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The development of porous well-defined hybrid materials (e.g., metal-organic frameworks or MOFs) will add a new dimension to a wide number of applications ranging from supercapacitors and electrodes to "smart" membranes and thermoelectrics. From this perspective, the understanding and tailoring of the electronic properties of MOFs are key fundamental challenges that could unlock the full potential of these materials. In this work, we focused on the fundamental insights responsible for the electronic properties of three distinct classes of bimetallic systems, M x-y M' y -MOFs, M x M' y -MOFs, and M x (ligand-M' y )-MOFs, in which the second metal (M') incorporation occurs through (i) metal (M) replacement in the framework nodes (type I), (ii) metal node extension (type II), and (iii) metal coordination to the organic ligand (type III), respectively. We employed microwave conductivity, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, powder X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, pressed-pellet conductivity, and theoretical modeling to shed light on the key factors responsible for the tunability of MOF electronic structures. Experimental prescreening of MOFs was performed based on changes in the density of electronic states near the Fermi edge, which was used as a starting point for further selection of suitable MOFs. As a result, we demonstrated that the tailoring of MOF electronic properties could be performed as a function of metal node engineering, framework topology, and/or the presence of unsaturated metal sites while preserving framework porosity and structural integrity. These studies unveil the possible pathways for transforming the electronic properties of MOFs from insulating to semiconducting, as well as provide a blueprint for the development of hybrid porous materials with desirable electronic structures.

We report on a method to produce free-standing graphene sheets from epitaxial graphene on silicon carbide (SiC) substrate. Doubly clamped nanomechanical resonators with lengths up to 20 microm were patterned using this technique and their resonant motion was actuated and detected optically. Resonance frequencies of the order of tens of megahertz were measured for most devices, indicating that the resonators are much stiffer than expected for beams under no tension. Raman spectroscopy suggests that the graphene is not chemically modified during the release of the devices, demonstrating that the technique is a robust means of fabricating large-area suspended graphene structures.

The ultrafast relaxation and recombination dynamics of photogenerated electrons and holes in epitaxial graphene are studied using optical-pump terahertz-probe spectroscopy. The conductivity in graphene at terahertz frequencies depends on the carrier concentration as well as the carrier distribution in energy. Time-resolved studies of the conductivity can therefore be used to probe the dynamics associated with carrier intraband relaxation and interband recombination. We report the electron-hole recombination times in epitaxial graphene for the first time. Our results show that carrier cooling occurs on subpicosecond time scales and that interband recombination times are carrier density dependent.