The selective amorphization of SiGe in Si/SiGe nanostructures via a 1 MeV Si + implant was investigated, resulting in single-crystal Si nanowires (NWs) and quantum dots (QDs) encapsulated in amorphous SiGe fins and pillars, respectively. The Si NWs and QDs are formed during high-temperature dry oxidation of single-crystal Si/SiGe heterostructure fins and pillars, during which Ge diffuses along the nanostructure sidewalls and encapsulates the Si layers. The fins and pillars were then subjected to a 3 × 10 15 ions/cm 2 1 MeV Si + implant, resulting in the amorphization of SiGe, while leaving the encapsulated Si crystalline for larger, 65-nm wide NWs and QDs. Interestingly, the 26-nm diameter Si QDs amorphize, while the 28-nm wide NWs remain crystalline during the same high energy ion implant. This result suggests that the Si/SiGe pillars have a lower threshold for Si-induced amorphization compared to their Si/SiGe fin counterparts. However, Monte Carlo simulations of ion implantation into the Si/SiGe nanostructures reveal similar predicted levels of displacements per cm 3 . Molecular dynamics simulations suggest that the total stress magnitude in Si QDs encapsulated in crystalline SiGe is higher than the total stress magnitude in Si NWs, which may lead to greater crystalline instability in the QDs during ion implant. The potential lower amorphization threshold of QDs compared to NWs is of special importance to applications that require robust QD devices in a variety of radiation environments.
Thornton, Chappel S.; Tuttle, Blair; Turner, Emily; Law, Mark E.; Pantelides, Sokrates T.; Wang, George T.; Jones, Kevin S.
A recently discovered, enhanced Ge diffusion mechanism along the oxidizing interface of Si/SiGe nanostructures has enabled the formation of single-crystal Si nanowires and quantum dots embedded in a defect-free, single-crystal SiGe matrix. Here, we report oxidation studies of Si/SiGe nanofins aimed at gaining a better understanding of this novel diffusion mechanism. A superlattice of alternating Si/Si0.7Ge0.3layers was grown and patterned into fins. After oxidation of the fins, the rate of Ge diffusion down the Si/SiO2interface was measured through the analysis of HAADF-STEM images. The activation energy for the diffusion of Ge down the sidewall was found to be 1.1 eV, which is less than one-quarter of the activation energy previously reported for Ge diffusion in bulk Si. Through a combination of experiments and DFT calculations, we propose that the redistribution of Ge occurs by diffusion along the Si/SiO2interface followed by a reintroduction into substitutional positions in the crystalline Si.
The controlled fabrication of vertical, tapered, and high-aspect ratio GaN nanowires via a two-step top-down process consisting of an inductively coupled plasma reactive ion etch followed by a hot, 85% H3PO4 crystallographic wet etch is explored. The vertical nanowires are oriented in the [0001] direction and are bound by sidewalls comprising of 3362 ¯ } semipolar planes which are at a 12° angle from the [0001] axis. High temperature H3PO4 etching between 60 °C and 95 °C result in smooth semipolar faceting with no visible micro-faceting, whereas a 50 °C etch reveals a micro-faceted etch evolution. High-angle annular dark-field scanning transmission electron microscopy imaging confirms nanowire tip dimensions down to 8–12 nanometers. The activation energy associated with the etch process is 0.90 ± 0.09 eV, which is consistent with a reaction-rate limited dissolution process. The exposure of the 3362 ¯ } type planes is consistent with etching barrier index calculations. The field emission properties of the nanowires were investigated via a nanoprobe in a scanning electron microscope as well as by a vacuum field emission electron microscope. The measurements show a gap size dependent turn-on voltage, with a maximum current of 33 nA and turn-on field of 1.92 V nm−1 for a 50 nm gap, and uniform emission across the array.
