Philosophiae Doctor - PhD / This project is aimed at fabricating a smart material. Zinc oxide and vanadium dioxide have received a great deal of attention in recent years because they are used in various applications. ZnO semiconductor in particular has a potential application in optoelectronic devices such as light emitting diodes (LED), sensors and in photovoltaic cell industry as a transparent electrode. VO2 also has found application in smart windows, solar technology and infrared smart devices. Hence the need to synthesis or fabricate a new smart material using VO2 and an active ZnO based nano-composites family in which ZnO matrix will be hosting thermally active VO2 nano-crystals is the basis of this study. Since VO2 behave as an MIT Mott’s type oxides and exhibits a thermally driven semiconductor-metal phase transition at about 68 oC and as a direct result ZnO:VO2 nano-composites would exhibit a reversible and modulated optical transmission in the infra-red (IR) while maintaining a constant optical transmission in the UV-Vis range. The synthesis is possible by pulsed laser deposition and ion implantation. Synthesis by pulsed laser deposition will involve thin films multilayer fabrication. ZnO buffer layer thin film will be deposited on the glass and ZnO single crystals and subsequent layer of VO2 and ZnO will be deposited on the substrate. X-ray diffraction (XRD) reveals that the series of ZnO thin films deposited by Pulsed Laser Deposition (PLD) on glass substrates has the hexagonal wurtzite structure with a c-axis preferential orientation. In addition the XRD results registered for VO2 samples indicate that all thin films exhibits a monoclinic VO2 (M) phase. UV-Vis NIR measurements of multilayered structures showed the optical tunability at the near-IR region and an enhanced transparency (>30 %) at the visible range.

Thesis advisor: Michael J. Naughton / In this dissertation, I first discuss many different kinds of transparent conductors in Chapter one. In Chapter two, I focus on transparent conductors based on crackle temples. I and my colleagues developed three (one sputter-free and two fully all-solution) methods to fabricate metallic networks as transparent conductors. The first kind of all-solution process is based on crackle photolithography and the resulting silver networks outperform all reported experimental values, including having sheet resistance more than an order of magnitude lower than ITO, yet with comparable transmittance. The second kind of all-solution proceed transparent conductor is obtained by integrating crackle photolithography-based microwires with nanowires and electroplate welding. This combination results in scalable film structures that are flexible, indium-free, vacuum-free, lithographic-facility-free, metallic-mask-free, with small domain size, high optical transmittance, and low sheet resistance (one order of magnitude smaller than conventional nanowire-based transparent conductors). / Thesis (PhD) — Boston College, 2019. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

Clean and affordable energy, especially solar energy, is becoming more and more important as our annual total energy consumption keeps rising. However, to make solar energy more affordable and accessible, the cost for fabrication, transportation and assembly of all components need to be reduced. As a crucial component for solar cells, transparent conductive electrode (TCE) can determine the cost and performance. A light weight, easy-to-fabricate and cost-effective new generation TCE is thus needed. While indium-doped tin oxide (ITO) has been the most widely used material for commercial applications as TCEs, its cost has gone up due to the limited global supply of indium. This is not only due to the scarcity of the element itself, but also the massive production of various opto-electronic devices such as TVs, smartphones and tablets. In order to reduce the cost for fabricating large area solar cells, substitute materials for ITO should be developed. These materials should have similar optical transmittance in the visible wavelength range, as well as similar electrical conductivity (sheet resistance) to ITO. This work starts with synthesizing ITO-replacing nano-materials, such as copper nanowires (CuNWs), derivative zinc oxide (ZnO) thin films, reduced graphene oxide (rGO) and so on. Further, we applied various deposition techniques, including spin-coating, spray-coating, Mayer-rod coating, filtration and transferring, to coat transparent substrates with these materials in order to fabricate TCEs. We characterize these materials and analyze their electrical/optical properties as TCEs. Additionally, these fabricated single-material-based TCEs were tested in various lab conditions, and their shortcomings (instability, rigidity, etc.) were highlighted. In order to address these issues, we hybridized the different materials to combine their strengths and compared the properties to single-material based TCEs. The multiple hybridized TCEs have comparable optical/electrical metrics to ITO. The doped-ZnO TCEs exhibit high optical transmittance over 90% in the visible range and low sheet resistance under 200Ω/sq. For CuNW-based composite electrodes, ~ 85% optical transmittance and ~ 25Ω/sq were observed. Meanwhile, the hybridization of materials adds additional features such as flexibility or resistance to corrosion. Finally, as a proof of concept, the CuNW-based composite TCEs were tested in dye-sensitized solar cells (DSSCs), showing similar performance to ITO based samples.

