Heteroepitaxial GaAs thin-films on flexible, large-area, single-crystal-like substrates for wide-ranging optoelectronic applications.

Recent advances in semiconductor based electronic devices can be attributed to the technological demands of ever increasing, application specific markets. These rapidly evolving markets for devices such as displays, wireless communication, photovoltaics, medical devices, etc. are demanding electronic devices that are increasingly thinner, smaller, lighter and flexible. High-quality, III-V epitaxial thin-films deposited on single-crystal substrates have yielded extremely high-performance, but are extremely expensive and rigid. Here we demonstrate heteroepitaxial deposition of GaAs thin-films on large-grained, single-crystal-like, biaxially-aligned, flexible, metallic substrates. We use molecular beam epitaxy (MBE) for the controlled growth of high quality GaAs layers on lattice matched Ge capped, flexible metal substrates. The structural, optical, interfacial and electrical characteristics and properties of the heteroepitaxial GaAs layers are analyzed and discussed. The results show that heteroepitaxial GaAs layers with good crystalline and optoelectronic properties can be realized for flexible, III-V based semiconductor devices. III-V materials integrated on large-grained, single-crystal-like, flexible, metallic substrates offer a potential route towards fabrication of large-area, high-performance electronic devices.

Electric-Field Emission Mechanism in Q-Carbon Field Emitters.

In this paper, we report the excellent field emission properties of Q-carbon and analyze its field emission characteristics through structural, morphological, and electronic property correlations, supported by density functional theory (DFT) simulation studies. The Q-carbon field emitters show impressive and stable field emission properties, such as a low turn-on electric field of ∼2.38 V/µm, a high emission current density of ∼33 µA/cm2, and a critical field of ∼2.44 V/µm for the transition from a linear region to the saturation region in the F-N plot. The outstanding field emission properties of Q-carbon are attributed to (i) a unique sp2/sp3 mixture in Q-carbon, (ii) sp2-bonded highly conductive amorphous carbon-rich channels inside the Q-carbon cluster, (iii) a large local field enhancement due to the local geometry and microstructure of Q-carbon, and (iv) the presence of sp2-bonded amorphous carbon regions in the composite film. The temperature-dependent field emission properties, such as extreme sensitivity and an enhancement in the emission current density with temperature, can be explained by the local density of states near the Fermi level and the excellent thermal stability of the Q-carbon field emitters. From DFT simulation studies, the computed work function and the field-enhancement factor were determined to be 3.62 eV and ∼2300, respectively, which explains the excellent field emission characteristics of Q-carbon. The obtained field emission properties, in most cases, were superior to those from other carbon/diamond-based field emitters, which will open new frontiers in field emission-based electronic applications.

Highly Stable Electrochemical Supercapacitor Performance of Self-Assembled Ferromagnetic Q-Carbon.

Novel phase Q-carbon thin films exhibit some intriguing features and have been explored for various potential applications. Herein, we report the growth of different Q-carbon structures (i.e., filaments, clusters, and microdots) by varying the laser energy density from 0.5 to 1.0 J/cm2 during pulsed laser annealing of amorphous diamond-like carbon films with different sp3-sp2 carbon compositions. These unique nano- and microstructures of Q-carbon demonstrate exceptionally stable electrochemical performance by cyclic voltammetry, galvanostatic charging-discharging, and electrochemical impedance spectroscopy for energy applications. The temperature-dependent magnetic studies (magnetization vs magnetic field and temperature) reveal the ferromagnetic nature of the Q-carbon microdots. The saturation magnetization and coercive field values decrease from 132 to 14 emu/cc and 155 to 92 Oe by increasing the temperature from 2 to 300 K, respectively. The electrochemical performances of Q-carbon filament, cluster, and microdot thin-film supercapacitors were investigated by two-electrode configurations, and the highest areal specific capacitance of ∼156 mF/cm2 was observed at a current density of 0.15 mA/cm2 in the Q-carbon microdot thin film. The Q-carbon microdot electrodes demonstrate an exceptional capacitance retention performance of ∼97.2% and Coulombic efficiency of ∼96.5% after 3000 cycles due to their expectational reversibility in the charging-discharging process. The kinetic feature of the ion diffusion associated with the charge storage property is also investigated, and small changes in equivalent series resistance of ∼9.5% and contact resistance of ∼9.1% confirm outstanding stability with active charge kinetics during the stability test. A high areal power density of ∼5.84 W/cm2 was obtained at an areal energy density of ∼0.058 W h/cm2 for the Q-carbon microdot structure. The theoretical quantum capacitance was obtained at ∼400 mF/cm2 by density functional theory calculation, which gives an idea about the overall capacitance value. The obtained areal specific capacitance, power density, and impressive long-term cyclic stability of Q-carbon thin-film microdot electrodes endorse substantial promise in high-performance supercapacitor applications.

