadores de cobre e cromo." reponame:Repositório Institucional da UFBA, 2012. http://www.repositorio.ufba.br/ri/handle/ri/11729.
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CAPES
A conversão catalítica do glicerol em insumos químicos de maior valor agregado é desejável para valorizar a cadeia de produção do biodiesel. O glicerol é obtido principalmente como co-produto do biodiesel, com rendimento de 10% em massa. Uma das vias mais promissoras na valorização do glicerol está na hidrogenólise do glicerol a propilenoglicol (1,2-PD), que é empregado como agente anti-congelante, na produção de polímeros, na indústria de alimentos e cosméticos. Muitos estudos têm relatado a hidrogenólise em fase líquida, que requer altas pressões de hidrogênio e demanda altos custos operacionais. Recentes estudos têm relatado a hidrogenólise do glicerol a 1,2-PDO em fase vapor, utilizando principalmente catalisadores a base de cobre. O principal catalisador empregado na hidrogenólise do glicerol tanto na fase liquida como vapor é a cromita de cobre, CuCr2O4. Neste trabalho, a atividade catalítica da cromita de cobre foi avaliada em fase vapor, estudando três fatores: a estruturação da cromita de cobre por diferentes temperaturas de calcinação (500-800°C); mudanças es truturais provocadas por diferentes métodos de síntese (Combustão e Pechini); e a modificação da estrutura da cromita pela introdução do alumínio em substituição do cromo. Todos os catalisadores foram caracterizados por DRX, FTIR, EDX, BET, TPR-H2 e área metálica do cobre. A hidrogenólise do glicerol em fase vapor se mostrou promissora e os resultados obtidos indicaram que a fase cromita de cobre propicia uma maior estabilidade para a fase ativa o cobre metálico. O aumento da área metálica do cobre é influenciado diretamente pelo método de síntese, maximizando a hidrogenólise. A introdução do alumínio provocou o aumento da seletividade ao propanodiol pela melhora nas propriedades texturais.
Salvador
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Olsson, Adam. "Graphene Growth through Chemical Vapor Deposition - Optimization of Growth and Transfer Parameters." Thesis, Umeå universitet, Institutionen för fysik, 2017. http://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-137546.
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The goal of this thesis work is to investigate the possibility to grow graphene by Chemical Vapor Deposition (CVD) on copper foil with acetylene as a precursor and varigon (5\% H$_2$ in Ar) as a carrier gas. The possibility of nitrogen doping by ammonia treatment during the growth process is also investigated. The possibility of graphene transfer, with the use of Poly(Methyl Metacrylate) (PMMA), from the copper onto another target substrate, Flourine doped Tin Oxide (FTO), is also explored. The main technique of characterization of the grown and transfered graphene is Raman spectroscopy, a great tool for investigating the number of graphene layers and amount of defects. Other characterization methods used are Scanning Electron Microscopy (SEM) X-ray Photoelectron Spectroscopy (XPS) to investigate morphology and elemental composition, respectively. The result of this thesis study is that graphene growth is entirely possible with acetylene as a precursor, as shown by the Raman spectroscopy, XPS and SEM. The grown graphene has a high quality with few layers and a low number of defects. The ammonia treatment, however, doesn't seem to have an immediate effect on the graphene growth. The XPS data indicates that there are no nitrogen doping in the graphene, though there might be a correlation between the ammonia and the number of layers, but further investigations has to be made. Transfer is also proven possible with the method developed. However, improvements to the transfer method can be done since there are both larger tares, caused by the transfer onto the FTO, as well as microscopic tares, possibly caused by thermal expansion of the PMMA.
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Butterfield, Martin Thomas. "Surface structure of ultrathin metal films deposited on copper single crystals." Thesis, Loughborough University, 2000. https://dspace.lboro.ac.uk/2134/33132.
