Atomic layer deposited (ALD) TiO2 protection layers may allow for the development of both highly efficient and stable photoanodes for solar fuel synthesis; however, the very different conductivities and photovoltages reported for TiO2-protected silicon anodes prepared using similar ALD conditions indicate that mechanisms that set these key properties are, as yet, poorly understood. In this report, we study hydrogen-containing annealing treatments and find that postcatalyst-deposition anneals at intermediate temperatures reproducibly yield decreased oxide/silicon interface trap densities and high photovoltage. A previously reported insulator thickness-dependent photovoltage loss in metal–insulator–semiconductor Schottky junction photoanodes is suppressed. This occurs simultaneously with TiO2 crystallization and an increase in its dielectric constant. At small insulator thickness, a record for a Schottky junction photoanode of 623 mV photovoltage is achieved, yielding a photocurrent turn-on at 0.92 V vs NHE or −0.303 V with respect to the thermodynamic potential for water oxidation.Keywords: atomic layer deposition; forming gas anneals; MIS; protection layers; Schottky junctions;

Optimization of the interface between high-k dielectrics and SiGe substrates is a challenging topic due to the complexity arising from the coexistence of Si and Ge interfacial oxides. Defective high-k/SiGe interfaces limit future applications of SiGe as a channel material for electronic devices. In this paper, we identify the surface layer structure of as-received SiGe and Al2O3/SiGe structures based on soft and hard X-ray photoelectron spectroscopy. As-received SiGe substrates have native SiOx/GeOx surface layers, where the GeOx-rich layer is beneath a SiOx-rich surface. Silicon oxide regrows on the SiGe surface during Al2O3 atomic layer deposition, and both SiOx and GeOx regrow during forming gas anneal in the presence of a Pt gate metal. The resulting mixed SiOx–GeOx interface layer causes large interface trap densities (Dit) due to distorted Ge–O bonds across the interface. In contrast, we observe that oxygen-scavenging Al top gates decompose the underlying SiOx/GeOx, in a selective fashion, leaving an ultrathin SiOx interfacial layer that exhibits dramatically reduced Dit.Keywords: Al2O3; atomic layer deposition; high-k; interface traps; MOSCAP; SiGe;

Resistance switching in TiO2 and many other transition metal oxide resistive random access memory materials is believed to involve the assembly and breaking of interacting oxygen vacancy filaments via the combined effects of field-driven ion migration and local electronic conduction leading to Joule heating. These complex processes are very difficult to study directly in part because the filaments form between metallic electrode layers that block their observation by most characterization techniques. By replacing the top electrode layer in a metal–insulator–metal memory structure with easily removable liquid electrolytes, either an ionic liquid (IL) with high resistance contact or a conductive aqueous electrolyte, we probe field-driven oxygen vacancy redistribution in TiO2 thin films under conditions that either suppress or promote Joule heating. Oxygen isotope exchange experiments indicate that exchange of oxygen ions between TiO2 and the IL is facile at room temperature. Oxygen loss significantly increases the conductivity of the TiO2 films; however, filament formation is not observed after IL gating alone. Replacing the IL with a more conductive aqueous electrolyte contact and biasing does produce electroformed conductive filaments, consistent with a requirement for Joule heating to enhance the vacancy concentration and mobility at specific locations in the film.Keywords: Conductive filament; electromigration; ionic liquid; Joule heating; TiO2;

We investigate the effects of pre- and postatomic layer deposition (ALD) defect passivation with hydrogen on the trap density and reliability of Al2O3/InGaAs gate stacks. Reliability is characterized by capacitance–voltage hysteresis measurements on samples prepared using different fabrication procedures and having different initial trap densities. Despite its beneficial capability to passivate both interface and border traps, a final forming gas (H2/N2) anneal (FGA) step is correlated with a significant hysteresis. This appears to be caused by hydrogen depassivation of defects in the gate stack under bias stress, supported by the observed bias stress-induced increase of interface trap density, and strong hydrogen isotope effects on the measured hysteresis. On the other hand, intentional air exposure of the InGaAs surface prior to Al2O3 ALD increases the initial interface trap density (Dit) but considerably lowers the hysteresis.Keywords: Al2O3; border traps; hydrogen depassivation; InGaAs; interface traps; MOSCAP; reliability;

