As the internet-of-things hardware integration continues to develop and the requirements for electronics keep diversifying and expanding, the necessity for specialized properties other than the classical semiconductor performance becomes apparent. The success of emerging semiconductor materials depends on the manufacturability and cost as much as on the properties and performance they offer. Solution-based semiconductors are an emerging concept that offers the advantage of being compatible with large-scale manufacturing techniques and have the potential to yield high-quality electronic devices at a lower cost than currently available solutions. In this work, patterns of high-quality MAPbBr3 perovskite single crystals in specific locations are achieved through the modification of the substrate properties and solvent engineering. The fabrication of the substrates involved modifying the surface adhesion forces through functionalization with self-assembled monolayers and patterning them by photolithography processes. Spin coating and blade coating were used to deposit the perovskite solution on the modified silicon substrates. While single crystal perovskites were obtained with the modification of substrates alone, solvent engineering helped with improving the Marangoni flows in the deposited droplets by increasing the contact angle and lowering the evaporation rate, therefore controlling and improving the shape of the grown perovskite crystals. The methodology is extended to other types of perovskites such as the transparent MAPbCl3 and the lead-free MABi2I9, demonstrating the adaptability of the process. Adapting the process to electrode arrays opened up the path towards the fabrication of optoelectronic devices including photodetectors and field-effect transistors, for which the first iterations are demonstrated. Overall, manufacturing and integration techniques permitting the fabrication of single crystalline devices, such as the method in this thesis work, are fundamental in pushing hybrid perovskites towards commercialization.

For years, electron beam induced deposition has been used to fabricate electrical contacts for micro and nanostructures. The role of the contact resistance is key to achieve high performance and efficiency in electrical devices. The present thesis reports on the electrical, structural and chemical characterization of electron beam deposited platinum electrodes that are exposed to different steps of thermal annealing and how they are used in four-probe devices of ultrathin graphite (uG) flakes (<100nm thickness). The device integration of liquid phase exfoliated uG is demonstrated, and its performance compared to devices made with analogous mechanically exfoliated uG. For both devices, similar contact resistances of ~2kΩ were obtained. The electrical measurements confirm a 99.5% reduction in contact resistance after vacuum thermal annealing at 300 °C. Parallel to this, Raman characterization confirms the formation of a nanocrystalline carbon structure over the electrode. While this could suggest an enhancement of the electrical transport in the device, an additional thermal annealing step in air at 300 °C, promoted the oxidation and removal of the carbon shell and confirmed that the contact resistance remained the same. Overall this shows that the carbon shell along the electrode has no significant role in the contact resistance. Finally, the challenges based on topographical analysis of the deposited electrodes are discussed. Reduction of the electrode’s height down to one-third of the initial value, increased surface roughness, formation of voids along the electrodes and the onset of platinum nanoparticles near the area of deposition, represent a challenge for future work.

In this work, nickel-gold multi-segmented magnetic nanowires were grown by electrodeposition in anodized alumina templates. The templates were fabricated by a two step anodization process of aluminum disks in an aqueous solution of oxalic acid. In this process, ordered pores grew in an alumina oxide layer at the exposed aluminum area. Each disk was electropolished before the anodization process and the features at its surface were characterized to assess the effect on the pore ordering. Nickel Watts and gold cyanide electrolyte baths were prepared to electrodeposit pure nickel and gold in the templates. Both solutions response to a range of externally applied voltages was characterized and a threshold voltage above which deposition occurs is reported. Single nanowires were isolated by chemically dissolving the template and dispersed in ethanol. Devices were fabricated with these isolated nanowires in which gold contacts were deposited to measure the resistance. A current pulse setup was implemented in a magnetoresistance system allowing to send current pulses with amplitude as low as 2nA and 50μs width. Magneto resistance measurement were carried out on the single nanowires devices and the effect of current pulses was studied. It was found that distinct resistance states can be achieved by applying a determined current pulse at a constant applied field and that the initial state can be recovered by removing excess charge from the nanowire. Finally, the effect of annealing the nanowires in an air atmosphere at 150°C for 24 hours is studied showing that the nickel sections oxidize and the gold sections remain unchanged.

