Showing papers by "Robert M. Wallace published in 2014"

Defect-Dominated Doping and Contact Resistance in MoS2

Abstract: Achieving low resistance contacts is vital for the realization of nanoelectronic devices based on transition metal dichalcogenides. We find that intrinsic defects in MoS2 dominate the metal/MoS2 contact resistance and provide a low Schottky barrier independent of metal contact work function. Furthermore, we show that MoS2 can exhibit both n-type and p-type conduction at different points on a same sample. We identify these regions independently by complementary characterization techniques and show how the Fermi level can shift by 1 eV over tens of nanometers in spatial resolution. We find that these variations in doping are defect-chemistry-related and are independent of contact metal. This raises questions on previous reports of metal-induced doping of MoS2 since the same metal in contact with MoS2 can exhibit both n- and p-type behavior. These results may provide a potential route for achieving low electron and hole Schottky barrier contacts with a single metal deposition.

The Unusual Mechanism of Partial Fermi Level Pinning at Metal–MoS2 Interfaces

Abstract: Density functional theory calculations are performed to unravel the nature of the contact between metal electrodes and monolayer MoS2. Schottky barriers are shown to be present for a variety of metals with the work functions spanning over 4.2–6.1 eV. Except for the p-type Schottky contact with platinum, the Fermi levels in all of the studied metal–MoS2 complexes are situated above the midgap of MoS2. The mechanism of the Fermi level pinning at metal–MoS2 contact is shown to be unique for metal–2D-semiconductor interfaces, remarkably different from the well-known Bardeen pinning effect, metal-induced gap states, and defect/disorder induced gap states, which are applicable to traditional metal–semiconductor junctions. At metal–MoS2 interfaces, the Fermi level is partially pinned as a result of two interface behaviors: first by a metal work function modification by interface dipole formation due to the charge redistribution, and second by the production of gap states mainly of Mo d-orbitals character by the ...

MoS2 P-type Transistors and Diodes Enabled by High Work Function MoOx Contacts

Abstract: The development of low-resistance source/drain contacts to transition-metal dichalcogenides (TMDCs) is crucial for the realization of high-performance logic components. In particular, efficient hole contacts are required for the fabrication of p-type transistors with MoS2, a model TMDC. Previous studies have shown that the Fermi level of elemental metals is pinned close to the conduction band of MoS2, thus resulting in large Schottky barrier heights for holes with limited hole injection from the contacts. Here, we show that substoichiometric molybdenum trioxide (MoOx, x < 3), a high work function material, acts as an efficient hole injection layer to MoS2 and WSe2. In particular, we demonstrate MoS2 p-type field-effect transistors and diodes by using MoOx contacts. We also show drastic on-current improvement for p-type WSe2 FETs with MoOx contacts over devices made with Pd contacts, which is the prototypical metal used for hole injection. The work presents an important advance in contact engineering of TM...

Hole Selective MoOx Contact for Silicon Solar Cells

Abstract: Using an ultrathin (∼15 nm in thickness) molybdenum oxide (MoOx, x < 3) layer as a transparent hole selective contact to n-type silicon, we demonstrate a room-temperature processed oxide/silicon solar cell with a power conversion efficiency of 14.3%. While MoOx is commonly considered to be a semiconductor with a band gap of 3.3 eV, from X-ray photoelectron spectroscopy we show that MoOx may be considered to behave as a high workfunction metal with a low density of states at the Fermi level originating from the tail of an oxygen vacancy derived defect band located inside the band gap. Specifically, in the absence of carbon contamination, we measure a work function potential of ∼6.6 eV, which is significantly higher than that of all elemental metals. Our results on the archetypical semiconductor silicon demonstrate the use of nm-thick transition metal oxides as a simple and versatile pathway for dopant-free contacts to inorganic semiconductors. This work has important implications toward enabling a novel cl...

Impact of Intrinsic Atomic Defects on the Electronic Structure of MoS2 Monolayers

Abstract: Monolayer MoS2 is a direct band gap semiconductor which has been recently investigated for low-power field effect transistors. The initial studies have shown promising performance, including a high on/off current ratio and carrier mobility with a high-κ gate dielectric. However, the performance of these devices strongly depends on the crystalline quality and defect morphology of the monolayers. In order to obtain a detailed understanding of the MoS2 electronic device properties, we examine possible defect structures and their impact on the MoS2 monolayer electronic properties, using density functional theory in combination with scanning tunneling microscopy to identify the nature of the most likely defects. Quantitative understanding based on a detailed knowledge of the atomic and electronic structures will facilitate the search of suitable defect passivation techniques. Our results show that S adatoms are the most energetically favorable type of defect and that S vacancies are energetically more favorable than Mo vacancies. This approach may be extended to other transition-metal dichalcogenides (TMDs), thus providing useful insights to optimize TMD-based electronic devices.

