Showing papers by "Robert M. Wallace published in 2012"

Nitrogen doping of graphene and its effect on quantum capacitance, and a new insight on the enhanced capacitance of N-doped carbon

Abstract: Many researchers have used nitrogen (N) as a dopant and/or N-containing functional groups to enhance the capacitance of carbon electrodes of electrical double layer (EDL) capacitors. However, the physical mechanism(s) giving rise to the interfacial capacitance of the N-containing carbon electrodes is not well understood. Here, we show that the area-normalized capacitance of lightly N-doped activated graphene with similar porous structure increased from 6 μF cm−2 to 22 μF cm−2 with 0 at%, and 2.3 at% N-doping, respectively. The quantum capacitance of pristine single layer graphene and various N-doped graphene was measured and a trend of upwards shifts of the Dirac Point with increasing N concentration was observed. The increase in bulk capacitance with increasing N concentration, and the increase of the quantum capacitance in the N-doped monolayer graphene versus pristine monolayer graphene suggests that the increase in the EDL type of capacitance of many, if not all, N-doped carbon electrodes studied to date, is primarily due to the modification of the electronic structure of the graphene by the N dopant. It was further found that the quantum capacitance is closely related to the N dopant concentration and N-doping provides an effective way to increase the density of the states of monolayer graphene.

Toward the Controlled Synthesis of Hexagonal Boron Nitride Films

Abstract: Atomically smooth hexagonal boron nitride (h-BN) layers have very useful properties and thus potential applications for protective coatings, deep ultraviolet (DUV) emitters, and as a dielectric for nanoelectronics devices. In this paper, we report on the growth of h-BN by a low-pressure chemical vapor deposition (LPCVD) process using diborane and ammonia as the gas precursors. The use of LPCVD allows synthesis of h-BN with a controlled number of layers defined by the growth conditions, temperature, time, and gas partial pressure. Furthermore, few-layer h-BN was also grown by a sequential growth method, and insights into the growth mechanism are described, thus forming the basis of future growth of h-BN by atomic layer epitaxy.

Reducing extrinsic performance-limiting factors in graphene grown by chemical vapor deposition.

Abstract: Field-effect transistors fabricated on graphene grown by chemical vapor deposition (CVD) often exhibit large hysteresis accompanied by low mobility, high positive backgate voltage corresponding to the minimum conductivity point (Vmin), and high intrinsic carrier concentration (n0). In this report, we show that the mobility reported to date for CVD graphene devices on SiO2 is limited by trapped water between the graphene and SiO2 substrate, impurities introduced during the transfer process and adsorbates acquired from the ambient. We systematically study the origin of the scattering impurities and report on a process which achieves the highest mobility (μ) reported to date on large-area devices for CVD graphene on SiO2: maximum mobility (μmax) of 7800 cm2/(V·s) measured at room temperature and 12 700 cm2/(V·s) at 77 K. These mobility values are close to those reported for exfoliated graphene on SiO2 and can be obtained through the careful control of device fabrication steps including minimizing resist resi...

Atomic layer deposition of dielectrics on graphene using reversibly physisorbed ozone.

Abstract: Integration of graphene field-effect transistors (GFETs) requires the ability to grow or deposit high-quality, ultrathin dielectric insulators on graphene to modulate the channel potential. Here, we study a novel and facile approach based on atomic layer deposition through ozone functionalization to deposit high-κ dielectrics (such as Al2O3) without breaking vacuum. The underlying mechanisms of functionalization have been studied theoretically using ab initio calculations and experimentally using in situ monitoring of transport properties. It is found that ozone molecules are physisorbed on the surface of graphene, which act as nucleation sites for dielectric deposition. The physisorbed ozone molecules eventually react with the metal precursor, trimethylaluminum to form Al2O3. Additionally, we successfully demonstrate the performance of dual-gated GFETs with Al2O3 of sub-5 nm physical thickness as a gate dielectric. Back-gated GFETs with mobilities of ∼19 000 cm2/(V·s) are also achieved after Al2O3 deposi...

