This thesis deals with the main aspects in chemical vapordeposition (CVD) of silicon (Si) and silicon-germanium (Si1-xGex) films for high-speed bipolar transistors.In situdoping of polycrystalline silicon (poly-Si)using phosphine (PH3) and disilane (Si2H6) in a low-pressure CVD reactor was investigated toestablish a poly-Si emitter fabrication process. The growthkinetics and P incorporation was studied for amorphous Si filmgrowth. Hydrogen (H) incorporated in the as-deposited films wasrelated to growth kinetics and the energy for H2desorption was extracted. Film properties such asresistivity, mobility, carrier concentration and grain growthwere studied after crystallization using either furnaceannealing or rapid thermal annealing (RTA). In order tointegrate an epitaxial base, non-selective epitaxial growth(NSEG) of Si and SiGe in a lamp-heated single-waferreduced-pressure CVD reactor was examined. The growth kineticsfor Si epitaxy and poly-Si deposition showed a differentdependence on the deposition conditions i.e. temperature andpressure. The growth rate difference was mainly due to growthkinetics rather than wafer surface emissivity effects. However,it was observed that the growth rate for Si epitaxy and poly-Sideposition was varying during growth and the time-dependencewas attributed to wafer surface emissivity variations. A modelto describe the emissivity effects was established, taking intoconsideration kinetics and the reactor heating mechanisms suchas heat absorption, emission andconduction. Growth ratevariations in opening of different sizes (local loading) andfor different oxide surface coverage (global loading) wereinvestigated. No local loading effects were observed, whileglobal loading effects were attributed to chemical as well astemperature effects. Finally, misfit dislocations formed in theSiGe epitaxy during NSEG were found to originate from theinterface between the epitaxial and polycrystalline regions.The dislocations tended to propagate across the activearea. <b>Keywords:</b>chemical vapor deposition (CVD), bipolarjunction transistor (BJT), heterojunction bipolar transistor(HBT), silicon-germanium (SiGe), epitaxy, poly-Si emitter,in situdoping, non-selective epitaxy (NSEG), loadingeffect, emissivity effect

Heterojunction bipolar transistors (HBT) based on SiGeC havebeen investigated. Two high-frequency architectures have beendesigned, fabricated and characterized. Different collectordesigns were applied either by using selective epitaxial growthdoped with phosphorous or by non-selective epitaxial growthdoped with arsenic. Both designs have a non-selectivelydeposited SiGeC base doped with boron and a poly-crystallineemitter doped with phosphorous. Selective epitaxial growth of the collector layer has beendeveloped by using a reduced pressure chemical vapor deposition(RPCVD) technique. The incorporation of phosphorous and defectformation during selective deposition of these layers has beenstudied. A major problem of phosphorous-doping during selectiveepitaxy is segregation. Different methods, e.g. chemical orthermal oxidation, are shown to efficiently remove thesegregated dopants. Chemical-mechanical polishing (CMP) hasalso been used as an alternative to solve this problem. The CMPstep was successfully integrated in the HBT process flow. Epitaxial growth of Si1-x-yGexCy layers for base layerapplications in bipolar transistors has been investigated indetail. The optimization of the growth parameters has beenperformed in order to incorporate carbon substitutionally inthe SiGe matrix without increasing the defect density in theepitaxial layers. The thermal stability of npn SiGe-based heterojunctionstructures has been investigated. The influence of thediffusion of dopants in SiGe or in adjacent layers on thethermal stability of the structure has also been discussed. SiGeC-based transistors with both non-selectively depositedcollector and selectively grown collector have been fabricatedand electrically characterized. The fabricated transistorsexhibit electrostatic current gain values in the range of 1000-2000. The cut-off frequency and maximum oscillation frequencyvary from 40-80 GHz and 15-30 GHz, respectively, depending onthe lateral design. The leakage current was investigated usinga selectively deposited collector design and possible causesfor leakage has been discussed. Solutions for decreasing thejunction leakage are proposed. <b>Key words:</b>Silicon-Germanium-Carbon (SiGeC),Heterojunction bipolar transistor (HBT), chemical vapordeposition (CVD), selective epitaxy, non-selective epitaxy,collector design, high-frequency measurement, dopantsegregation, thermal stability.

