Identification of dipole disorder in low temperature solution processed oxides: its utility and suppression for transparent high performance solution-processed hybrid electronics.

The ability to deposit high-quality inorganic semiconductors and dielectrics from solution at low process temperatures (∼200 °C) has become a very important research focus. During the course of our investigation, we identify the presence of an induced dipole present in solid state solution processed inorganic oxide insulator layers processed at reduced temperature (200-350 °C) from either molecular precursors, or well-dispersed metal oxide nanoparticles. Chemical composition analysis coupled with electrical measurements shows that the dielectric instability occurs due to proton migration via the Grotthuss mechanism inducing a long lived dipole disorder. Thus we established conditions for suppressing this effect to afford "ideal" high-k dielectric layer. Using this methodology, solution processed all inorganic thin film transistors (TFTs) with charge carrier mobilities exceeding 6 cm2 V-1 s-1 operating at low voltage (5 V) have been achieved. In addition, we show the broad utility of the perovskite high-k dielectric when processed with state of the art polymer and single crystal organic semiconductors yielding mobilities of approx. 7 cm2 V-1 s-1 at only 4 V. These transparent devices demonstrate excellent electrical device stability and a threshold voltage shift of only 0.41 V over 14 h, which is comparable, or better than sputtered oxide films.

Electronic Structure of Low-Temperature Solution-Processed Amorphous Metal Oxide Semiconductors for Thin-Film Transistor Applications.

The electronic structure of low temperature, solution-processed indium-zinc oxide thin-film transistors is complex and remains insufficiently understood. As commonly observed, high device performance with mobility >1 cm2 V-1 s-1 is achievable after annealing in air above typically 250 °C but performance decreases rapidly when annealing temperatures ≤200 °C are used. Here, the electronic structure of low temperature, solution-processed oxide thin films as a function of annealing temperature and environment using a combination of X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and photothermal deflection spectroscopy is investigated. The drop-off in performance at temperatures ≤200 °C to incomplete conversion of metal hydroxide species into the fully coordinated oxide is attributed. The effect of an additional vacuum annealing step, which is beneficial if performed for short times at low temperatures, but leads to catastrophic device failure if performed at too high temperatures or for too long is also investigated. Evidence is found that during vacuum annealing, the workfunction increases and a large concentration of sub-bandgap defect states (re)appears. These results demonstrate that good devices can only be achieved in low temperature, solution-processed oxides if a significant concentration of acceptor states below the conduction band minimum is compensated or passivated by shallow hydrogen and oxygen vacancy-induced donor levels.