Air stable p-doping of WSe2 by covalent functionalization.

Abstract: Covalent functionalization of transition metal dichalcogenides (TMDCs) is investigated for air-stable chemical doping. Specifically, p-doping of WSe2 via NOx chemisorption at 150 °C is explored, with the hole concentration tuned by reaction time. Synchrotron based soft X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) depict the formation of various WSe2–x–yOxNy species both on the surface and interface between layers upon chemisorption reaction. Ab initio simulations corroborate our spectroscopy results in identifying the energetically favorable complexes, and predicting WSe2:NO at the Se vacancy sites as the predominant dopant species. A maximum hole concentration of ∼1019 cm–3 is obtained from XPS and electrical measurements, which is found to be independent of WSe2 thickness. This degenerate doping level facilitates 5 orders of magnitude reduction in contact resistance between Pd, a common p-type contact metal, and WSe2. More generally, the work presents a platform for man...

Hole contacts on transition metal dichalcogenides: interface chemistry and band alignments.

Abstract: MoOx shows promising potential as an efficient hole injection layer for p-FETs based on transition metal dichalcogenides. A combination of experiment and theory is used to study the surface and interfacial chemistry, as well as the band alignments for MoOx/MoS2 and MoOx/WSe2 heterostructures, using photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory. A Mo5+ rich interface region is identified and is proposed to explain the similar low hole Schottky barriers reported in a recent device study utilizing MoOx contacts on MoS2 and WSe2.

MoS2 functionalization for ultra-thin atomic layer deposited dielectrics

Abstract: The effect of room temperature ultraviolet-ozone (UV-O3) exposure of MoS2 on the uniformity of subsequent atomic layer deposition of Al2O3 is investigated. It is found that a UV-O3 pre-treatment removes adsorbed carbon contamination from the MoS2 surface and also functionalizes the MoS2 surface through the formation of a weak sulfur-oxygen bond without any evidence of molybdenum-sulfur bond disruption. This is supported by first principles density functional theory calculations which show that oxygen bonded to a surface sulfur atom while the sulfur is simultaneously back-bonded to three molybdenum atoms is a thermodynamically favorable configuration. The adsorbed oxygen increases the reactivity of MoS2 surface and provides nucleation sites for atomic layer deposition of Al2O3. The enhanced nucleation is found to be dependent on the thin film deposition temperature.

Atomically thin heterostructures based on single-layer tungsten diselenide and graphene.

Abstract: Heterogeneous engineering of two-dimensional layered materials, including metallic graphene and semiconducting transition metal dichalcogenides, presents an exciting opportunity to produce highly tunable electronic and optoelectronic systems. In order to engineer pristine layers and their interfaces, epitaxial growth of such heterostructures is required. We report the direct growth of crystalline, monolayer tungsten diselenide (WSe2) on epitaxial graphene (EG) grown from silicon carbide. Raman spectroscopy, photoluminescence, and scanning tunneling microscopy confirm high-quality WSe2 monolayers, whereas transmission electron microscopy shows an atomically sharp interface, and low energy electron diffraction confirms near perfect orientation between WSe2 and EG. Vertical transport measurements across the WSe2/EG heterostructure provides evidence that an additional barrier to carrier transport beyond the expected WSe2/EG band offset exists due to the interlayer gap, which is supported by theoretical local ...

Atomic Layer Deposition of a High-k Dielectric on MoS2 Using Trimethylaluminum and Ozone

Abstract: We present an Al2O3 dielectric layer on molybdenum disulfide (MoS2), deposited using atomic layer deposition (ALD) with ozone/trimethylaluminum (TMA) and water/TMA as precursors. The results of atomic force microscopy and low-energy ion scattering spectroscopy show that using TMA and ozone as precursors leads to the formation of uniform Al2O3 layers, in contrast to the incomplete coverage we observe when using TMA/H2O as precursors. Our Raman and X-ray photoelectron spectroscopy measurements indicate minimal variations in the MoS2 structure after ozone treatment at 200 °C, suggesting its excellent chemical resistance to ozone.