Single-crystal-like germanium thin films on large-area, compliant, light-weight, flexible, single-crystal-like substrates.

Germanium (Ge) films were heteroepitaxially grown on flexible, large-area, single-crystal-like metallic substrates. Multiple, heteroepitaxial, buffer layers of nanoscale dimensions were deposited on the triaxially textured, single-crystal-like, thermo-mechanically processed Ni-W alloy substrates. Ge films were deposited on a CeO2-terminated, heteroepitaxial buffer stack on the metallic substrate using electron beam evaporation. X-ray diffraction θ-2θ scans showed a very strong Ge (400) peak and the full width at half-maximum (FWHM) of the Ge (400) rocking curve was 0.93°. The Ge (111) ϕ-scan showed a FWHM value ∼4°. Based on the X-ray ω-scan, ϕ-scan and (111), (110), and (001) X-ray pole-figures, the Ge film deposited on the flexible, metallic substrate had a cube-on-cube heteroepitaxial relationship with the single-crystal-like metallic substrate. Reflection-high-energy-diffraction (RHEED) patterns from the Ge layer was streaky indicative of a smooth and essentially single-crystal-like Ge film. Cross-section TEM examination revealed a sharp interface between the Ge film and the topmost buffer layer, CeO2, with a low defect density. The CeO2 layer serves as a highly compliant layer that modulates its lattice parameter to attain excellent lattice-matching to the heteroepitaxial Ge layer. Ge films grown on these flexible metal substrates exhibited electron mobilities in the range of 175-250 cm2V-1s-1. Such single-crystal-like semiconductor films on low-cost, flexible, large-area, scalable, single-crystal-like metallic substrates could potentially enable high-performance electronic devices for a range of applications.

Interface Defect Hydrogen Depassivation and Capacitance-Voltage Hysteresis of Al2O3/InGaAs Gate Stacks.

We investigate the effects of pre- and postatomic layer deposition (ALD) defect passivation with hydrogen on the trap density and reliability of Al2O3/InGaAs gate stacks. Reliability is characterized by capacitance-voltage hysteresis measurements on samples prepared using different fabrication procedures and having different initial trap densities. Despite its beneficial capability to passivate both interface and border traps, a final forming gas (H2/N2) anneal (FGA) step is correlated with a significant hysteresis. This appears to be caused by hydrogen depassivation of defects in the gate stack under bias stress, supported by the observed bias stress-induced increase of interface trap density, and strong hydrogen isotope effects on the measured hysteresis. On the other hand, intentional air exposure of the InGaAs surface prior to Al2O3 ALD increases the initial interface trap density (Dit) but considerably lowers the hysteresis.

Temperature Dependent Border Trap Response Produced by a Defective Interfacial Oxide Layer in Al2O3/InGaAs Gate Stacks.

Intentional oxidation of an As2-decapped (100) In0.57Ga0.43As substrate by additional H2O dosing during initial Al2O3 gate dielectric atomic layer deposition (ALD) increases the interface trap density (Dit), lowers the band edge photoluminescence (PL) intensity, and generates Ga-oxide detected by X-ray photoelectron spectroscopy (XPS). Aberration-corrected high resolution transmission electron microscopy (TEM) reveals formation of an amorphous interfacial layer which is distinct from the Al2O3 dielectric and which is not present without the additional H2O dosing. Observation of a temperature dependent border trap response, associated with the frequency dispersion of the accumulation capacitance and conductance of metal-oxide-semiconductor (MOS) structures, is found to be correlated with the presence of this defective interfacial layer. MOS capacitors prepared with additional H2O dosing show a notable decrease (∼20%) of accumulation dispersion over 5 kHz to 500 kHz when the measurement temperature decreases from room temperature to 77 K, while capacitors prepared with an abrupt Al2O3/InGaAs interface display little change (<2%) with temperature. Similar temperature-dependent border trap response is also observed when the (100) InGaAs surface is treated with a previously reported HCl(aq) wet cleaning procedure prior to Al2O3 ALD. These results point out the sensitivity of the temperature dependence of the border trap response in metal oxide/III-V MOS gate stacks to the presence of processing-induced interface oxide layers, which alter the dynamics of carrier trapping at defects that are not located at the semiconductor interface.