Atomic precision advanced manufacturing (APAM) leverages the highly reactive nature of Si dangling bonds relative to H- or Cl-passivated Si to selectively adsorb precursor molecules into lithographically defined areas with sub-nanometer resolution. Due to the high reactivity of dangling bonds, this process is confined to ultra-high vacuum (UHV) environments, which currently limits its commercialization and broad-based appeal. In this work, we explore the use of halogen adatoms to preserve APAM-derived lithographic patterns outside of UHV to enable facile transfer into real-world commercial processes. Specifically, we examine the stability of H-, Cl-, Br-, and I-passivated Si(100) in inert N2 and ambient environments. Characterization with scanning tunneling microscopy and x-ray photoelectron spectroscopy (XPS) confirmed that each of the fully passivated surfaces were resistant to oxidation in 1 atm of N2 for up to 44 h. Varying levels of surface degradation and contamination were observed upon exposure to the laboratory ambient environment. Characterization by ex situ XPS after ambient exposures ranging from 15 min to 8 h indicated the Br– and I–passivated Si surfaces were highly resistant to degradation, while Cl–passivated Si showed signs of oxidation within minutes of ambient exposure. As a proof-of-principle demonstration of pattern preservation, a H–passivated Si sample patterned and passivated with independent Cl, Br, I, and bare Si regions was shown to maintain its integrity in all but the bare Si region post-exposure to an N2 environment. The successful demonstration of the preservation of APAM patterns outside of UHV environments opens new possibilities for transporting atomically-precise devices outside of UHV for integrating with non-UHV processes, such as other chemistries and commercial semiconductor device processes.
Parker, Tyler P.; Silva-Quinones, Dhamelyn0x S.; Wang, George T.; Teplyakov, Andrew V.
Area-selective atomic layer deposition (AS-ALD) is an appealing bottom-up fabrication technique that can produce atomic-scale device features, overcoming challenges in current industrial techniques such as edge alignment errors. TiCI4 is a common thermal ALD precursor for Ti02 thin films, which are appealing candidates for DRAM capacitors due to their excellent dielectric constants. Hydrogen and chlorine termination passivate the Si surface, allowing for selective deposition of TiCI4 onto HO-terminated areas. However, selectivity loss occurs after several ALD cycles. Ti oxide nucleates onto surface defects on Cl- and H-Si resists. Previously, the use of H-Si as an ALD resist has been studied extensively, but less work has focused on chemical forces driving nucleation, especially for Cl-Si. Here, formation of defect nuclei was investigated with selectivity loss during Ti02 ALD with TiCI4 and water on the (100) and (111) crystal surfaces of hydrogenated, chlorinated, and oxidized Si.
We demonstrate the ability to fabricate vertically stacked Si quantum dots (QDs) within SiGe nanowires with QD diameters down to 2 nm. These QDs are formed during high-temperature dry oxidation of Si/SiGe heterostructure pillars, during which Ge diffuses along the pillars' sidewalls and encapsulates the Si layers. Continued oxidation results in QDs with sizes dependent on oxidation time. The formation of a Ge-rich shell that encapsulates the Si QDs is observed, a configuration which is confirmed to be thermodynamically favorable with molecular dynamics and density functional theory. The type-II band alignment of the Si dot/SiGe pillar suggests that charge trapping on the Si QDs is possible, and electron energy loss spectra show that a conduction band offset of at least 200 meV is maintained for even the smallest Si QDs. Our approach is compatible with current Si-based manufacturing processes, offering a new avenue for realizing Si QD devices.
This project sought to develop a fundamental understanding of the mechanisms underlying a newly observed enhanced germanium (Ge) diffusion process in silicon germanium (SiGe) semiconductor nanostructures during thermal oxidation. Using a combination of oxidationdiffusion experiments, high resolution imaging, and theoretical modeling, a model for the enhanced Ge diffusion mechanism was proposed. Additionally, a nanofabrication approach utilizing this enhanced Ge diffusion mechanism was shown to be applicable to arbitrary 3D shapes, leading to the fabrication of stacked silicon quantum dots embedded in SiGe nanopillars. A new wet etch-based method for preparing 3D nanostructures for highresolution imaging free of obscuring material or damage was also developed. These results enable a new method for the controlled and scalable fabrication of on-chip silicon nanostructures with sub-10 nm dimensions needed for next generation microelectronics, including low energy electronics, quantum computing, sensors, and integrated photonics.
While it is likely practically a bad idea to shrink a transistor to the size of an atom, there is no arguing that it would be fantastic to have atomic-scale control over every aspect of a transistor – a kind of crystal ball to understand and evaluate new ideas. This project showed that it was possible to take a niche technique used to place dopants in silicon with atomic precision and apply it broadly to study opportunities and limitations in microelectronics. In addition, it laid the foundation to attaining atomic-scale control in semiconductor manufacturing more broadly.
Silva-Quinones, Dhamelyz; Butera, Robert E.; Wang, George T.; Teplyakov, Andrew V.
