Showing papers by "Robert M. Wallace published in 2015"

High-K materials and metal gates for CMOS applications

Abstract: The scaling of complementary metal oxide semiconductor (CMOS) transistors has led to the silicon dioxide layer used as a gate dielectric becoming so thin that the gate leakage current becomes too large. This led to the replacement of SiO2 by a physically thicker layer of a higher dielectric constant or ‘high-K’ oxide such as hafnium oxide. Intensive research was carried out to develop these oxides into high quality electronic materials. In addition, the incorporation of Ge in the CMOS transistor structure has been employed to enable higher carrier mobility and performance. This review covers both scientific and technological issues related to the high-K gate stack – the choice of oxides, their deposition, their structural and metallurgical behaviour, atomic diffusion, interface structure, their electronic structure, band offsets, electronic defects, charge trapping and conduction mechanisms, reliability, mobility degradation and oxygen scavenging to achieve the thinnest oxide thicknesses. The high K oxides were implemented in conjunction with a replacement of polycrystalline Si gate electrodes with metal gates. The strong metallurgical interactions between the gate electrodes and the HfO2 which resulted an unstable gate threshold voltage resulted in the use of the lower temperature ‘gate last’ process flow, in addition to the standard ‘gate first’ approach. Work function control by metal gate electrodes and by oxide dipole layers is discussed. The problems associated with high K oxides on Ge channels are also discussed.

Atomically thin resonant tunnel diodes built from synthetic van der Waals heterostructures

Abstract: Vertical integration of two-dimensional van der Waals materials is predicted to lead to novel electronic and optical properties not found in the constituent layers. Here, we present the direct synthesis of two unique, atomically thin, multi-junction heterostructures by combining graphene with the monolayer transition-metal dichalcogenides: molybdenum disulfide (MoS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2). The realization of MoS2-WSe2-graphene and WSe2-MoS2-graphene heterostructures leads to resonant tunnelling in an atomically thin stack with spectrally narrow, room temperature negative differential resistance characteristics.

Highly Scalable, Atomically Thin WSe2 Grown via Metal–Organic Chemical Vapor Deposition

Abstract: Tungsten diselenide (WSe2) is a two-dimensional material that is of interest for next-generation electronic and optoelectronic devices due to its direct bandgap of 1.65 eV in the monolayer form and excellent transport properties. However, technologies based on this 2D material cannot be realized without a scalable synthesis process. Here, we demonstrate the first scalable synthesis of large-area, mono and few-layer WSe2 via metal–organic chemical vapor deposition using tungsten hexacarbonyl (W(CO)6) and dimethylselenium ((CH3)2Se). In addition to being intrinsically scalable, this technique allows for the precise control of the vapor-phase chemistry, which is unobtainable using more traditional oxide vaporization routes. We show that temperature, pressure, Se:W ratio, and substrate choice have a strong impact on the ensuing atomic layer structure, with optimized conditions yielding >8 μm size domains. Raman spectroscopy, atomic force microscopy (AFM), and cross-sectional transmission electron microscopy (...

Manganese Doping of Monolayer MoS2: The Substrate Is Critical

Abstract: Substitutional doping of transition metal dichalcogenides (TMDs) may provide routes to achieving tunable p–n junctions, bandgaps, chemical sensitivity, and magnetism in these materials. In this study, we demonstrate in situ doping of monolayer molybdenum disulfide (MoS2) with manganese (Mn) via vapor phase deposition techniques. Successful incorporation of Mn in MoS2 leads to modifications of the band structure as evidenced by photoluminescence and X-ray photoelectron spectroscopy, but this is heavily dependent on the choice of substrate. We show that inert substrates (i.e., graphene) permit the incorporation of several percent Mn in MoS2, while substrates with reactive surface terminations (i.e., SiO2 and sapphire) preclude Mn incorporation and merely lead to defective MoS2. The results presented here demonstrate that tailoring the substrate surface could be the most significant factor in substitutional doping of TMDs with non-TMD elements.