Most electrical, magnetic or optical devices are today based on several, usually extremely thin layers of different materials.  In this thesis chemical synthesis processes have been developed for growth of less stable and metastable layers, and even multilayers, of nickel containing compounds. A chemical vapor deposition (CVD) method for deposition of metastable Ni3N has been developed.  The deposition process employs ammonia as nitrogen precursor. An atomic layer deposition (ALD) process for deposition of both polycrystalline and epitaxial NiO and using low oxygen activity, has also been developed. Both deposition processes utilizes bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel(II) (Ni(thd)2) as the metal precursor. The Ni3N deposition proceeds via surface reactions. The growth rate is very sensitive to the partial pressure of ammonia, why adsorbed –NHx species are believed to be of importance for the film growth. Similar reactions can be expected between the metal precursor and H2O. For ALD of NiO a large excess of water was needed For the multilayered structures of Ni3N/NiO, growth processes, working at low activities of oxygen and hydrogen, are needed to avoid oxidation or reduction of the underlying layer. Chemical vapor growth methods such as CVD and ALD are often suffering from using high activities of hydrogen or oxygen to deposit metals and oxides. An alternative deposition pathway for metal deposition, without any hydrogen in the vapor, has been demonstrated. The metal has been formed by decomposition of the metastable nitride Ni3N in a post-annealing process.  Ni3N decomposes via different mechanisms, depending on environment in the annealing process. The different mechanisms result in different degrees of ordering in the resulting Ni films. From the knowledge gained about the chemical growth of NiO and Ni3N as well as the decomposition of Ni3N, well-defined multilayer structures have been produced in different combinations of NiO, Ni3N and Ni.

This thesis is based on experimental studies in chemical physics. Titanium dioxide (TiO2) and phthalocyanine’s (Pc’s), interesting in many future perspectives, have been deposited as thin films and studied as follows. Information has been obtained on e.g. molecular orientation, crystal structure, depth profile of the chemical composition, electrochemical properties and electronic structure. This has been achieved by means of a combination of techniques: X-ray photoelectron spectroscopy (XPS), near edge x-ray absorption fine structure (NEXAFS), density functional theory calculations (DFT), UV-visible absorption spectroscopy (UVVIS) and cyclic voltammetry (CV). Metal-free phthalcyanine (H2Pc) has been shown to form films with different crystal structure and molecular orientation depending on deposition method, evaporation/sublimation or powder deposition, on commercial conducting glass (fluorine doped tin oxide, FTO), which is used e.g. in solar cells and organic light emitting devices (OLEDs). The unoccupied molecular orbitals are divided in x, y and z space coordinates of the molecule and also divided in inequivalent nitrogen components. The electronic structure is also studied for a sublimated titanyl phthalocyanine (TiOPc) film and related to the metal-free phthalocyanine. The ligand field around the titanium atom in TiOPc is compared with that of TiO2 to delineate the unoccupied levels recorded by means of x-ray absorption spectroscopy. Nanostructured TiO2 films were manufactured by screen printing/doctor blading on FTO. Such films were additionally covered with lutetium diphthalocyanine (LuPc2) by means of surface assembly from solution. LuPc2-, LuPc2+ and LuPc2H were identified and the stability of the electrochromic reactions in this system was monitored. Chemical vapor deposition (CVD) has been used to grow nanometer sized anatase TiO2 crystals on pre-oxidized Si (111) without formation of interfacial carbon and with an interface layer of the size of 15- 25Å. The interface layer was found to be amorphous TiSixOy with graded stoichiometry.