Metal–Graphene–Metal Sandwich Contacts for Enhanced Interface Bonding and Work Function Control

Abstract: Only a small fraction of all available metals has been used as electrode materials for carbon-based devices due to metal-graphene interface debonding problems. We report an enhancement of the bonding energy of weakly interacting metals by using a metal-graphene-metal sandwich geometry, without sacrificing the intrinsic π-electron dispersions of graphene that is usually undermined by strong metal-graphene interface hybridization. This sandwich structure further makes it possible to effectively tune the doping of graphene with an appropriate selection of metals. Density functional theory calculations reveal that the strengthening of the interface interaction is ascribed to an enhancement of interface dipole-dipole interactions. Raman scattering studies of metal-graphene-copper sandwiches are used to validate the theoretically predicted tuning of graphene doping through sandwich structures.

Uniform Wafer-Scale Chemical Vapor Deposition of Graphene on Evaporated Cu (111) Film with Quality Comparable to Exfoliated Monolayer

Abstract: This article demonstrated monolayer graphene grown on annealed Cu (111) films on standard oxidized 100-mm Si wafers with higher quality than existing reports. Large area Raman mapping indicated high uniformity (>97% coverage) of monolayer graphene with immeasurable defects (>95% defect-negligible) across the entire wafer. Key to these results is the phase transition of evaporated copper films from amorphous to (111) preferred crystalline, which resulted in subsequent growth of high quality graphene, as corroborated by X-ray diffraction and electron backscatter diffraction. Noticeably, such phase transition of the copper film was observed on a technologically ubiquitous Si wafer with a standard amorphous thermal oxide. A modified two-step etching transfer process was introduced to preserve the clean surface and electrical property of transferred monolayer graphene. The fabricated graphene field effect transistor on a flexible polyimide film achieved peak mobility over 4900 cm2/(V s) at ambient condition.

Interfacial oxide re-growth in thin film metal oxide III-V semiconductor systems

Abstract: The Al2O3/GaAs and HfO2/GaAs interfaces after atomic layer deposition are studied using in situ monochromatic x-ray photoelectron spectroscopy. Samples are deliberately exposed to atmospheric conditions and interfacial oxide re-growth is observed. The extent of this re-growth is found to depend on the dielectric material and the exposure temperature. Comparisons with previous studies show that ex situ characterization can result in misleading conclusions about the interface reactions occurring during the metal oxide deposition process.

In situ atomic layer deposition half cycle study of Al2O3 growth on AlGaN

Abstract: The atomic layer deposition (ALD) of Al2O3 on the native oxide and hydrofluoric acid treated Al0.25Ga0.75 N surface was studied using in situ X-ray photoelectron spectroscopy (XPS), after each individual “half cycle” of the ALD process. Initially, Al2O3, Ga2O3, and N-O states were detected on both surfaces at differing concentrations. During the course of the deposition process, the N-O bonds are seen to decrease to within XPS detection limits, as well as a small decrease in the Ga2O3 concentration. The Al2O3 growth rate initially is seen to be very low, indication of low reactivity between the trimethyl-aluminum molecule and the AlGaN surface.

Trimethyl-aluminum and ozone interactions with graphite in atomic layer deposition of Al2O3

Abstract: A study of the chemical interactions between the atomic layer deposition (ALD) Al2O3 precursors trimethlyaluminum (TMA) and ozone (TMA/O3) and sp2 carbon surfaces is presented. In-situ x-ray photoelectron spectroscopy is used to study these interactions, while ex-situ atomic force microscopy (AFM) is used to monitor the surface morphology. Ozone functionalization of the sp2 carbon surface is discussed and the dependence of TMA/O3 reactions over a range of ALD process conditions is examined. The utilization of a 6-cycle room temperature TMA/O3 ALD seed layer to nucleate the conformal growth of Al2O3 by TMA/H2O at 200 °C as well as the quality of such films is discussed. Two stages of ozone reactions are observed: first the ozone appears to remove adsorbed species from the graphite surface before reacting with the surface. The deposition of Al2O3 is found to be strongly dependant on the N2 purge time as well as the precursor pulse sequence. It is shown that the quality of these low temperature deposited fil...