Surface Defects on Natural MoS2

Abstract: Transition metal dichalcogenides (TMDs) are being considered for a variety of electronic and optoelectronic devices such as beyond complementary metal-oxide-semiconductor (CMOS) switches, light-emitting diodes, solar cells, as well as sensors, among others. Molybdenum disulfide (MoS2) is the most studied of the TMDs in part because of its availability in the natural or geological form. The performance of most devices is strongly affected by the intrinsic defects in geological MoS2. Indeed, most sources of current transition metal dichalcogenides have defects, including many impurities. The variability in the electrical properties of MoS2 across the surface of the same crystal has been shown to be correlated with local variations in stoichiometry as well as metallic-like and structural defects. The presence of impurities has also been suggested to play a role in determining the Fermi level in MoS2. The main focus of this work is to highlight a number of intrinsic defects detected on natural, exfoliated MoS...

Impurities and Electronic Property Variations of Natural MoS2 Crystal Surfaces.

Abstract: Room temperature X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICPMS), high resolution Rutherford backscattering spectrometry (HR-RBS), Kelvin probe method, and scanning tunneling microscopy (STM) are employed to study the properties of a freshly exfoliated surface of geological MoS2 crystals. Our findings reveal that the semiconductor 2H-MoS2 exhibits both n- and p-type behavior, and the work function as measured by the Kelvin probe is found to vary from 4.4 to 5.3 eV. The presence of impurities in parts-per-million (ppm) and a surface defect density of up to 8% of the total area could explain the variation of the Fermi level position. High resolution RBS data also show a large variation in the MoSx composition (1.8 < x < 2.05) at the surface. Thus, the variation in the conductivity, the work function, and stoichiometry across small areas of MoS2 will have to be controlled during crystal growth in order to provide high quality uniform materials for future device fa...

Surface oxidation energetics and kinetics on MoS2 monolayer

Abstract: In this work, surface oxidation of monolayer MoS2 (one of the representative semiconductors in transition-metal dichalcogenides) has been investigated using density functional theory method. Oxygen interaction with MoS2 shows that, thermodynamically, the surface tends to be oxidized. However, the dissociative absorption of molecular oxygen on the MoS2 surface is kinetically limited due to the large energy barrier at low temperature. This finding elucidates the air stability of MoS2 surface in the atmosphere. Furthermore, the presence of defects significantly alters the surface stability and adsorption mechanisms. The electronic properties of the oxidized surface have been examined as a function of oxygen adsorption and coverage as well as substitutional impurities. Our results on energetics and kinetics of oxygen interaction with the MoS2 monolayer are useful for the understanding of surface oxidation, air stability, and electronic properties of transition-metal dichalcogenides at the atomic scale.

HfSe2 Thin Films: 2D Transition Metal Dichalcogenides Grown by Molecular Beam Epitaxy

Abstract: In this work, we demonstrate the growth of HfSe2 thin films using molecular beam epitaxy. The relaxed growth criteria have allowed us to demonstrate layered, crystalline growth without misfit dislocations on other 2D substrates such as highly ordered pyrolytic graphite and MoS2. The HfSe2 thin films exhibit an atomically sharp interface with the substrates used, followed by flat, 2D layers with octahedral (1T) coordination. The resulting HfSe2 is slightly n-type with an indirect band gap of ∼1.1 eV and a measured energy band alignment significantly different from recent DFT calculations. These results demonstrate the feasibility and significant potential of fabricating 2D material based heterostructures with tunable band alignments for a variety of nanoelectronic and optoelectronic applications.

Comprehensive structural and optical characterization of MBE grown MoSe2 on graphite, CaF2 and graphene

Abstract: We report the structural and optical properties of a 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 three 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 three decades. Overcoming the observed small grains by promoting mobility of Mo adatoms would make MBE a powerful technique to achieve high quality 2D materials and heterostructures.

HfO2 on UV–O3 exposed transition metal dichalcogenides: interfacial reactions study

Abstract: The surface chemistry of MoS2, WSe2 and MoSe2 upon ultraviolet (UV)?O3 exposure was studied in situ by x-ray photoelectron spectroscopy (XPS). Differences in reactivity of these transition metal dichalcogenides (TMDs) towards oxidation during UV?O3 were observed and correlated with density functional theory calculations. Also, sequential HfO2 depositions were performed by atomic layer deposition (ALD) while the interfacial reactions were monitored by XPS. It is found that the surface oxides generated on MoSe2 and WSe2 during UV?O3 exposure were reduced by the ALD process (?self-cleaning effect?). The effectiveness of the oxide reduction on these TMDs is discussed and correlated with the HfO2 film uniformity.