The reactions of boric acid and 4-fluorophenylboronic acid with H- and Cl-terminated Si(100) surfaces in solution were investigated. X-ray photoelectron spectroscopy (XPS) studies reveal that both molecules react preferentially with Cl-Si(100) and not with H-Si(100) at identical conditions. On Cl-Si(100), the reactions introduce boron onto the surface, forming a Si-O-B structure. The quantification of boron surface coverage demonstrates that the 4-fluorophenylboronic acid leads to ∼2.8 times higher boron coverage compared to that of boric acid on Cl-Si(100). Consistent with these observations, density functional theory studies show that the reaction of boric acid and 4-fluorophenylboronic acid is more favorable with the Cl- versus H-terminated surface and that on Cl-Si(100) the reaction with 4-fluorophenylboronic acid is ∼55.3 kJ/mol more thermodynamically favorable than the reaction with boric acid. The computational studies were also used to demonstrate the propensity of the overall approach to form high-coverage monolayers on these surfaces, with implications for selective-area boron-based monolayer doping.
The adsorption of AlCl3 on Si(100) and the effect of annealing the AlCl3-dosed substrate were studied to reveal key surface processes for the development of atomic-precision, acceptor-doping techniques. This investigation was performed via scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. At room temperature, AlCl3 readily adsorbed to the Si substrate dimers and dissociated to form a variety of species. Annealing the AlCl3-dosed substrate at temperatures below 450 °C produced unique chlorinated aluminum chains (CACs) elongated along the Si(100) dimer row direction. An atomic model for the chains is proposed with supporting DFT calculations. Al was incorporated into the Si substrate upon annealing at 450 °C and above, and Cl desorption was observed for temperatures beyond 450 °C. Al-incorporated samples were encapsulated in Si and characterized by secondary ion mass spectrometry (SIMS) depth profiling to quantify the Al atom concentration, which was found to be in excess of 1020 cm-3 across a ∼2.7 nm-thick δ-doped region. The Al concentration achieved here and the processing parameters utilized promote AlCl3 as a viable gaseous precursor for novel acceptor-doped Si materials and devices for quantum computing.
The III-nitride semiconductors have many attractive properties for field-emission vacuum electronics, including high thermal and chemical stability, low electron affinity, and high breakdown fields. Here, we report top-down fabricated gallium nitride (GaN)-based nanoscale vacuum electron diodes operable in air, with record ultralow turn-on voltages down to ∼0.24 V and stable high field-emission currents, tested up to several microamps for single-emitter devices. We leverage a scalable, top-down GaN nanofabrication method leading to damage-free and smooth surfaces. Gap-dependent and pressure-dependent studies provide new insights into the design of future, integrated nanogap vacuum electron devices. The results show promise for a new class of high-performance and robust, on-chip, III-nitride-based vacuum nanoelectronics operable in air or reduced vacuum.
Ekanayaka, Thilini K.; Hao, Guanhua; Mosey, Aaron; Dale, Ashley S.; Jiang, Xuanyuan; Yost, Andrew J.; Sapkota, Keshab R.; Wang, George T.; Zhang, Jian; N’Diaye, Alpha T.; Marshall, Andrew; Cheng, Ruihua; Naeemi, Azad; Xu, Xiaoshan; Dowben, Peter A.
Nonvolatile, molecular multiferroic devices have now been demonstrated, but it is worth giving some consideration to the issue of whether such devices could be a competitive alternative for solid‐state nonvolatile memory. For the Fe (II) spin crossover complex [Fe{H2B(pz)2}2(bipy)], where pz = tris(pyrazol‐1‐yl)‐borohydride and bipy = 2,2′‐bipyridine, voltage‐controlled isothermal changes in the electronic structure and spin state have been demonstrated and are accompanied by changes in conductance. Higher conductance is seen with [Fe{H2B(pz)2}2(bipy)] in the high spin state, while lower conductance occurs for the low spin state. Plausibly, there is the potential here for low‐cost molecular solid‐state memory because the essential molecular thin films are easily fabricated. However, successful device fabrication does not mean a device that has a practical value. Here, we discuss the progress and challenges yet facing the fabrication of molecular multiferroic devices, which could be considered competitive to silicon.
Mie-resonant dielectric metasurfaces are excellent candidates for both fundamental studies related to light-matter interactions and for numerous applications ranging from holography to sensing to nonlinear optics. To date, however, most applications using Mie metasurfaces utilize only weak light-matter interaction. Here, we go beyond the weak coupling regime and demonstrate for the first time strong polaritonic coupling between Mie photonic modes and intersubband (ISB) transitions in semiconductor heterostructures. Furthermore, along with demonstrating ISB polaritons with Rabi splitting as large as 10%, we also demonstrate the ability to tailor the strength of strong coupling by engineering either the semiconductor heterostructure or the photonic mode of the resonators. Unlike previous plasmonic-based works, our new all-dielectric metasurface approach to generate ISB polaritons is free from ohmic losses and has high optical damage thresholds, thereby making it ideal for creating novel and compact mid-infrared light sources based on nonlinear optics.
