Monolayer Doping of Germanium with Arsenic: A New Chemical Route to Achieve Optimal Dopant Activation.

Reported here is a new chemical route for the wet chemical functionalization of germanium (Ge), whereby arsanilic acid is covalently bound to a chlorine (Cl)-terminated surface. This new route is used to deliver high concentrations of arsenic (As) dopants to Ge, via monolayer doping (MLD). Doping, or the introduction of Group III or Group V impurity atoms into the crystal lattice of Group IV semiconductors, is essential to allow control over the electronic properties of the material to enable transistor devices to be switched on and off. MLD is a diffusion-based method for the introduction of these impurity atoms via surface-bound molecules, which offers a nondestructive alternative to ion implantation, the current industry doping standard, making it suitable for sub-10 nm structures. Ge, given its higher carrier mobilities, is a leading candidate to replace Si as the channel material in future devices. Combining the new chemical route with the existing MLD process yields active carrier concentrations of dopants (>1 × 1019 atoms/cm3) that rival those of ion implantation. It is shown that the dose of dopant delivered to Ge is also controllable by changing the size of the precursor molecule. X-ray photoelectron spectroscopy (XPS) data and density functional theory (DFT) calculations support the formation of a covalent bond between the arsanilic acid and the Cl-terminated Ge surface. Atomic force microscopy (AFM) indicates that the integrity of the surface is maintained throughout the chemical procedure, and electrochemical capacitance voltage (ECV) data shows a carrier concentration of 1.9 × 1019 atoms/cm3 corroborated by sheet resistance measurements.

Vapor-Phase Passivation of Chlorine-Terminated Ge(100) Using Self-Assembled Monolayers of Hexanethiol.

Continued scaling of electronic devices shows the need to incorporate high mobility alternatives to silicon, the cornerstone of the semiconductor industry, into modern field effect transistor (FET) devices. Germanium is well-poised to serve as the channel material in FET devices as it boasts an electron and hole mobility more than twice and four times that of Si, respectively. However, its unstable native oxide makes its passivation a crucial step toward its potential integration into future FETs. The International Roadmap for Devices and Systems (IRDS) predicts continued aggressive scaling not only of the device size but also of the pitch in nanowire arrays. The development of a vapor-phase chemical passivation technique will be required to prevent the collapse of these structures that can occur because of the surface tension and capillary forces that are experienced when tight-pitched nanowire arrays are processed via liquid-phase chemistry. Reported here is a vapor-phase process using hexanethiol for the passivation of planar Ge(100) substrates. Results benchmarking it against its well-established liquid-phase equivalent are also presented. X-ray photoelectron spectroscopy was used to monitor the effectiveness of the developed vapor-phase protocol, where the presence of oxide was monitored at 0, 24, and 168 h. Water contact angle measurements compliment these results by demonstrating an increase in hydrophobicity of the passivated substrates. Atomic force microscopy monitored the surface topology before and after processing to ensure the process does not cause roughening of the surface, which is critical to demonstrate suitability for nanostructures. It is shown that the 200 min vapor-phase passivation procedure generates stable, passivated surfaces with less roughness than the liquid-phase counterpart.

Ultra-fast and scalable sidewall functionalisation of single-walled carbon nanotubes with carboxylic acid.

A simple and fast method for the functionalisation of single-walled carbon nanotubes with carboxylic acid terminated molecules, at varying molar fractions, is presented.

Phosphorus monolayer doping (MLD) of silicon on insulator (SOI) substrates.

This paper details the application of phosphorus monolayer doping of silicon on insulator substrates. There have been no previous publications dedicated to the topic of MLD on SOI, which allows for the impact of reduced substrate dimensions to be probed. The doping was done through functionalization of the substrates with chemically bound allyldiphenylphosphine dopant molecules. Following functionalization, the samples were capped and annealed to enable the diffusion of dopant atoms into the substrate and their activation. Electrical and material characterisation was carried out to determine the impact of MLD on surface quality and activation results produced by the process. MLD has proven to be highly applicable to SOI substrates producing doping levels in excess of 1 × 1019 cm-3 with minimal impact on surface quality. Hall effect data proved that reducing SOI dimensions from 66 to 13 nm lead to an increase in carrier concentration values due to the reduced volume available to the dopant for diffusion. Dopant trapping was found at both Si-SiO2 interfaces and will be problematic when attempting to reach doping levels achieved by rival techniques.

Oxide removal and stabilization of bismuth thin films through chemically bound thiol layers.

