Laser Chemical Vapor Deposition (LCVD) is a process by which reagent gases are thermally activated to react by means of a laser focused on a substrate. The reaction produces a ceramic or metallic deposit. This investigation focuses on the use of LCVD as a method for producing laminated composites, specifically carbon/silicon carbide laminates. The laminates that were produced were examined using scanning electron microscopy (SEM) and electron dispersive spectroscopy (EDS) to determine composition. Deposit geometrical characteristics such as laminate thickness and volcano depth as well as deposit morphology were also determined using SEM. Another subset of experiments was performed for the purpose of simultaneously depositing carbon and silicon carbide, ie., codeposition.

<p>Laser-induced chemical vapor deposition (LCVD) is a process enabling the deposition of solid material from a gas phase in the form of free-standing microstructures with high aspect ratios. The deposition rate, wire diameter, and material properties are sensitive to changes in temperature and gas pressure. Through experimentation these dependencies are clarified for carbon and tungsten-coated carbon microhelices to be used as heating elements in cold gas microthrusters for space applications. The integration of heaters into the thruster will raise the temperature of the gas; thus, improving the efficiency of the thruster based on specific impulse.</p><p>Deposition rate is measured during the fabrication process, and the geometrical dimensions of the spring are determined through microscopy analysis. By experimentally measuring the spring rate, material properties such as shear modulus and modulus of elasticity for LCVD-deposited carbon can be determined as a function of process parameters. </p><p>Electrothermal characterization of carbon and tungsten-coated microcoils is performed by resistively heating the coils and measuring their surface temperature and resistance in atmospheres relevant to their operating environments. Through high-resolution microscopy analysis, sources having detrimental effects on the coils are detected and minimized. The results gained from these experiments are important for efforts in improving the performance of cold gas microthrusters.</p>

<p>Nanoparticles of iron, cobalt and tungsten oxide were synthesised by photolytic laser assisted chemical vapour deposition (LCVD). An excimer laser (operating at 193 nm) was used as an excitation source. The LCVD process, was monitored <i>in situ</i> by optical emission spectroscopy (OES). The synthesised particles were further analysed using transmission electron spectroscopy (TEM), X-ray diffraction (XRD), high resolution scanning electron microscopy (HRSEM), X-ray fluorescence spectroscopy (XRF), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.</p><p>Iron and cobalt single crystalline nanoparticles were synthesized using ferrocene and cobaltocene precursors. The diameter of the particles could be tailored by the experimental parameters (e.g., partial pressure and laser power) and were in the range 1 - 50 nm in diameter. In both cases, the particles were covered by a carbon shell, typically 7 nm thick. A thin graphitic layer was observed at the interface metal-carbon. Amorphous carbon was deposited on top of the graphitic carbon. Particle temperature, reaching the boiling point of the respective metal, was observed by OES of the thermal emission during the laser-induced particle formation process (and subsequent heating). Both bcc and fcc Fe phases were formed, both hcp and fcc for the Co phases. Size dependent magnetic properties were observed using superconducting quantum interference device (SQUID) measurements, where super-paramagnetic magnetic domains dominated for <i>d</i> < 10 nm. The iron particles were further processed, whereby the amorphous shell was removed by refluxing in nitric acid. In a subsequent step, the graphitic surface was functionalized by attaching an octyl ester, rendering the particles hydrophobic.</p><p>Tungsten oxides were synthesized from combinations of WF₆/H₂/O₂ as precursors. No particles could be deposited if H₂ was removed from the gas-mixture. The as-deposited oxide nanoparticle film was amorphous. A monoclinic WO₃ particle film could be achieved by annealing the amorphous oxide. Above 400°C, the oxide particles increased in size from ca. 20 nm to 60 nm through coalescence. The gas-sensing properties of the tungsten oxide were tested by conductance measurements using H₂S as analyte. The sensitivity of the amorphous oxide nanoparticle film was found to be superior to that of a crystalline oxide nanoparticle film. </p>

