Atomic Layer Deposition of WO3-Doped In2O3 for Reliable and Scalable BEOL-Compatible Transistors.

Tungsten oxide (WO3) doped indium oxide (IWO) field-effect transistors (FET), synthesized using atomic layer deposition (ALD) for three-dimensional integration and back-end-of-line (BEOL) compatibility, are demonstrated. Low-concentration (1∼4 W atom %) WO3-doping in In2O3 films is achieved by adjusting cycle ratios of the indium and tungsten precursors with the oxidant coreactant. Such doping suppresses oxygen deficiency from In2O2.5 to In2O3 stoichiometry with only 1 atom % W, allowing devices to turn off stably and enhancing threshold voltage stability. The ALD IWO FETs exhibit superior performance, including a low subthreshold slope of 67 mV/decade and negligible hysteresis. Strong tunability of the threshold voltage (Vth) is achieved through W concentration tuning, with 2 atom % IWO FETs showing an optimized Vth for enhancement-mode and a high drain current. ALD IWO FETs have remarkable stability under bias stress and nearly ideal performance extending to sub-100 nm channel lengths, making them promising candidates for high-performance monolithic 3D integrated devices.

Understanding the Mechanism of Electronic Defect Suppression Enabled by Nonidealities in Atomic Layer Deposition.

Silicon germanium (SiGe) is a multifunctional material considered for quantum computing, neuromorphic devices, and CMOS transistors. However, implementation of SiGe in nanoscale electronic devices necessitates suppression of surface states dominating the electronic properties. The absence of a stable and passive surface oxide for SiGe results in the formation of charge traps at the SiGe-oxide interface induced by GeOx. In an ideal ALD process in which oxide is grown layer by layer, the GeOx formation should be prevented with selective surface oxidation (i.e., formation of an SiOx interface) by controlling the oxidant dose in the first few ALD cycles of the oxide deposition on SiGe. However, in a real ALD process, the interface evolves during the entire ALD oxide deposition due to diffusion of reactant species through the gate oxide. In this work, this diffusion process in nonideal ALD is investigated and exploited: the diffusion through the oxide during ALD is utilized to passivate the interfacial defects by employing ozone as a secondary oxidant. Periodic ozone exposure during gate oxide ALD on SiGe is shown to reduce the integrated trap density (Dit) across the band gap by nearly 1 order of magnitude in Al2O3 (<6 × 1010 cm-2) and in HfO2 (<3.9 × 1011 cm-2) by forming a SiOx-rich interface on SiGe. Depletion of Ge from the interfacial layer (IL) by enhancement of volatile GeOx formation and consequent desorption from the SiGe with ozone insertion during the ALD growth process is confirmed by electron energy loss spectroscopy (STEM-EELS) and hypothesized to be the mechanism for reduction of the interfacial defects. In this work, the nanoscale mechanism for defect suppression at the SiGe-oxide interface is demonstrated, which is engineering of diffusion species in the ALD process due to facile diffusion of reactant species in nonideal ALD.

In-situ reflectometry to monitor locally-catalyzed initiation and growth of nanowire assemblies.

We investigate in-situ laser reflectometry for measuring the axial growth rate in chemical vapor deposition of assemblies of well-aligned vertical germanium nanowires grown epitaxially on single crystal substrates. Finite difference frequency domain optical simulations were performed in order to facilitate quantitative analysis and interpretation of the measured reflectivity data. The results show an insensitivity of the reflected intensity oscillation period to nanowire diameter and density within the range of experimental conditions investigated. Compared to previous quantitative in-situ measurements performed on III-V nanowire arrays, which showed two distinct rate regimes, we observe a constant, steady-state nanowire growth rate. Furthermore, we show that the measured reflectivity decay can be used to determine the germanium nanowire nucleation time with good precision. This technique provides an avenue to monitor growth of nanowires in a variety of materials systems and growth conditions.

