Conducting metallopolymers possess attractive electronic properties for use in sensors, photoelectronic devices, catalysts, and other applications. Modification of the conducting polymer backbone, through chemical or electrochemical methods, enables control of catalytic, electronic, and optical properties of the metal via inductive modulation of the electron density. Understanding in detail the relationship between the metal and polymer backbone could lead to more effective metallopolymer materials. We hope to study this relationship by probing the band gaps, excited state energy levels, catalytic activity, and sensor function in four metallopolymer systems. Devices with sub-stochiometric ratios of Cu2ZnSnS4 NPs (CZTS: (Cu2Sn)1-xZn1/xS)(0≥x≥0.75)) grown in Cu(II) conducting metallopolymers were produced to study band gap tuning in hybrid materials. The valence and conductance bands of CZTS (x = 0.60) aligned with the HOMO/LUMO of the Cu(II) metallopolymer. Changing the alignment facilitated charge transfer in the hybrid material, leading to photovoltaic materials with efficiencies of ~0.1%. Chemoresistive ionophore sensors were developed by incorporating selective binding groups, such as thiourea, into conducting polymer backbones. Thiourea monomers and polymers showed high selectivity for Pb(II) ions over many competitive ions. XPS experiments demonstrated that reversible chelation of Pb(II) ions could be achieved through a simple uptake/rinse process. The conductivity of the thiourea polymer increased fifty-fold, from 7.75×10−2 S/cm2 to 3.5 S/cm2, after Pb(II) exposure. Sensitivity measurements indicated the sensors have limits of detection near 10−10 M. Highly conjugated ligands were synthesized to explore effective sensitization of visible and near-IR emitting lanthanides. (3,4-ethylenedioxy)thiophene was appended to dipyridophenazine and dipyridoquinoxaline to introduce a group that could be easily electropolymerized. These bi-functional ligands emitted from π-π* and an inter-ligand charge transfer excited states, and therefore, two distinct triplet states were observed. These separate energy pathways allowed for efficient sensitization of both visible (Tb(III), Eu(III), Dy(III)) and near-IR emitting (Nd(III), Yb(III), Er(III)) ions. Finally, we explored the oxidation of a rhodium-containing conducting metallopolymer and the subsequent effect on the activity of the metal center. Oxidation of the backbone led to ancillary ligand attenuation, allowing for control of the catalytically active species in the conducting metallopolymer. Rh(I,III) monomer and metallopolymer catalytic studies showed potential for new heterogenous/homogeneous hybrid catalysts. / text

Supramolecular interactions are of great importance in the fabrication of new functional materials. In particular, colloidal assembly via supramolecular pathway has contributed to numerous innovations in material chemistry, on account of its specific, directional and dynamic non-covalent interactions. By taking advantage of the non-covalent supramolecular interactions, tailored complementary colloidal building blocks which are normally incompatible with each other could be integrated interdependently, forming novel hybrid materials with emerging properties. This thesis mainly focuses on the design, preparation and characterization of novel colloidal assemblies based on cucurbit[n]urils host-guest interactions, including hybrid ‘raspberry-like’ colloids, catalytic polymeric nanocomposites, advanced structured colloids, and supramolecular polymer colloidal hydrogel.