Laser-induced chemical vapor deposition (LCVD) is a process enabling the deposition of solid material from a gas phase in the form of free-standing microstructures with high aspect ratios. The deposition rate, wire diameter, and material properties are sensitive to changes in temperature and gas pressure. Through experimentation these dependencies are clarified for carbon and tungsten-coated carbon microhelices to be used as heating elements in cold gas microthrusters for space applications. The integration of heaters into the thruster will raise the temperature of the gas; thus, improving the efficiency of the thruster based on specific impulse. Deposition rate is measured during the fabrication process, and the geometrical dimensions of the spring are determined through microscopy analysis. By experimentally measuring the spring rate, material properties such as shear modulus and modulus of elasticity for LCVD-deposited carbon can be determined as a function of process parameters. Electrothermal characterization of carbon and tungsten-coated microcoils is performed by resistively heating the coils and measuring their surface temperature and resistance in atmospheres relevant to their operating environments. Through high-resolution microscopy analysis, sources having detrimental effects on the coils are detected and minimized. The results gained from these experiments are important for efforts in improving the performance of cold gas microthrusters.

Nanoparticles of iron, cobalt and tungsten oxide were synthesised by photolytic laser assisted chemical vapour deposition (LCVD). An excimer laser (operating at 193 nm) was used as an excitation source. The LCVD process, was monitored in situ by optical emission spectroscopy (OES). The synthesised particles were further analysed using transmission electron spectroscopy (TEM), X-ray diffraction (XRD), high resolution scanning electron microscopy (HRSEM), X-ray fluorescence spectroscopy (XRF), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Iron and cobalt single crystalline nanoparticles were synthesized using ferrocene and cobaltocene precursors. The diameter of the particles could be tailored by the experimental parameters (e.g., partial pressure and laser power) and were in the range 1 - 50 nm in diameter. In both cases, the particles were covered by a carbon shell, typically 7 nm thick. A thin graphitic layer was observed at the interface metal-carbon. Amorphous carbon was deposited on top of the graphitic carbon. Particle temperature, reaching the boiling point of the respective metal, was observed by OES of the thermal emission during the laser-induced particle formation process (and subsequent heating). Both bcc and fcc Fe phases were formed, both hcp and fcc for the Co phases. Size dependent magnetic properties were observed using superconducting quantum interference device (SQUID) measurements, where super-paramagnetic magnetic domains dominated for d &lt; 10 nm. The iron particles were further processed, whereby the amorphous shell was removed by refluxing in nitric acid. In a subsequent step, the graphitic surface was functionalized by attaching an octyl ester, rendering the particles hydrophobic. Tungsten oxides were synthesized from combinations of WF6/H2/O2 as precursors. No particles could be deposited if H2 was removed from the gas-mixture. The as-deposited oxide nanoparticle film was amorphous. A monoclinic WO3 particle film could be achieved by annealing the amorphous oxide. Above 400°C, the oxide particles increased in size from ca. 20 nm to 60 nm through coalescence. The gas-sensing properties of the tungsten oxide were tested by conductance measurements using H2S as analyte. The sensitivity of the amorphous oxide nanoparticle film was found to be superior to that of a crystalline oxide nanoparticle film.

The primary goal of this research was to develop the laser chemical vapor deposition (LCVD) process to be able to directly deposit carbon nanotubes onto substrates selectively. LCVD has traditionally been used to directly deposit complex geometries of other materials, including many metals and ceramics. Carbon nanotube deposits were formed using codeposition and other techniques. Multiwall carbon nanotubes as small as 7 nm were synthesized. Utilizing electron microscopy, deposits were characterized to determine the effects of laser power, catalyst and hydrocarbon concentration, time, pressure, and other variables on the number of nanotubes formed, their size, and their spatial location. The most important variables were shown to be hydrocarbon and catalyst concentration and laser power. These results were analyzed and statistics based models were developed to express these trends. Additionally, the process was also used successfully to deposit linear patterns of carbon nanotubes. Carbon nanotube deposits were also carried out in the presence of an electric field. It was demonstrated that a field of sufficient strength could be used to orient tube growth. LCVD is a thermally driven process and a thermal feedback and control system is typically employed to allow for real time control of the reaction zone temperatures. The current thermal imaging system installed on the LCVD reactor is limited to operation at temperatures above which nanotube deposition occurs. A heat and mass transport model was therefore developed to simulate deposition temperatures and provide an estimate of the desired laser power needed to achieve a desired reaction temperature. This model included all significant modes of heat transport including conduction, natural convection and radiation. Temperature dependant material properties were also employed to help achieve greater accuracy. Additionally, the model was designed to be able to simulate a scanning laser beam which was used to deposit linear patterns of carbon nanotubes. Modeling calculations of laser heating compared favorably with experimental data. The results of this work show that LCVD has potential for use in the commercial market for selective direct deposition of patterns of aligned carbon nanotubes on multiple substrate materials.