As the integration scale of transistors/devices in a chip/system keeps increasing, effective cooling has become more and more important in microelectronics. To address the thermal dissipation issue, one important solution is to develop thermal interface materials with higher performance. Carbon nanotubes, given their high intrinsic thermal and mechanical properties, and their high thermal and chemical stabilities, have received extensive attention from both academia and industry as a candidate for high-performance thermal interface materials. The thesis is devoted to addressing some challenges related to the potential application of carbon nanotubes as thermal interface materials in microelectronics. These challenges include: 1) controlled synthesis of vertically aligned carbon nanotubes on various bulk substrates via chemical vapor deposition and the fundamental understanding involved; 2) development of a scalable annealing process to improve the intrinsic properties of synthesized carbon nanotubes; 3) development of a state-of-art assembling process to effectively implement high-quality vertically aligned carbon nanotubes into a flip-chip assembly; 4) a reliable thermal measurement of intrinsic thermal transport property of vertically aligned carbon nanotube films; 5) improvement of interfacial thermal transport between carbon nanotubes and other materials. The major achievements are summarized. 1. Based on the fundamental understanding of catalytic chemical vapor deposition processes and the growth mechanism of carbon nanotube, fast synthesis of high-quality vertically aligned carbon nanotubes on various bulk substrates (e.g., copper, quartz, silicon, aluminum oxide, etc.) has been successfully achieved. The synthesis of vertically aligned carbon nanotubes on the bulk copper substrate by the thermal chemical vapor deposition process has set a world record. In order to functionalize the synthesized carbon nanotubes while maintaining their good vertical alignment, an in situ functionalization process has for the first time been demonstrated. The in situ functionalization renders the vertically aligned carbon nanotubes a proper chemical reactivity for forming chemical bonding with other substrate materials such as gold and silicon. 2. An ultrafast microwave annealing process has been developed to reduce the defect density in vertically aligned carbon nanotubes. Raman and thermogravimetric analyses have shown a distinct defect reduction in the CNTs annealed in microwave for 3 min. Fibers spun from the as-annealed CNTs, in comparison with those from the pristine CNTs, show increases of ~35% and ~65%, respectively, in tensile strength (~0.8 GPa) and modulus (~90 GPa) during tensile testing; an ~20% improvement in electrical conductivity (~80000 S m⁻¹) was also reported. The mechanism of the microwave response of CNTs was discussed. Such an microwave annealing process has been extended to the preparation of reduced graphene oxide. 3. Based on the fundamental understanding of interfacial thermal transport and surface chemistry of metals and carbon nanotubes, two major transfer/assembling processes have been developed: molecular bonding and metal bonding. Effective improvement of the interfacial thermal transport has been achieved by the interfacial bonding. 4. The thermal diffusivity of vertically aligned carbon nanotube (VACNT, multi-walled) films was measured by a laser flash technique, and shown to be ~30 mm² s⁻¹ along the tube-alignment direction. The calculated thermal conductivities of the VACNT film and the individual CNTs are ~27 and ~540 W m⁻¹ K⁻¹, respectively. The technique was verified to be reliable although a proper sampling procedure is critical. A systematic parametric study of the effects of defects, buckling, tip-to-tip contacts, packing density, and tube-tube interaction on the thermal diffusivity was carried out. Defects and buckling decreased the thermal diffusivity dramatically. An increased packing density was beneficial in increasing the collective thermal conductivity of the VACNT film; however, the increased tube-tube interaction in dense VACNT films decreased the thermal conductivity of the individual CNTs. The tip-to-tip contact resistance was shown to be ~1×10⁻⁷ m² K W⁻¹. The study will shed light on the potential application of VACNTs as thermal interface materials in microelectronic packaging. 5. A combined process of in situ functionalization and microwave curing has been developed to effective enhance the interface between carbon nanotubes and the epoxy matrix. Effective medium theory has been used to analyze the interfacial thermal resistance between carbon nanotubes and polymer matrix, and that between graphite nanoplatlets and polymer matrix.