Alternative plasmonic materials of Transparent Nitrides and Conductive Oxides (TNCOs) including Indium Tin Oxide (ITO), Al-doped ZnO (AZO) and Titanium Nitride (TiN), have been proposed as novel material platforms for Si-compatible plasmonics and metamaterials, showing enhanced light-matter interaction over a broad spectral range. It has been recently shown that these materials feature reduced optical losses compared with conventional noble metals such as Au and Ag in the visible and near-infrared spectral range. However, it is still an open challenge to tailor the structural and optical properties of these materials, and to further reduce their optical losses, in order to effectively utilize them in photonic devices. In this thesis work, I demonstrate wide tunability of the optical and structural properties of ITO, AZO and TiN thin films, by using post-deposition annealing treatments, enabling significant reduction of their optical losses. By measuring the optical bandgaps of the investigated materials, I show that the tunability of the optical properties originates from the modulation of the free carrier concentration induced by the annealing treatment. Moreover, I perform XRD characterization of the fabricated films, indicating that the annealing also effectively tunes the grain size, which is consistent with the change of the optical properties. Eventually, I investigate the role of the annealing gases for ITO and AZO, demonstrating that free-carrier modulation in ITO and AZO is due to the change in the density of oxygen vacancies after post-deposition annealing. In particular, TNCOs possess epsilon-near-zero (ENZ) condition in near-infrared range with optical loss ε^"<1, thus providing enhanced internal fields in the medium at the ENZ condition. In collaboration with Prof. Nader Engheta and the previous post-doc in our group Dr. Antonio Capretti, we demonstrate enhanced second-harmonic generation (SHG) and third-harmonic generation (THG) from ITO thin films driven by ENZ condition. It results that the SHG generation efficiency is comparable with that of a crystalline quartz plate of thickness 0.5 mm, and that the THG generation efficiency is ∼600 times larger than crystalline silicon. As an application for the fabricated TiN material, I investigate PL intensity and lifetime in Hyperbolic Metamaterials (HMMs) coupled with emitting Si Quantum Dots (QDs). In collaboration with Hiroshi Sugimoto in Prof. Minoru Fujii’s group and the previous post-doc in our group Dr. Sandeep Inampudi, we demonstrate up to 1.6-times enhanced decay rate of QDs emission. Photonic devices based on TNCO plasmonic materials offer an effective approach for the engineering of novel Si-based photonic devices with enhanced light-matter coupling over a broad spectral range. As an application for the fabricated ITO, in collaboration with Hongwei Zhao in Prof. Jonathan Klamkin’s group, electro-absorption modulators are numerically investigated to show high extinction ration of greater than 6dB, while insertion loss is less than 1.3dB for wavelength range from 1.25 µm to 1.42 µm. Additionally, we demonstrate tunable optical properties of ITO thin films in mid-infrared spectrum by thermal annealing of ITO in oxygen environment. In collaboration with Sajan Shrestha and Adam Overvig in Prof. NanFang Yu’s group, we fabricate 2D periodic arrays of ITO and show wide tuning of plasmonic resonances of ITO nanostructure from 4 µm to 10 µm. Combining with the tunability of ITO thin films in near-infrared, the ITO material platform provides a promising method for the control and engineering of Si-based tunable plasmonic and metamaterial devices in the infrared spectrum. Finally, in collaboration with my colleague Ren Wang, we experimentally demonstrate silicon nanodisk arrays with tunable anapole mode excitation in the visible spectrum. The proposed high index nanostructures can be used to enhance absorption rate for applications in semiconductor photodetector.

