Low-temperature electronic transport of metal doped carbon nanotube molecular hybrids and Nitrogen-doped nanocrystalline diamond

Abstract

This thesis explores the magnetism and spin-related properties in carbon-based molecular hybrid materials, with a focus on expanding our understanding of low-dimensional carbon structures and their potential electronic applications. The investigation spans from one-dimensional systems, such as carbon nanotubes (CNTs) functionalized with single-molecule magnets (SMMs), to three-dimensional systems like nitrogen-doped ultra nanocrystalline diamond (UNCD). In these carbon structures, electronic transport is intricately tied to microstructural features, such as grain boundaries and impurity clusters, which hold significant potential for the development of all-carbon electronic devices. The research begins with a detailed examination of the chemical functionalization of multi-walled carbon nanotubes (MWCNTs) through controlled acid treatment to achieve precise metal doping. Using Raman spectroscopy and complementary techniques like ICP-MS and ToF-SIMS, we successfully demonstrate how functionalization levels influence the magnetic properties of CNT hybrids loaded with magnetic metals from the lanthanide series (Gd, Tb, Dy). The study reveals that low percentages of metal doping (0.5% to 1.0%) preserve the magnetic bistability of SMMs post-grafting, while higher doping levels lead to complex magnetic behaviors including super paramagnetism, quasi-ferromagnetism, and potential Kondo lattice behavior inCNT-heavy metal systems. We also explore the spin-phonon coupling in Gd-filled double-walled CNTs, where the onset of superparamagnetic properties at low temperatures is coupled with phonon mode stiffening observed via Raman spectroscopy. This enhanced coupling offers promising pathways for developing efficient molecular qubits through the modulation of spin-phonon interactions in one-dimensional systems. The second part of the thesis investigates into the microwave plasma-assisted chemical vapor deposition (MWCVD) growth of nitrogen-doped nanocrystalline diamond (NCD) thin films on different substrates. By pioneering upgrades to the MWCVD system, I was able to achieve reliable growth of high-quality nanocrystalline diamond thin films. Notably, I observed a novel nanostructure, termed Diaphite-a previously unreported feature, in these NCD films, consisting of nanodiamond grains coherently linked with graphene-like rings. This structure, along with the non-equilibrium growth conditions induced by nitrogen doping and secondary nucleation, presents unique polymorphic features in artificially grown diamonds. Detailed low-temperature transport measurements on four different samples—ranging from 7.5% to 20% nitrogen doping—uncovered complex transport phenomena such as 3D weak localization (WL), variable-range hopping (VRH), and unusual magnetoresistance (MR) behavior. In particular, the 7.5% N2-doped UNCD film on quartz exhibited 3D weak localization (WL) at low fields and anti-weak localization (AWL) at higher fields, with distinct magnetoresistance characteristics depending on the direction of the applied magnetic field. The 20% N2-doped films on both quartz and silicon showed more metallic-like behavior, with magneto-resistance characterized by a B1/2 dependence at low temperatures, suggesting an intricate relationship between doping level, microstructure, and electron transport. These findings significantly expand our understanding of the role that microstructural and chemical modifications play in determining the electronic and magnetic properties of carbon-based materials. This work provides a foundational platform for future research into carbon electronics, offering potential breakthroughs in spintronics, molecular transistors, quantum computing, and other advanced electronic applications.