We describe the self-assembly of gold and iron oxide nanoparticles regulated by a chemical reaction cycle that hydrolyzes a carbodiimide-based fuel. In a reaction with the chemical fuel, the nanoparticles are chemically activated to a state that favors assembling into clusters. The activated state is metastable and decays to the original precursor reversing the assembly. The dynamic interplay of activation and deactivation results in a material of which the behavior is regulated by the amount of fuel added to the system; they either did not assemble, assembled transiently, or assembled permanently in kinetically trapped clusters. Because of the irreversibility of the kinetically trapped clusters, we found that the behavior of the self-assembly was prone to hysteresis effects. The final state of the system in the energy landscape depended on the pathway of preparation. For example, when a large amount of fuel was added at once, the material would end up kinetically trapped in a local minimum. When the same amount of fuel was added in small batches with sufficient time for the system to re-equilibrate, the final state would be the global minimum. A better understanding of pathway complexity in the energy landscape is crucial for the development of fuel-driven supramolecular materials.

Surface effects strongly dominate the intrinsic properties of semiconductor nanowires (NWs), an observation that is commonly attributed to the presence of surface states and their modification of the electronic band structure. Although the effects of the exposed, bare NW surface have been widely studied with respect to charge carrier transport and optical properties, the underlying electronic band structure, Fermi level pinning, and surface band bending profiles are not well explored. Here, we directly and quantitatively assess the Fermi level pinning at the surfaces of composition-tunable, intrinsically n-type InGaAs NWs, as one of the prominent, technologically most relevant NW systems, by using correlated photoluminescence (PL) and X-ray photoemission spectroscopy (XPS). From the PL spectral response, we reveal two dominant radiative recombination pathways, that is, direct near-band edge transitions and red-shifted, spatially indirect transitions induced by surface band bending. The separation of their relative transition energies changes with alloy composition by up to more than ∼40 meV and represent a direct measure for the amount of surface band bending. We further extract quantitatively the Fermi level to surface valence band maximum separation using XPS, and directly verify a composition-dependent transition from downward to upward band bending (surface electron accumulation to depletion) with increasing Ga-content x(Ga) at a crossover near x(Ga) ∼ 0.2. Core level spectra further demonstrate the nature of extrinsic surface states being caused by In-rich suboxides arising from the native oxide layer at the InGaAs NW surface.

We delineate the optimized growth parameter space for high-uniformity catalyst-free InGaAs nanowire (NW) arrays on Si over nearly the entire alloy compositional range using selective area molecular beam epitaxy. Under the required high group-V fluxes and V/III ratios, the respective growth windows shift to higher growth temperatures as the Ga-content x(Ga) is tuned from In-rich to Ga-rich InGaAs NWs. Using correlated x-ray diffraction, transmission electron microscopy, and micro-photoluminescence spectroscopy, we identify structural defects to govern luminescence linewidths in In-rich (x(Ga) < 0.4) and Ga-rich (x(Ga) > 0.6) NWs, whereas limitations at intermediate Ga-content (0.4 < x(Ga) < 0.6) are mainly due to compositional inhomogeneities. Most remarkably, the catalyst-free InGaAs NWs exhibit a characteristic transition in crystal structure from wurtzite to zincblende (ZB) dominated phase near x(Ga) ∼ 0.4 that is further reflected in a cross-over from blue-shifted to red-shifted photoluminescence emission relative to the band edge emission of the bulk ZB InGaAs phase.