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Ultrathin films of Cobalt, Iron and Manganese have been thennally evaporated onto an fcc Copper (111) single crystal substrate and investigated using a variety of surface structural teclmiques. The small lattice mismatch between these metals and the Cu (111) substrate make them an ideal candidate for the study of the phenomena of pseudomorphic film growth. This is important for the understanding of the close relationship between film structure and magnetic properties. Growing films with the structure of their substrate rather than their bulk phase may provide an opportunity to grow materials with novel physical and magnetic properties, and hence new technological applications. Both Cobalt and Iron have been found to initially maintain a registry with the fee Cu (111) surface in a manner consistent with pseudomorphic growth. This growth is complicated by island rather than layer-by-layer growth in the initials stages of the film. In both cases a change in the structure of the film seems to occur at a point where the coalescence of islands in the film may be expected to occur. When the film does change structure they do not form a perfect over-layer with the structure of their bulk counterpart. The films do contain a number of features representative of the bulk phase but also contain considerable disorder and possibly remnants of fcc (111) structure. The order present in these films can be greatly improved by annealing. Manganese appears to grow with an fee Mn (111) lattice spacing and there is no sign of a change in structure in films of up to 4.61 ML thick. The gradual deposition and annealing of a film to 300°C, with a total deposition time the same as that for a 1 ML thick film, causes a surface reconstruction to occur that is apparent in a R30° (√3×√3) LEED pattern. This is attributed to the formation of a surface alloy, which is also supported by the local expansion of the Cu lattice in the (111) direction.
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Liao, Wen, Daniel Bost, and John G. Ekerdt. "Growth of Ultra-thin Ruthenium and Ruthenium Alloy Films for Copper Barriers." Universitätsbibliothek Chemnitz, 2016. http://nbn-resolving.de/urn:nbn:de:bsz:ch1-qucosa-207151.
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We report approaches to grow ultrathin Ru films for application as a seed layer and Cu diffusion barrier. For chemical vapor deposition (CVD) with Ru3(CO)12 we show the role surface hydroxyl groups have in nucleating the Ru islands that grow into a continuous film in a Volmer-Weber process, and how the nucleation density can be increased by applying a CO or NH3 overpressure. Thinner continuous films evolve in the presence of a CO overpressure. We report an optimun ammonia overpressure for Ru nucleation and that leads to deposition of smoother Ru thin films. Finally, we report a comparison of amorphous Ru films that are alloyed with P or B and demonstrate 3-nm thick amorphous Ru(B) films function as a Cu diffusion barrier.
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Plappert, Elisabeth-Charlotte. "Synthesis and characterization of copper and titanium compounds and their application as precursors in chemical vapor deposition /." [S.l.] : [s.n.], 1995. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=10996.
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Bekdüz, Bilge [Verfasser], and Gerd [Akademischer Betreuer] Bacher. "Thermal and Plasma Enhanced Chemical Vapor Deposition of Graphene on Copper and Germanium / Bilge Bekdüz ; Betreuer: Gerd Bacher." Duisburg, 2020. http://d-nb.info/121603883X/34.
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Xiao, Zhifeng 1966. "Experimental and theoretical studies of the solubility of copper in liquid and vapor in the system NaC1-HC1-HO." Thesis, McGill University, 1999. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=36733.
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Copper solubility in water vapor and liquid was measured in the HCl-NaCl-H 2O system at temperatures up to 400°C and vapor-saturated pressure by two series of experiments. The thermodynamic data from these experiments were then applied to model the genesis of volcanogenic massive sulfide deposits and the partitioning of copper between vapor and liquid.The solubility of copper in liquid was measured in vapor-saturated aqueous HCl/NaCl solutions at temperatures ranging from 40 to 300°C, total chloride concentrations from 0.01 to 1 m, and pH from 0 to 3.5. Copper was found to dissolve primarily as CuCl(aq), CuCl2- and CuCl32-. Data collected from the experiments were regressed to determine the equilibrium constants as functions of temperature (K): Cu(s) + 1/4O2(g) + H+ + xCl- = CuClx1-x +1/2 H2O(l), where x varied from 1 to 3.
