[Show abstract][Hide abstract] ABSTRACT: The hydrolysis of β-O-4 bonds in two lignin model compounds was studied in an acidic ionic liquid, 1-H-3-methylimidazolium chloride. The β-O-4 bonds of both guaiacylglycerol-β-guaiacyl ether and veratrylglycerol-β-guaiacyl ether underwent catalytic hydrolysis to produce guaiacol as the primary product with more than 70% yield at 150 C. Up to 32 wt%
substrate concentration could be treated in the system without a decrease in guaiacol production. The ionic liquid could be reused without loss of activity in guaiacol production from both guaiacylglycerol-β-guaiacyl ether and veratrylglycerol-β-guaiacyl ether. A possible mechanism accounting for the guaiacol production is presented.
[Show abstract][Hide abstract] ABSTRACT: The recently developed ability to grow layers of transition metal oxides with atomic precision by means of physical vapor deposition has opened up a possibility of monolithic integration of these oxides on semiconductors. Here we review the recent progress in integrating ferroelectric films with Si and Ge, and their potential applications in electronics and nanophotonics. Perovskite films described in the talk were grown by molecular beam epitaxy (MBE) and, when possible, chemical routes were tested via atomic layer deposition (ALD). Design of the structures and analysis of the experimental results were aided by density functional theory (DFT).
[Show abstract][Hide abstract] ABSTRACT: In this paper, we report on the highly conductive layer formed at the crystalline γ-alumina/SrTiO3
interface, which is attributed to oxygen vacancies. We describe the structure of thin γ-alumina layers deposited by molecular beam epitaxy on SrTiO3 (001) at growth temperatures in the range of 400–800 °C, as determined by reflection-high-energy electron diffraction, x-ray diffraction, and high-resolution electron microscopy. In situ
x-ray photoelectron spectroscopy was used to confirm the presence of the oxygen-deficient layer. Electrical characterization indicates sheet carrier densities of ∼1013 cm−2 at room temperature for the sample deposited at 700 °C, with a maximum electron Hall mobility of 3100 cm2V−1s−1 at 3.2 K and room temperature mobility of 22 cm2V−1s−1. Annealing in oxygen is found to reduce the carrier density and turn a conductive sample into an insulator.
[Show abstract][Hide abstract] ABSTRACT: The current work explores the crystalline perovskite oxide, strontium hafnate, as a potential high-k gate dielectric for Ge-based transistors. SrHfO3 (SHO) is grown directly on Ge by atomic layer deposition and becomes crystalline with epitaxial registry after post-deposition vacuum annealing at ∼700 °C for 5 min. The 2 × 1 reconstructed, clean Ge (001) surface is a necessary template to achieve crystalline films upon annealing. The SHO films exhibit excellent crystallinity, as shown by x-ray diffraction and transmission electron microscopy. The SHO films have favorable electronic properties for consideration as a high-k gate dielectric on Ge, with satisfactory band offsets (>2 eV), low leakage current (<10−5 A/cm2 at an applied field of 1 MV/cm) at an equivalent oxide thickness of 1 nm, and a reasonable dielectric constant (k ∼ 18). The interface trap density (Dit
) is estimated to be as low as ∼2 × 1012 cm−2 eV−1 under the current growth and anneal conditions. Some interfacial reaction is observed between SHO and Ge at temperatures above ∼650 °C, which may contribute to increased Dit
value. This study confirms the potential for crystalline oxides grown directly on Ge by atomic layer deposition for advanced electronic applications.
[Show abstract][Hide abstract] ABSTRACT: We report the epitaxial growth of γ-Al2O3 on SrTiO3 (STO) substrates by atomic layer deposition (ALD). The ALD growth of γ-Al2O3 on STO(001) single crystal substrates was performed at a temperature of 345 °C. Trimethylaluminum and water were used as co-reactants. In-situ reflection high-energy electron diffraction and ex-situ x-ray diffraction were used to determine the crystallinity of the Al2O3 films. In-situ x-ray photoelectron spectroscopy was used to characterize the Al2O3/STO heterointerface. The formation of a Ti3+ feature is observed in the Ti 2p spectrum of STO after the first few ALD cycles of Al2O3 and even after exposure of the STO substrate to trimethylaluminum alone at 345 °C. The presence of a Ti3+ feature is a direct indication of oxygen vacancies at the Al2O3/STO heterointerface, which provide the carriers for the quasi-two dimensional electron gas at the interface.