In situ surface pre-treatment study of GaAs and In0.53Ga0.47As

Abstract: The impact of using multiple cycles of trimethyl-aluminum (TMA) prior to Al2O3 deposition on the properties of (NH4)2S treated In0.53Ga0.47As and GaAs substrates was investigated by in situ x-ray photoelectron spectroscopy. Increasing the number of TMA cycles prior to Al2O3 atomic layer deposition (ALD) was seen to decrease the concentration of As-As detected at the oxide-semiconductor interface. The impact of annealing the (NH4)2S treated GaAs surface in situ prior to ALD, in various environments, was also investigated.

Optimization of the ammonium sulfide (NH4)2S passivation process on InSb(111)A

Abstract: The passivation of the InSb semiconductor surface and related alloys is of interest due to their small bandgaps and high bulk mobilities, which make them favorable materials for use in quantum-well transistors and long wavelength optoelectronic devices. One of the most common passivation approaches is an ammonium sulfide ((NH4)2S) treatment; however, there are variations in the reported processing conditions for this procedure. This study represents a broad review of the different sulfur treatment parameters used as well as determining the optimal processing parameters in terms of length of time the sample is in the solution and the (NH4)2S concentration, by measuring the level of the residual native oxides, and surface roughness, by means of x-ray photoelectron spectroscopy and atomic force microscopy, respectively.

In‐situ X‐ray photoelectron spectroscopy of trimethyl aluminum and water half‐cycle treatments on HF‐treated and O3‐oxidized GaN substrates

Abstract: We have investigated the effect of trimethyl aluminum (TMA) and water (H2O) half-cycle treatments on HF-treated, and O3-oxidized GaN surfaces at 300 °C. The in-situ X-ray photoelectron spectroscopy results indicate no significant re-growth of Ga–O–N or self-cleaning on HF-treated and O3-oxidized GaN substrates with exposure to water and TMA. This result is different from the self-cleaning effect of Ga2O3 seen on sulfur-treated GaAs or InGaAs substrates. O3 causes aggressive oxidation of GaN substrate and direct O–N bonding compared to H2O. (© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Low-κ organic layer as a top gate dielectric for graphene field effect transistors

Abstract: We demonstrate the characteristics of dual gated graphene field effect transistors using a thin layer (∼7 nm) of parylene-C as a top-gate dielectric. Our devices exhibit good dielectric properties with minimal doping, low leakage current (∼10−6 A/cm2 at ±2 V), and a dielectric constant of ∼2.1. Additionally, Raman spectroscopy did not reveal any process induced defects after dielectric deposition. Electrical characterization performed in air showed a carrier mobility of ∼5050 cm2/Vs with hysteresis less than 30 mV during top gate operation (−2.5 V to 2.5 V) which indicates that parylene and its interface with graphene does not have a significant amount of trapped charges.

Reducing Extrinsic Performance- LimitingFactorsinGrapheneGrownby Chemical Vapor Deposition

Abstract: raphene grown by chemical vapor deposition (CVD) on Cu provides a promising pathway for the fabrica- tion of graphene field-effect transistors (FETs) on a large scale. 1 However, the per- formanceofCVDgrapheneFETsreportedto date is degraded relative to FETs fabricated using exfoliated graphene. CVD graphene FETs often exhibit strong hysteresis accom- panied with low mobility, large Vmin, and high n0. It has been reported that the pre- ABSTRACT Field-effect transistors fabri- cated on graphene grown by chemical vapor deposition (CVD) often exhibit large hysteresis accompanied by low mobility, high positive backgate voltage corresponding to the minimum conductivitypoint(Vmin),andhighintrinsiccarrier concentration (n0 ). In this report, we show that the mobility reported to date for CVD graphene devices on SiO2 is limited by trapped water between the graphene and SiO2 substrate, impurities introduced during the transfer process and adsorbates acquired from the ambient. We systematically study the origin of the scattering impurities and report on a process which achieves the highest mobility (μ )r eported to date on large-area devices for CVD graphene on SiO2 :m aximum mobility (μmax )o f 7800 cm 2 /(V3s) measured at room temperature and 12700 cm 2 /(V3s) at 77 K. These mobility values are close to those reported for exfoliated graphene on SiO2and can be obtained through the careful control of device fabrication steps including minimizing resist residue and non-aqueous transfer combined

