Bismuth trichloride as a molecular precursor for silicon doping

Dopant impurity species can be incorporated into the silicon (001) surface via the adsorption and dissociation of simple precursor molecules. Examples include phosphine (PH3), arsine (AsH3), and diborane (B2H6) for the incorporation of phosphorus, arsenic, and boron, respectively. Through exploitation of precursor surface chemistry, the spatial locations of these incorporated dopants can be controlled at the atomic scale via the patterning of a hydrogen lithographic resist layer using scanning tunneling microscopy (STM). There is strong interest in the spatial control of bismuth atoms incorporated into silicon for quantum technological applications; however, there is currently no known precursor for the incorporation of bismuth that is compatible with this STM-based lithographic method. Here, we explore the precursor chemistry (adsorption, diffusion, and dissociation) of bismuth trichloride (BiCl3) on Si(001). We show atomic-resolution STM images of BiCl3 exposed Si(001) surfaces at low coverage and combine this with density functional theory calculations to produce a model of the surface processes and the observed features. Our results show that, at room temperature, BiCl3 completely dissociates to produce bismuth ad-atoms, ad-dimers, and surface-bound chlorine, and we explain how BiCl3 is a strong candidate for a bismuth precursor compound compatible with lithographic patterning at the sub-nanometer scale

C-reactive protein elevation predicts in-hospital deterioration after aneurysmal subarachnoid hemorrhage: a retrospective observational study.

BACKGROUND There is increasing evidence that inflammation plays a role in the pathogenesis of aneurysmal subarachnoid hemorrhage (aSAH) and in the development of delayed cerebral ischemia (DCI). However, the assessment and interpretation of classically defined inflammatory parameters is difficult in aSAH patients. The objective of this study was to investigate the relationship between easily assessable findings (hyperventilation, fever, white blood cell count (WBC), and C-reactive protein (CRP)) and the occurrence of DCI and unfavorable neurological outcome at discharge in aSAH patients. METHODS Retrospective analysis of prospectively collected data from a single center cohort. We evaluated the potential of clinical signs of inflammation (hyperventilation, fever) and simple inflammatory laboratory parameters CRP and WBC to predict unfavorable outcomes at discharge and DCI in a multivariate analysis. A cutoff value for CRP was calculated by Youden's J statistic. Outcome was measured using the modified Rankin score at discharge, with an unfavorable outcome defined as modified Rankin scale (mRS) > 3. RESULTS We included 97 consecutive aSAH patients (63 females, 34 males, mean age 58 years) in the analysis. Twenty-one (22%) had major disability or died by the time of hospital discharge. Among inflammatory parameters, CRP over 100 mg/dl on day 2 was an independent predictor for worse neurological outcome at discharge. The average C-reactive protein level in the first 14 days was higher in patients with a worse neurological outcome (96.6, SD 48.3 vs 56.3 mg/dl, SD 28.6) in the first 14 days after aSAH. C-reactive protein on day 2 was an indicator of worse neurological outcome. No inflammatory parameter was an independent predictor of DCI. After multivariate adjustment, DCI, increased age, and more than 1 day of mechanical ventilation were significant predictors of worse neurological outcome. CONCLUSIONS Early elevated CRP levels were a significant predictor of worse neurological outcome at hospital discharge and may be a useful marker of later deterioration in aSAH

Room Temperature Incorporation of Arsenic Atoms into the Germanium (001) Surface**

Germanium has emerged as an exceptionally promising material for spintronics and quantum information applications, with significant fundamental advantages over silicon. However, efforts to create atomic-scale devices using donor atoms as qubits have largely focused on phosphorus in silicon. Positioning phosphorus in silicon with atomic-scale precision requires a thermal incorporation anneal, but the low success rate for this step has been shown to be a fundamental limitation prohibiting the scale-up to large-scale devices. Here, we present a comprehensive study of arsine (AsH3) on the germanium (001) surface. We show that, unlike any previously studied dopant precursor on silicon or germanium, arsenic atoms fully incorporate into substitutional surface lattice sites at room temperature. Our results pave the way for the next generation of atomic-scale donor devices combining the superior electronic properties of germanium with the enhanced properties of arsine/germanium chemistry that promises scale-up to large numbers of deterministically placed qubits

Room Temperature Incorporation of Arsenic Atoms into the Germanium (001) Surface

Germanium has emerged as an exceptionally promising material for spintronics and quantum information applications, with significant fundamental advantages over silicon. However, efforts to create atomic-scale devices using donor atoms as qubits have largely focused on phosphorus in silicon. Positioning phosphorus in silicon with atomic-scale precision requires a thermal incorporation anneal, but the low success rate for this step has been shown to be a fundamental limitation prohibiting the scale-up to large-scale devices. Here, we present a comprehensive study of arsine (AsH3) on the germanium (001) surface. We show that, unlike any previously studied dopant precursor on silicon or germanium, arsenic atoms fully incorporate into substitutional surface lattice sites at room temperature. Our results pave the way for the next generation of atomic-scale donor devices combining the superior electronic properties of germanium with the enhanced properties of arsine/germanium chemistry that promises scale-up to large numbers of deterministically placed qubits

Single-Atom Control of Arsenic Incorporation in Silicon for High-Yield Artificial Lattice Fabrication

