Chemical functionalisation of silicon and germanium nanowires

The reduced dimensionality of nanowires implies that surface effects significantly influence their properties, which has important implications for the fabrication of nanodevices such as field effect transistors and sensors. This review will explore the strategies available for wet chemical functionalisation of silicon (Si) and germanium (Ge) nanowires. The stability and electrical properties of surface modified Si and Ge nanowires is explored. While this review will focus primarily on nanowire surfaces, much has been learned from work on planar substrates and differences between 2D and nanowire surfaces will be high-lighted. The possibility of band gap engineering and controlling electronic characteristics through surface modification provides new opportunities for future nanowire based applications. Nano-sensing is emerging as a major application of modified Si nanowires and the progress of these devices to date is discussed

Inducing imperfections in germanium nanowires

Nanowires with inhomogeneous heterostructures such as polytypes and periodic twin boundaries are interesting due to their potential use as components for optical, electrical, and thermophysical applications. Additionally, the incorporation of metal impurities in semiconductor nanowires could substantially alter their electronic and optical properties. In this highlight article, we review our recent progress and understanding in the deliberate induction of imperfections, in terms of both twin boundaries and additional impurities in germanium nanowires for new/enhanced functionalities. The role of catalysts and catalyst–nanowire interfaces for the growth of engineered nanowires via a three-phase paradigm is explored. Three-phase bottom-up growth is a feasible way to incorporate and engineer imperfections such as crystal defects and impurities in semiconductor nanowires via catalyst and/or interfacial manipulation. “Epitaxial defect transfer” process and catalyst–nanowire interfacial engineering are employed to induce twin defects parallel and perpendicular to the nanowire growth axis. By inducing and manipulating twin boundaries in the metal catalysts, twin formation and density are controlled in Ge nanowires. The formation of Ge polytypes is also observed in nanowires for the growth of highly dense lateral twin boundaries. Additionally, metal impurity in the form of Sn is injected and engineered via third-party metal catalysts resulting in above-equilibrium incorporation of Sn adatoms in Ge nanowires. Sn impurities are precipitated into Ge bi-layers during Ge nanowire growth, where the impurity Sn atoms become trapped with the deposition of successive layers, thus giving an extraordinary Sn content (>6 at.%) in Ge nanowires. A larger amount of Sn impingement (>9 at.%) is further encouraged by utilizing the eutectic solubility of Sn in Ge along with impurity trapping

Engineering metallic nanoparticles for enhancing and probing catalytic reactions

Recent developments in tailoring the structural and chemical properties of colloidal metal nanoparticles (NPs) have led to significant enhancements in catalyst performance. Controllable colloidal synthesis has also allowed tailor-made NPs to serve as mechanistic probes for catalytic processes. The innovative use of colloidal NPs to gain fundamental insights into catalytic function will be highlighted across a variety of catalytic and electrocatalytic applications. The engineering of future heterogenous catalysts is also moving beyond size, shape and composition considerations. Advancements in understanding structure-property relationships have enabled incorporation of complex features such as tuning surface strain to influence the behavior of catalytic NPs. Exploiting plasmonic properties and altering colloidal surface chemistry through functionalization are also emerging as important areas for rational design of catalytic NPs. This news article will highlight the key developments and challenges to the future design of catalytic NPs

AuxAg1-x alloy seeds: A way to control growth, morphology and defect formation in Ge nanowires

Germanium (Ge) nanowires are of current research interest for high speed nanoelectronic devices due to the lower band gap and high carrier mobility compatible with high K-dielectrics and larger excitonic Bohr radius ensuing a more pronounced quantum confinement effect [1-6]. A general way for the growth of Ge nanowires is to use liquid or a solid growth promoters in a bottom-up approach which allow control of the aspect ratio, diameter, and structure of 1D crystals via external parameters, such as precursor feedstock, temperature, operating pressure, precursor flow rate etc [3, 7-11]. The Solid-phase seeding is preferred for more control processing of the nanomaterials and potential suppression of the unintentional incorporation of high dopant concentrations in semiconductor nanowires and unrequired compositional tailing of the seed-nanowire interface [2, 5, 9, 12]. There are therefore distinct features of the solid phase seeding mechanism that potentially offer opportunities for the controlled processing of nanomaterials with new physical properties. A superior control over the growth kinetics of nanowires could be achieved by controlling the inherent growth constraints instead of external parameters which always account for instrumental inaccuracy. The high dopant concentrations in semiconductor nanowires can result from unintentional incorporation of atoms from the metal seed material, as described for the Al catalyzed VLS growth of Si nanowires [13] which can in turn be depressed by solid-phase seeding. In addition, the creation of very sharp interfaces between group IV semiconductor segments has been achieved by solid seeds [14], whereas the traditionally used liquid Au particles often leads to compositional tailing of the interface [15] . Korgel et al. also described the superior size retention of metal seeds in a SFSS nanowire growth process, when compared to a SFLS process using Au colloids [12]. Here in this work we have used silver and alloy seed particle with different compositions to manipulate the growth of nanowires in sub-eutectic regime. The solid seeding approach also gives an opportunity to influence the crystallinity of the nanowires independent of the substrate. Taking advantage of the readily formation of stacking faults in metal nanoparticles, lamellar twins in nanowires could be formed