Realization of low-resistance electrical contacts on both sides of a solar cell is essential for obtaining the best possible performance. A key component of a solar cell is a metal contact on the illuminated side of the cell which should efficiently collect carriers. These contacts can be formed using an opaque metal grid/finger pattern. The metal electrode may be used alone or in combination with a broad-area transparent conductive film. This work aims at investigating the impact of the electrical contacting scheme employed in InGaN/GaN Schottky barrier solar cells on their performance. InGaN is a III-V compound semiconductor and has a tunable direct band-gap (0.7 eV to 3.4 eV) which spans most of the solar spectrum; this fact, along with other beneficial material properties, motivates the study of InGaN photovoltaic devices. A number of groups have recently investigated InGaN-based homo-junction and hetero-junction p-i-n solar cells. However, very few groups have worked on InGaN Schottky solar cells. Compared to p-n junctions, Schottky barrier solar cells are cheaper to grow and fabricate; they are also expected to improve the spectral response because of near surface depletion regions in the shorter wavelength regions. In this particular work on InGaN based solar cells, a Schottky diode structure was used to avoid the issue of highly resistive p-type InGaN. In this study, platinum (Pt) is used to form a Schottky barrier with an InGaN/GaN absorber region. Electrical and optical properties of platinum films are investigated as a function of their thickness. InGaN/GaN Schottky solar cells with platinum as the transparent conductive film are reported and their performance is evaluated as a function of the metal thickness. / Master of Science

Nanostructured composites are attracting intense interest for electronic and optoelectronic device applications, specifically as active elements in thin film photovoltaic (PV) device architectures. These systems implement fundamentally different concepts of enhancing energy conversion efficiencies compared to those seen in current commercial devices. This is possible through considerable flexibility in the manipulation of device-relevant properties through control of the interplay between the nanostructure and the optoelectronic response. In the present work, inorganic nanocomposites of semiconductor Ge embedded in transparent conductive indium tin oxide (ITO) as well as Ge in zinc oxide (ZnO) were produced by a single step RF-magnetron sputter deposition process.It is shown that, by controlling the design of the nanocomposites as well as heat treatment conditions, decreases in the physical dimensions of Ge nanophase size provided an effective tuning of the optical absorption and charge transport properties. This effect of changes in the optical properties of nanophase semiconductors with respect to size is known as the quantum confinement effect. Variation in the embedding matrix material between ITO and ZnO with corresponding characterization of optoelectronic properties exhibit notable differences in the presence and evolution of an interfacial oxide within these composites. Further studies of interfacial structures were performed using depth-profiling XPS and Raman spectroscopy, while study of the corresponding electronic effects were performed using room temperature and temperature-dependent Hall Effect. Optical absorption was noted to shift to higher onset energies upon heat treatment with a decrease in the observed Ge domain size, indicating quantum confinement effects within these systems. This contrasts to previous investigations that have involved the introduction of nanoscale Ge into insulating, amorphous oxides. Comparison of these different matrix chemistries highlights the overarching role of interfacial structures on quantum-size characteristics. The opportunity to tune the spectral response of these PV materials, via control of semiconductor phase assembly in the nanocomposite, directly impacts the potential for the use of these materials as sensitizing elements for enhanced solar cell conversion efficiency.

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.