Abstract In this work the LCVD of copper and nickel from the precursor gases Cu(hfac)tmvs and Ni(CO)4 has been investigated. The in-house constructed LCVD system and processes and the practical utilisation of these in prototype integrated circuit edit work are described. The investigated process parameters include laser power, laser scan speed, precursor partial pressure and the effect of H2 and He carrier gases. The deposited metal conductor lines have been examined by LIMA, AFM, FIB secondary electron/ion micrography, and by electrical measurements. Furthermore, the study of experimental FIB circuit edit processes is carried out and discussed with particular emphasis on ion beam induced ESD damages. It is shown how the LCVD and FIB methods can be combined to create a novel method to carry out successfully circuit edit cases where both methods alone will fail. The combined FIB/LCVD- method is shown to be highly complementary and effective in practical circuit edit work in terms of reduced process time and improved yield. Circuit edit cases where both technologies are successfully used in a complementary way are presented. Selected examples of some special circuit edit cases include RF- circuit editing, a high resolution method for FIB-deposited tungsten conductor line resistance reduction and large area EMI shielding of IC surfaces. Based on the research it was possible for a formal workflow for the combined process to be developed and this approach was applied to 132 circuit edit cases with 85% yield. The combined method was applied to 30% of the total number of edit cases. Finally, the developed process and constructed system was commercialized.