The polarization response such as ferroelectric and ferroelastic switching in ferroelectrics is the important feature for ferroelectric and electromechanical applications. In polycrystalline form ferroelectrics, effects of the microstructural parameters such as texture, grain size, and residual stress are there and have not fully been understood. Among these effects, (1) the origin of grain size effects on ferroelastic switching, (2) mechanical stress effects on polarization switching, and (3) ferroelectric switching kinetics and the relationship to grain boundaries are investigated.<br>Firstly, the microscopic origin of ferroelastic switching suppression in smaller grains is discovered using a microscopic probing technique (piezoresponse force microscopy). It is demonstrated that there is no independent grain size effect on ferroelastic switching; the grain size affects the domain structure in a grain, and the domain structure plays an important role in the ferroelastic switching suppression. This result suggests that the grain size is not an independent critical parameter for the electromechanical property degradation in a grain < 1 m as the ferroelastic switching is a dominant component for the electromechanical property.<br>The study about the mechanical stress effects on the electric field induced polarization switching rationalizes the emergence of the electric field induced low-symmetry phases observed in tetragonal Pb(Zr,Ti)O3 and BaTiO3 ceramics after poling. It is demonstrated that a shear stress plays an important role in stabilizing the monoclinic phase in Pb(Zr,Ti)O3 whereas a normal stress along the polarization axis is a key for the monoclinic phase in BaTiO3 with a thermodynamic approach. It is suggested that the fraction of the low-symmetry phase, which is important for the large electromechanical property, can be engineered by applying an appropriate stress.<br>For the work about ferroelectric switching kinetics, the first direct Barkhausen noise associated with ferroelectric switching is measured. The domain switching time is quantified by the frequency of the Barkhausen noise. It is discovered that the dominant domain wall pinning site is grain boundaries based on the domain wall jump distance between pinning sites calculated from the switching time. This result suggests that the technique is a good tool for understanding the relationship between microstructure – domain wall kinetics.<br>In sum, the mechanisms of the polarization switching suppression due to domain structure and grain boundaries, and the emergence of the low symmetry phases due to stresses are revealed. These discoveries facilitate further improvements of the device performances with engineering the domain structure, grain boundaries and residual stress.<br>

Abstract: Metal-Organic Frameworks (MOFs) are a class of highly porous, hybrid, functional and crystalline extended coordination compounds. Their exceptional properties renders them ideal for a wide range of applications including gas storage and catalysis. Especially for catalysis, MOFs are receiving attention as well-defined supports for organometallic heterogeneous catalysis with noticeably the post-synthetic grafting of transition metal complexes on secondary building units (SBU) containing hydroxides moieties. The objective of this dissertation is to explore the synthesis, reactivity and functionalization of MOFs with SBU containing hydroxides units by transition metal catalyst using the Surface Organometallic Chemistry (SOMC) approach. Chapter 1, gives an introduction to the field of MOF and their applications to catalysis through the functionalization of hydroxide containing SBUs. This chapter introduces also the SOMC strategy with an overview of its catalytic application for olefin metathesis and CO2 conversion. Chapter 2 and 3 give a detailed application of SOMC to MOFs with the selective grafting of the W(≡CtBu)(CH2tBu)3 complex on the highly crystalline and mesoporous Zr-NU-1000 MOF. The obtained single site material, Zr-Nu-1000-W, is fully characterized using state of the art experimental methods and all the steps leading to the final grafted moieties were identified by DFT. Zr-NU-1000-W is active for olefin metathesis and is further fine-tuned by activation with EtAlCl2 giving a more selective and stable catalyst. Moreover, the nature of the grafted species could be modulated by pre-activation of the initial W(≡CtBu)(CH2tBu)3 complex with dmpe giving W(≡CtBu)(=CHtBu)(CH2tBu)(dmpe) also grafted on Zr-NU-1000. Chapter 4 and 5, describe the deliberate design and bulk synthesis of a new zirconium MOF, Zr-she-MOF-2, and highlight the discovery of a new highly connected MOF, RE-urx-MOF-1, based on a careful combination of rare earth (RE) metals with heterobifunctional triangular tetrazolate-based ligand. Additionally, the replacement of the tetrazolate functionality by carboxylate, leads to the formation of a different MOF structure RE-gea-MOF-4 having the gea topology with the presence of 18-connected nonanuclear RE cluster. Both Zr-she-MOF-2 and RE-gea-MOF-4 are active for the coupling of epoxides with CO2 to form cyclic carbonate in the presence of Bu4NBr. Finally, Chapter 6 will discuss the conclusions and perspectives of this dissertation.

