Disk-shaped molecules with large aromatic π-surfaces are a class of organic semiconductors in which the charge-carrier transport properties could be greatly facilitated by preferred intermolecular stacking of the π-surfaces. The optical and electronic properties are not only determined by the core aromatic structure of these disk-shaped molecules but are also strongly dependent on the side chains, which directly impact the molecular self-assembly behavior in condensed phases. Triphenylene-tris(naphthaleneimidazole) (TP-TNI) is a recently reported n-type semiconductor featuring a large π-core and branched side chains, with an electron-transporting mobility reaching 10^-4 cm² V^-1 s^-1. To further improve material performance, a detailed study is needed to understand the dependence of carrier transport properties on both the core electronic structure and side chain. Here, we present the detailed synthesis and characterization of a TP-TNI derivative bearing linear side chains, which has demonstrated a field-effect electron-transport mobility of up to 1.3 × 10^-3 cm² V^-1 s^-1. The more than 1 order improvement in electron-transport properties over the branched side chain homologue can be correlated to ordered twisted packing in the thin film, as revealed by in situ variable temperature grazing incidence wide-angle X-ray scattering studies. In-depth theoretical understanding of the frontier orbitals, reorganization energies, and charge-transfer integrals of TP-TNI molecules has provided further insight into the relationship between the molecular stacking geometry and charge-transport properties.

We fabricate a field-effect transistor by covalently functionalizing PbS nanoparticles with tetrathiafulvalenetetracarboxylate. Following experimental results from cyclic voltammetry and ambient-pressure X-ray photoelectron spectroscopy, we postulate a near-resonant alignment of the PbS 1Sh state and the organic HOMO, which is confirmed by atomistic calculations. Considering the large width of interparticle spacing, we observe an abnormally high field-effect hole mobility, which we attribute to the postulated resonance. In contrast to nanoparticle devices coupled through common short-chained ligands, our system maintains a large degree of macroscopic order as revealed by X-ray scattering. This provides a different approach to the design of hybrid organic-inorganic nanomaterials, circumvents the problem of phase segregation, and holds for versatile ways to design ordered, coupled nanoparticle thin films.

Charge transport in conjugated polymer semiconductors has traditionally been thought to be limited to a low-mobility regime by pronounced energetic disorder. Much progress has recently been made in advancing carrier mobilities in field-effect transistors through developing low-disorder conjugated polymers. However, in diodes these polymers have to date not shown much improved mobilities, presumably reflecting the fact that in diodes lower carrier concentrations are available to fill up residual tail states in the density of states. Here, we show that the bulk charge transport in low-disorder polymers is limited by water-induced trap states and that their concentration can be dramatically reduced through incorporating small molecular additives into the polymer film. Upon incorporation of the additives we achieve space-charge limited current characteristics that resemble molecular single crystals such as rubrene with high, trap-free SCLC mobilities up to 0.2 cm²/Vs and a width of the residual tail state distribution comparable to k_BT.

A variety of optical applications rely on the absorption and reemission of light. The quantum yield of this process often plays an essential role. When the quantum yield deviates from unity by significantly less than 1%, applications such as luminescent concentrators and optical refrigerators become possible. To evaluate such high performance, we develop a measurement technique for luminescence efficiency with sufficient accuracy below one part per thousand. Photothermal threshold quantum yield is based on the quantization of light to minimize overall measurement uncertainty. This technique is used to guide a procedure capable of making ensembles of near-unity emitting cadmium selenide/cadmium sulfide (CdSe/CdS) core-shell quantum dots. We obtain a photothermal threshold quantum yield luminescence efficiency of 99.6 ± 0.2%, indicating nearly complete suppression of nonradiative decay channels.

Nonradiative processes limit optoelectronic functionality of nanocrystals and curb their device performance. Nevertheless, the dynamic structural origins of nonradiative relaxations in such materials are not understood. Here, femtosecond electron diffraction measurements corroborated by atomistic simulations uncover transient lattice deformations accompanying radiationless electronic processes in colloidal semiconductor nanocrystals. Investigation of the excitation energy dependence in a core/shell system shows that hot carriers created by a photon energy considerably larger than the bandgap induce structural distortions at nanocrystal surfaces on few picosecond timescales associated with the localization of trapped holes. On the other hand, carriers created by a photon energy close to the bandgap of the core in the same system result in transient lattice heating that occurs on a much longer 200 picosecond timescale, dominated by an Auger heating mechanism. Elucidation of the structural deformations associated with the surface trapping of hot holes provides atomic-scale insights into the mechanisms deteriorating optoelectronic performance and a pathway towards minimizing these losses in nanocrystal devices.