The influence of surface preparation on low temperature HfO2 ALD on InGaAs (001) and (110) surfaces.

Current logic devices rely on 3D architectures, such as the tri-gate field effect transistor (finFET), which utilize the (001) and (110) crystal faces simultaneously thus requiring passivation methods for the (110) face in order to ensure a pristine 3D surface prior to further processing. Scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), and correlated electrical measurement on MOSCAPs were utilized to compare the effects of a previously developed in situ pre-atomic layer deposition (ALD) surface clean on the InGaAs (001) and (110) surfaces. Ex situ wet cleans are very effective on the (001) surface but not the (110) surface. Capacitance voltage indicated the (001) surface with no buffered oxide etch had a higher C(max) hypothesized to be a result of poor nucleation of HfO2 on the native oxide. An in situ pre-ALD surface clean employing both atomic H and trimethylaluminum (TMA) pre-pulsing, developed by Chobpattana et al. and Carter et al. for the (001) surface, was demonstrated to be effective on the (110) surface for producing low D(it) high C(ox) MOSCAPs. Including TMA in the pre-ALD surface clean resulted in reduction of the magnitude of the interface state capacitance. The XPS studies show the role of atomic H pre-pulsing is to remove both carbon and oxygen while STM shows the role of TMA pre-pulsing is to eliminate H induced etching. Devices fabricated at 120 °C and 300 °C were compared.

Passivation of InGaAs(001)-(2 × 4) by Self-Limiting Chemical Vapor Deposition of a Silicon Hydride Control Layer.

A saturated Si-Hx seed layer for gate oxide or contact conductor ALD has been deposited via two separate self-limiting and saturating CVD processes on InGaAs(001)-(2 × 4) at substrate temperatures of 250 and 350 °C. For the first self-limiting process, a single silicon precursor, Si3H8, was dosed at a substrate temperature of 250 °C, and XPS results show the deposited silicon hydride layer saturated at about 4 monolayers of silicon coverage with hydrogen termination. STS results show the surface Fermi level remains unpinned following the deposition of the saturated silicon hydride layer, indicating the InGaAs surface dangling bonds are electrically passivated by Si-Hx. For the second self-limiting process, Si2Cl6 was dosed at a substrate temperature of 350 °C, and XPS results show the deposited silicon chloride layer saturated at about 2.5 monolayers of silicon coverage with chlorine termination. Atomic hydrogen produced by a thermal gas cracker was subsequently dosed at 350 °C to remove the Si-Cl termination by replacing with Si-H termination as confirmed by XPS, and STS results confirm the saturated Si-Hx bilayer leaves the InGaAs(001)-(2 × 4) surface Fermi level unpinned. Density function theory modeling of silicon hydride surface passivation shows an Si-Hx monolayer can remove all the dangling bonds and leave a charge balanced surface on InGaAs.

Dual passivation of intrinsic defects at the compound semiconductor/oxide interface using an oxidant and a reductant.

Studies have shown that metal oxide semiconductor field-effect transistors fabricated utilizing compound semiconductors as the channel are limited in their electrical performance. This is attributed to imperfections at the semiconductor/oxide interface which cause electronic trap states, resulting in inefficient modulation of the Fermi level. The physical origin of these states is still debated mainly because of the difficulty in assigning a particular electronic state to a specific physical defect. To gain insight into the exact source of the electronic trap states, density functional theory was employed to model the intrinsic physical defects on the InGaAs (2 × 4) surface and to model the effective passivation of these defects by utilizing both an oxidant and a reductant to eliminate metallic bonds and dangling-bond-induced strain at the interface. Scanning tunneling microscopy and spectroscopy were employed to experimentally determine the physical and electronic defects and to verify the effectiveness of dual passivation with an oxidant and a reductant. While subsurface chemisorption of oxidants on compound semiconductor substrates can be detrimental, it has been shown theoretically and experimentally that oxidants are critical to removing metallic defects at oxide/compound semiconductor interfaces present in nanoscale channels, oxides, and other nanostructures.