This thesis describes the concept of programmable materials with tunable physical properties applicable to soft robots. We present these materials for three major applications in soft robotics: sensing, actuation, and robotic manipulation. The strain sensors recognize the internal stimuli in a soft robot, whereas the conductors collect the sensors’ signals to the control part. In the first part, we want to develop both stretchable strain sensors and conductors from a single material by programming a nanowire network’s electrical property, which we achieve through Electrical Welding (e-welding). We demonstrate the transformation of a Silver Nanowire (AgNW)-polymer sponge from a strain sensor to a stretchable conductor through e-welding. Using this method, we produced a soft hybrid e-skin having both a sensor and conductor from a single material. In the second part, we propose new active actuation solutions by obtaining quick, tunable pressure inside a soft material that we achieve through a liquid-gas phase transition of a stored liquid using an efficient electrode. We discuss the significant design variables to improve the performance and propose a new design for the electrodes, for enhancing actuation speed. We propose using low voltage equipment to trigger the phase transition to produce compact actuation technology for portable applications. Using this method, we produced a portable soft gripper. In the third and last part, we want to develop a simple robotic manipulation technology using a single-chambered soft body instead of a multi-chambered system. We propose using on-demand stiffness change in soft material to control the shape change of a single-chambered soft body. For this, we introduce a new concept of a stiffness tunable hybrid fiber: a fiber with stiff and soft parts connected in a series. We demonstrate a substantial change in membrane stiffness in the fiber through locking/unlocking of the soft part of the fiber. We integrated these fibers into a pneumatically operated single-chambered soft body to control its stiffness for on-demand shape change. If applied together, these three concepts could result in a fully printable, cheap, light, and easily controllable new generation soft robots with augmented functionalities.

No description available.

<p>  </p> <p>Integration of functional thin films on flexible substrates has piqued interests owing to the needs of flexible devices. Selecting a suitable flexible substrate is crucial for such integration. Recently, muscovite mica has been developed as a flexible platform for functional thin film epitaxy growth. Mica can be easily peeled off due to the weak van der Waals interaction between different layers of mica, along with other advantages including cheap, high elasticity and thermal stability, biocompatible, <em>etc</em>. On the other hand, vertically aligned nanocomposites (VANs) have been attractive because of their unique anisotropic structures, which can achieve physical property anisotropy, easy tunability, out-of-plane strain engineering as well as combined multifunctionality. However, limited work on the integration of nanocomposite thin films on mica with tunable physical properties has been reported due to growth challenges. </p> <p>In this dissertation, different ceramic-metal VAN systems integrated on mica substrates towards different functionalities using pulsed laser deposition (PLD) have been demonstrated. The first chapter is on the integration of BaTiO3-Au nanocomposite system on mica. Tunable optical properties have been achieved by controlling the geometries of the Au nanostructures between nanoparticles and nanopillars by varying the growth temperature. The laser energy was also found to play a role in terms of the Au pillar dimension. The second chapter is on the integration of BaZrO3-Co VAN system on mica towards flexible spintronics. Tunable, anisotropic ferromagnetic property has been realized by controlling the aspect ratio of the Co pillars. The third chapter is on integration of BaTiO3-Fe VAN system on mica towards multiferroics. Different buffer layers have been tried out to facilitate the growth of VAN structure. Room temperature ferroelectric and anisotropic ferromagnetic properties of the films have been confirmed. The last chapter is focused on multiphase nitride-metal nanocomposite design and integration, with films showing unique optical and magnetic properties. The reliability and stability of the physical properties of the films have been verified though bending tests. The growth mechanism and criteria of ceramic-metal nanocomposite on mica have also been discussed. These demonstrations all pave a new way towards the integration and design of multifunctional nanocomposites towards flexible nanodevices.</p>