Distinguishing Oxygen Vacancy Electromigration and Conductive Filament Formation in TiO2 Resistance Switching Using Liquid Electrolyte Contacts.

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.

Design principles for maximizing photovoltage in metal-oxide-protected water-splitting photoanodes.

Metal oxide protection layers for photoanodes may enable the development of large-scale solar fuel and solar chemical synthesis, but the poor photovoltages often reported so far will severely limit their performance. Here we report a novel observation of photovoltage loss associated with a charge extraction barrier imposed by the protection layer, and, by eliminating it, achieve photovoltages as high as 630 mV, the maximum reported so far for water-splitting silicon photoanodes. The loss mechanism is systematically probed in metal-insulator-semiconductor Schottky junction cells compared to buried junction p(+)n cells, revealing the need to maintain a characteristic hole density at the semiconductor/insulator interface. A leaky-capacitor model related to the dielectric properties of the protective oxide explains this loss, achieving excellent agreement with the data. From these findings, we formulate design principles for simultaneous optimization of built-in field, interface quality, and hole extraction to maximize the photovoltage of oxide-protected water-splitting anodes.

Electrochemical impedance spectroscopy for quantitative interface state characterization of planar and nanostructured semiconductor-dielectric interfaces.

The performance of nanostructured semiconductors is frequently limited by interface defects that trap electronic carriers. In particular, high aspect ratio geometries dramatically increase the difficulty of using typical solid-state electrical measurements (multifrequency capacitance- and conductance-voltage testing) to quantify interface trap densities (D it). We report on electrochemical impedance spectroscopy (EIS) to characterize the energy distribution of interface traps at metal oxide/semiconductor interfaces. This method takes advantage of liquid electrolytes, which provide conformal electrical contacts. Planar Al2O3/p-Si and Al2O3/p-Si0.55Ge0.45 interfaces are used to benchmark the EIS data against results obtained from standard electrical testing methods. We find that the solid state and EIS data agree very well, leading to the extraction of consistent D it energy distributions. Measurements carried out on pyramid-nanostructured p-Si obtained by KOH etching followed by deposition of a 10 nm ALD-Al2O3 demonstrate the application of EIS to trap characterization of a nanostructured dielectric/semiconductor interface. These results show the promise of this methodology to measure interface state densities for a broad range of semiconductor nanostructures such as nanowires, nanofins, and porous structures.

Low temperature thermal ALD of a SiNx interfacial diffusion barrier and interface passivation layer on SixGe1- x(001) and SixGe1- x(110).

Atomic layer deposition of a silicon rich SiNx layer on Si0.7Ge0.3(001), Si0.5Ge0.5(001), and Si0.5Ge0.5(110) surfaces has been achieved by sequential pulsing of Si2Cl6 and N2H4 precursors at a substrate temperature of 285 °C. XPS spectra show a higher binding energy shoulder peak on Si 2p indicative of SiOxNyClz bonding while Ge 2p and Ge 3d peaks show only a small amount of higher binding energy components consistent with only interfacial bonds, indicating the growth of SiOxNy on the SiGe surface with negligible subsurface reactions. Scanning tunneling spectroscopy measurements confirm that the SiNx interfacial layer forms an electrically passive surface on p-type Si0.70Ge0.30(001), Si0.50Ge0.50(110), and Si0.50Ge0.50(001) substrates as the surface Fermi level is unpinned and the electronic structure is free of states in the band gap. DFT calculations show that a Si rich a-SiO0.4N0,4 interlayer can produce lower interfacial defect density than stoichiometric a-SiO0.8N0.8, substoichiometric a-Si3N2, or stoichiometric a-Si3N4 interlayers by minimizing strain and bond breaking in the SiGe by the interlayer. Metal-oxide-semiconductor capacitors devices were fabricated on p-type Si0.7Ge0.3(001) and Si0.5Ge0.5(001) substrates with and without the insertion of an ALD SiOxNy interfacial layer, and the SiOxNy layer resulted in a decrease in interface state density near midgap with a comparable Cmax value.