Data obtained on the solubility of copper in the liquid phase were used to model gold-copper and gold-zinc mineralization in VMS deposits. Equilibrium path calculations, employing EQ3/6, predict temperatures of precipitation, the paragenetic sequence of minerals, and the chemical composition of chimneys associated with vents on the seafloor at 21°N, East Pacific Rise. The modeling results suggest that the co-precipitation of gold with copper and zinc at different temperatures is determined by the behavior of their complexes in the solution. However, among the models simulated, only the conductive cooling model and combined mixing and cooling model predict the co-precipitation of gold and copper at high temperature (>300°C) and gold-zinc at low temperature (<250°C), which is common in VMS deposits.
The solubility of CuCl(s) in the vapor was measured in a vapor-saturated H2O(I)-H2O(v)-NaCl-HCl (NaCl/HCl; 9:1) system at temperatures ranging from 360 to 400°C, and total chloride concentration from 0.01 to 5 m. At 360°C, the copper solubility can be described by the reaction: CuCl(s) + H2O(v) = CuCl⁺H2O(v), and the equilibrium relationship for this reaction by KC = mCuCl⁺H2Ov /rH2Ov , where mCuCl⁺H2Ov is the molality of copper in the vapor phase and rH2Ov is the density of water vapor; the log KC value is ~-2.01. At 380°C and 400°C, copper solubility is controlled by the reaction: CuCl(s) + 4 H2O(v) = CuCl ⁺ 4H 2O(v). The equilibrium relationship for this reaction is KC = mCuCl⁺4H2O v/r4 H2Ov , and the values of log KC values are 0.22 and 1.17 at 380 and 400°C, respectively.
Partition coefficients for copper between vapor and liquid were calculated for the CuCl-NaCl-HCl-H2O(l)-H2O(v) system at the following conditions, where T = 400°C, P = water vapor saturated pressure, mNaCl = 0.5--2.3m, and mHCl = 0.001 m. The close similiarity of the partition coefficients for copper to those of sodium under the same conditions suggests that partitioning data for NaCl can be used to estimate copper (I) chloride partition coefficients at conditions for which no data are available.
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Eddy, Steven Kyle. "Chemical Vapor Deposition Based Synthesis of Graphene for Corrosion Mitigation of Copper and Fabrication of Extended Fullerene-Based Structures." Thesis, The University of Arizona, 2014. http://hdl.handle.net/10150/320065.
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Lassègue, Pierre. "Oxydation en lit fluidisé et dépôt de métaux par CVD en lit fluidisé sur nanotubes de carbone multi-parois - Application à l'industrie aéronautique." Thesis, Toulouse, INPT, 2016. http://www.theses.fr/2016INPT0132.
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Cette thèse s’inscrit dans le cadre du développement de nouveaux matériaux composites multifonctionnels, permettant de remplacer l’aluminium en tant qu’élément constituant le packaging de l’électronique embarquée dans les avions, afin de rendre ces derniers plus légers. L’association d’un polymère mécaniquement résistant avec des nano-charges conductrices est une alternative prometteuse. Cette thèse concerne l’étude du procédé de Dépôt Chimique à partir d’une phase Vapeur (CVD) en lit fluidisé pour déposer des métaux conducteurs, tels que le fer et le cuivre, à la surface de nanotubes de carbone multi-parois (MWCNTs) produits industriellement (Arkema Graphistrength®C100), enchevêtrés en pelotes poreuses de 388 μm de diamètre. Tout d’abord, afin d’augmenter la réactivité de surface des nanotubes, un procédé d’oxydation en lit fluidisé a été étudié à température ambiante, à partir de plusieurs mélanges gazeux à base d’ozone. Les diverses analyses réalisées (MET, spectroscopie IR, XPS,..) montrent que des groupements chimiques de type hydroxyl, acide carboxylique, éther, … sont greffés de façon uniforme sur toute la surface externe des MWCNTs et que leurs parois externes sont aussi gravées de