In situ TEM characterization of shear-stress-induced interlayer sliding in the cross section view of molybdenum disulfide.

Abstract: The experimental study of interlayer sliding at the nanoscale in layered solids has been limited thus far by the incapability of mechanical and imaging probes to simultaneously access sliding interfaces and overcome through mechanical stimulus the van der Waals and Coulombic interactions holding the layers in place. For this purpose, straightforward methods were developed to achieve interlayer sliding in molybdenum disulfide (MoS2) while under observation within a transmission electron microscope. A method to manipulate, tear, and slide free-standing atomic layers of MoS2 is demonstrated by electrostatically coupling it to an oxidized tungsten probe attached to a micromanipulator at a bias above ±7 V. A first-principles model of a MoS2 bilayer polarized by a normal electric field of 5 V/nm, emanating from the tip, demonstrates the appearance of a periodic negative sliding potential energy barrier when the layers slide into the out-of-registry stacking configuration, hinting at electrostatic gating as a me...

Al2O3 on Black Phosphorus by Atomic Layer Deposition: An in Situ Interface Study.

Abstract: In situ “half cycle” atomic layer deposition (ALD) of Al2O3 was carried out on black phosphorus (“black-P”) surfaces with modified phosphorus oxide concentrations. X-ray photoelectron spectroscopy is employed to investigate the interfacial chemistry and the nucleation of the Al2O3 on black-P surfaces. This work suggests that exposing a sample that is initially free of phosphorus oxide to the ALD precursors does not result in detectable oxidation. However, when the phosphorus oxide is formed on the surface prior to deposition, the black-P can react with both the surface adventitious oxygen contamination and the H2O precursor at a deposition temperature of 200 °C. As a result, the concentration of the phosphorus oxide increases after both annealing and the atomic layer deposition process. The nucleation rate of Al2O3 on black-P is correlated with the amount of oxygen on samples prior to the deposition. The growth of Al2O3 follows a “substrate inhibited growth” behavior where an incubation period is required...

GaN as an interfacial passivation layer: tuning band offset and removing fermi level pinning for III-V MOS devices.

Abstract: The use of an interfacial passivation layer is one important strategy for achieving a high quality interface between high-k and III–V materials integrated into high-mobility metal–oxide–semiconductor field-effect transistor (MOSFET) devices. Here, we propose gallium nitride (GaN) as the interfacial layer between III–V materials and hafnium oxide (HfO2). Utilizing first-principles calculations, we explore the structural and electronic properties of the GaN/HfO2 interface with respect to the interfacial oxygen contents. In the O-rich condition, an O8 interface (eight oxygen atoms at the interface, corresponding to 100% oxygen concentration) displays the most stability. By reducing the interfacial O concentration from 100 to 25%, we find that the interface formation energy increases; when sublayer oxygen vacancies exist, the interface becomes even less stable compared with O8. The band offset is also observed to be highly dependent on the interfacial oxygen concentration. Further analysis of the electronic s...

Low temperature synthesis of graphite on Ni films using inductively coupled plasma enhanced CVD

Abstract: Controlled synthesis of graphite at low temperatures is a desirable process for a number of applications. Here, we present a study on the growth of thin graphite films on polycrystalline Ni films at low temperatures, about 380 °C, using inductively coupled plasma enhanced chemical vapor deposition. Raman analysis shows that the grown graphite films are of good quality as determined by a low ID/IG ratio, ∼0.43, for thicknesses ranging from a few layers of graphene to several nanometer thick graphitic films. The growth of graphite films was also studied as a function of time, precursor gas pressure, hydrogen concentration, substrate temperature and plasma power. We found that graphitic films can be synthesized on polycrystalline thin Ni films on SiO2/Si substrates after only 10 seconds at a substrate temperature as low as 200 °C. The amount of hydrogen radicals, adjusted by changing the hydrogen to methane gas ratio and pressure, was found to dramatically affect the quality of graphite films due to their dual role as a catalyst and an etchant. We also find that a plasma power of about 50 W is preferred in order to minimize plasma induced graphite degradation.