Dual passivation of GaAs (110) surfaces using O2/H2O and trimethylaluminum.

The nucleation and passivation of oxide deposition was studied on defect-free GaAs (110) surfaces to understand passivation of surfaces containing only III-V heterobonds. The passivation process on GaAs (110) was studied at the atomic level using scanning tunneling microscopy while the electronic structure was determined by scanning tunneling spectroscopy (STS). The bonding of the oxidant and reductant were modeled with density functional theory. To avoid Fermi level pinning during gate oxide atomic layer deposition, a dual passivation procedure was required using both a reductant, trimethylaluminum (TMA), and an oxidant, O2 or H2O. Dosing GaAs (110) with TMA resulted in the formation of an ordered complete monolayer of dimethylaluminum which passivates the group V dangling bonds but also forms metal-metal bonds with conduction band edge states. These edge states were suppressed by dosing the surface with oxidants O2 or H2O which selectively react with group III-aluminum bonds. The presence of an ordered Al monolayer with a high nucleation density was indirectly confirmed by XPS and STS.

Atomic imaging of atomic layer deposition oxide nucleation with trimethylaluminum on As-rich InGaAs(001) 2 × 4 vs Ga/In-rich InGaAs(001) 4 × 2.

Formation of a contaminant free, flat, electrically passive interface to a gate oxide such as a-Al(2)O(3) is the critical step in fabricating III-V metal oxide semiconductor field effect transistors; while the bulk oxide is amorphous, the interface may need to be ordered to prevent electrical defect formation. A two temperature in situ cleaning process is shown to produce a clean, flat group III or group V rich InGaAs surface. The dependence of initial surface reconstruction and dosing temperature of the seeding of aluminum with trimethylaluminum dosing is observed to produce an ordered unpinned passivation layer on InGaAs(001)-(4 × 2) surface at sample temperatures below 190 °C. Conversely, the InGaAs(001)-(2 × 4) surface is shown to generate an unpinned passivation layer with a seeding temperature up to 280 °C. For both reconstructions, the chemical drive force is consistent with formation of As-Al-As bonds. The optimal seed layer protects the surface from background contamination.

Scanning tunneling microscopy/spectroscopy study of atomic and electronic structures of In2O on InAs and In0.53Ga0.47As(001)-(4×2) surfaces.

Interfacial bonding geometry and electronic structures of In(2)O on InAs and In(0.53)Ga(0.47)As(001)-(4×2) have been investigated by scanning tunneling microscopy/scanning tunneling spectroscopy (STM/STS). STM images show that the In(2)O forms an ordered monolayer on both InAs and InGaAs surfaces. In(2)O deposition on the InAs(001)-(4×2) surface does not displace any surface atoms during both room temperature deposition and postdeposition annealing. Oxygen atoms from In(2)O molecules bond with trough In/Ga atoms on the surface to form a new layer of O-In/Ga bonds, which restore many of the strained trough In/Ga atoms into more bulklike tetrahedral sp(3) bonding environments. STS reveals that for both p-type and n-type clean In(0.53)Ga(0.47)As(001)-(4×2) surfaces, the Fermi level resides near the valence band maximum (VBM); however, after In(2)O deposition and postdeposition annealings, the Fermi level position is close to the VBM for p-type samples and close to the conduction band minimum for n-type samples. This result indicates that In(2)O bonding eliminates surface states within the bandgap and forms an unpinned interface when bonding with In(0.53)Ga(0.47)As/InP(001)-(4×2). Density function theory is used to confirm the experimental finding.

Atomic imaging of the monolayer nucleation and unpinning of a compound semiconductor surface during atomic layer deposition.