Battery research has been going full steam and with that the search for alternative anodes. Among many proposed electrode materials, little attention has been given to phosphorus. Phosphorus boasts the third highest gravimetric charge capacity and the highest volumetric charge capacity of all elements. Because of that, it would be an attractive battery anode material were it not for its poor cyclability with significant capacity loss immediately after the first cycle. This is known to be the consequence of considerable volume changes of phosphorus during charge/discharge cycles. In this work, we propose circumventing this issue by mixing amorphous red phosphorus with carbon nanotubes. By employing a non-destructive sublimation-deposition method, we have synthesized composites where the synergetic effect between phosphorus and carbon nanotubes allow for an improvement in the electrochemical performance of battery anodes. In fact, it has been shown that carbon nanotubes can act as an effective buffer to phosphorus volumetric expansions and contractions during charging and discharging of the half-cells [1]. By modifying the synthesis parameters, we have also been able to change the degree of crystallinity of the phosphorus matrix in the composites. In fact, the less common phase of red phosphorus, named fibrous phosphorus, was obtained, and that explains some of the varying electrochemical performances observed in the composites. Overall, it is found that a higher surface area of amorphous phosphorus allows for a better anode material when using single-walled carbon nanotubes as fillers.

Device fabrication on multi walled carbon nanotubes (MWCNTs) using electrical beam lithography (EBL), electron beam induced deposition (EBID), ion beam induced deposition (IBID) methods was carried out, followed by device electrical characterization using a conventional probe station. A four-probe configuration was utilized to measure accurately the electrical resistivity of MWCNTs with similar results obtained from devices fabricated by different methods. In order to reduce the contact resistance of the beam deposited platinum electrodes, single step vacuum thermal annealing was performed. Microscopy and spectroscopy were carried out on the beam deposited electrodes to follow the structural and chemical changes occurring during the vacuum thermal annealing. For the first time, a core-shell type structure was identified on EBID Pt and IBID Pt annealed electrodes and analogous free standing nanorods previously exposed to high temperature. We believe this observation has important implications for transport properties studies of carbon materials. Apart from that, contamination of carbon nanostructure, originating from the device fabrication methods, was also studied. Finally, based on the observations of faster processing time together with higher yield and flexibility for device preparation, we investigated EBID to fabricate devices for other discrete carbon nanostructures.

Increasing demands for efficient energy storage in microelectronics has pushed the scientific community towards finding suitable materials that can effectively deliver high pulse power in miniaturized systems. Polymer-ceramic composites are considered to be one possible solution towards the fabrication of high energy density capacitors, whether as embedded capacitors or gate insulators in organic field effect transistors (OFETs). Selecting high permittivity ceramics mixed with polymers with high breakdown field strengths would be the wisest approach towards enhancing energy storage. As such, novel ferroelectric polymers such as P(VDF-TrFE-CTFE) are being developed and researched, all displaying record dielectric values (K > 50) as promising candidates for high energy density composite capacitors (> 25 J/cm3). However, much work is still needed to understand the interaction mechanisms between the phases. We aim to seek an understanding of the processing challenges, especially in terms of fabricating thin film ferroelectric polymers and their application in nanocomposite capacitors while effectively maintaining optimized performance when embedded in flexible electronics. A process for synthesizing high performance P(VDF-TrFE) thin films is developed realizing the importance of controlling several process parameters to achieve high quality devices. Electrical and physicochemical characterization demonstrate how the performance of the polymer films improves with prolonged annealing periods by allowing sufficient time for solvent evaporation, crystallization and preferential-orientation of the crystallites. The polymer P(VDF-TrFE) is then used as a host material with barium titanate (BTO) nanoparticles below 100 nm (K = 150) as a ceramic filler in nanocomposite films. Facile surface modification by hydroxylation proved to be essential in the performance of the devices in terms of leakage current. A decrease of approximately 2 orders of magnitude in current leakage is recorded in surface modified BTO displaying potential for higher breakdown strength. Besides developing a process for P(VDF-TrFE) and low leakage composites, the importance of dispersion techniques and filler loadings are also discussed. Combining higher BTO volume fractions dispersed via colloidal milling enhances the effective permittivity by ~112% and lowers energy dissipation to a maximum of 0.1 at higher frequencies (1 MHz).