Spontaneous, Defect-Free Kinking via Capillary Instability during Vapor-Liquid-Solid Nanowire Growth.

Kinking, a common anomaly in nanowire (NW) vapor-liquid-solid (VLS) growth, represents a sudden change of the wire's axial growth orientation. This study focuses on defect-free kinking during germanium NW VLS growth, after nucleation on a Ge (111) single crystal substrate, using Au-Ge catalyst liquid droplets of defined size. Statistical analysis of the fraction of kinked NWs reveals the dependence of kinking probability on the wire diameter and the growth temperature. The morphologies of kinked Ge NWs studied by electron microscopy show two distinct, defect-free, kinking modes, whose underlying mechanisms are explained with the help of 3D multiphase field simulations. Type I kinking, in which the growth axis changes from vertical [111] to ⟨110⟩, was observed in Ge NWs with a nominal diameter of ∼ 20 nm. This size coincides with a critical diameter at which a spontaneous transition from ⟨111⟩ to ⟨110⟩ growth occurs in the phase field simulations. Larger diameter NWs only exhibit Type II kinking, in which the growth axis changes from vertical [111] directly to an inclined ⟨111⟩ axis during the initial stages of wire growth. This is caused by an error in sidewall facet development, which produces a shrinkage in the area of the (111) growth facet with increasing NW length, causing an instability of the Au-Ge liquid droplet at the tip of the NW.

Core-Shell Germanium/Germanium-Tin Nanowires Exhibiting Room-Temperature Direct- and Indirect-Gap Photoluminescence.

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.

From Twinning to Pure Zincblende Catalyst-Free InAs(Sb) Nanowires.

III-V nanowires are candidate building blocks for next generation electronic and optoelectronic platforms. Low bandgap semiconductors such as InAs and InSb are interesting because of their high electron mobility. Fine control of the structure, morphology, and composition are key to the control of their physical properties. In this work, we present how to grow catalyst-free InAs1-xSbx nanowires, which are stacking fault and twin defect-free over several hundreds of nanometers. We evaluate the impact of their crystal phase purity by probing their electrical properties in a transistor-like configuration and by measuring the phonon-plasmon interaction by Raman spectroscopy. We also highlight the importance of high-quality dielectric coating for the reduction of hysteresis in the electrical characteristics of the nanowire transistors. High channel carrier mobilities and reduced hysteresis open the path for high-frequency devices fabricated using InAs1-xSbx nanowires.

Ultrafast electron and phonon response of oriented and diameter-controlled germanium nanowire arrays.

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.

Dimensional Scaling of Ferroelectric Properties of Hafnia-Zirconia Thin Films: Electrode Interface Effects.

Hafnia-based ferroelectric (FE) thin films are promising candidates for semiconductor memories. However, a fundamental challenge that persists is the lack of understanding regarding dimensional scaling, including thickness scaling and area scaling, of the functional properties and their heterogeneity in these films. In this work, excellent ferroelectricity and switching endurance are demonstrated in 4 nm-thick Hf0.5Zr0.5O2 (HZO) capacitors with molybdenum electrodes in capacitors as small as 65 nm × 45 nm in size. The HZO layer in these capacitors can be crystallized into the ferroelectric orthorhombic phase at the low temperature of 400 °C, making them compatible for back-end-of-line (BEOL) FE memories. With the benefits of thickness scaling, low operation voltage (1.2 V) is achieved with high endurance (>1010 cycles); however, a significant fatigue regime is noted. We observed that the bottom electrode, rather than the top electrode, plays a dominant role in the thickness scaling of HZO ferroelectric behavior. Furthermore, ultrahigh switched polarization (remanent polarization 2Pr ∼ 108 µC cm-2) is observed in some nanoscale devices. This study advances the understanding of dimensional scaling effects in HZO capacitors for high-performance FE memories.

Thermal stability and surface passivation of Ge nanowires coated by epitaxial SiGe shells.