[Show abstract][Hide abstract] ABSTRACT: In this work, hydrogen production from water is demonstrated via a p-type silicon photocathode with a thin epitaxial strontium titanate, SrTiO3 (STO), as capping layer by molecular beam epitaxy. The advantages of using STO are the ideal conduction band alignment and perfect lattice match between single crystalline SrTiO3 and Si, so the photogenerated electrons can transport through the capping layer with a reduced recombination rate. The STO/p-Si photocathode exhibited a maximum photocurrent density and open circuit potential of 35 mA/cm2 and 450 mV, respectively. There was no observable decrease in performance after 10 hr operation in 0.5M H 2 SO 4. We found the efficiency and performance were highly dependent on the size and spacing of the structured metal catalyst. Scaled down the metal catalysts feature size into nanometer region can greatly improve the efficiency. In addition, samples with graphene (Grahene/p-Si) as the lateral transport channel and capping layer shown an enhanced fill factor compared with that of STO/p-Si.
Electron Devices Meeting (IEDM), 2014 IEEE International, San Francisco, CA; 12/2014
[Show abstract][Hide abstract] ABSTRACT: The rapidly increasing global demand for energy combined with the environmental impact of fossil fuels has spurred the search for alternative sources of clean energy. One promising approach is to convert solar energy into hydrogen fuel using photoelectrochemical cells. However, the semiconducting photoelectrodes used in these cells typically have low efficiencies and/or stabilities. Here we show that a silicon-based photocathode with a capping epitaxial oxide layer can provide efficient and stable hydrogen production from water. In particular, a thin epitaxial layer of strontium titanate (SrTiO3) was grown directly on Si(001) by molecular beam epitaxy. Photogenerated electrons can be transported easily through this layer because of the conduction-band alignment and lattice match between single-crystalline SrTiO3 and silicon. The approach was used to create a metal-insulator-semiconductor photocathode that, under a broad-spectrum illumination at 100 mW cm(-2), exhibits a maximum photocurrent density of 35 mA cm(-2) and an open circuit potential of 450 mV; there was no observable decrease in performance after 35 hours of operation in 0.5M H2SO4. The performance of the photocathode was also found to be highly dependent on the size and spacing of the structured metal catalyst. Therefore, mesh-like Ti/Pt nanostructured catalysts were created using a nanosphere lithography lift-off process and an applied-bias photon-to-current efficiency of 4.9% was achieved.
[Show abstract][Hide abstract] ABSTRACT: This work demonstrates the growth of crystalline SrTiO3 (STO) directly on germanium via a chemical method. After thermal deoxidation, the Ge substrate is transferred in vacuo to the deposition chamber where a thin film of STO (2 nm) is deposited by atomic layer deposition (ALD) at 225 °C. Following post-deposition annealing at 650 °C for 5 min, the STO film becomes crystalline with epitaxial registry to the underlying Ge (001) substrate. Thicker STO films (up to 15 nm) are then grown on the crystalline STO seed layer. The crystalline structure and orientation are confirmed via reflection high-energy electron diffraction, X-ray diffraction, and transmission electron microscopy. Electrical measurements of a 15-nm thick epitaxial STO film on Ge show a large dielectric constant (k ≈ 90), but relatively high leakage current of ≈10 A/cm2 for an applied field of 0.7 MV/cm. To suppress the leakage current, an aluminum precursor is cycled during ALD growth to grow crystalline Al-doped STO (SrTi1-xAlxO3-δ) films. With sufficient Al doping (≈13%), the leakage current decreases by two orders of magnitude for an 8-nm thick film. The current work demonstrates the potential of ALD-grown crystalline oxides to be explored for advanced electronic applications, including high-mobility Ge-based transistors.
[Show abstract][Hide abstract] ABSTRACT: We present a vertical gate-all-around Si nanowire (SiNW) metal-oxide-semiconductor field-effect transistor with high-κ dielectric and TiN metal gate. The process flow is fully compatible with CMOS technologies. SiNWs are fabricated by deep Si reactive ion etching, gate-stack is formed by atomic layer deposition, and metal salicide is utilized as drain contact. The fabricated p-type gate-all-around SiNW metal-oxide-semiconductor field-effect transistors that have a gate length of 320 nm exhibit excellent characteristics with ION/IOFF > 104, subthreshold slope of 87 mV/decade, and 25 mV/V of drain-induced barrier lowering. Low-temperature characteristics are also presented. The demonstrated devices have potential applications in novel low-power logic circuits and as selection transistors for 4F2 cross-point memory cells.
IEEE Transactions on Electron Devices 11/2014; 61(11):3896-3900. DOI:10.1109/TED.2014.2353658 · 2.36 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Resistive switching in single crystal anatase TiO2 grown by atomic layer deposition on Si (001) with an epitaxial single crystal SrTiO3 buffer layer is characterized and analyzed. Although switching occurs via a valence-change mechanism involving motion of oxygen vacancies, electrical characteristics highly reminiscent of electrochemical metallization memories – low leakage current in the high-resistance state, highly linear current-voltage characteristics in the low-resistance state, and a very high on/off current ratio – are observed. We postulate that these characteristics may be associated with formation of TinO2n-1 Magnéli or Magnéli-like nanophases in the low-resistance state. In addition, quantized conductance is observed in the low-resistance state, with the number of conducting ballistic channels being highly controllable via application of different compliance currents during the memory SET process. For compliance currents of 10-200µA, low resistance state conductances corresponding to 1 to 4 conductance channels, controllable to within a single quantum of conductance, are observed.
