Recent advances in third generation photovoltaics, particularly the rapid increase in perovskite power conversion efficiencies, may provide a cheap alternative to silicon solar cells in the near future. A key component to these devices is the transparent front electrode, and in the case of Dye Sensitized Solar Cells, it is the most expensive part. A lightweight, cost-effective, robust, and easy-to-fabricate new generation TCE is required to enable competition with silicon. Indium Tin Oxide, commonly used in touchscreen devices, Organic Light Emitting Diodes (OLEDs), and thin film photovoltaics, is widely used and commonly referred to as the industry standard. As the global supply of indium decreases and the demand for this TCE increases, a similar alternative TCE is required to accompany the next generation solar cells that promise energy with lighter and significantly cheaper modules. This alternative TCE needs to provide similar sheet resistance and optical transmittance to ITO, while also being mechanically and chemically robust. The work in this thesis begins with an exploration of several synthesized ITO replacement materials, such as copper nanowires, conductive polymer PEDOT:PSS, zinc oxide thin films, reduced graphene oxide and combinations of the above. A guiding philosophy to this work was prioritizing cheap, easy deposition methods and overall scalability. Shortcomings of these TCEs were investigated and different materials were hybridized to take advantage of each layers strengths for development of an ideal ITO replacement. For CuNW-based composite electrodes, ~85% optical transmittance and ~25 Ω/sq were observed and characterized to understand the underlying mechanisms for optimization. The second half of this work is an examination of many different perovskite synthesis methods first to achieve highest performance, and then to integrate compatible methods with our CuNW TCEs. Several literature methods investigated were irreproducible, and those that were successful posed difficulties integrating with CuNW-based TCEs. Those shortcomings are discussed, and how future work might skirt the issues revealed here to produce a very low cost, high performance perovskite solar cell.

We report the synthesis of ultra-high aspect ratio copper nanowires (CuNW) and fabrication of CuNW-based transparent conductive electrodes (TCE) with high optical transmittance (> 80%) and excellent sheet resistance (R-s < 30 Omega/sq). These CuNW TCEs are subsequently hybridized with aluminum-doped zinc oxide (AZO) thin-film coatings, or platinum thinfilm coatings, or nickel thin-film coatings. Our hybrid transparent electrodes can replace indium tin oxide (ITO) films in dye-sensitized solar cells (DSSCs) as either anodes or cathodes. We highlight the challenges of integrating bare CuNWs into DSSCs, and demonstrate that hybridization renders the solar cell integrations feasible. The CuNW/AZO-based DSSCs have reasonably good open-circuit voltage (V-oc = 720 mV) and short-circuit current-density (J(sc) = 0.96 mA/cm(2)), which are comparable to what is obtained with an ITO-based DSSC fabricated with a similar process. Our CuNW-Ni based DSSCs exhibit a good open-circuit voltage (V-oc = 782 mV) and a decent short-circuit current (J(sc) = 3.96 mA/cm2), with roughly 1.5% optical-to-electrical conversion efficiency.

Electron Beam Induced Deposition (EBID) is a direct write fabrication process with applications in circuit edit and debug, mask repair, and rapid prototyping. However, it suffers from significant drawbacks, most notably low purity. Work over the last several years has demonstrated that deposition from bulk liquid precursors, rather than organometallic gaseous precursors, results in high purity deposits of low resistivity (LPEBID). In this work, it is shown that the deposits resulting from LP-EBID are only highly conductive when deposited at line doses below 25μC/cm. When the dose exceeds this value, the resulting structure is highly porous providing a poor conductive pathway. It is also shown that beam current has no significant effect on the resistivity of the deposits. Nanowires with resistivity significantly lower than the previous best result of 67μΩ•cm were achieved, with the lowest resistivity being only 6.6μΩ•cm, only a factor of 4 higher than that bulk copper of 1.7μΩ•cm.