Bismuth has been identified as a material of interest for electronic applications due to its extremely high electron mobility and quantum confinement effects observed at nanoscale dimensions. However, it is also the case that Bi nanostructures are readily oxidised in ambient air, necessitating additional capping steps to prevent surface re-oxidation, thus limiting the processing potential of this material. This article describes an oxide removal and surface stabilization method performed on molecular beam epitaxy (MBE) grown bismuth thin-films using ambient air wet-chemistry. Alkanethiol molecules were used to dissolve the readily formed bismuth oxides through a catalytic reaction; the bare surface was then reacted with the free thiols to form an organic layer which showed resistance to complete reoxidation for up to 10 days.

Organo-arsenic molecular layers on silicon for high-density doping.

This article describes for the first time the controlled monolayer doping (MLD) of bulk and nanostructured crystalline silicon with As at concentrations approaching 2 × 10(20) atoms cm(-3). Characterization of doped structures after the MLD process confirmed that they remained defect- and damage-free, with no indication of increased roughness or a change in morphology. Electrical characterization of the doped substrates and nanowire test structures allowed determination of resistivity, sheet resistance, and active doping levels. Extremely high As-doped Si substrates and nanowire devices could be obtained and controlled using specific capping and annealing steps. Significantly, the As-doped nanowires exhibited resistances several orders of magnitude lower than the predoped materials.

Synthesis of tripodal [2]rotaxanes: high concentration principlet.

Symmetrical and non-symmetrical tripodal [2]rotaxanes (1) incorporating 1,1'-disubstituted-4,4'-bipyridinium cations (2) and 34-crown-10 (3) have been prepared directly from 4,4'-bipyridine or from monocationic intermediates in high yields at room temperature and atmospheric pressure under conditions that permit the use of high reagent concentrations (0.1-0.2 M, 150-200 g(-1)).

Minimally invasive techniques for the treatment of intervertebral disk herniation.

Hemilaminectomy with diskectomy, the original surgical option to address intervertebral disk herniation, was superseded by open microdiskectomy, a less invasive technique recognized as the surgical benchmark with which minimally invasive spine surgery techniques have been compared as they have been developed. These minimally invasive surgical techniques for patients with herniated nucleus pulposus and radiculopathy include laser disk decompression, arthroscopic microdiskectomy, laparoscopic techniques, foraminal endoscopy, and microendoscopic diskectomy. Each has its own complications and requires a long learning curve to develop familiarity with the technique. Patient selection, and especially disk morphology, are the most important factors in choice of technique. The optimal candidate has a previously untreated single-level herniation with limited migration or sequestration of free fragments.

Divalent metal nanoparticles.

Nanoparticles can be used as the building blocks for materials such as supracrystals or ionic liquids. However, they lack the ability to bond along specific directions as atoms and molecules do. We report a simple method to place target molecules specifically at two diametrically opposed positions in the molecular coating of metal nanoparticles. The approach is based on the functionalization of the polar singularities that must form when a curved surface is coated with ordered monolayers, such as a phase-separated mixture of ligands. The molecules placed at these polar defects have been used as chemical handles to form nanoparticle chains that in turn can generate self-standing films.

Self-assembly of a tripodal pseudorotaxane on the surface of a titanium dioxide nanoparticle.

This paper describes the self-assembly of a heterosupramolecular system consisting of a tripodal viologen, adsorbed at the surface of a titanium dioxide nanoparticle, that threads a crown ether to form a pseudorotaxane. The viologen, a 1,1'-disubstituted-4,4'-bipyridinium salt with a rigid tripodal anchor group, has been synthesized. This viologen is adsorbed at the surface of a titanium dioxide nanoparticle in solution. As intended, this tripodal viologen is both oriented normal to and displaced from the surface of the nanoparticle and threads a crown ether to form the heterosupramolecular complex. The threading of the crown ether by the tripodal viologen to form the above pseudorotaxane complex at the surface of a titanium dioxide nanoparticle has been studied by (1)H NMR, optical absorption spectroscopy, and cyclic voltammetry.

Assembly of an electronically switchable rotaxane on the surface of a titanium dioxide nanoparticle.

This paper describes the self-assembly of a heterosupramolecular system consisting of a tripodal [2]rotaxane adsorbed at the surface of a titanium dioxide nanoparticle. The tripodal [2]rotaxane consists of a dumbbell-shaped molecule, incorporating two electron-poor viologens, threading an electron-rich crown ether. The [2]rotaxane also incorporates a bulky tripodal linker group at one end and a bulky stopper group at the other end. The [2]rotaxane is adsorbed, via the tripodal linker group, at the surface of a titanium dioxide nanoparticle. The structure and function of the resulting hetero[2]rotaxane have been studied in detail by (1)H NMR spectroscopy and cyclic voltammetry. A key finding is that it is possible to electronically address and switch the above hetero[2]rotaxane.