Low temperature fabrication and characterization of nickel germanide Schottky source/drain contacts for implant-less germanium p-channel metal-oxide-semiconductor field-effect transistors

Abstract: In this work, nickel germanide Schottky contacts have been fabricated on n-type germanium (n-Ge) with an optimum barrier height of 0.63 eV. For rapid thermal annealing (RTA) temperatures above 300 °C, all phases of nickel and germanium convert to nickel mono-germanide (NiGe). However, higher RTA temperatures are also found to cause agglomeration of the NiGe phase and higher leakage current. So, the optimum temperature for Schottky-based source/drain contact formation on n-Ge is ∼300 °C, where the nickel mono-germanide phase is formed but without phase agglomeration.

Investigation of interfacial oxidation control using sacrificial metallic Al and La passivation layers on InGaAs

Abstract: The ability of metallic Al and La interlayers to control the oxidation of InGaAs substrates is examined by monochromatic x-ray photoelectron spectroscopy (XPS) and compared to the interfacial chemistry of atomic layer deposition (ALD) of Al2O3 directly on InGaAs surfaces. Al and La layers were deposited by electron-beam and effusion cell evaporators, respectively, on In0.53Ga0.47As samples with and without native oxides present. It was found that both metals are extremely efficient at scavenging oxygen from III–V native oxides, which are removed below XPS detection limits prior to ALD growth. However, metallic Ga/In/As species are simultaneously observed to form at the semiconductor–metal interface. Upon introduction of the samples to the ALD chamber, these metal bonds are seen to oxidize, leading to Ga/In–O bond growth that cannot be controlled by subsequent trimethyl-aluminum (TMA) exposures. Deposition on an oxide-free InGaAs surface results in both La and Al atoms displacing group III atoms near the s...

In-situ studies of III-V surfaces and high-k atomic layer deposition

Abstract: Atomic layer deposition (ALD) of high dielectric constant (high-k) materials for ULSI technologies is now widely adopted in Si-based CMOS production. Extending the scaling of integrated circuit technology has now resulted in the investigation of transistors incorporating alternative channel materials, such as III-V compounds. The control of the interfacial chemistry between a high-k dielectric and III-V materials presents a formidable challenge compared to that surmounted by Si-based technologies. The bonding configuration is obviously more complicated for a compound semiconductor, and thus an enhanced propensity to form interfacial defects is anticipated, as well as the need for surface passivation methods to mitigate such defects. In this work, we outline our recent results using in-situ methods to study the ALD high-k/III-V interface. We begin by briefly summarizing our results for III-As compounds, and then further discuss recent work on III-P and III-Sb compounds. While arsenides are under consideration for nMOS devices, antimonides are of interest for pMOS. InP is under consideration for quantum well channel MOS structures in order to serve as a better nMOS channel interface. In all cases, a high-k dielectric interface is employed to limit off-state tunneling current leakage.

Uniform wafer-scale synthesis of graphene on evaporated Cu (111) film with quality comparable to exfoliated monolayer

Abstract: Monolayer graphene has been grown on crystallized Cu (111) films on standard oxidized Si 100 mm wafers. The monolayer graphene demonstrates high uniformity (>97% coverage), with immeasurable defects (>95% defect-negligible) across the entire wafer. Key to these results is the phase transition of evaporated copper films from amorphous to crystalline at the growth temperature as corroborated by X-ray diffraction and electron backscatter diffraction. Noticeably, phase transition of copper film is observed on technologically ubiquitous oxidized Si wafer where the oxide is a standard amorphous thermal oxide. Ion mass spectroscopy indicates that the copper films can be purposely hydrogen-enriched during a hydrogen anneal which subsequently affords graphene growth with a sole carbonaceous precursor for low defect densities. Owing to the strong hexagonal lattice match, the graphene domains align to the Cu (111) domains, suggesting a pathway for increasing the graphene grains by maximizing the copper grain sizes. Fabricated graphene transistors on a flexible polyimide film yield a peak carrier mobility ~4,930 cm2/Vs.

High-resolution characterization of activated graphene for supercapacitor applications

Abstract: Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 – August 2, 2012.