Phase stability of transition metal dichalcogenide by competing ligand field stabilization and charge density wave

Abstract: Transition metal dichalcogenides (TMDs) have been investigated extensively for potential application as device materials in recent years. TMDs are found to be stable in trigonal prismatic (H), octahedral (T), or distorted octahedral (Td) coordination of the transition metal. However, the detailed understanding of stabilities of TMDs in a particular phase is lacking. In this work, the detailed TMD phase stability using first-principles calculations based on density functional theory (DFT) has been investigated to clarify the mechanism of phase stabilities of TMDs, consistent with the experimental observation. Our results indicate that the phase stability of TMDs can be explained considering the relative strength of two competing mechanisms: ligand field stabilization of d-orbitals corresponding to transition metal coordination geometry, and charge density wave (CDW) instability accompanied by a periodic lattice distortion (PLD) causing the phase transition in particular TMDs.

A comparative study of atomic layer deposition of Al 2 O 3 and HfO 2 on AlGaN/GaN

Abstract: The atomic layer depositions of Al2O3 and HfO2 on AlGaN/GaN were systematically studied. The band alignments of Al2O3/AlGaN and HfO2/AlGaN were investigated using in situ X-ray photoelectron spectroscopy. A conduction band offset of 1.8 and 1.1 eV were observed for Al2O3/AlGaN and HfO2/AlGaN, respectively. The Al2O3 and HfO2 dielectric layers were found to reduce the leakage current as expected with respect to metal/AlGaN/GaN Schottky diodes, but neither changes the surface states of AlGaN. The positive ionized surface donor states density and average interface state density (D it ) below the AlGaN conduction band edge (0.34 < E C − E T < 0.50 eV), extracted from capacitance voltage (C–V) curves, were ~5 × 1013 cm−2 and 1.1 × 1014 cm−2 eV−1, respectively.

In situ plasma enhanced atomic layer deposition half cycle study of Al2O3 on AlGaN/GaN high electron mobility transistors

Abstract: A half cycle study of plasma enhanced atomic layer deposited (PEALD) Al2O3 on AlGaN is investigated using in situ X-ray photoelectron spectroscopy, low energy ion scattering, and ex situ electrical characterizations. A faster nucleation or growth is detected from PEALD relative to purely thermal ALD using an H2O precursor. The remote O2 plasma oxidizes the AlGaN surface slightly at the initial stage, which passivates the surface and reduces the OFF-state leakage. This work demonstrates that PEALD is a useful strategy for Al2O3 growth on AlGaN/GaN devices.

Seeding atomic layer deposition of alumina on graphene with yttria.

Abstract: Integrating graphene into nanoelectronic device structure requires interfacing graphene with high-κ dielectric materials. However, the dewetting and thermal instability of dielectric layers on top of graphene makes fabricating a pinhole-free, uniform, and conformal graphene/dielectric interface challenging. Here, we demonstrate that an ultrathin layer of high-κ dielectric material Y2O3 acts as an effective seeding layer for atomic layer deposition of Al2O3 on graphene. Whereas identical Al2O3 depositions lead to discontinuous film on bare graphene, the Y2O3 seeding layer yields uniform and conformal films. The morphology of the Al2O3 film is characterized by atomic force microscopy and transmission electron microscopy. C-1s X-ray photoemission spectroscopy indicates that the underlying graphene remains intact following Y2O3 seed and Al2O3 deposition. Finally, photoemission measurements of the graphene/SiO2/Si, Y2O3/graphene/SiO2, and Al2O3/Y2O3/graphene/SiO2 interfaces indicate n-type doping of graphene w...

In-situ XPS study of ALD ZnO passivation of p-In 0.53 Ga 0.47 As

Abstract: The effects of ALD ZnO passivation of ammonium hydroxide cleaned p-In0.53Ga0.47As is studied in detail with in-situ x-ray photoelectron spectroscopy (XPS), and metal-oxide-semiconductor capacitors (MOSCAPs) are fabricated in order to judge the effectiveness of ZnO as a passivation layer. Diethylzinc (DEZ) and water are used as precursors. Multiple DEZ pulses are used in the first ALD cycle in order to determine the oxide cleanup ability of DEZ. XPS results indicate that DEZ can chemically reduce Ga3+ and As5+ to Ga1+ and As3+ respectively, with the majority of change occurring before the first water pulse. DEZ is found to have minimal oxide cleanup ability, with the overall the amount of As oxide reduced by approximately 15% and Ga oxide remaining unchanged. ZnO passivated MOSCAPs with HfO2 dielectric show significant improvement over MOSCAPs without ZnO passivation. Accumulation frequency dispersion, hysteresis and D it are all reduced dramatically.