Neste trabalho, foi realizado o crescimento de nanotubos de carbono pela técnica de deposição química a vapor (CVD) térmica catalítica, utilizando-se filmes finos de níquel como material catalisador, gás metano (CH4) como fonte de hidrocarboneto e nitrogênio (N2) como gás de arraste. Amostras processadas sobre filmes de Ni de 15 nm de espessura, depositados sobre substrato de óxido de silício (SiO2), com temperatura de processo de 900 ºC e tempo de 15 minutos promoveram uma maior densidade de síntese de nanotubos de carbono, utilizando-se um fluxo na proporção de 2 partes de N2 para 1 parte de CH4. Comprovou-se sua síntese através da visualização de sua morfologia por microscopia eletrônica de varredura (SEM) e microscopia eletrônica de transmissão (TEM), além da extração de seu espectro característico por espectroscopia Raman e espectroscopia de dispersão de raio-X (EDS). Em um segundo estudo, depositaram-se sobre substratos de vidro filmes transparentes e condutores (TCF) à base de nanotubos de carbono de paredes múltiplas (MWCNT) comerciais, pela técnica de dip coating. Para isso, realizou-se a dispersão dos nanotubos sob diversas concentrações em água deionizada (DI) com o auxílio do surfactante dodecil sulfato de sódio (SDS), com posterior funcionalização através do ataque químico por ácido nítrico (HNO3), visando sua aplicação na fabricação de células solares. Foram utilizados os equipamento de quatro pontas e curva corrente x tensão (IV) para caracterização elétrica, transmitância por espectrofotometria para caracterização óptica, SEM para a visualização de sua morfologia e espectroscopia Raman para a análise química de suas estruturas. Valores de resistência de folha de 2x105 W/ e transmitância de 65% foram obtidos nas amostras mais concentradas, com 0,2 mg de nanotubos por ml de água DI. Uma etapa de limpeza em água DI pós deposição foi feita para remoção do excesso de surfactante presente no filme, o que prejudica tanto as características elétricas e ópticas, por ser um dielétrico e não ser transparente. Essa limpeza melhorou o valor de transmitância, porém aumentou a resistência de folha, devido à remoção parcial dos nanotubos presentes no filme, interrompendo em certos pontos a malha que promovia a passagem de corrente elétrica. O ataque químico por HNO3 promoveu a criação de algumas quebras na estrutura do carbono, o que é verificado pelo aumento da banda D, característico da presença de defeitos. / In this work, the growth of CNTs was investigated, using chemical vapor deposition (CVD) thermal catalytic technique, carried out by utilizing thin films of nickel as catalyst material, methane (CH4) as hydrocarbon source and nitrogen (N2) as carrier gas. Samples processed onto 15 nm thick Ni films, deposited on silicon oxide (SiO2) substrates, at a temperature of 900 °C for 15 minutes, promoted a higher density of carbon nanotubes, using a gas mixture at the ratio of 2 parts of N2 and 1 part of CH4. This was verified by analysing the nanotubes morphology by scanning electron microscopy (SEM) and transmission electronic microscopy (TEM) and by the extraction of its characteristic spectrum by Raman spectroscopy and energy dispersive spectroscopy (EDS). In a second study, transparent conductive films (TCF) based on commercial multi-walled carbon nanotubes (MWCNT) were deposited on glass substrates by the dip coating technique. To do so, carbon nanotubes (CNTs) with different concentrations were dispersed in deionized water (DI) with the addition of the surfactant sodium dodecyl sulfate (SDS), and subsequent functionalization through chemical attack by nitric acid (HNO3), aiming their application in solar cell fabrication. The four point probe equipment and current x voltage curve (IV) was used for electrical characterization, transmittance for optical characterization, SEM to visualize their morphology and Raman spectroscopy for chemical analysis of their structures. Sheet resistance values of 2x105 W/ and transmittance of 65% were obtained in the most concentrated samples, with 0.2 mg per ml of nanotubes in deionized water (DI). A cleaning stage in DI water after deposition was taken for removal of surfactant excess in the film, which harms both the electrical and optical characteristics, as it is a dielectric and not transparent. This cleaning improved the transmittance value, but increased the sheet resistance due to partial removal of the nanotubes in the film, interrupting at certain points the mesh of CNTs that promoted the passage of electric current. The chemical attack by HNO3 promoted the functionalization by creating some breaks in the carbon structure, which is checked by the observation of the increasing in D band, which is characteristic of defects.