State-of-the-art silicon water splitting photoelectrochemical cells employ oxide protection layers that exhibit electrical conductance in between that of dielectric insulators and electronic conductors, optimizing both built-in field and conductivity. The SiO2-like layer interposed between a deposited protective oxide film and its Si substrate plays a key role as a tunnel oxide that can dominate the total device impedance. In this report, we investigate the effects of changes in interfacial SiO2 resistance and capacitance in the oxide bilayer through both solid state leakage current and capacitance–voltage measurements and through electrochemical methods applied to water splitting cells. Modelling is performed to describe both types of data in a simple and intuitive way, allowing for insights to be developed into the connections among both the dielectric (charge storage) and conductive (charge transport) properties of bilayer protective oxides and their effects on oxygen evolution performance. Finally, atomic layer deposited (ALD) Al2O3 is studied as an insulator layer with conductivity intermediate between that of tunnel oxide SiO2 and the more conductive ALD-TiO2, to further generalize this understanding.

Germanium–tin alloy nanowires hold promise as silicon-compatible optoelectronic elements with the potential to achieve a direct band gap transition required for efficient light emission. In contrast to Ge1–xSnx epitaxial thin films, free-standing nanowires deposited on misfitting germanium or silicon substrates can avoid compressive, elastic strains that inhibit formation of a direct gap. We demonstrate strong room temperature photoluminescence, consistent with band edge emission from both Ge core nanowires, elastically strained in tension, and the almost unstrained Ge1–xSnx shells grown around them. Low-temperature chemical vapor deposition of these core-shell structures was achieved using standard precursors, resulting in Sn incorporation that significantly exceeds the bulk solubility limit in germanium.Keywords: core−shell nanowire; Germanium−tin; optoelectronics; photoluminescence;

Silicon photoanodes protected by atomic layer deposited (ALD) TiO2 show promise as components of water splitting devices that may enable the large-scale production of solar fuels and chemicals. Minimizing the resistance of the oxide corrosion protection layer is essential for fabricating efficient devices with good fill factor. Recent literature reports have shown that the interfacial SiO2 layer, interposed between the protective ALD-TiO2 and the Si anode, acts as a tunnel oxide that limits hole conduction from the photoabsorbing substrate to the surface oxygen evolution catalyst. Herein, we report a significant reduction of bilayer resistance, achieved by forming stable, ultrathin (<1.3 nm) SiO2 layers, allowing fabrication of water splitting photoanodes with hole conductances near the maximum achievable with the given catalyst and Si substrate. Three methods for controlling the SiO2 interlayer thickness on the Si(100) surface for ALD-TiO2 protected anodes were employed: (1) TiO2 deposition directly on an HF-etched Si(100) surface, (2) TiO2 deposition after SiO2 atomic layer deposition on an HF-etched Si(100) surface, and (3) oxygen scavenging, post-TiO2 deposition to decompose the SiO2 layer using a Ti overlayer. Each of these methods provides a progressively superior means of reliably thinning the interfacial SiO2 layer, enabling the fabrication of efficient and stable water oxidation silicon anodes.Keywords: atomic layer deposition; interfacial layer; oxygen scavenging; photoelectrochemical cells; Si(100) interface; silicon dioxide; silicon photoanodes; titanium dioxide; water splitting

Intentional oxidation of an As2-decapped (100) In0.57Ga0.43As substrate by additional H2O dosing during initial Al2O3 gate dielectric atomic layer deposition (ALD) increases the interface trap density (Dit), lowers the band edge photoluminescence (PL) intensity, and generates Ga-oxide detected by X-ray photoelectron spectroscopy (XPS). Aberration-corrected high resolution transmission electron microscopy (TEM) reveals formation of an amorphous interfacial layer which is distinct from the Al2O3 dielectric and which is not present without the additional H2O dosing. Observation of a temperature dependent border trap response, associated with the frequency dispersion of the accumulation capacitance and conductance of metal-oxide-semiconductor (MOS) structures, is found to be correlated with the presence of this defective interfacial layer. MOS capacitors prepared with additional H2O dosing show a notable decrease (∼20%) of accumulation dispersion over 5 kHz to 500 kHz when the measurement temperature decreases from room temperature to 77 K, while capacitors prepared with an abrupt Al2O3/InGaAs interface display little change (<2%) with temperature. Similar temperature-dependent border trap response is also observed when the (100) InGaAs surface is treated with a previously reported HCl(aq) wet cleaning procedure prior to Al2O3 ALD. These results point out the sensitivity of the temperature dependence of the border trap response in metal oxide/III–V MOS gate stacks to the presence of processing-induced interface oxide layers, which alter the dynamics of carrier trapping at defects that are not located at the semiconductor interface.Keywords: Al2O3; atomic layer deposition; border traps; InGaAs; interlayer; MOSCAP