Oxidation of GaSb(100) and its Control Studied by Scanning Tunneling Microscopy and Spectroscopy

Abstract: Atomic-scale knowledge and control of oxidation of GaSb(100), which is a potential interface for energy-efficient transistors, are still incomplete, largely due to an amorphous structure of GaSb(100) oxides. We elucidate these issues with scanning-tunneling microscopy and spectroscopy. The unveiled oxidation-induced building blocks cause defect states above Fermi level around the conduction-band edge. By interconnecting the results to previous photoemission findings, we suggest that the oxidation starts with substituting second-layer Sb sites by oxygen. Adding small amount of indium on GaSb(100), resulting in a (4 × 2)-In reconstruction, before oxidation produces a previously unreported, crystalline oxidized layer of (1 × 3)-O free of gap states.

Atomically Traceable Nanostructure Fabrication.

Abstract: Reducing the scale of etched nanostructures below the 10 nm range eventually will require an atomic scale understanding of the entire fabrication process being used in order to maintain exquisite control over both feature size and feature density. Here, we 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. Hydrogen depassivation lithography is the first step of the nanoscale fabrication process followed by selective atomic layer deposition of up to 2.8 nm of titania to make a nanoscale etch mask. Contrast with the background is shown, indicating different mechanisms for growth on the desired patterns and on the H passivated background. The patterns are then transferred into the bulk using reactive ion etching to form 20 nm tall nanostructures with linewidths down to ~6 nm. To illustrate the limitations of this process, arrays of holes and lines are fabricated. The various nanofabrication process steps are performed at disparate locations, so process integration is discussed. Related issues are discussed including using fiducial marks for finding nanostructures on a macroscopic sample and protecting the chemically reactive patterned Si(100)-H surface against degradation due to atmospheric exposure.

Invited) Excellent Wetting Behavior of Yttria on 2D Materials

Abstract: The integration of two-dimensional materials into nanoelectronic devices requires contact with high-κ dielectric For better performance, it is indispensable to grow uniform and conformal dielectric materials In this paper, we show the excellent wetting behavior of yttrium oxide (yttria, Y2O3) thin films on graphene using several interface and surface science techniques The uniformity of the Y2O3 was characterized using scanning tunneling microscopy, atomic force microscopy, transmission electron microscopy, and low energy ion scattering Photoemission was used to investigate the surface chemistry and the charge doping level of graphene by evaluating the C 1s core level Furthermore, the favorable wetting behavior of yttria is exploited as an effective buffer layer for atomic layer deposition of Al2O3 on non-functionalized graphene surface

Materials Genome—Article

Abstract: Given the demand for constantly scaling micro- electronic devices to ever smaller dimensions, a SiO2 gate dielectric was substituted with a higher dielectric-constant material, Hf(Zr)O2, in order to minimize current leakage through dielectric thin film. However, upon interfacing with high dielectric constant (high-κ) dielectrics, the electron mobility in the conventional Si channel degrades due to Coulomb scattering, surface-roughness scattering, remote- phonon scattering, and dielectric-charge trapping. III-V and Ge are two promising candidates with superior mobility over Si. Nevertheless, Hf(Zr)O2/III-V(Ge) has much more complicated interface bonding than Si-based interfaces. Successful fabrication of a high-quality device critically depends on understanding and engineering the bonding confi gurations at Hf(Z r)O2/III-V(Ge) interfaces for the optimal design of device interfaces. Thus, an accurate atomic insight into the interface bonding and mechanism of interface gap states formation becomes essential. Here, we utilize first- principle calculations to investigate the interface between HfO2 and GaAs. Our study shows that As—As dimer bonding, Ga partial oxidation (between 3+ and 1+) and Ga— dangling bonds constitute the major contributions to gap states. These findings provide insightful guidance for optimum interface passivation.