façon modérée et localisée. Au final, il apparait que les défauts créés et les fonctions oxygénées greffées ont permis d’accroitre le nombre de sites de nucléation sur la surface des nanotubes et donc la masse de métal déposé. Le dépôt de fer à partir de ferrocène Fe(C5H5)2 a été étudié à haute température (entre 400 et 650°C), sous différentes ambiances gazeuses (azote, hydrogène, air, vapeur d’eau). Les analyses réalisées (MEB-FEG, DRX, MET, ICP-MS, ...) montrent un dépôt uniforme du bord jusqu’au coeur des pelotes, de nanoparticules à base de carbure de fer Fe3C prisonnières de l’enchevêtrement des nanotubes. La présence d’hydrogène a permis de minimiser la formation parasite de nano-objets (tubes et fibres). Le dépôt de cuivre à partir d’acétylacétonate de cuivre (II) Cu(C5H7O2)2 a été étudié entre 250 et 280°C sous hydrogène. Les caractérisations réalisées indiquent que des nanoparticules de Cu pur ont été déposées sur l’ensemble des parois externes des MWCNTs, du bord au coeur des pelotes. L’ensemble des résultats obtenus démontre que le procédé de CVD en lit fluidisé est capable de déposer de façon uniforme des métaux à la surface de nanotubes de carbone enchevêtrés en pelotes poreuses, pour des conditions opératoires spécifiquement choisiesThis Ph.D project is part of the development of new composite multi-functional materials allowing replacing aluminum in the on-board electronic packaging of airplanes, to make them lighter. The combination of a polymer mechanically resistant with conductive nano-fillers is a promising alternative. The thesis concerns the study of the Fluidized Bed Chemical Vapor Deposition (CVD) process of conductive metals, such as iron and copper, on the surface of industrial multi-walled carbon nanotubes (MWCNTs, Arkema Graphistrength®C100) tangled in porous balls of 388 μm in diameter. First, in order to increase the surface reactivity of nanotubes, an oxidation process in fluidized bed has been studied at room temperature, from several gaseous mixtures containing ozone. The various analyses (TEM, IR spectroscopy, XPS, …) show that hydroxyl, carboxylic acid, ether, … chemical bonds are grafted uniformly on all the outer surface of MWCNTs and that their outer walls are locally and moderately etched. At the end, it appears that the created defects and the oxygen containing bonds have allowed to increase the number of nucleation sites on the nanotubes surface and then the weight of the deposited metal. The iron deposit from ferrocene Fe(C5H5)2 has been studied at high temperature (between 400 and 650°C) under different gaseous atmospheres (nitrogen, hydrogen, air, water vapor). The analyses (FEG SEM, XRD, TEM, ICP-MS, ...) show a uniform deposit from the outer part to the center of the balls, of nanoparticles containing iron carbide Fe3C. The presence of hydrogen has allowed minimizing the parasitic formation of nano-objects (tubes and fibers). The copper deposition from copper (II) acetylacetonate Cu(C5H7O2)2 has been studied at 250-280°C under hydrogen. The characterizations indicate that nanoparticles of pure copper have been deposited on all the MWCNT outer walls, from the outer part to the center of the balls. The whole results obtained prove that the Fluidized Bed CVD process is able to deposit uniformly metals on the outer surface of MWCNTs tangled in porous balls, for specifically chosen operating conditions
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Xiao, Zhifeng. "Experimental and theoretical studies of the solubility of copper in liquid and vapor in the system NaCl-HCl-H¦2O." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape4/PQDD_0033/NQ64695.pdf.
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Thompson, John O. 1962. "The importance of elemental stacking order and layer thickness in controlling the formation kinetics of copper indium diselenide." Thesis, University of Oregon, 2007. http://hdl.handle.net/1794/6197.