The attachment of dopant precursor molecules to depassivated areas of hydrogen-terminated silicon templated with a scanning tunneling microscope (STM) has been used to create electronic devices with subnanometer precision, typically for quantum physics experiments. This process, which we call atomic precision advanced manufacturing (APAM), dopes silicon beyond the solid-solubility limit and produces electrical and optical characteristics that may also be useful for microelectronic and plasmonic applications. However, scanned probe lithography lacks the throughput required to develop more sophisticated applications. Here, we demonstrate and characterize an APAM device workflow where scanned probe lithography of the atomic layer resist has been replaced by photolithography. An ultraviolet laser is shown to locally and controllably heat silicon above the temperature required for hydrogen depassivation on a nanosecond timescale, a process resistant to under- and overexposure. STM images indicate a narrow range of energy density where the surface is both depassivated and undamaged. Modeling that accounts for photothermal heating and the subsequent hydrogen desorption kinetics suggests that the silicon surface temperatures reached in our patterning process exceed those required for hydrogen removal in temperature-programmed desorption experiments. A phosphorus-doped van der Pauw structure made by sequentially photodepassivating a predefined area and then exposing it to phosphine is found to have a similar mobility and higher carrier density compared with devices patterned by STM. Lastly, it is also demonstrated that photodepassivation and precursor exposure steps may be performed concomitantly, a potential route to enabling APAM outside of ultrahigh vacuum.
Silva-Quinones, Dhamelyz; He, Chuan; Butera, Robert E.; Wang, George T.; Teplyakov, Andrew V.
The reaction of boron trichloride with the H- and Cl-terminated Si(1 0 0) surfaces was investigated to understand the interaction of this molecule with the surface for designing wet chemistry-based silicon surface doping processes using a carbon- and oxygen-free precursor. The process was followed with X-ray photoelectron spectroscopy (XPS). Within the reaction conditions investigated, the reaction is highly effective on Cl-Si(1 0 0) for temperatures below 70 °C, at which point both surfaces react with BCl3. The XPS investigation followed the formation of a B 1s peak at 193.5 eV corresponding to (B-O)x species. Even the briefest exposure to ambient conditions lead to hydroxylation of surface borochloride species. However, the Si 2p signature at 102 eV allowed for a confirmation of the formation of a direct Si-B bond. Density functional theory was utilized to supplement the analysis and identify possible major surface species resulting from these reactions. This work provides a new pathway to obtain a functionalized silicon surface with a direct Si-B bond that can potentially be exploited as a means of selective, ultra-shallow, and supersaturated doping.
Silva-Quinones, Dhamelyz; He, Chuan; Dwyer, Kevin J.; Butera, Robert E.; Wang, George T.; Teplyakov, Andrew V.
The reactivity of liquid hydrazine (N2H4) with respect to H-, Cl-, and Br-terminated Si(100) surfaces was investigated to uncover the principles of nitrogen incorporation into the interface. This process has important implications in a wide variety of applications, including semiconductor surface passivation and functionalization, nitride growth, and many others. The use of hydrazine as a precursor allows for reactions that exclude carbon and oxygen, the primary sources of contamination in processing. In this work, the reactivity of N2H4 with H- and Cl-terminated surfaces prepared by traditional solvent-based methods and with a Br-terminated Si(100) prepared in ultrahigh vacuum was compared. The reactions were studied with X-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy, and the observations were supported by computational investigations. The H-terminated surface led to the highest level of nitrogen incorporation; however, the process proceeds with increasing surface roughness, suggesting possible etching or replacement reactions. In the case of Cl-terminated (predominantly dichloride) and Br-terminated (monobromide) surfaces, the amount of nitrogen incorporation on both surfaces after the reaction with hydrazine was very similar despite the differences in preparation, initial structure, and chemical composition. Density functional theory was used to propose the possible surface structures and to analyze surface reactivity.
Physica E: Low-Dimensional Systems and Nanostructures
Addamane, S.J.; Rashidi, A.; Mansoori, A.; Dawson, N.M.; Shima, D.M.; Rotter, T.J.; Wang, George T.; Balakrishnan, G.