Abstract Recent advances in materials synthesis resulted in a rediscovery of the low cost copper in its one and two-dimensional forms and project newer applications of this metal in fields not considered before. In this thesis, one-dimensional copper, i.e. nanowires are synthesized by a hydrothermal route and explored for their chemical, electrical, catalytic and plasmonic properties with highlighted advantages, benefited from their size and shape compared to thin film and bulk copper. Characterization of copper nanowires and their native oxides were performed using a number of analytical techniques such as X-ray photoelectron and Auger spectroscopy, Raman spectroscopy, X-ray diffraction as well as scanning probe and electron microscopy techniques to elucidate the oxidation mechanism and to assess the feasibility of the oxidized materials for various applications. A few atomic layers of cuprous oxide seem to form on the surface of the nanowires instantly, maybe already during synthesis, which then slowly grows further when exposing the nanowires to ambient air leading to the appearance of cupric oxide as well. Because of the surface oxides, individual nanowires and their bundled networks exhibit semiconducting behavior, which complicates the direct use of such materials for interconnections in electronics. However, even with the presence of native oxides, copper nanowires hold promise in many other applications such as the ones explored here for plasmonics and heterogeneous catalysis. As demonstrated in this work, surface plasmon absorption properties of the nanowires can be exploited for chemical sensing of surface adsorbed molecules (model compound Rhodamine 6G) by efficiently amplifying its Raman spectrum without using any lithographically defined sensor template. Further, it is shown that phenol contamination in water may be efficiently eliminated by converting it to nontoxic polyphenol as well as to CO2 owing to the highly efficient catalytic property of the mixed oxide phases on the surface of the nanowires. The results published in this thesis contribute to the understanding of the chemical and physical behavior of copper nanowires and other low dimensional copper nanostructures that undergo rapid surface oxidation. / Tiivistelmä Jatkuva elektronisten laitteiden ja anturien pienentäminen on hyvin linjassa teknologian kehittymisen kanssa. Pyrkimys monitoimisiin ja tehokkaisiin materiaaleihin on muuttanut tavanomaisten materiaalien käsitystä. Viimeisimmät edistysaskeleet materiaalisynteesissä ovat johtaneet edullisen kuparin uudelleenlöytämiseen sen yksi- ja kaksidimensionaalisissa muodoissa ennustaen metallille uusia sovellutuksia alueilla, joissa sitä ei ole aiemmin hyödynnetty. Tässä väitöstyössä on tutkittu hydrotermisesti syntetisoitujen yksiulotteisten kuparinanojohtimien kemiallisia, sähköisiä, katalyyttisiä ja plasmonisia ominaisuuksia sekä näiden pieneen kokoon ja muotoon perustuvia etuoja ohutkalvo- ja bulkkikupariin verrattuna. Kuparinanojohtimia ja niiden luonnollisia oksideja karakterisoitiin useilla analyysitekniikoilla kuten röntgenelektroni- ja Auger-eletronispektroskopialla, Raman-spektroskopialla, röntgendiffraktiolla sekä pyyhkäisykärki- ja elektronimikroskopialla selvittäen hapettumismekanismeja ja oksidien soveltuvuutta eri käyttötarkoituksiin. Muutaman atomikerroksen paksuinen kupari(I)oksidikerros havaittiin muodostuvan välittömästi, luultavasti jo materiaalisynteesin aikana nanojohtimien pinnalle. Nanojohtimien altistuessa ympäröivälle ilmalle oksidikerros kehittyi hitaasti johtaen kupari(II)oksidin muodostumiseen. Pintaoksidien johdosta yksittäiset nanojohtimet ja niistä yhteenkasautuneet verkostot käyttäytyvät puolijohdemaisesti mikä monimutkaistaa näiden materiaalien käyttöä sellaisenaan elektroniikan johtimissa. Luonnollisista oksideista huolimatta kuparinanojohtimet ovat lupaavia monissa muissa sovelluksissa, kuten tässä työssä tutkituissa plasmonisessa ja heterogeenisessä katalyysissä. Väitöstyössä osoitetaan, että nanojohtimen pintaplasmonisia absorptio-ominaisuuksia voidaan hyödyntää pintaan absorboituneiden molekyylien kemiallisessa havainnoinnissa (mallinnettu yhdiste rodamiini 6G) vahvistamalla Raman–spektriä käyttämättä lainkaan litografiapohjaista anturisapluunaa. Myöskin vesien fenolikontaminaatio voidaan tehokkaasti muuntaa myrkyttömiksi polyfenoleiksi ja hiiidioksidiksi hyödyntämällä nanojohtimien pinnalla olevia oksideja tehokkaana katalyyttinä (jopa parempi kuin kaupallisten kupariin pohjautuvat katalyytit). Tässä väitöstyössä julkaistut tulokset edistävät kuparinanojohtimien sekä muiden pienikokoisten ja nopeasti hapettuvien kuparinanorakenteiden kemiallisen ja fyysisen käytöksen ymmärtämistä. Tieteellisten kehitysaskeleiden lisäksi tämä väitöstyö voi myös toimia lähteenä pienirakenteisten yleisten metallien sovelluksille.

