Black Si Photocathode with a Conformal and Amorphous MoSx Catalytic Layer Grown Using Atomic Layer Deposition for Photoelectrochemical Hydrogen Evolution.

We demonstrated how the photoelectrochemical (PEC) performance was enhanced by conformal deposition of an amorphous molybdenum sulfide (a-MoSx) thin film on a nanostructured surface of black Si using atomic layer deposition (ALD). The a-MoSx is found to predominantly consist of an octahedral structure (S-deficient metallic phase) that exhibits high electrocatalytic activity for the hydrogen evolution reaction with a Tafel slope of 41 mV/dec in an acid electrolyte. The a-MoSx has a smaller work function (4.0 eV) than that of crystalline 2H-MoS2 (4.5 eV), which induces larger energy band bending at the p-Si surface, thereby facilitating interface charge transfer. These features enabled us to achieve an outstanding kinetic overpotential of ∼0.2 V at 10 mA/cm2 and an onset potential of 0.27 V at 1 mA/cm2. Furthermore, the a-MoSx layer provides superior protection against corrosion of the Si surface, enabling long-term PEC operation of more than 50 h while maintaining 87% or more performance. This work highlights the remarkable advantages of the ALD a-MoSx layer and leads to a breakthrough in the architectural design of PEC cells to ensure both high performance and stability.

Highly Uniform Resistive Switching Performances Using Two-Dimensional Electron Gas at a Thin-Film Heterostructure for Conductive Bridge Random Access Memory.

This research demonstrates, for the first time, the development of highly uniform resistive switching devices with self-compliance current for conductive bridge random access memory using two-dimensional electron gas (2DEG) at the interface of an Al2O3/TiO2 thin-film heterostructure via atomic layer deposition (ALD). The cell is composed of Cu/Ti/Al2O3/TiO2, where Cu/Ti and Al2O3 overlayers are used as the active/buffer metals and solid electrolyte, respectively, and the 2DEG at the interface of Al2O3/TiO2 heterostructure, grown by the ALD process, is adopted as a bottom electrode. The Cu/Ti/Al2O3/TiO2 device shows reliable resistive switching characteristics with excellent uniformity under a repetitive voltage sweep (direct current sweep). Furthermore, it exhibits a cycle endurance over 107 cycles under short pulse switching. Remarkably, a reliable operation of multilevel data writing is realized up to 107 cycles. The data retention time is longer than 106 s at 85 °C. The uniform resistance switching characteristics are achieved via the formation of small (∼a few nm width) Cu filament with a short tunnel gap (<0.5 nm) owing to the 2DEG at the Al2O3/TiO2 interface. The performance and operation scheme of this device may be appropriate in neuromorphic applications.

Field-Effect Device Using Quasi-Two-Dimensional Electron Gas in Mass-Producible Atomic-Layer-Deposited Al2O3/TiO2 Ultrathin (<10 nm) Film Heterostructures.

We report the field-effect transistors using quasi-two-dimensional electron gas generated at an ultrathin (∼10 nm) Al2O3/TiO2 heterostructure interface grown via atomic layer deposition (ALD) on a SiO2/Si substrate without using a single crystal substrate. The 2DEG at the Al2O3/TiO2 interface originates from oxygen vacancies generated at the surface of the TiO2 bottom layer during ALD of the Al2O3 overlayer. High-density electrons (∼1014 cm-2) are confined within a ∼2.2 nm distance from the Al2O3/TiO2 interface, resulting in a high on-current of ∼12 µA/µm. The ultrathin TiO2 bottom layer is easy to fully deplete, allowing an extremely low off-current, a high on/off current ratio over 108, and a low subthreshold swing of ∼100 mV/decade. Via the implementation of ALD, a mature thin-film process can facilitate mass production as well as three-dimensional integration of the devices.