We synthesized nanoscale TiO2–RuO2 alloys by atomic layer deposition (ALD) that possess a high work function and are highly conductive. As such, they function as good Schottky contacts to extract photogenerated holes from n-type silicon while simultaneously interfacing with water oxidation catalysts. The ratio of TiO2 to RuO2 can be precisely controlled by the number of ALD cycles for each precursor. Increasing the composition above 16% Ru sets the electronic conductivity and the metal work function. No significant Ohmic loss for hole transport is measured as film thickness increases from 3 to 45 nm for alloy compositions ≥ 16% Ru. Silicon photoanodes with a 2 nm SiO2 layer that are coated by these alloy Schottky contacts having compositions in the range of 13–46% Ru exhibit average photovoltages of 525 mV, with a maximum photovoltage of 570 mV achieved. Depositing TiO2–RuO2 alloys on nSi sets a high effective work function for the Schottky junction with the semiconductor substrate, thus generating a large photovoltage that is isolated from the properties of an overlying oxygen evolution catalyst or protection layer.Keywords: atomic layer deposition; MIS junctions; photoanodes; photovoltage; Schottky junctions; TiO2 alloys

Nitrogen incorporation to produce negative fixed charge in Al2O3 gate insulator layers is investigated as a path to achieve enhancement mode GaN device operation. A uniform distribution of nitrogen across the resulting AlOxNy films is obtained using N2 plasma enhanced atomic layer deposition (ALD). The flat band voltage (Vfb) increases to a significantly more positive value with increasing nitrogen concentration. Insertion of a 2 nm thick Al2O3 interlayer greatly decreases the trap density of the insulator/GaN interface, and reduces the voltage hysteresis and frequency dispersion of gate capacitance compared to single-layer AlOxNy gate insulators in GaN MOSCAPs.Keywords: atomic layer deposition; GaN; interface trap density; metal oxide semiconductor; negative fixed charge; nitrogen incorporation

A fundamental challenge in developing photoelectrochemical cells for the renewable production of solar chemicals and fuels is the simultaneous requirement of efficient light absorption and robust stability under corrosive conditions. Schemes for corrosion protection of semiconductor photoelectrodes such as silicon using deposited layers were proposed and attempted for several decades, but increased operational lifetimes were either insufficient or the resulting penalties for device efficiency were prohibitive. In recent years, advances in atomic layer deposition (ALD) of thin coatings have made novel materials engineering possible, leading to substantial and simultaneous improvements in stability and efficiency of photoelectrochemical cells. The self-limiting, layer-by-layer growth of ALD makes thin films with low pinhole densities possible and may also provide a path to defect control that can generalize this protection technology to a large set of materials necessary to fully realize photoelectrochemical cell technology for artificial photosynthesis.

Effective passivation of interface defects in high-k metal oxide/Ge gate stacks is a longstanding goal of research on germanium metal-oxide-semiconductor devices. In this paper, we use photoelectron spectroscopy to probe the formation of a GeO2 interface layer between an atomic layer deposited Al2O3 gate dielectric and a Ge(100) substrate during forming gas anneal (FGA). Capacitance- and conductance-voltage data were used to extract the interface trap density energy distribution. These results show selective passivation of interface traps with energies in the top half of the Ge band gap under annealing conditions that produce GeO2 interface layer growth. First-principles modeling of Ge/GeO2 and Ge/GeO/GeO2 structures and calculations of the resulting partial density of states (PDOS) are in good agreement with the experiment results.Keywords: Al2O3; first-principles modeling; Ge; high-k; interface traps