This thesis is an attempt to understand ways to improve thermo-mechanical and structural properties of nano-structured materials. A detailed study on computational design and analysis of metallic nanowires is carried out. Molecular dynamic simulation method is applied. In particular, FCC metallic nanowires, NiAl, and CuZr nanowires are studied. Various bottom-up approaches are suggested with improved structural and thermo¬mechanical properties. In the first part of the thesis, Cu nanowires are considered. Existence of a novel and stable pentagonal multi-shell nanobridge structure of Cu under high strain rate tensile loading is reported. Such a structure shows enhanced mechanical properties. A three-fold pseudo-elastic-plastic shape recovery mechanism in such nanowires is established. This study also shows that the length of the pentagonal nanobridge structures can be characterized by its inelastic strain. It is also reported that an initial FCC structure is transformed into a new HCP structure. The evidence of HCP structure is confirmed with the help of experimental data published in the literature. Subsequent to the above study, a novel mechanism involving coupled temperature-stress dependent reorientation in FCC nanowires is investigated. A detailed map is generated for size dependent stress-temperature induced solid-solid reorientation in Cu nanowires. In the second part of the thesis, deformation mechanisms in NiAl based intermetallic nanowires are studied. A novel mechanism of temperature and cross-section dependent pseudo-elastic/pseudo-plastic shape and strain recovery by an initial B2 phase of NiAl nanowire is reported. Such a recoverable strain, which is as high as ~ 30%, can potentially be utilized to realize various types of shape memory and strain sensing phenomena in nano-scale devices. An asymmetry in tensile and compressive yield strength behavior is also observed, which is due to the softening and hardening of the nanowires under tensile and compressive loadings, respectively. Two different deformation mechanisms dominated by twinning under tension and slip under compression are found. Most interestingly, a superplastic behavior with a failure strain of up to 700% in the intermetallic NiAl nanowires is found to exist at a temperature of 0.36Tm. Such superplastic behavior is attributed to the transformation of the nanowire from a crystalline phase to an amorphous phase after yielding of the nanowire. In the last part the work, another type of nanowires having Cu-Zr system is considered. A novel stress induced martensitic phase transformation from an initial B2 phase to BCT phase in a CuZr nanowire under tensile loading is reported. It is further shown that such a stress induced martenistic phase transformation can be achieved under both tensile as well as compressive loadings. Tensile-compressive asymmetry in the stress-strain behavior is observed due to two different phase transformation mechanisms having maximum transformation strains of ~ 5% under compressive loading and ~ 20% under tensile loading. A size and temperature dependent tensile phase transformation in the nanowire is also observed. Small nanowires show a single step tensile phase transformation whereas the nanowires with larger size show a two step deformation mechanism via an intermediate R-phase hardening followed by R-phase yielding. A study of energetic behavior of these nanowires reveals uniform distribution of stress over the nanowire cross-section and such stress distribution can lead to a significant improvement in its thermo-mechanical properties. Similar improvement is demonstrated by designing the nanowires via manipulating the surface configuration of B2-CuZr system. It is found that the CuZr nanowires with Zr atoms at the surface sites are energetically more stable and also give a uniform distribution of stresses across the cross-section. This leads to the improvement in yield strength as well as failure strain. An approach to design energetically stable nano-structured materials via manipulating the surface configurations with improved thermo-mechanical properties is demonstrated which can help in fundamental understanding and development of similar structures with more stability and enhanced structural properties. Further ab-initio and experimental studies on the confirmation of the stability of the nanowires via manipulating the surface site is an open area of research and related future scopes are highlighted in the closure.