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xiii, 84 p. ; ill.This dissertation describes the deposition and characterization of an amorphous thin film with a composition near that of CuInSe 2 (CIS). The creation of an amorphous intermediate leads to a crystalline film at low annealing temperatures. Thin films were deposited from elemental sources in a custom built high vacuum chamber. Copper-selenium and indium-selenium binary layered samples were investigated to identify interfacial reactions that would form undesired binary intermediate compounds resulting in the need for high temperature annealing. Although the indium-selenium system did not form interfacial compounds on deposit, indium crystallized when the indium layer thickness exceeded 15 angstroms, disrupting the continuity of the elemental layers. Copper-selenium elemental layers with a repeat thickness of over 30 angstroms or compositions with less than 63% selenium formed CuSe on deposit. Several deposition schemes were investigated to identify the proper deposition pattern and thicknesses to form the CIS amorphous film. Simple co-deposition resulted in the nucleation of CIS. A simple stacking of the three elements in the older Se-In-Cu at a repeat thickness of 60 angstroms resulted in the nucleation of CuSe and sometimes CIS. The CIS most likely formed due to the disruption of the elemental layers by the growth of the CuSe. Reduction of the repeat thickness to 20 angstroms eliminated the nucleation of CuSe, as predicted by the study of the binary Cu-Se layered samples, but resulted in the nucleation of CIS, similar to the co-deposited samples. To eliminate both the thick Cu-Se region, and prevent the intermixing of all three elements, a more complex deposition pattern was initiated. The copper and selenium repeat thicknesses were reduced into a Se-Cu-Se-Cu-Se pattern followed by deposition of the indium layer at a total repeat thickness of 60 angstroms. At a Se:Cu ratio of 2:1 and the small repeat thickness, no Cu-Se phases nucleated. Additionally, the Cu-In interface was eliminated. For this deposition scheme, films with a selenium rich composition relative to CuInSez were generally amorphous. Those that were Cu-In rich always nucleated CIS on deposit. Annealing of all samples produced crystalline CIS.
Adviser: David C. Johnson
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Li, Kecheng. "Direct Liquid Evaporation Chemical Vapor Deposition(DLE-CVD) of Nickel, Manganese and Copper-Based Thin Films for Interconnects in Three-Dimensional Microelectronic Systems." Thesis, Harvard University, 2016. http://nrs.harvard.edu/urn-3:HUL.InstRepos:33493366.
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Electrical interconnects are an intrinsic part of any electronic system. These interconnects have to perform reliably under a wide range of environmental conditions and survive stresses induced from thermal, mechanical, corrosive and electrical factors. Semiconductor technology is predominantly planar in nature, posing a severe limitation to the degree of device integrations into systems such as micro-processors or memories. 3D transistor FinFET (Fin type Field Effect Transistors) has been used by Intel since the advent of its 22 nm technology node, and has now advanced further down to 14 nm. While the technology nodes have consistently been shrinking in line with Moore’s law, increasing difficulties in scaling down the feature sizes in transistors is urging the industry to seek alternative fabrication approaches for the extension of Moore’s law. The most promising solution thus far is 3D heterogeneous integration, which will stack logical and analog chips together to enable multi functions chip without the need to scale the size of transistors with Moore’s law. Furthermore, as wearable electronics are fast growing in the next big wave in consumer electronics after the smartphone era, interconnects face the unique challenge of having to be embedded into fashion and withstand the mechanical stresses from everyday activity. This makes the role interconnects even more important as well as making it the main bottleneck to unleashing the full performance of the 3D microelectronics systems.
This thesis explores the fabrication, characterization and application of Nickel, Manganese, Copper based thin films for the interconnects of 3D microelectronics systems. Direct Liquid Evaporation-Chemical Vapor Deposition (DLE-CVD) technique has been proven to be a high-throughput process for high-quality Nickel, Manganese, Copper based thin films with excellent conformality in complex architectures as the interconnects for state-of-the-art 3D microelectronics systems.
Chapter 2 introduces the advantages of DLE-CVD process and its application in deposition of Nickel, Manganese and Copper based thin films. DLE-CVD process is used to deliver consistent and high vapor concentrations of Nickel, Manganese and Copper precursors to coat nanostructures with high aspect ratios.