The reaction of trimethyl aluminum on the group III rich reconstructions of InAs(0 0 1) and In(0.53)Ga(0.47)As(0 0 1) is observed with scanning tunneling microscopy/spectroscopy. At high coverage, a self-terminated ordered overlayer is observed that provides the monolayer nucleation density required for subnanometer thick transistor gate oxide scaling and removes the surface Fermi level pinning that is present on the clean InGaAs surface. Density functional theory simulations confirm that an adsorbate-induced reconstruction is the basis of the monolayer nucleation density and passivation.

Initiation of a passivated interface between hafnium oxide and In(Ga)As(0 0 1)-(4x2).

Hafnium oxide interfaces were studied on two related group III rich semiconductor surfaces, InAs(0 0 1)-(4x2) and In(0.53)Ga(0.47)As(0 0 1)-(4x2), via two different methods: reactive oxidation of deposited Hf metal and electron beam deposition of HfO(2). The interfaces were investigated with scanning tunneling microscopy and spectroscopy (STS). Single Hf atom chemisorption sites were identified that are resistant to oxidation by O(2), but Hf islands are reactive to O(2). After e(-) beam deposition of <<1 ML of HfO(2), single chemisorption sites were identified. At low coverage (<1 ML), the n-type and p-type HfO(2)/InGaAs(0 0 1)-(4x2) interfaces show p-type character in STS, which is typical of clean InGaAs(0 0 1)-(4x2). After annealing below 200 degrees C, full coverage HfO(2)/InGaAs(0 0 1)-(4x2) (1-3 ML) has the surface Fermi level shifted toward the conduction band minimum for n-type InGaAs, but near the valence band maximum for p-type InGaAs. This is consistent with the HfO(2)/InGaAs(0 0 1)-(4x2) interface being at least partially unpinned, i.e., a low density of states in the band gap. The partially unpinned interface results from the modest strength of the bonding between HfO(2) and InGaAs(0 0 1)-(4x2) that prevents substrate atom disruption. The fortuitous structure of HfO(2) on InAs(0 0 1)-(4x2) and InGaAs(0 0 1)-(4x2) allows for the elimination of the partially filled dangling bonds on the surface, which are usually responsible for Fermi level pinning.

Electronic properties of adsorbates on GaAs(001)-c(2x8)/(2x4).

A systematic experimental and theoretical study was performed to determine the causes of oxide-induced Fermi level pinning and unpinning on GaAs(001)-c(2 x 8)/(2 x 4). Scanning tunneling spectroscopy (STS) and density functional theory (DFT) were used to study four different adsorbates' (O(2), In(2)O, Ga(2)O, and SiO) bonding to the GaAs(001)-c(2 x 8)/(2 x 4) surface. The STS results revealed that out of the four adsorbates studied, only one left the Fermi level unpinned, Ga(2)O. DFT calculations were used to elucidate the causes of the Fermi level pinning. Two distinct pinning mechanisms were identified: direct (adsorbate induced states in the band gap region) and indirect pinnings (generation of undimerized As atoms). For O(2) dissociative chemisorption onto GaAs(001)-c(2 x 8)/(2 x 4), the Fermi level pinning was only indirect, while direct Fermi level pinning was observed when In(2)O was deposited on GaAs(001)-c(2 x 8)/(2 x 4). In the case of SiO on GaAs(001)-c(2 x 8)/(2 x 4), the Fermi level pinning was a combination of the two mechanisms.

Direct and indirect causes of Fermi level pinning at the SiO/GaAs interface.

The correlation between atomic bonding sites and the electronic structure of SiO on GaAs(001)-c(2x8)/(2x4) was investigated using scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and density functional theory (DFT). At low coverage, STM images reveal that SiO molecules bond Si end down; this is consistent with Si being undercoordinated and O being fully coordinated in molecular SiO. At approximately 5% ML (monolayer) coverage, multiple bonding geometries were observed. To confirm the site assignments from STM images, DFT calculations were used to estimate the total adsorption energies of the different bonding geometries as a function of SiO coverage. STS measurements indicated that SiO pins the Fermi level midgap at approximately 5% ML coverage. DFT calculations reveal that the direct causes of Fermi level pinning at the SiO GaAs(001)-(2x4) interface are a result of either local charge buildups or the generation of partially filled dangling bonds on Si atoms.