Tobin Kaufman-Osborn

Atomic imaging of the irreversible sensing mechanism of NO2 adsorption on copper phthalocyanine.

Ambient NO2 adsorption onto copper(II) phthalocyanine (CuPc) monolayers is observed using ultrahigh vacuum (UHV) scanning tunneling microscopy (STM) to elucidate the molecular sensing mechanism in CuPc chemical vapor sensors. For low doses (1 ppm for 5 min) of NO2 at ambient temperatures, isolated chemisorption sites on the CuPc metal centers are observed in STM images. These chemisorbates almost completely desorb from the CuPc monolayer after annealing at 100 °C for 30 min. Conversely, for high NO2 doses (10 ppm for 5 min), the NO2 induces a fracture of the CuPc domains. This domain fracture can only be reversed by annealing above 150 °C, which is consistent with dissociative chemisorption into NO and atomic O accompanied by surface restructuring. This high stability implies that the domain fracture results from tightly bound adsorbates, such as atomic O. Existence of atomic O on or under the CuPc layer, which results in domain fracture, is revealed by XPS analysis and ozone-dosing experiments. The observed CuPc domain fracturing is consistent with a mechanism for the dosimetric sensing of NO2 and other reactive gases by CuPc organic thin film transistors (OTFTs).

Preparation of gallium nitride surfaces for atomic layer deposition of aluminum oxide

A combined wet and dry cleaning process for GaN(0001) has been investigated with XPS and DFT-MD modeling to determine the molecular-level mechanisms for cleaning and the subsequent nucleation of gate oxide atomic layer deposition (ALD). In situ XPS studies show that for the wet sulfur treatment on GaN(0001), sulfur desorbs at room temperature in vacuum prior to gate oxide deposition. Angle resolved depth profiling XPS post-ALD deposition shows that the a-Al2O3 gate oxide bonds directly to the GaN substrate leaving both the gallium surface atoms and the oxide interfacial atoms with XPS chemical shifts consistent with bulk-like charge. These results are in agreement with DFT calculations that predict the oxide/GaN(0001) interface will have bulk-like charges and a low density of band gap states. This passivation is consistent with the oxide restoring the surface gallium atoms to tetrahedral bonding by eliminating the gallium empty dangling bonds on bulk terminated GaN(0001).

Atomic imaging of nucleation of trimethylaluminum on clean and H2O functionalized Ge(100) surfaces.

The direct reaction of trimethylaluminum (TMA) on a Ge(100) surface and the effects of monolayer H(2)O pre-dosing were investigated using ultrahigh vacuum techniques, such as scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). At room temperature (RT), a saturation TMA dose produced 0.8 monolayers (ML) of semi-ordered species on a Ge(100) surface due to the dissociative chemisorption of TMA. STS confirmed the chemisorption of TMA passivated the bandgap states due to dangling bonds. By annealing the TMA-dosed Ge surface, the STM observed coverage of TMA sites decreased to 0.4 ML at 250 °C, and to 0.15 ML at 450 °C. XPS analysis showed that only carbon content was reduced during annealing, while the Al coverage was maintained at 0.15 ML, consistent with the desorption of methyl (-CH(3)) groups from the TMA adsorbates. Conversely, saturation TMA dosing at RT on the monolayer H(2)O pre-dosed Ge(100) surface followed by annealing at 200 °C formed a layer of Ge-O-Al bonds with an Al coverage a factor of two greater than the TMA only dosed Ge(100), consistent with Ge-OH activation of TMA chemisorption and Ge-H blocking of CH(3) chemisorption. The DFT shows that the reaction of TMA has lower activation energy and is more exothermic on Ge-OH than Ge-H sites. It is proposed that the H(2)O pre-dosing enhances the concentration of adsorbed Al and forms thermally stable Ge-O-Al bonds along the Ge dimer row which could serve as a nearly ideal atomic layer deposition nucleation layer on Ge(100) surface.

Atomic imaging and modeling of H2O2(g) surface passivation, functionalization, and atomic layer deposition nucleation on the Ge(100) surface

Passivation, functionalization, and atomic layer deposition nucleation via H2O2(g) and trimethylaluminum (TMA) dosing was studied on the clean Ge(100) surface at the atomic level using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Chemical analysis of the surface was performed using x-ray photoelectron spectroscopy, while the bonding of the precursors to the substrate was modeled with density functional theory (DFT). At room temperature, a saturation dose of H2O2(g) produces a monolayer of a mixture of -OH or -O species bonded to the surface. STS confirms that H2O2(g) dosing eliminates half-filled dangling bonds on the clean Ge(100) surface. Saturation of the H2O2(g) dosed Ge(100) surface with TMA followed by a 200 °C anneal produces an ordered monolayer of thermally stable Ge-O-Al bonds. DFT models and STM simulations provide a consistent model of the bonding configuration of the H2O2(g) and TMA dosed surfaces. STS verifies the TMA/H2O2/Ge surface has an unpinned Fermi level with no states in the bandgap demonstrating the ability of a Ge-O-Al monolayer to serve as an ideal template for further high-k deposition.