Realistic Metal–Graphene Contact Structures

Abstract: The contact resistance of metal–graphene junctions has been actively explored and exhibited inconsistencies in reported values. The interpretation of these electrical data has been based exclusively on a side-contact model, that is, metal slabs sitting on a pristine graphene sheet. Using in situ X-ray photoelectron spectroscopy to study the wetting of metals on as-synthesized graphene on copper foil, we show that side-contact is sometimes a misleading picture. For instance, metals like Pd and Ti readily react with graphitic carbons, resulting in Pd- and Ti-carbides. Carbide formation is associated with C–C bond breaking in graphene, leading to an end-contact geometry between the metals and the periphery of the remaining graphene patches. This work validates the spontaneous formation of the metal–graphene end-contact during the metal deposition process as a result of the metal–graphene reaction instead of a simple carbon diffusion process.

Accumulation capacitance frequency dispersion of III-V metal-insulator-semiconductor devices due to disorder induced gap states

Abstract: The origin of the anomalous frequency dispersion in accumulation capacitance of metal-insulator-semiconductor devices on InGaAs and InP substrates is investigated using modeling, electrical characterization, and chemical characterization. A comparison of the border trap model and the disorder induced gap state model for frequency dispersion is performed. The fitting of both models to experimental data indicate that the defects responsible for the measured dispersion are within approximately 0.8 nm of the surface of the crystalline semiconductor. The correlation between the spectroscopically detected bonding states at the dielectric/III-V interface, the interfacial defect density determined using capacitance-voltage, and modeled capacitance-voltage response strongly suggests that these defects are associated with the disruption of the III-V atomic bonding and not border traps associated with bonding defects within the high-k dielectric.

MoS2 P-type Transistors and Diodes Enabled by High Workfunction MoOx Contacts

Abstract: The development of low-resistance source/drain contacts to transition metal dichalcogenides (TMDCs) is crucial for the realization of high-performance logic components. In particular, efficient hole contacts are required for the fabrication of p-type transistors with MoS2, a model TMDC. Previous studies have shown that the Fermi level of elemental metals is pinned close to the conduction band of MoS2, thus resulting in large Schottky barrier heights for holes with limited hole injection from the contacts. Here, we show that substoichiometric molybdenum trioxide (MoOx, x<3), a high workfunction material, acts as an efficient hole injection layer to MoS2 and WSe2. In particular, we demonstrate MoS2 p-type field-effect transistors and diodes by using MoOx contacts. We also show drastic on-current improvement for p-type WSe2 FETs with MoOx contacts over devices made with Pd contacts, which is the prototypical metal used for hole injection. The work presents an important advance in contact engineering of TMDCs and will enable future exploration of their performance limits and intrinsic transport properties.

A crystalline oxide passivation for Al2O3/AlGaN/GaN

Abstract: In situ X-ray photoelectron spectroscopy and low energy electron diffraction are performed to study the formation of a crystalline oxide on the AlGaN surface. The oxidation of the AlGaN surface is prepared by annealing and remote N2 + O2 plasma pretreatments resulting in a stable crystalline oxide. The impact of the oxide on the interface state density is studied by capacitance voltage (C-V) measurements. It is found that a remote plasma exposure at 550 °C shows the smallest frequency dispersion. Crystalline oxide formation may provide a novel passivation method for high quality AlGaN/GaN devices.

Molecular beam epitaxial growth of MoSe2 on graphite, CaF2 and graphene

Abstract: We report the structural and optical properties of molecular beam epitaxy (MBE) grown 2-dimensional (2D) material molybdenum diselenide (MoSe2) on graphite, CaF2 and epitaxial graphene. Extensive characterizations reveal that 2H- MoSe2 grows by van-der-Waals epitaxy on all 3 substrates with a preferred crystallographic orientation and a Mo:Se ratio of 1:2. Photoluminescence at room temperature (~1.56 eV) is observed in monolayer MoSe2 on both CaF2 and epitaxial graphene. The band edge absorption is very sharp, <60 meV over 3 decades. Overcoming the observed small grains by promoting mobility of Mo atoms would make MBE a powerful technique to achieve high quality 2D materials and heterostructures.