The special electronic configuration of carbon enables the existence of wide ranging allotropes taking all possible dimensionalities. The allotropes of carbon are characterized by the type of hybridized bonding forming its structure, ranging from pure sp2 as in graphene, carbon nanotubes and fullerenes, to pure sp3 as in diamond. Amorphous and diamond-like carbon consists of a mixture of both hybridizations. This variation in hybridization in carbon materials enables a wide spectrum of properties, ranging from high bulk mechanical hardness, tribological properties and chemical inertness made possible by moving towards pure sp3 bonding to the extraordinary electrical conductivity, optical properties and in-plane mechanical strength resulting from pure sp2 bonding. Two allotropes at the extremes of this spectrum, diamond like carbon (DLC) and graphene, are investigated in this thesis; the former is investigated as a protective coating in hard drive applications, while the latter is investigated in the context of chemically derived graphene as material for transparent conducting electrode applications. DLC thin films are a main component in computer hard drives, acting as a protective coating against corrosion and mechanical wear of the magnetic layer and read-write head. The thickness of DLC films greatly affects the storage density in such devices, as larger separation between the read/write head and the magnetic layer decreases the storage density. A targeted DLC thickness of 2 nm would increase the storage density towards 1 Tbits/inch2. However, difficulty achieving continuous films at such thicknesses by commonly used sputtering methods challenges the industry to investigate alternative methods. Filtered cathodic vacuum arc (FCVA) has been proposed as an efficient technique to provide continuous, smooth and ultra-thin DLC films. We investigate the influence of deposition angle, deposition time, and substrate biasing to define the optimum process window to obtain smooth and sp3-rich DLC films on model Si substrates. Graphene has attracted worldwide attention since its recent discovery in 2004, due to its extraordinary properties. One of the most promising applications of graphene is its use as a transparent conducting electrode in photovoltaic and display applications. Unfortunately, large scale deposition of graphene is still a challenge and a limiting factor. Solution processing of graphene oxide, a type of chemically derived graphene that forms well dispersed single sheet solutions, is an easy method of depositing large scale graphene films. Subsequent reduction allows recovering part of the properties of graphene. However, residual defects and oxide groups remain in the sheet even after optimal reduction processes, making it difficult to achieve the extraordinary electrical and transport properties of graphene. We investigate the structural, chemical, and morphological implications of plasma oxidation of CVD graphene to better understand the nature of graphene oxide. One of the common threads of this study is the use of Raman spectroscopy (RS) X-ray photoelectron spectroscopy (XPS), and Atomic force microscopy (AFM) to understand the structural and compositional changes of both FCVA-deposited DLC films and plasma-oxidized graphene. In both cases, the analysis allows to obtain detailed insight into structural evolution of sp3 and sp2-rich films during plasma processing. Optimum FCVA deposited DLC films were obtained at a deposition angle of 70° for 30 sec deposition time on a biased substrate (-100 V), in terms of both surface roughness and sp3 content. RMS roughness of deposited films were around 0.15 nm with a ~50% sp3 content. Structural and chemical changes of oxygen plasma treated CVD graphene were shown to vary over three distinct stages depending on the time of plasma exposure. Initial exposure up to 3 seconds was mainly accompanied by structural changes without net uptake of oxygen, introducing more defects and smaller crystallite size into the graphene sheet. Extended exposure resulted in a nano-crystalline structure with a crystallite size of around 4 nm with a significant uptake of oxygen. Significant degree of disorder and loss of materials were eventually observed at exposure times larger than 10 s. A three stage model of graphene oxidation was suggested summing up the observed variations.

Diluted magnetic oxide (DMO) research is a growing field of interdisciplinary study like spintronic devices and medical imaging. A definite agreement among researchers concerning the origin of ferromagnetism in DMO has yet to be reached. This thesis presents a study on the structural and magnetic properties of DMO thin films. It attempts to contribute to the understanding of ferromagnetism (FM) origin in DMO. Pure ZnO and Mn doped ZnO thin films have been deposited by pulsed laser deposition (PLD) using different deposition conditions. This was conducted in order to correlate the change between structural and magnetic properties. Structural properties of the films were characterized using x-ray diffraction (XRD) and scanning electron microscopy (SEM). The superconducting quantum interference device (SQUID) was used to investigate the magnetic properties of these films. The structural characterizations showed that the quality of pure ZnO and Mn doped ZnO films increased as oxygen pressure (PO) increased during deposition. All samples were insulators. In Mn doped films, Mn concentration decreased as PO increased. The Mn doped ZnO samples were deposited at 600˚C and oxygen pressure from 50-500mTorr. All Mn doped films displayed room temperature ferromagnetism (RTFM). However, at 5 K a superparamagnetic (SPM) behavior was observed in these samples. This result was accounted for by the supposition that there were secondary phase(s) causing the superparamagnetic behavior. Our findings hope to strengthen existing research on DMO origins and suggest that secondary phases are the core components that suppress the ferromagnetism. Although RTFM and SPM at low temperature has been observed in other systems (e.g., Co doped ZnO), we are the first to report this behavior in Mn doped ZnO. Future research might extend the characterization and exploration of ferromagnetism in this system.