Neste trabalho, foi realizado o crescimento de nanotubos de carbono pela técnica de deposição química a vapor (CVD) térmica catalítica, utilizando-se filmes finos de níquel como material catalisador, gás metano (CH4) como fonte de hidrocarboneto e nitrogênio (N2) como gás de arraste. Amostras processadas sobre filmes de Ni de 15 nm de espessura, depositados sobre substrato de óxido de silício (SiO2), com temperatura de processo de 900 ºC e tempo de 15 minutos promoveram uma maior densidade de síntese de nanotubos de carbono, utilizando-se um fluxo na proporção de 2 partes de N2 para 1 parte de CH4. Comprovou-se sua síntese através da visualização de sua morfologia por microscopia eletrônica de varredura (SEM) e microscopia eletrônica de transmissão (TEM), além da extração de seu espectro característico por espectroscopia Raman e espectroscopia de dispersão de raio-X (EDS). Em um segundo estudo, depositaram-se sobre substratos de vidro filmes transparentes e condutores (TCF) à base de nanotubos de carbono de paredes múltiplas (MWCNT) comerciais, pela técnica de dip coating. Para isso, realizou-se a dispersão dos nanotubos sob diversas concentrações em água deionizada (DI) com o auxílio do surfactante dodecil sulfato de sódio (SDS), com posterior funcionalização através do ataque químico por ácido nítrico (HNO3), visando sua aplicação na fabricação de células solares. Foram utilizados os equipamento de quatro pontas e curva corrente x tensão (IV) para caracterização elétrica, transmitância por espectrofotometria para caracterização óptica, SEM para a visualização de sua morfologia e espectroscopia Raman para a análise química de suas estruturas. Valores de resistência de folha de 2x105 W/ e transmitância de 65% foram obtidos nas amostras mais concentradas, com 0,2 mg de nanotubos por ml de água DI. Uma etapa de limpeza em água DI pós deposição foi feita para remoção do excesso de surfactante presente no filme, o que prejudica tanto as características elétricas e ópticas, por ser um dielétrico e não ser transparente. Essa limpeza melhorou o valor de transmitância, porém aumentou a resistência de folha, devido à remoção parcial dos nanotubos presentes no filme, interrompendo em certos pontos a malha que promovia a passagem de corrente elétrica. O ataque químico por HNO3 promoveu a criação de algumas quebras na estrutura do carbono, o que é verificado pelo aumento da banda D, característico da presença de defeitos. / In this work, the growth of CNTs was investigated, using chemical vapor deposition (CVD) thermal catalytic technique, carried out by utilizing thin films of nickel as catalyst material, methane (CH4) as hydrocarbon source and nitrogen (N2) as carrier gas. Samples processed onto 15 nm thick Ni films, deposited on silicon oxide (SiO2) substrates, at a temperature of 900 °C for 15 minutes, promoted a higher density of carbon nanotubes, using a gas mixture at the ratio of 2 parts of N2 and 1 part of CH4. This was verified by analysing the nanotubes morphology by scanning electron microscopy (SEM) and transmission electronic microscopy (TEM) and by the extraction of its characteristic spectrum by Raman spectroscopy and energy dispersive spectroscopy (EDS). In a second study, transparent conductive films (TCF) based on commercial multi-walled carbon nanotubes (MWCNT) were deposited on glass substrates by the dip coating technique. To do so, carbon nanotubes (CNTs) with different concentrations were dispersed in deionized water (DI) with the addition of the surfactant sodium dodecyl sulfate (SDS), and subsequent functionalization through chemical attack by nitric acid (HNO3), aiming their application in solar cell fabrication. The four point probe equipment and current x voltage curve (IV) was used for electrical characterization, transmittance for optical characterization, SEM to visualize their morphology and Raman spectroscopy for chemical analysis of their structures. Sheet resistance values of 2x105 W/ and transmittance of 65% were obtained in the most concentrated samples, with 0.2 mg per ml of nanotubes in deionized water (DI). A cleaning stage in DI water after deposition was taken for removal of surfactant excess in the film, which harms both the electrical and optical characteristics, as it is a dielectric and not transparent. This cleaning improved the transmittance value, but increased the sheet resistance due to partial removal of the nanotubes in the film, interrupting at certain points the mesh of CNTs that promoted the passage of electric current. The chemical attack by HNO3 promoted the functionalization by creating some breaks in the carbon structure, which is checked by the observation of the increasing in D band, which is characteristic of defects.

Indium tin oxide (ITO) thin films have been used as transparent electrodes in many technological applications such as display panels, solar cells, touch screens and electrochromic devices. Commercial grade ITO thin films are usually deposited by sputtering. Solution-based coating methods, such as sol-gel however, can be simple and economic alternative method for obtaining oxide films and also ITO. In this thesis, &ldquo / ITO sols&rdquo / and &ldquo / ITO nanoparticle-incorporated hybrid ITO coating sols&rdquo / were prepared using indium chloride (InCl3