Artificial lattices constructed from individual dopant atoms within a semiconductor crystal hold promise to provide novel materials with tailored electronic, magnetic, and optical properties. These custom engineered lattices are anticipated to enable new, fundamental discoveries in condensed matter physics and lead to the creation of new semiconductor technologies including analog quantum simulators and universal solid-state quantum computers. In this work, we report precise and repeatable, substitutional incorporation of single arsenic atoms into a silicon lattice. We employ a combination of scanning tunnelling microscopy hydrogen resist lithography and a detailed statistical exploration of the chemistry of arsine on the hydrogen terminated silicon (001) surface, to show that single arsenic dopants can be deterministically placed within four silicon lattice sites and incorporated with 97$\pm$2% yield. These findings bring us closer to the ultimate frontier in semiconductor technology: the deterministic assembly of atomically precise dopant and qubit arrays at arbitrarily large scales

Adsorption and Thermal Decomposition of Triphenyl Bismuth on Silicon (001)

We investigate the adsorption and thermal decomposition of triphenyl bismuth (TPB) on the silicon (001) surface using atomic-resolution scanning tunneling microscopy, synchrotron-based X-ray photoelectron spectroscopy, and density functional theory calculations. Our results show that the adsorption of TPB at room temperature creates both bismuth–silicon and phenyl–silicon bonds. Annealing above room temperature leads to increased chemical interactions between the phenyl groups and the silicon surface, followed by phenyl detachment and bismuth subsurface migration. The thermal decomposition of the carbon fragments leads to the formation of silicon carbide at the surface. This chemical understanding of the process allows for controlled bismuth introduction into the near surface of silicon and opens pathways for ultra-shallow doping approaches

Bottom-up assembly of metallic germanium

Extending chip performance beyond current limits of miniaturisation requires new materials and functionalities that integrate well with the silicon platform. Germanium fits these requirements and has been proposed as a high-mobility channel material, a light emitting medium in silicon-integrated lasers, and a plasmonic conductor for bio-sensing. Common to these diverse applications is the need for homogeneous, high electron densities in three-dimensions (3D). Here we use a bottom-up approach to demonstrate the 3D assembly of atomically sharp doping profiles in germanium by a repeated stacking of two-dimensional (2D) high-density phosphorus layers. This produces high-density (1019 to 1020 cm−3) low-resistivity (10−4Ω · cm) metallic germanium of precisely defined thickness, beyond the capabilities of diffusion-based doping technologies. We demonstrate that free electrons from distinct 2D dopant layers coalesce into a homogeneous 3D conductor using anisotropic quantum interference measurements, atom probe tomography, and density functional theory

Atomic-Scale Patterning of Arsenic in Silicon by Scanning Tunneling Microscopy

Over the past two decades, prototype devices for future classical and quantum computing technologies have been fabricated by using scanning tunneling microscopy and hydrogen resist lithography to position phosphorus atoms in silicon with atomic-scale precision. Despite these successes, phosphine remains the only donor precursor molecule to have been demonstrated as compatible with the hydrogen resist lithography technique. The potential benefits of atomic-scale placement of alternative dopant species have, until now, remained unexplored. In this work, we demonstrate the successful fabrication of atomic-scale structures of arsenic-in-silicon. Using a scanning tunneling microscope tip, we pattern a monolayer hydrogen mask to selectively place arsenic atoms on the Si(001) surface using arsine as the precursor molecule. We fully elucidate the surface chemistry and reaction pathways of arsine on Si(001), revealing significant differences to phosphine. We explain how these differences result in enhanced surface immobilization and in-plane confinement of arsenic compared to phosphorus, and a dose-rate independent arsenic saturation density of 0.24 ± 0.04 monolayers. We demonstrate the successful encapsulation of arsenic delta-layers using silicon molecular beam epitaxy, and find electrical characteristics that are competitive with equivalent structures fabricated with phosphorus. Arsenic delta-layers are also found to offer confinement as good as similarly prepared phosphorus layers, while still retaining >80% carrier activation and sheet resistances of <2 kω/square. These excellent characteristics of arsenic represent opportunities to enhance existing capabilities of atomic-scale fabrication of dopant structures in silicon, and may be important for three-dimensional devices, where vertical control of the position of device components is critical. Copyright © 2020 American Chemical Society

Determination of the preferred reaction pathway of acetophenone on Si(001) using photoelectron diffraction.

The adsorption configurations of a technologically relevant model organic adsorbate on the silicon (001) surface were studied using energy scanned X-ray photoelectron diffraction (PhD). Previous work has established the existence of an interesting vertically-aligned ("flagpole") configuration, where the acetophenone attaches to Si(001) via the acetyl group carbon and oxygen atoms. DFT calculations have predicted two energetically similar variants of this structure, where the phenyl ring is orientated parallel or perpendicular to the rows of silicon dimers on this reconstructed surface. However, previously published experimental measurements, including scanning tunnelling microscopy, X-ray photoelectron spectroscopy, and near-edge X-ray absorption fine structure investigations were unable to distinguish between these two configurations. Here, we apply the unique experimental capabilities of the PhD technique to this system and demonstrate that the dominant adsorption configuration has the phenyl ring parallel to the dimer rows (the end-bridge structure). This information in turn facilitates the determination of the dominant reaction pathway for acetophenone on Si(001), which has remained elusive until now. Information about subtle preferences in reaction pathways that affect the alignment and orientation of organic adsorbates such as acetophenone on technologically-relevant semiconductor surfaces such as Si(001) is critical for the fabrication of future atomically-precise atomic and molecular-scale electronic devices utilising the organic-silicon interface, and this work demonstrates the unique and complementary capabilities of PhD for providing this information. [Abstract copyright: Creative Commons Attribution license.