The optical properties of InAs quantum dashes (QDashes) grown on InP and InAs quantum dots (QDots) grown on GaAs in a dashes- or dots-in-a-well (DWELL) configuration are comparatively investigated using temperature-dependent photoluminescence (PL) measurements. The trends in PL characteristics such as exciton energy, spectral bandwidth and integrated intensity with respect to temperature are found to be distinctly dissimilar between the two systems. A rate-equation model involving exciton recombination and thermal transfer in a localized-state ensemble is used to quantitively interpret the experimental data. These results suggest that QDashes in this configuration exhibit PL properties more consistent with a lower degree of carrier localization compared to QDots. A preliminary structural analysis highlighting the shape/size differences between the two nanostructures is also presented.
Reducing ion beam damage from the focused ion beam (FIB) during fabrication of cross sections is a well-known challenge for materials characterization, especially cross sectional characterization of nanostructures. To address this, a new method has been developed for cross section fabrication enabling high resolution transmission electron microscopy (TEM) analysis of 3-D nanostructures free of surrounding material and free of damage detectable by TEM analysis. Before FIB processing, nanopillars are encapsulated in a sacrificial oxide which acts as a protective layer during FIB milling. The cross sectional TEM lamella containing the nanopillars is then mounted and thinned with some modifications to conventional FIB sample preparation that provide stability for the lamella during the following wet-chemical dip etch. The wet-chemical etch of the TEM lamella removes the sacrificial oxide layer, freeing the nanopillars from any material that would obscure TEM imaging. Both high resolution TEM and aberration corrected scanning TEM images of Si/SiGe pillars with diameters down to 30 nm demonstrate the successful application of this approach.
The attachment of dopant precursor molecules to depassivated areas of hydrogen-terminated silicon templated with a scanning tunneling microscope (STM) has been used to create electronic devices with sub-nanometer precision, typically for quantum physics demonstrations, and to dope silicon past the solid-solubility limit, with potential applications in microelectronics and plasmonics. However, this process, which we call atomic precision advanced manufacturing (APAM), currently lacks the throughput required to develop sophisticated applications because there is no proven scalable hydrogen lithography pathway. Here, we demonstrate and characterize an APAM device workflow where STM lithography has been replaced with photolithography. An ultraviolet laser is shown to locally heat silicon controllably above the temperature required for hydrogen depassivation. STM images indicate a narrow range of laser energy density where hydrogen has been depassivated, and the surface remains well-ordered. A model for photothermal heating of silicon predicts a local temperature which is consistent with atomic-scale STM images of the photo-patterned regions. Finally, a simple device made by exposing photo-depassivated silicon to phosphine is found to have a carrier density and mobility similar to that produced by similar devices patterned by STM.
Recent years have seen an explosion in research efforts discovering and understanding novel electronic and optical properties of topological quantum materials (TQMs). In this LDRD, a synergistic effort of materials growth, characterization, electrical-magneto-optical measurements, combined with density functional theory and modeling has been established to address the unique properties of TQMs. Particularly, we have carried out extensive studies in search for Majorana fermions (MFs) in TQMs for topological quantum computation. Moreover, we have focused on three important science questions. 1) How can we controllably tune the properties of TQMs to make them suitable for quantum information applications? 2) What materials parameters are most important for successfully observing MFs in TQMs? 3) Can the physical properties of TQMs be tailored by topological band engineering? Results obtained in this LDRD not only deepen our current knowledge in fundamental quantum physics but also hold great promise for advanced electronic/photonic applications in information technologies. ACKNOWLEDGEMENTS The work at Sandia National Labs was supported by a Laboratory Directed Research and Development project. Device fabrication was performed at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. We are grateful to many people inside and outside Sandia for their support and fruitful collaborations. This report describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525.
Three-dimensional chemical etch processes for III-nitride (AlGaInN) materials and devices remain significantly underdeveloped due to its apparent inertness to common wet etchants. Further knowledge and development of anisotropic and three-dimensional top-down etch techniques are needed to fully realize the potential of the III-nitrides in new electronic and photonic nano and micro device concepts. Here, we explore the etch characteristics of GaN, AlGaN, and AlN using a two-step dry plus wet etch approach, which allows for the exposure of crystal facets with non-zero and differing etch rates. We apply general geometric principles of crystallographic dissolution processes to enable the prediction of facet-determined etch structures, including high aspect ratio nanowires and nanowalls.