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.

Enhanced Switching Reliability of Hf0.5Zr0.5O2 Ferroelectric Films Induced by Interface Engineering.

Ferroelectric materials have been widely researched for applications in memory and energy storage. Among these materials and benefiting from their excellent chemical compatibility with complementary metal-oxide-semiconductor (CMOS) devices, hafnia-based ferroelectric thin films hold great promise for highly scaled semiconductor memories, including nonvolatile ferroelectric capacitors and transistors. However, variation in the switched polarization of this material during field cycling and a limited understanding of the responsible mechanisms have impeded their implementation in technology. Here, we show that ferroelectric Hf0.5Zr0.5O2 (HZO) capacitors that are nearly free of polarization "wake-up"─a gradual increase in switched polarization as a function of the number of switching cycles─can be achieved by introducing ultrathin HfO2 buffer layers at the HZO/electrodes interface. High-resolution transmission electron microscopy (HRTEM) reveals crystallite sizes substantially greater than the film thickness for the buffer layer capacitors, indicating that the presence of the buffer layers influences the crystallization of the film (e.g., a lower ratio of nucleation rate to growth rate) during postdeposition annealing. This evidently promotes the formation of a polar orthorhombic (O) phase in the as-fabricated buffer layer samples. Synchrotron X-ray diffraction (XRD) reveals the conversion of the nonpolar tetragonal (T) phase to the polar orthorhombic (O) phase during electric field cycling in the control (no buffer) devices, consistent with the polarization wake-up observed for these capacitors. The extent of T-O transformation in the nonbuffer samples is directly dependent on the duration over which the field is applied. These results provide insight into the role of the HZO/electrodes interface in the performance of hafnia-based ferroelectrics and the mechanisms driving the polarization wake-up effect.

Atomic layer-deposited tunnel oxide stabilizes silicon photoanodes for water oxidation.

A leading approach for large-scale electrochemical energy production with minimal global-warming gas emission is to use a renewable source of electricity, such as solar energy, to oxidize water, providing the abundant source of electrons needed in fuel synthesis. We report corrosion-resistant, nanocomposite anodes for the oxidation of water required to produce renewable fuels. Silicon, an earth-abundant element and an efficient photovoltaic material, is protected by atomic layer deposition (ALD) of a highly uniform, 2 nm thick layer of titanium dioxide (TiO(2)) and then coated with an optically transmitting layer of a known catalyst (3 nm iridium). Photoelectrochemical water oxidation was observed to occur below the reversible potential whereas dark electrochemical water oxidation was found to have low-to-moderate overpotentials at all pH values, resulting in an inferred photovoltage of ~550 mV. Water oxidation is sustained at these anodes for many hours in harsh pH and oxidative environments whereas comparable silicon anodes without the TiO(2) coating quickly fail. The desirable electrochemical efficiency and corrosion resistance of these anodes is made possible by the low electron-tunnelling resistance (<0.006 Ω cm(2) for p(+)-Si) and uniform thickness of atomic-layer deposited TiO(2).

Nanocrystallite Seeding of Metastable Ferroelectric Phase Formation in Atomic Layer-Deposited Hafnia-Zirconia Alloys.

Hafnia-based ferroelectric thin films are promising for semiconductor memory and neuromorphic computing applications. Amorphous, as-deposited, thin-film binary alloys of HfO2 and ZrO2 transform to the metastable, orthorhombic ferroelectric phase during post-deposition annealing and cooling. This transformation is generally thought to involve formation of a tetragonal precursor phase that distorts into the orthorhombic phase during cooling. In this work, we systematically study the effects of atomic layer deposition (ALD) temperature on the ferroelectricity of post-deposition-annealed Hf0.5Zr0.5O2 (HZO) thin films. Seed crystallites having interplanar spacings consistent with the polar orthorhombic phase are observed by a plan-view transmission electron microscope in HZO thin films deposited at an elevated ALD temperature. After ALD under conditions that promote formation of these nanocrystallites, high-polarization (Pr > 18 µC/cm2) ferroelectric switching is observed after rapid thermal annealing (RTA) at low temperature (350 °C). These results indicate the presence of minimal non-ferroelectric phases retained in the films after RTA when the ALD process forms nanocrystalline particles that seed subsequent formation of the polar orthorhombic phase.