Selectivity of metal oxide atomic layer deposition on hydrogen terminated and oxidized Si(001)-(2×1) surface

Abstract: In this work, the authors used density-functional theory methods and x-ray photoelectron spectroscopy to study the chemical composition and growth rate of HfO2, Al2O3, and TiO2 thin films grown by in-situ atomic layer deposition on both oxidized and hydrogen-terminated Si(001) surfaces. The growth rate of all films is found to be lower on hydrogen-terminated Si with respect to the oxidized Si surface. However, the degree of selectivity is found to be dependent of the deposition material. TiO2 is found to be highly selective with depositions on the hydrogen terminated silicon having growth rates up to 180 times lower than those on oxidized Si, while similar depositions of HfO2 and Al2O3 resulted in growth rates more than half that on oxidized silicon. By means of density-functional theory methods, the authors elucidate the origin of the different growth rates obtained for the three different precursors, from both energetic and kinetic points of view.

High quality HfO2/p-GaSb(001) metal-oxide-semiconductor capacitors with 0.8 nm equivalent oxide thickness

Abstract: We investigate in-situ cleaning of GaSb surfaces and its effect on the electrical performance of p-type GaSb metal-oxide-semiconductor capacitor (MOSCAP) using a remote hydrogen plasma. Ultrathin HfO2 films grown by atomic layer deposition were used as a high permittivity gate dielectric. Compared to conventional ex-situ chemical cleaning methods, the in-situ GaSb surface treatment resulted in a drastic improvement in the impedance characteristics of the MOSCAPs, directly evidencing a much lower interface trap density and enhanced Fermi level movement efficiency. We demonstrate that by using a combination of ex-situ and in-situ surface cleaning steps, aggressively scaled HfO2/p-GaSb MOSCAP structures with a low equivalent oxide thickness of 0.8 nm and efficient gate modulation of the surface potential are achieved, allowing to push the Fermi level far away from the valence band edge high up into the band gap of GaSb.

Diffusion of In0.53Ga0.47As elements through hafnium oxide during post deposition annealing

Abstract: Diffusion of indium through HfO2 after post deposition annealing in N2 or forming gas environments is observed in HfO2/In0.53Ga0.47As stacks by low energy ion scattering and X-ray photo electron spectroscopy and found to be consistent with changes in interface layer thickness observed by transmission electron microscopy. Prior to post processing, arsenic oxide is detected at the surface of atomic layer deposition-grown HfO2 and is desorbed upon annealing at 350 °C. Reduction of the interfacial layer thickness and potential densification of HfO2, resulting from indium diffusion upon annealing, is confirmed by an increase in capacitance.

In situ x-ray photoelectron spectroscopy and capacitance voltage characterization of plasma treatments for Al2O3/AlGaN/GaN stacks

Abstract: We investigate the Al2O3/AlGaN/GaN metal-oxide-semiconductor structure pretreated by O2 anneals, N2 remote plasma, and forming gas remote plasma prior to atomic layer deposition of Al2O3 using in situ X-ray photoelectron spectroscopy, low energy electron diffraction, and capacitance- voltage measurements. Plasma pretreatments reduce the Ga-oxide/oxynitride formation and the interface state density, while inducing a threshold voltage instability.

Pattern transfer of hydrogen depassivation lithography patterns into silicon with atomically traceable placement and size control

Abstract: Reducing the scale of etched nanostructures below the 10 nm range eventually will require an atomic scale understanding of the masks being used in order to maintain exquisite control over both feature size and feature density. Here, the authors demonstrate a method for tracking atomically resolved and controlled structures from initial template definition through final nanostructure metrology, opening up a pathway for top–down atomic control over nanofabrication. First, hydrogen depassivation lithography is performed on hydrogen terminated Si(100) using a scanning tunneling microscope, which spatially defined chemically reactive regions. Next, atomic layer deposition of titanium dioxide produces an etch-resistant hard mask pattern on these regions. Reactive ion etching then transfers the mask pattern onto Si with pattern height of 17 nm, critical dimension of approximately 6 nm, and full-pitch down to 13 nm. The effects of linewidth, template atomic defect density, and line-edge roughness are examined in the context of controlling fabrication with arbitrary feature control, suggesting a possible critical dimension down to 2 nm on 10 nm tall features. A metrology standard is demonstrated, where the atomically resolved mask template is used to determine the size of a nanofabricated sample showing a route to image correction.