A rapid, mask-less deposition technique for writing metal tracks has been developed. The technique was based on laser-induced chemical vapour deposition. The novelty in the technique was the usage of pulsed ultrafast lasers instead of continuous wave lasers in pyrolytic dissociation of the chemical precursor. The motivation of the study was that (1) ultrafast laser pulses have smaller heat affected zones thus the deposition resolution would be higher, (2) the ultrashort pulses are absorbed in most materials (including those transparent to the continuous wave light at the same wavelength) thus the deposition would be compatible with a large range of materials, and (3) the development of higher frequency repetition rate ultrafast lasers would enable higher deposition rates. A deposition system was set-up for the study to investigate the ultrafast laser deposition of tungsten from tungsten hexacarbonyl chemical vapour precursors. A 405 nm laser diode was used for continuous wave deposition experiments that were optimized to achieve the lowest track resistivity. These results were used for comparison with the ultrafast laser track deposition. The usage of the 405 nm laser diode was itself novel and beneficial due to the low capital and running cost, high wall plug efficiency, high device lifetime, and shallower optical penetration depth in silicon substrates compared to green argon ion lasers which were commonly used by other investigators. The lowest as-deposited track resistivity achieved in the continuous wave laser experiments on silicon dioxide coated silicon was 93±27 µΩ cm (16.6 times bulk tungsten resistivity). This deposition was done with a laser output power of 350 mW, scan speed of 10 µm/s, deposition pressure of 0.5 mBar, substrate temperature of 100 °C and laser spot size of approximately 7 µm. The laser power, scan speed, deposition pressure and substrate temperature were all optimized in this study. By annealing the deposited track with hydrogen at 650 °C for 30 mins, removal of the deposition outside the laser spot was achieved and the overall track resistivity dropped to 66±7 µΩ cm (11.7 times bulk tungsten resistivity). For ultrafast laser deposition of tungsten, spot dwell experiments showed that a thin film of tungsten was first deposited followed by quasi-periodic structures perpendicular to the linear polarization of the laser beam. The wavelength of the periodic structures was approximately half the laser wavelength (λ/2) and was thought to be formed due to interference between the incident laser and scattered surface waves similar to that in laser-induced surface periodic structures. Deposition of the quasi-periodic structures was possible on stainless steel, silicon dioxide coated silicon wafers, borosilicate glass and polyimide films. The thin-films were deposited when the laser was scanned at higher laser speeds such that the number of pulses per spot was lower (η≤11,000) and using a larger focal spot diameter of 33 µm. The lowest track resistivity for the thin-film tracks on silicon dioxide coated silicon wafers was 37±4 µΩ cm (6.7 times bulk tungsten resistivity). This value was achieved without post-deposition annealing and was lower than the annealed track deposited using the continuous wave laser. The ultrafast tungsten thin-film direct write technique was tested for writing metal contacts to single layer graphene on silicon dioxide coated silicon substrates. Without the precursor, the exposure of the graphene to the laser at the deposition parameters damaged the graphene without removing it. This was evidenced by the increase in the Raman D peak of the exposed graphene compared to pristine. The damage threshold was estimated to be 53±7 mJ/cm2 for a scanning speed of 500 µm/s. The deposition threshold of thin-film tungsten on graphene at that speed was lower at 38±8 mJ/cm2. However, no graphene was found when the deposited thin-film tungsten was dissolved in 30 wt% H2O2 that was tested to have no effect on the graphene for the dissolution time of one hour. The graphene likely reacted with the deposited tungsten to form tungsten carbide which was reported to dissolve in H2O2. Tungsten carbide was also found on the tungsten tracks deposited on reduced graphene oxide samples. The contact resistance between tungsten and graphene was measured by both transfer length and four-point probe method with an average value of 4.3±0.4 kΩ µm. This value was higher than reported values using noble metals such as palladium (2.8±0.4 kΩ µm), but lower than reported values using other metals that creates carbides such as nickel (9.3±1.0 kΩ µm). This study opened many potential paths for future work. The main issue to address in the tungsten ultrafast deposition was the deposition outside the laser spot. This prevented uniform deposition in successive tracks close to one another. The ultrafast deposition technique also needs verification using other precursors to understand the precursor requirements for this process. An interesting future study would be a combination with a sulphur source for the direct write of tungsten disulphide, a transition metal dichalcogenide that has a two-dimensional structure similar to graphene. This material has a bandgap and is sought after for applications in high-end electronics, spintronics, optoelectronics, energy harvesting, flexible electronics, DNA sequencing and personalized medicine. Initial tests using sulphur micro-flakes on silicon and stainless-steel substrates exposed to the tungsten precursor and ultrafast laser pulses produced multilayer tungsten disulphide as verified in Raman measurements.

Laser Chemical Vapor Deposition (LCVD) has been shown to have great potential for the manufacture of small, complex, two or three dimensional metal and ceramic parts. One of the most promising applications of the technology is in the fabrication of an integrated dispenser cathode assembly. This application requires the deposition of a boron nitridemolybdenum composite structure. In order to realize this structure, work was done to improve the control and understanding of the LCVD process and to determine experimental conditions conducive to the growth of the required materials. A series of carbon fiber and line deposition studies were used to characterize processshape relationships and study the kinetics of carbon LCVD. These studies provided a foundation for the fabrication of the first high aspect ratio multilayered LCVD wall structures. The kinetics studies enabled the formulation of an advanced computational model in the FLUENT CFD package for studying energy transport, mass and momentum transport, and species transport within a forced flow LCVD environment. The model was applied to two different material systems and used to quantify deposition rates and identify ratelimiting regimes. A computational thermalstructural model was also developed using the ANSYS software package to study the thermal stress state within an LCVD deposit during growth. Georgia Techs LCVD system was modified and used to characterize both boron nitride and molybdenum deposition independently. The focus was on understanding the relations among process parameters and deposit shape. Boron nitride was deposited using a B3N3H6-N2 mixture and growth was characterized by sporadic nucleation followed by rapid bulk growth. Molybdenum was deposited from the MoCl5-H2 system and showed slow, but stable growth. Each material was used to grow both fibers and lines. The fabrication of a boron nitridemolybdenum composite was also demonstrated. In sum, this work served to both advance the general science of Laser Chemical Vapor Deposition and to elucidate the practicality of fabricating ceramicmetal composites using the process.