[Show abstract][Hide abstract] ABSTRACT: TiO2 is being widely explored as an active resistive switching (RS) material for resistive random access memory. We report a detailed analysis of the RS characteristics of single-crystal anatase-TiO2 thin films epitaxially grown on silicon by atomic layer deposition. We demonstrate that although the valence change mechanism is responsible for the observed RS, single-crystal anatase-TiO2 thin films show electrical characteristics that are very different from the usual switching behaviors observed for polycrystalline or amorphous TiO2, and instead very similar to those found in electrochemical metallization memory. In addition, we demonstrate highly stable and reproducible quantized conductance that is well controlled by application of a compliance current and that suggests the localized formation of conducting Magnéli-like nanophases. The quantized conductance observed results in multiple well-defined resistance states suitable for implementation of multilevel memory cells.
[Show abstract][Hide abstract] ABSTRACT: Strontium titanate, SrTiO3 (STO), thin films incorporated with lanthanum are grown on Si (001) substrates at a thickness range of 5–25 nm. Atomic layer deposition (ALD) is used to grow the LaxSr1−xTiO3 (La:STO) films after buffering the Si (001) substrate with four-unit-cells of STO deposited by molecular beam epitaxy. The crystalline structure and orientation of the La:STO films are confirmed via reflection high-energy electron diffraction, X-ray diffraction, and cross-sectional transmission electron microscopy. The low temperature ALD growth (∼225 °C) and post-deposition annealing at 550 °C for 5 min maintains an abrupt interface between Si (001) and the crystalline oxide. Higher annealing temperatures (650 °C) show more complete La activation with film resistivities of ∼2.0 × 10−2 Ω cm for 20-nm-thick La:STO (x ∼ 0.15); however, the STO-Si interface is slightly degraded due to the increased annealing temperature. To demonstrate the selective incorporation of lanthanum by ALD, a layered heterostructure is grown with an undoped STO layer sandwiched between two conductive La:STO layers. Based on this work, an epitaxial oxide stack centered on La:STO and BaTiO3 integrated with Si is envisioned as a material candidate for a ferroelectric field-effect transistor.
[Show abstract][Hide abstract] ABSTRACT: The use of PH3 as the P source in the growth of amorphous ruthenium–phosphorus (Ru(P)) alloy films by dual-source chemical vapor deposition (CVD) with Ru3(CO)12 to produce thin (~ 3 nm) Cu diffusion barriers is examined. Comparisons are made to films grown using P(CH3)3. Carbon contamination of 10 at.% carbon or less was observed in PH3-produced Ru(P) films, compared to greater than 30 atomic % carbon in films using P(CH3)3, and lower resistivity was also observed. PH3 was found to be much more reactive than previously-used P precursors, requiring the use of very low PH3 partial pressures (~ 0.13 mPa) and a sequenced addition process that allowed accumulated P to diffuse into the Ru(P) film during growth. X-ray reflectivity and atomic force microscopy indicate that films of good continuity and smoothness can be grown by CVD in the 3 nm thickness range. X-ray diffraction shows the amorphous phase to be stable for annealing at 400 °C for 3 h. Electric field stress tests to failure for Cu/Ru(P)/SiO2/Si stacks indicate that low-carbon Ru(P) barrier films function at least as well as their higher-carbon counterparts as Cu barriers and better than Ta/TaN stacks of similar thickness grown for comparison purposes.
Thin Solid Films 05/2014; 558:160–164. DOI:10.1016/j.tsf.2014.03.018 · 2.13 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Adsorption of the atomic layer deposition (ALD) precursor bis(N-tert-butyl-N′-ethylpropionamidinato) cobalt(II) (CoAMD) on SiO2, carbon-doped oxide (CDO), and Cu is reported. Adsorption was performed under ALD cycling conditions with and without H2 coreactant to mimic the first and second ALD half reactions on the substrates. Resultant surface chemistries were evaluated by X-ray photoelectron spectroscopy. Adsorption of CoAMD proved self-limiting and the precursor reduced readily on Cu with and without H2 coreactant to form Co0. Residual C and N signals on Cu suggest that amidinate ligands and decomposition fragments from CoAMD adsorb on the Cu surface. On SiO2 and CDO, CoAMD chemisorbs on O containing moieties, primarily OH, to form Co2+. Accumulation of Co after three ALD cycles was greatest on Cu and least on CDO.
Chemistry of Materials 04/2014; 26(8):2642–2646. DOI:10.1021/cm5002237 · 8.54 Impact Factor