Chapter 3 demonstrates the atom probe tomography (APT) as an effective method for understanding the 3D microstructure and compositional properties in thin films at an atomic scale. 3D compositional information of DLE-CVD NiNx, NiSi thin films from inside and outside regions of the trench structures have been investigated using APT. The APT characterization technique provides a unique tool that can be applied both to the design of 3D nanostructured microelectronic devices and to the further understanding of the fundamental physical properties.
Chapter 4 highlights the application of DLE-CVD manganese and copper based thin film process in the complex nanostructures for 3D microelectronic systems. Narrow trenches with width under 30 nm are the key nanostructure in the local interconnects in 3D FINFET with technology node smaller than 14 nm for use in microelectronic chips. It can be filled with DLE-CVD copper and copper-manganese alloy in a bottom-up fashion using a surfactant-catalyzed CVD process. An ultrathin manganese nitride layer (~ 3 nm) acts as a diffusion barrier and an adhesion layer. Through-silicon vias (TSVs) plays a crucial role in advancing the 3D integration of semiconductor devices by improving the performances of interconnections between chips. Using DLE-CVD processes, conformal, smooth and continuous copper/copper-manganese seed layers can be prepared in TSVs with aspect ratio greater than 25:1. manganese Nitride film is deposited via the DLE-CVD process to serve as an adhesion and barrier layer. Dow Chemicals achieved void-free TSV filling through the electroplating process.
Chapter 5 shows the application of the DLE-CVD manganese and copper based thin film process in the metallization of polyaramids for the application in the interconnects embedded in wearable electronic systems. Conformal and conductive coatings of copper-manganese have been successfully deposited on Kevlar fibers using the DLE-CVD process with complete film coverage. The mechanical resistance of copper-manganese coated Kevlar was tested via our in-house robotic arm system, demonstrating how the electrical resistance of the wire remains unchanged despite being flexed repeatedly to a bend of 5mm radius for half a million times.Engineering and Applied Sciences - Applied Physics
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Courrege, Maeva. "Caractérisation des interactions plasma/parois dans un disjoncteur haute tension." Thesis, Toulouse 3, 2017. http://www.theses.fr/2017TOU30162/document.
Full textAbstract:
Les disjoncteurs à haute tension, présents dans le réseau électrique, permettent d'assurer en toute sécurité la distribution de l'électricité. Lorsqu'un défaut est détecté, ou lors d'une intervention de maintenance, l'ouverture des contacts électriques au sein du disjoncteur entraine l'apparition d'un arc électrique à ses bornes. La protection et la coupure ne seront effectives que lorsque l'arc électrique aura été coupé. De nombreux paramètres, géométriques et physiques entrent en jeu dans la capacité de coupure d'un disjoncteur. L'objectif de ces travaux de thèse consistait à analyser l'impact du plasma sur les différents matériaux constituant le disjoncteur. Une démarche purement théorique est abordée à travers l'utilisation du logiciel commercial ANSYS Fluent. Ces travaux sont menés en collaboration avec la société Siemens qui fournit les données expérimentales indispensables à la discussion et à la validation du modèle. Dans ce travail nous considérons dans un premier temps l'ablation des tuyères en téflon. Ce phénomène est pris en compte dans notre étude, au travers d'un modèle d'ablation basé sur la théorie de T. Christen. L'ablation des parois joue un rôle fondamental sur la montée en pression dans les volumes de chauffage, et a une incidence directe sur la réalisation de la coupure. Ainsi le rôle et la