We correlate interfacial defect state densities with the chemical composition of the Al2O3/GaN interface in metal-oxide-semiconductor (MOS) structures using synchrotron photoelectron emission spectroscopy (PES), cathodoluminescence and high-temperature capacitance–voltage measurements. The influence of the wet chemical pretreatments involving (1) HCl+HF etching or (2) NH4OH(aq) exposure prior to atomic layer deposition (ALD) of Al2O3 were investigated on n-type GaN (0001) substrates. Prior to ALD, PES analysis of the NH4OH(aq) treated surface shows a greater Ga2O3 component compared to either HCl+HF treated or as-received surfaces. The lowest surface concentration of oxygen species is detected on the acid etched surface, whereas the NH4OH treated sample reveals the lowest carbon surface concentration. Both surface pretreatments improve electrical characteristics of MOS capacitors compared to untreated samples by reducing the Al2O3/GaN interface state density. The lowest interfacial trap density at energies in the upper band gap is detected for samples pretreated with NH4OH. These results are consistent with cathodoluminescence data indicating that the NH4OH treated samples show the strongest band edge emission compared to as-received and acid etched samples. PES results indicate that the combination of reduced carbon contamination while maintaining a Ga2O3 interfacial layer by NH4OH(aq) exposure prior to ALD results in fewer interface traps after Al2O3 deposition on the GaN substrate.Keywords: atomic layer deposition; GaN; interface trap density; metal oxide semiconductor; surface treatments;

Ultrafast carrier dynamics in arrays of single crystal and relatively uniform-diameter Ge nanowires (NWs) are investigated by transient absorption measurements and effective medium simulations. We present the first quantitative analysis of a Ge NW–air metamaterial, translating the photon response of the assemblies to carrier dynamics. Three time regimes of the ultrafast recombination process are identified: Auger recombination dominant (0–5 ps), “fast” surface trapping and recombination dominant (5–20 ps), and a mix of “fast” recombination and “slow” surface trapping (20–200 ps). The rates of surface recombination and their dependences on pump fluence are determined, highlighting the different interactions of electrons and holes with Ge NW surface and interface states. Structural and excitation conditions can be engineered to extend the photogenerated electron and hole lifetimes. Small wire diameters and low pump powers enhance the electron lifetime because charging of defect states in the surface oxide layer produces a potential barrier for electrons to be trapped at Ge/GeOx interface. This phenomenon simultaneously causes an enhancement of hole lifetime for relatively large wire diameters and large pump powers.

Carrier and phonon dynamics in dense arrays of aligned, single-crystal Ge nanowires (NWs) of controlled diameter are investigated by ultrafast optical pump–probe measurements, effective medium calculations, and elasticity analysis. Both a pronounced induced absorption and the amplitude and spectral range of Fabry–Perot oscillations observed in the probe signal are predicted for the NW array/air metamaterial by effective medium calculations. Detected temporal oscillations of reflectivity are consistent with excitation of radial breathing mode acoustic phonons by the intense pump pulse.

We report on the effects on water oxidation performance of varying (1) the nanoscale TiO2 thickness and (2) the catalyst material in catalyst/TiO2/SiO2/Si anodes. Uniform films of atomic layer deposited TiO2 are prepared in the thickness range ∼1–12 nm on degenerately-doped p+-Si, yielding water oxidation overpotentials at 1 mA cm−2 of 300 mV to 600 mV in aqueous solution (pH 0 to 14). Electron/hole transport through Schottky tunnel junction structures of varying TiO2 thickness was studied using the reversible redox couple ferri/ferrocyanide. The dependence of the water oxidation overpotential on ALD-TiO2 thickness, with all other anode design features unchanged, exhibits a linear trend corresponding to ∼21 mV of added overpotential at 1 mA cm−2 per nanometer of TiO2 for TiO2 thicknesses greater than ∼2 nm. For thinner TiO2 layers, an approximately thickness-independent overpotential is observed. The linear behavior for anodes with thicker TiO2 layers is consistent with the predicted effect of bulk TiO2-limited electronic conduction on the voltage required to sustain the current density across the TiO2/SiO2 insulator stack. Eight different oxygen evolution catalysts of thickness 1–3 nm are studied. For the anodes investigated, 3 nm of Ir or Ru gave the best water oxidation performance, but both thinner layers and other catalysts can be quite effective, suggesting the potential for reduced materials cost. Lastly, a flat band voltage analysis of solid state thin film capacitors was done for five different gate metals on n-Si to probe junction energetics directly relevant to a photoanode. The results are consistent with a Schottky junction in which the Fermi level at the semiconductor surface is unpinned.

Epitaxial growth of a highly strained, coherent SiGe alloy shell around a Ge nanowire core is investigated as a method to achieve surface passivation and carrier confinement, important in realizing nanowire devices. The high photoluminescence intensity observed from the core–shell nanowires with spectral features similar to that of bulk Ge indicates effective surface passivation. Thermal stability of these core–shell heterostructures has been systematically investigated, with a method demonstrated to avoid misfit strain relaxation during postgrowth annealing.