For its inherent advantages, such as lightweight, low cost, flexibility, and opportunity to cover large surface areas, organic solar cells have attracted more and more attention in both academia and industry. However, the efficiency of organic solar cell is still much lower than silicon solar cells, but steadily rising as it now stands above 8%. The architecture of bulk heterojunction solar cells can improve the performance of organic solar cell a lot, but these improvements are highly dependent on the morphology of photoactive layer. Therefore, by controlling the morphology of photoactive layer, most commonly composed of a P3HT donor polymer and PCBM small molecule, the performance of organic solar cells could be optimized. The use of solvent additives in the solution formulation is particularly interesting, because it is a low cost method of controlling the phase separation of the photoactive layer and possibly removing the need for subsequent thermal and solvent vapor annealing. However, the role of the solvent additive remains not well understood and much debate remains on the mechanisms by which it impacts phase separation. In the first part of this thesis, we investigate the role of the solvent additive on the individual components (solvent, donor and acceptor) of the solution and the photoactive layer both in the bulk solution, during solution-processing and in the post-processing solid state of the film. In the second part of this thesis, we investigate the role of the additive on the blended solution state and resulting thin film phase separation. Finally, we propose a new method of controlling phase separation based on the insight into the role of the solvent additive. In the first part, we used an additive [octandiethiol (OT)] in the solvent to help the aggregation of P3HT in the solution. From the UV-vis experiments, the crystallinity of P3HT in the solutions increased while it decreased in thin films with steady increase of additive concentration. This method could be used for one step, annealing-free fabrication of organic solar cell with high performance. The solution can potentially be used to prepare ink for the large scale roll-to-roll ink-jet printing of P3HT thin films. Secondly, from the experiments it is found that differences in the evaporation rate and solubility of the components of the photoactive layer may be part of the reason for morphological changes. With lower evaporation rate than the host solvent, the additive concentration in the solution keeps increasing with time during the final stages of spin coating. In addition, the phase separation is increased with the increase of additive concentration, as demonstrated by AFM and TEM. By controlling the additive concentration, it is possible to control the phase separation of photoactive layer in pristine device. It is also found that the additive can change the wetting ability of the solvent to produce films with high surface coverage. With this information in hand, we modified the solution process of BHJ layers. A layer of crystals was deposited from the OT-containing solution by postponing the start of the spin coating for several minutes (delay time) after the solution is dropped on the surface of substrate. We found this to be a very effective method of increasing the phase separation and crystallinity of the photoactive materials. This effect was not possible when using oDCB solvent without any additive.

The improvement of blood cell sorting techniques in recent years have attracted the attention of many researchers due to the possible benefits that these methods can lead in biology, regenerative medicine, materials science and therapeutic area. In this work a cell sorting technique based on filtration is described. The separation occurs by means of a microfluidic device, suitably designed, manufactured and tested, that is connected to an external experimental set-up. The fabrication process can be divided in two parts: at first it is described the manufacturing process of a filtering membrane, with holes of specific size that allow the passage of only certain cell types. Following the microfluidic device is fabricated through the mechanical micromilling. The membrane and the microdevice are suitably bonded and tested by means of an external connection with syringe pumps that inject blood samples at specific flow rates. The device is designed to separate blood cells and tumor cells only by using differences in size and shape. In particular during the first experiments red blood cells and platelets are sorted from white blood cells; in the other experiments red blood cells and platelets are separated from white blood cells and tumor cells. The microdevice has proven to be very efficient, in fact a capture efficiency of 99% is achieved. For this reason it could be used in identification and isolation of circulating tumor cells, a very rare cancer cell type whose presence in the bloodstream could be symptom of future solid tumor formation. The various experiments have also demonstrated that tumor cells survive even after the separation treatment, and then the suffered stress during the sorting process does not harm the biological sample.