The Virtual Chemical Vapor Deposition (CVD) Process Development Project provides the context for the two areas of the research presented in this dissertation. The first area, generally referred to as feedback in this dissertation, focuses on student learning and the interactions of students and instructors that take place in the project, specifically focused on characterizing feedback and determining the influence of feedback as student teams progress towards completing the project. The characteristics of feedback found in this project are presented within a situative perspective using the analytical framework of episodes. The characteristics include: a list and categorization of episode themes, the structure and flow of episodes during the coaching session, the sub-structure present within individual episodes, and the types of feedback present. This dissertation shows how these characteristics frame participation in a community of practice and can be used as tools to scaffold instructor feedback in project-based learning. Episodes analysis is also used to investigate how feedback on professional skills can help to enculturate students into a community of practice and influence their fluency with professional skills and engagement in more technical activities. The second area examines the spread of this innovative project from its home institution to other institutions. In this area an analysis of the spread of the Virtual CVD Process Development Project in the high school setting is presented. The project was found to provide versatility for instructors and afford student learning in the areas of motivation, cognition, and epistemological beliefs. These two areas inform each other. As the project is assessed at different institutions, it is continually improved and the sensitivity of different aspects of the project is explored, e.g., the aspects of the project that are crucial to maintain effectiveness are identified. One of these aspects is the feedback that takes place in the project. As the project is further examined at the home institution in depth, more can be learned about the best ways it can be delivered. This information informs scaffolding that then can be provided to faculty at other institutions such that they can attend to crucial aspects of the project in the most efficient, effective manner, improving not only the probability of successful adaptation, but also the likelihood that the project will further diffuse to other institutions. / Graduation date: 2013

This report details work toward the fabrication of a single-electron transistor created from a single-walled carbon nanotube (SWNT). Specifically discussed is a method for growing carbon nanotubes (CNTs) via carbon vapor deposition (CVD). The growth is catalyzed by a solution of 0.02g Fe(NO3)3·9H2O, 0.005g MoO2(acac)2, and 0.015g of alumina particles in 15mL methanol. SWNT diameter ranges from 0.6 to 3.0 nm. Also discussed is a method to control nanotube growth location by patterning samples with small islands of catalyst. A novel “maskless” photolithographic process is used to focus light from a lightweight commercial digital projector through a microscope. Catalyst islands created by this method are approximately 400 μm2 in area.

This report details work toward the fabrication of a single-electron transistor created from a single-walled carbon nanotube (SWNT). Specifically discussed is a method for growing carbon nanotubes (CNTs) via carbon vapor deposition (CVD). The growth is catalyzed by a solution of 0.02g Fe(NO3)3·9H2O, 0.005g MoO2(acac)2, and 0.015g of alumina particles in 15mL methanol. SWNT diameter ranges from 0.6 to 3.0 nm. Also discussed is a method to control nanotube growth location by patterning samples with small islands of catalyst. A novel “maskless” photolithographic process is used to focus light from a lightweight commercial digital projector through a microscope. Catalyst islands created by this method are approximately 400 μm2 in area.