Hexagonal close-packed structure of au nanocatalysts solidified after ge nanowire vapor-liquid-solid growth.

We report that approximately 10% of the Au catalysts that crystallize at the tips of Ge nanowires following growth have the close-packed hexagonal crystal structure rather than the equilibrium face-centered-cubic structure. Transmission electron microscopy results using aberration-corrected imaging, and diffraction and compositional analyses, confirm the hexagonal phase in these 40-50 nm particles. Reports of hexagonal close packing in Au, even in nanoparticle form, are rare, and the observations suggest metastable pathways for the crystallization process. These results bring new considerations to the stabilization of the liquid eutectic alloy at low temperatures that allows for vapor-liquid-solid growth of high quality, epitaxial Ge nanowires below the eutectic temperature.

Link between Gas Phase Reaction Chemistry and the Electronic Conductivity of Atomic Layer Deposited Titanium Oxide Thin Films.

In situ monitoring of gas phase composition reveals the link between the changing gas phase chemistry during atomic layer deposition (ALD) half-cycle reactions and the electronic conductivity of ALD-TiO2 thin films. Dimethylamine ((CH3)2NH, DMA) is probed as the main product of both the TDMAT and water vapor half-reactions during the TDMAT/H2O ALD process. In-plane electronic transport characterization of the ALD grown films demonstrates that the presence of DMA, a reducing agent, in the ALD chamber throughout each half-cycle is correlated with both an increase in the films' electronic conductivity, and observation of titanium in the 3+ oxidation state by ex situ X-ray photoelectron spectroscopy analysis of the films. DMA annealing of as-grown TiO2 films in the ALD chamber produces a similar effect on their electronic characteristics, indicating the importance of DMA-induced oxygen deficiency of ALD-TiO2 in dictating the electronic conductivity of as-grown films.

Bending and precipitate formation mechanisms in epitaxial Ge-core/GeSn-shell nanowires.

Core-shell Ge/GeSn nanowires provide a route to dislocation-free single crystal germanium-tin alloys with desirable light emission properties because the Ge core acts as an elastically compliant substrate during misfitting GeSn shell growth. However, the uniformity of tin incorporation during reduced pressure chemical vapor deposition may be limited by the kinetics of mass transfer to the shell during GeSn growth. The balance between Sn precursor flux and available surfaces for GeSn nucleation and growth determines whether defects are formed and their type. On the one hand, when the Sn precursor delivery is insufficient, local variations in Sn arrival rate at the nanowire surfaces during GeSn growth produce asymmetries in shell growth that induce wire bending. This inhomogeneous elastic dilatation due to the varying composition occurs via deposition of Sn-poor regions on some of the {112} sidewall facets of the nanowires. On the other hand, when the available nanowire surface area is insufficient to accommodate the arriving Sn precursor flux, Sn-rich precipitate formation results. Between these two extremes, there exists a regime of growth conditions and nanowire densities that permits defect-free GeSn shell growth.

Gold-catalyzed vapor-liquid-solid germanium-nanowire nucleation on porous silicon.

Nanoporous Si(111) substrates are used to study the effects of Au catalyst coarsening on the nucleation of vapor-liquid-solid-synthesized epitaxial Ge nanowires (NWs) at temperatures less than 400 degrees C. Porous Si substrates, with greater effective interparticle separations for Au surface diffusion than nonporous Si, inhibit catalyst coarsening and agglomeration prior to NW nucleation. This greatly reduces the variation in wire diameter and length and increases the yield compared to nucleation on identically prepared nonporous Si substrates.