quantification des vapeurs de C2F4 sont discutés et détaillés. La deuxième interaction plasma/matériau qu'il convenait d'étudier est celle avec l'électrode mobile constituée d'un mélange tungstène cuivre. Cette interaction est rarement étudiée au niveau des travaux de la littérature. La mise en place nécessite le développement de modèles de sous couches, en proche voisinage de l'électrode, basés sur des balances d'énergie et de flux qui permettent de déterminer par des approches hors équilibre la température des électrodes et le taux de production de vapeurs. Sur une configuration réelle de disjoncteur les caractéristiques temporelles des grandeurs physiques (température, vitesses, pression) et électriques (courant, tension) sont présentées et discutées dans la phase fort courant. Nous concluons sur la nécessité de considérer l'ablation du C2F4 pour une bonne description de la montée en pression dans les volumes de chauffage car ils conditionnent le soufflage au moment du passage par le zéro du courant, et sur la nécessité de prendre en compte les vapeurs de cuivre car celles-ci sont présentes au passage par zéro du courant et conditionnent alors le pouvoir de coupure du disjoncteurHigh-voltage circuit breakers, present in the power grid, ensure in safety the electricity distribution. When an error is detected, or for a maintenance operation, the opening of the electrical contacts within the circuit breaker causes the appearance of an electric arc at its terminals. Protection and cut-off will only be effective if the electrical arc cut off. Many parameters, geometric and physical, are involved in the breaking capacity of a circuit breaker. The aim of this work is to analyze the impact of plasma on the various materials making up the circuit breaker. A purely theoretical approach is tackled through the use of the commercial software ANSYS Fluent. This work is carried out in collaboration with Siemens, which provides the experimental data necessary for the discussion and validation of the model. In this work, we first consider the ablation of teflon nozzles. This phenomenon is taken into account in our study, using an ablation model based on the theory of T. Christen. The ablation of the walls plays a fundamental role on the rise in pressure in the heating volumes, and has a direct effect on the cut-off realization. Thus, the role and quantification of C2F4 vapors are discussed and detailed. The second plasma / material interaction that should be studied is that with the mobile electrode made of a tungsten copper mixture. This interaction is rarely studied in the literature. The implementation requires the development of sub-layers models in the vicinity of the electrode, based on energy and flux balances, which make it possible to determine by non-equilibrium approaches the temperature of the electrodes and the rate of vapor production. On a real circuit breaker configuration, the temporal characteristics of the physical (temperature, velocities, pressure) and electrical (current, voltage) quantities are presented and discussed in the high current phase. We conclude on the need to consider the ablation of C2F4 for a good description of the rise in pressure in the heating volumes because they condition the blowing at the moment of current-zero and on the need to take into account the copper vapors because these are present at the zero crossing of the current and then condition the breaking capacity of the circuit breaker
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Waechtler, Thomas, Steffen Oswald, Nina Roth, Alexander Jakob, Heinrich Lang, Ramona Ecke, Stefan E. Schulz, et al. "Copper Oxide Films Grown by Atomic Layer Deposition from Bis(tri-n-butylphosphane)copper(I)acetylacetonate on Ta, TaN, Ru, and SiO2." Universitätsbibliothek Chemnitz, 2009. http://nbn-resolving.de/urn:nbn:de:bsz:ch1-200900734.