The objective of this dissertation is to shed light on the physical properties of InN epilayers grown by High-Pressure Chemical Vapor Deposition (HPCVD) for optical device applications. Physical properties of HPCVD grown InN layers were investigated by X-ray diffraction, Raman scattering, infrared reflection spectroscopies, and atomic force microscopy. The dependencies of physical properties as well as surface morphologies of InN layers grown either directly on sapphire substrates or on GaN/sapphire templates on varied growth conditions were studied. The effect of crucial growth parameters such as growth pressure, V/III molar ratio, precursor pulse separation, substrate material, and mass transport along the flow direction on the optical and structural properties, as well as on the surface morphologies were investigated separately. At present, growth of high-quality InN material by conventional growth techniques is limited due to low dissociation temperature of InN (~600 ºC) and large difference in the partial pressures of TMI and NH3 precursors. In this research, HPCVD technique, in which ambient nitrogen is injected into reaction zone at super-atmospheric growth pressures, was utilized to suppress surface dissociation of InN at high temperatures. At high pressures, long-range and short-range orderings indicate that c-lattice constant is shorter and E2(high) mode frequency is higher than those obtained from low-pressure growth techniques, revealing that InN structure compressed either due to a hydrostatic pressure during the growth or thermal contraction during the annealing. Although the influence of varied growth parameters usually exhibit consistent correlation between long-range and short-range crystalline orderings, inconsistent correlation of these indicate inclination of InN anisotropy. InN layers, grown directly on α-sapphire substrates, exhibit InN (1 0 1) Bragg reflex. This might be due to a high c/a ratio of sapphire-grown InN epilayers compared to that of GaN/sapphire-grown InN epilayers. Optical analysis indicates that free carrier concentration, ne, in the range of 1–50 × 1018 cm–3 exhibits consistent tendency with longitudinal-optic phonon. However, for high ne values, electrostatic forces dominate over inter-atomic forces, and consistent tendency between ne and LO phonon disappears. Structural results reveal that growth temperature increases ~6.6 ºC/bar and V/III ratio affects indium migration and/or evaporation. The growth temperature and V/III ratio of InN thin films are optimized at ~850 ºC and 2400 molar ratio, respectively. Although high in-plane strain and c/a ratio values are obtained for sapphire-grown epilayers, FWHM values of long-range and short-range orderings and free carrier concentration value are still lower than those of GaN/sapphire-grown epilayers. Finally, vibrational and optical properties of chalcopyrite ZGP crystal on the (001), (110), and (10) crystalline planes were investigated by Raman scattering and infrared (IR) reflection spectroscopies. Raman scattering exhibits a nonlinear polarizability on the c-plane, and a linear polarizability on the a- and b-planes of ZGP crystal. Also, birefringence of ZGP crystal was calculated from the hydrostatic pressure difference between (110) and (10) crystalline planes for mid-frequency B2(LO) mode.

This thesis describes the design, fabrication and characterization of AlGaN/GaN Heterostructure Field E ect Transistors (HFETs) grown by a Metal Organic Chemical Vapor Deposition (MOCVD) on sapphire substrates. The objective of this research is to develop AlGaN/GaN power devices with high breakdown voltage (greater than 1 kV) and low turn-on resistance. Various characteristics such as current drive (Idss), transconductance (gm) and threshold voltage (Vth) have also been measured and the results have been discussed. Two major challenges with the development of high breakdown voltage AlGaN/GaN HFETs in the past have been high material defect density and non-optimized fabrication technologies which gives rise to bu er leakage and surface leakage, respectively. In this thesis, mesa isolation, ohmic and gate metal contacts, and passivation techniques, have been discussed to improve the performance of these power transistors in terms of low contact resistance and low gate leakage. The relationship between breakdown voltage and Rds(ON)A with respect to the gate-drain length (Lgd) is also discussed. First, unit cell devices were designed (two-fingered cells with Wg = 100, 300, 400 m) and characterized, and then they were extended to form large area devices (upto Wg = 40 mm). The design goals were classied into three parts: - High Breakdown Voltage: This was achieved by designing devices with variations in Lgd, - Low turn-on resistance: This was achieved by optimizing the annealing temperatures as well as incorporating additional thick metal pads, as well as optimizing the passivation etch recipe, - Low Gate Leakage: The gate leakage was reduced signicantly by using a gate metal with a larger barrier height. All devices with Lgd larger than 10 m exhibited excellent breakdown voltage characteristics of over 800 V, and it progressed as the Lgd increased. The turn-on resistance was also reduced signicantly below 20 m-cm2, for devices with Lgd = 15, 25, and 20 m. The gate leakage was measured for all devices upto 200 V, and was in the range of 10-100 nA, which is one of the best values reported for multi-ngered devices with Lgd in the range of 2.4-5 mm. Some of the key challenges faced in fabrication were determining a better gate metal layer to reduce gate leakage, optimizing the passivation via etch recipe, and reducing surface leakage.