We report on the design, fabrication, and characterization of heterostructure In-Zn-O (IZO) thin-film transistors (TFTs) with improved performance characteristics and robust operation. The heterostructure layer is fabricated by stacking a solution-processed IZO film on top of a buffer layer, which is deposited previously using an electron beam (e-beam) evaporator. A thin buffer layer at the dielectric interface can help to template the structure of the channel. The control of the precursors and of the solvent used during the sol-gel process can help lower the temperature needed for the sol-gel condensation reaction to proceed cleanly. This boosts the overall performance of the device with a significantly reduced subthreshold swing, a four-fold mobility increase, and a two-order of magnitude larger on/off ratio. Atomistic simulations of the a-IZO structure using molecular dynamics (both classical and ab initio) and hybrid density functional theory (DFT) calculations of the electronic structure reveal the potential atomic origin of these effects.