GaSb Oxide Thermal Stability Studied by Dynamic- XPS

Abstract: The thermal decomposition of the native GaSb oxides is studied using time resolved x-ray photoelectron spectroscopy with a temperature resolution of better than 1 K. The expected transfer of oxygen from Sb-O to Ga-O before the eventual desorption of all oxides is observed. However, an initial reaction resulting in the reduction of Sb2O3 along with the concurrent increase in both Ga2O3 and Sb2O4 is detected in the temperature range of 450–525 K. Using the relative changes in atomic concentrations of the chemical species observed; the initial reaction pathway is proposed.

Electronic properties of InP (001)/HfO2 (001) interface: Band offsets and oxygen dependence

Abstract: Using ab-initio methods, atomic structures and electronic properties of InP (001)/HfO2 (001) interface are studied within the framework of density functional theory. We examine the InP/HfO2 model interface electronic structures under varying oxidation conditions. The effects of indium and phosphorous concentrations on interfacial bonding, defect states, band offsets, and the thermodynamic stability at the interface are also investigated. The origin of interfacial gap states in InP (001)/HfO2 (001) interface are proposed, mainly from the P-rich oxides, which is validated by our experimental work. This highlights the importance of surface passivation prior to high-κ deposition based on the in situ spectroscopic results of atomic layer deposition of HfO2 on InP.

Silicon interfacial passivation layer chemistry for high-k/InP interfaces.

Abstract: The interfacial chemistry of thin (1 nm) silicon (Si) interfacial passivation layers (IPLs) deposited on acid-etched and native oxide InP(100) samples prior to atomic layer deposition (ALD) is investigated. The phosphorus oxides are scavenged completely from the acid-etched samples but not completely from the native oxide samples. Aluminum silicate and hafnium silicate are possibly generated upon ALD and following annealing. The thermal stability of a high-k/Si/InP (acid-etched) stack are also studied by in situ annealing to 400 and 500 °C under ultrahigh vacuum, and the aluminum oxide/Si/InP stack is the most thermally stable. An indium out-diffusion to the sample surface is observed through the Si IPL and the high-k dielectric, which may form volatile species and evaporate from the sample surface.

Digermane Deposition on Si(100) and Ge(100): from Adsorption Mechanism to Epitaxial Growth

Abstract: Controlled fabrication of nanometer-scale devices such as quantum dots and nanowires requires an understanding of the initial chemisorption mechanisms involved in epitaxial growth. Vapor phase epitaxy can provide controlled deposition when using precursors that are not reactive with the H-terminated surfaces at ambient temperatures. For instance, digermane (Ge2H6) has potential as such a precursor for Ge ALE on Si(100) surfaces at moderate temperatures; yet, its adsorption configuration and subsequent decomposition pathways are not well understood. In situ Fourier transform infrared spectroscopy and first principles calculations reveal that Ge2H6 chemisorbs through a β-hydride elimination mechanism, forming Ge2H5 and H on both Si(100)-(2 × 1) and Ge(100)-(2 × 1) surfaces, instead of the previously proposed Ge–Ge bond breaking mechanism, and subsequently decomposes into an ad-dimer. The resulting coverage of Ge after a saturation exposure is estimated to be about 0.3 monolayers. Interestingly, the decompos...

Ab Initio Study of H2 Associative Desorption on Ad-Dimer Reconstructed Si(001) and Ge(001)-(2×1) Surfaces

Abstract: We investigate the pathways of hydrogen migration and associative desorption of H2 on the Si(001) and Ge(001)-(2×1) reconstructed surfaces with adsorbed ad-dimers, using density functional theory m...

Pattern Transfer of Hydrogen Depassivation Lithography Patterns into Silicon with Atomically Traceable Placement and Size Control | NIST

Abstract: Reducing the scale of etched nanostructures below the 10 nm range eventually will require an atomic scale understanding of the masks being used in order to maintain exquisite control over both feature size and feature density. Here, the authors demonstrate a method for tracking atomically resolved and controlled structures from initial template definition through final nanostructure metrology, opening up a pathway for top–down atomic control over nanofabrication. First, hydrogen depassivation lithography is performed on hydrogen terminated Si(100) using a scanning tunneling microscope, which spatially defined chemically reactive regions. Next, atomic layer deposition of titanium dioxide produces an etch-resistant hard mask pattern on these regions. Reactive ion etching then transfers the mask pattern onto Si with pattern height of 17 nm, critical dimension of approximately 6 nm, and full-pitch down to 13 nm. The effects of linewidth, template atomic defect density, and line-edge roughness are examined in ...