Monolayer Passivation of Ge(100) Surface via Nitridation and Oxidation

The monolayer passivation of Ge(100) surface via formation of Ge-N and Ge-O surface species was studied using scanning tunneling microscopy (STM) and density functional theory (DFT). Direct nitridation using an electron cyclotron resonance (ECR) plasma source formed an ordered Ge-N structure on a Ge(100) surface at 500C. DFT calculations found the hydrogen passivation on this Ge-N ordered structure could reduce the bandgap states by decreasing the dangling bonds and the bond strain. Oxidation of Ge(100) using H2O produced an –OH and –H terminated surface with very few Ge ad-atoms, while e-beam evaporation of GeO2 formed semi-ordered Ge-O structures and Ge ad-species at room temperature. Annealing above 300C formed suboxide rows on both H2O and GeO2 dosed surfaces, and the scanning tunneling spectroscopy (STS) showed that the Fermi level was pinned near the valence band edge on the n-type Ge surfaces covered by suboxides.

Density-Functional Theory Molecular Dynamics Simulations and Experimental Characterization of a-Al₂O₃/SiGe Interfaces.

Density-functional theory molecular dynamics simulations were employed to investigate direct interfaces between a-Al2O3 and Si0.50Ge0.50 with Si- and Ge-terminations. The simulated stacks revealed mixed interfacial bonding. While Si-O and Ge-O bonds are unlikely to be problematic, bonding between Al and Si or Ge could result in metallic bond formation; however, the internal bonds of a-Al2O3 are sufficiently strong to allow just weak Al bonding to the SiGe surface thereby preventing formation of metallic-like states but leave dangling bonds. The oxide/SiGe band gaps were unpinned and close to the SiGe bulk band gap. The interfaces had SiGe dangling bonds, but they were sufficiently filled that they did not produce midgap states. Capacitance-voltage (C-V) spectroscopy and angle-resolved X-ray photoelectron spectroscopy experimentally confirmed formation of interfaces with low interface trap density via direct bonding between a-Al2O3 and SiGe.

Combined wet and dry cleaning of SiGe(001)

Combined wet and dry cleaning via hydrofluoric acid (HF) and atomic hydrogen on Si0.6Ge0.4(001) surface was studied at the atomic level using ultrahigh vacuum scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and x-ray photoelectron spectroscopy to understand the chemical transformations of the surface. Aqueous HF removes native oxide, but residual carbon and oxygen are still observed on Si0.6Ge0.4(001) due to hydrocarbon contamination from post HF exposure to ambient. The oxygen contamination can be eliminated by shielding the sample from ambient via covering the sample in the HF cleaning solution until the sample is introduced to the vacuum chamber or by transferring the sample in an inert environment; however, both processes still leave carbon contaminant. Dry in-situ atomic hydrogen cleaning above 330 °C removes the carbon contamination on the surface consistent with a thermally activated atomic hydrogen reaction with surface hydrocarbon. A postdeposition anneal at 550 °C ind...

Passivation and Nucleation of Ge(100) via H2O and HOOH Dosing

Germanium is a promising candidate for potential channel materials due to its higher hole and electron mobility. To minimize the oxide-semiconductor interfacial defect density, a proper passivation layer must be used before the oxide layer is deposited1. The passivation layer must be very thin, ideally one monolayer, to allow for increased scaling of the equivalent oxide thickness (EOT). H2O provides a well-ordered chemisorption monolayer (ML) at room temperature without disrupting surface Ge atoms2. In this study, a monolayer of H2O chemisorbates is shown to activate TMA chemisorption due to the Ge-OH bonds catalyzing the formation of an ultrathin passivation layer which can serve as an ideal ALD nucleation template on a Ge surface3. However, since H2O chemisorption results in equal density of Ge-H and Ge-OH sites on the Ge(100), H2O can only provide a maximum of 0.5 monolayer of Ge-OH sites, limiting the TMA nucleation density. By using HOOH dosing, the density of Ge-OH sites can be doubled thereby increasing the potential TMA nucleation density. This study compares the passivation of the Ge(100) surface via H2O and HOOH, for the application of nucleating ALD growth on the surface, using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). This study will also look into similar H2O/HOOH passivation and TMA nucleation techniques on SiGe.