Full textAbstract:
The thermal atomic layer deposition (ALD) of copper oxide films from the non-fluorinated yet liquid precursor bis(tri-n-butylphosphane)copper(I)acetylacetonate, [(nBu3P)2Cu(acac)], and wet O2 on Ta, TaN, Ru and SiO2 substrates at temperatures of < 160°C is reported. Typical temperature-independent growth was observed at least up to 125°C with a growth-per-cycle of ~ 0.1 Å for the metallic substrates and an ALD window extending down to 100°C for Ru. On SiO2 and TaN the ALD window was observed between 110 and 125°C, with saturated growth shown on TaN still at 135°C. Precursor self-decomposition in a chemical vapor deposition mode led to bi-modal growth on Ta, resulting in the parallel formation of continuous films and isolated clusters. This effect was not observed on TaN up to about 130°C and neither on Ru or SiO2 for any processing temperature. The degree of nitridation of the tantalum nitride underlayers considerably influenced the film growth. With excellent adhesion of the ALD films on all substrates studied, the results are a promising basis for Cu seed layer ALD applicable to electrochemical Cu metallization in interconnects of ultralarge-scale integrated circuits. © 2009 The Electrochemical Society. All rights reserved. Es wird die thermische Atomlagenabscheidung (ALD) von Kupferoxidschichten, ausgehend von der unfluorierten, flüssigen Vorstufenverbindung Bis(tri-n-butylphosphan)kupfer(I)acetylacetonat, [(nBu3P)2Cu(acac)], sowie feuchtem Sauerstoff, auf Ta-, TaN-, Ru- und SiO2-Substraten bei Temperaturen < 160°C berichtet. Typisches temperaturunabhängiges Wachstum wurde zumindest bis 125°C beobachtet. Damit verbunden wurde für die metallischen Substrate ein Zyklenwachstum von ca. 0.1 Å erzielt sowie ein ALD-Fenster, das für Ru bis zu einer Temperatur von 100°C reicht. Auf SiO2 und TaN wurde das ALD-Fenster zwischen 110 und 125°C beobachtet, wobei auch bei 135°C noch gesättigtes Wachstum auf TaN gezeigt werden konnte. Die selbständige Zersetzung des Precursors ähnlich der chemischen Gasphasenabscheidung führte zu einem bimodalen Schichtwachstum auf Ta, wodurch gleichzeitig geschlossene Schichten und voneinander isolierte Cluster gebildet wurden. Dieser Effekt wurde auf TaN bis zu einer Temperatur von 130°C nicht beobachtet. Ebensowenig trat er im untersuchten Temperaturbereich auf Ru oder SiO2 auf. Der Nitrierungsgrad der TaN-Schichten beeinflusste hierbei das Schichtwachstum stark. Mit einer sehr guten Haftung der ALD-Schichten auf allen untersuchten Substratmaterialien erscheinen die Ergebnisse vielversprechend für die ALD von Kupferstartschichten, die für die elektrochemische Kupfermetallisierung in Leitbahnsystemen ultrahochintegrierter Schaltkreise anwendbar sind
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Guesmi, Ismaël. "Dépôt de couches minces de cuivre sur substrats polymères de forme complexes par pulvérisation cathodique magnétron avec ionisation de la vapeur." Phd thesis, Université Paris Sud - Paris XI, 2012. http://tel.archives-ouvertes.fr/tel-00703850.
Full textAbstract:
De nombreuses applications industrielles nécessitent le dépôt de films métalliques à la surface de polymères afin de conférer une fonction de conduction électrique à ces matériaux isolants. Cette étude a été motivée par la volonté de la société Radiall, dont une partie de l'activité concerne la réalisation de connecteurs à haute performance, de remplacer le procédé de métallisation par voie humide par un procédé de dépôt par voie sèche plasma. Le travail présenté ici porte ainsi sur l'étude du procédé de pulvérisation cathodique magnétron avec ionisation de la vapeur par plasma radiofréquence (RF-IPVD) pour le dépôt de couches minces de cuivre sur substrats de formes complexes en poly-sulfure de phénylène. Cette thèse regroupe d'une part les résultats concernant la métallisation des connecteurs et d'autre part l'analyse de la phase plasma. La validation du procédé RF-IPVD a comporté plusieurs étapes : i) le développement du traitement du polymère par plasma ICP avant dépôt du film de cuivre afin que l'adhérence satisfasse la norme ISO 2409. ii) la détermination des paramètres d'élaboration permettant d'optimiser la conductivité des films et leur conformité sur les substrats 3D. Ces travaux se sont concrétisés par la définition d'un réacteur pilote dans l'optique de réaliser la transposition à l'échelle industrielle du procédé RF-IPVD. Plusieurs études à caractère fondamental ont également été menées afin, d'une part, de comprendre les mécanismes régissant l'adhérence (analyses XPS) et ceux régissant la résistivité (analyses DRX). D'autre part, l'utilisation de divers diagnostics de la phase plasma ont été employés afin de comprendre les mécanismes de transfert d'énergie prenant place dans le milieu gazeux et responsables des propriétés des dépôts.