Groundbreaking progress in molecule-based optoelectronic devices for lighting, display and energy-harvesting technologies demands highly efficient and easily processable functional materials with tunable properties governed by their molecular/supramolecular structure variations. To date, functional coordination compounds whose function is governed by non-covalent weak forces (e.g., metallophilic, dπ-acid/dπ-base stacking, halogen/halogen and/or d/π interactions) remain limited. This is unlike the situation for metal-free organic semiconductors, as most metal complexes incorporated in optoelectronic devices have their function determined by the properties of the monomeric molecular unit (e.g., Ir(III)-phenylpyridine complexes in organic light-emitting diodes (OLEDs) and Ru(II)-polypyridyl complexes in dye-sensitized solar cells (DSSCs)). This dissertation represents comprehensive results of both experimental and theoretical studies, descriptions of synthetic methods and possible application allied to monovalent coinage metal-based functional materials. The main emphasis is given to the design and synthesis of functional materials with preset material properties such as light-emitting materials, light-harvesting materials and conducting materials. In terms of advances in fundamental scientific phenomena, the major highlight of the work in this dissertation is the discovery of closed-shell polar-covalent metal-metal bonds manifested by ligand-unassisted d10-d10 covalent bonds between Cu(I) and Au(I) coinage metals in the ground electronic state (~2.87 Å; ~45 kcal/mol). Moreover, this dissertation also reports pairwise intermolecular aurophilic interactions of 3.066 Å for an Au(I) complex, representing the shortest ever reported pairwise intermolecular aurophilic distances among all coinage metal(I) cyclic trimetallic complexes to date; crystals of this complex also exhibit gigantic luminescence thermochromism of 10,200 cm-1 (violet to red). From applications prospective, the work herein presents monovalent coinage metal-based functional optoelectronic materials such as heterobimetallic complexes with near-unity photoluminescence quantum yield, metallic or semiconducting integrated donor-acceptor stacks and a new class of Au(III)-based black absorbers with cooperative intermolecular iodophilic (I…I) interactions that sensitize the harvesting of all UV, all visible, and a broad spectrum of near-IR regions of the solar spectrum. These novel functional materials of cyclic trimetallic coinage metal complexes have been characterized by a broad suit of spectroscopic and structural analysis methods in the solid state and solution.

No description available.

<p>The traditional semiconductor device scaling based on Moore’s law is reaching its physical limits. New materials hosting rich physical phenomena such as correlated electronic behavior may be essential to identify novel approaches for information processing. The tunable band structures in such systems enables the design of hardware for neuromorphic computing. Strongly correlated perovskite nickelates (ReNiO3) represent a class of quantum materials that possess exotic electronic properties such as metal-to-insulator transitions. In this thesis, detailed studies of NdNiO3 thin films from wafer-scale synthesis to structure characterization and to electronic device demonstration will be discussed.</p> <p>Atomic layer deposition (ALD) of correlated oxide thin films is essential for emerging electronic technologies and industry. We reported the scalable ALD growth of neodymium nickelate (NdNiO3) with high crystal quality using Nd(iPrCp)3, Ni(tBu2-amd)2 and ozone (O3) as precursors. By controlling various growth parameters such as precursor dose time and reactor temperature, we have optimized ALD condition for perovskite phase of NdNiO3­. We studied the structure and electrical properties of ALD NdNiO3 films epitaxially grown on LaAlO3 and confirmed their properties were comparable to those synthesized by physical vapor deposition methods. </p> <p>ReNiO3 undergoes a dramatic phase transition by hydrogen doping with catalytic electrodes independent of temperature. The electrons from hydrogen occupy Ni 3<em>d</em> orbitals and create strongly correlated insulating state with resistance changes up to eight orders of magnitudes. At room temperature, protons remain in the lattice locally near catalytic electrodes and can move by electrical fields due to its charge. The effect of high-speed voltage pulses on the migration of protons in NdNiO3 devices is discussed. After voltage pulses were applied with changing the voltage magnitude in nanosecond time scale, the resistance changes of the nickelate device were investigated. </p> <p>Reconfigurable perovskite nickelate devices were demonstrated and a single device can switch between multiple electronic functions such as neuron, synapse, resistor, and capacitor controlled by a single electrical pulse. Raman spectroscopy showed that differences in local proton distributions near the Pd electrode leads to different functions. This body of results motivates the search for novel materials where subtle compositional or structural differences can enable different gaps that can host neuromorphic functions.</p>