Ferroelectric nanoparticles, wires and tubes: synthesis, characterisation and applications

Nanostructured materials are central to the evolution of future electronics and information technologies. Ferroelectrics have already been established as a dominant branch in the electronics sector because of their diverse application range such as ferroelectric memories, ferroelectric tunnel junctions, etc. The on-going dimensional downscaling of materials to allow packing of increased numbers of components onto integrated circuits provides the momentum for the evolution of nanostructured ferroelectric materials and devices. Nanoscaling of ferroelectric materials can result in a modification of their functionality, such as phase transition temperature or Curie temperature (TC), domain dynamics, dielectric constant, coercive field, spontaneous polarisation and piezoelectric response. Furthermore, nanoscaling can be used to form high density arrays of monodomain ferroelectric nanostructures, which is desirable for the miniaturisation of memory devices. This review article highlights some research breakthroughs in the fabrication, characterisation and applications of nanoscale ferroelectric materials over the last decade, with priority given to novel synthetic strategies

Visualising discrete structural transformations in germanium nanowires during ion beam irradiation and subsequent annealing

In this article we detail the application of electron microscopy to visualise discrete structural transitions incurring in single crystalline Ge nanowires upon Ga-ion irradiation and subsequent thermal annealing. Sequences of images for nanowires of varying diameters subjected to an incremental increase of the Ga-ion dose were obtained. Intricate transformations dictated by a nanowire's geometry indicate unusual distribution of the cascade recoils in the nanowire volume, in comparison to planar substrates. Following irradiation, the same nanowires were annealed in the TEM and corresponding crystal recovery followed in situ. Visualising the recrystallisation process, we establish that full recovery of defect-free nanowires is difficult to obtain due to defect nucleation and growth. Our findings will have large implications in designing ion beam doping of Ge nanowires for electronic devices but also for other devices that use single crystalline nanostructured Ge materials such as thin membranes, nanoparticles and nanorods

Galvanic replacement of sub 20 nm Ag nanoparticles in organic media

Galvanic replacement is a versatile synthetic strategy for the synthesis of alloy and hollow nanostructures. The structural evolution of single crystalline and multiply twinned nanoparticles <20 nm in diameter and capped with oleylamine is systematically studied. Changes in chemical composition are dependent on the size and crystallinity of the parent nanoparticle. The effects of reaction temperature and rate of precursor addition are also investigated. Galvanic replacement of single crystal spherical and truncated cubic nanoparticles follows the same mechanism to form hollow octahedral nanoparticles, a mechanism which is not observed for galvanic replacement of Ag templates in aqueous systems. Multiply twinned nanoparticles can form nanorings or solid alloys by manipulating the reaction conditions. Oleylamine-capped Ag nanoparticles are highly adaptable templates to synthesize a range of hollow and alloy nanostructures with tuneable localised surface plasmon resonance

Nanoscale ferroelectric and piezoelectric properties of Sb2S3 nanowire arrays

We report the first observation of piezoelectricity and ferroelectricity in individual Sb2S3 nanowires embedded in anodic alumina templates. Switching spectroscopy-piezoresponse force microscopy (SS-PFM) measurements demonstrate that individual, c-axis-oriented Sb2S3 nanowires exhibit ferroelectric as well as piezoelectric switching behavior. Sb2S3 nanowires with nominal diameters of 200 and 100 nm showed d33(eff) values around 2 pm V–1, while the piezo coefficient obtained for 50 nm diameter nanowires was relatively low at around 0.8 pm V–1. A spontaneous polarization (Ps) of approximately 1.8 μC cm–2 was observed in the 200 and 100 nm Sb2S3 nanowires, which is a 100% enhancement when compared to bulk Sb2S3 and is probably due to the defect-free, single-crystalline nature of the nanowires synthesized. The 180° ferroelectric monodomains observed in Sb2S3 nanowires were due to uniform polarization alignment along the polar c-axis

Chemical approaches for doping nanodevice architectures

Advanced doping technologies are key for the continued scaling of semiconductor devices and the maintenance of device performance beyond the 14 nm technology node. Due to limitations of conventional ion-beam implantation with thin body and 3D device geometries, techniques which allow precise control over dopant diffusion and concentration, in addition to excellent conformality on 3D device surfaces, are required. Spin-on doping has shown promise as a conventional technique for doping new materials, particularly through application with other dopant methods, but may not be suitable for conformal doping of nanostructures. Additionally, residues remain after most spin-on-doping processes which are often difficult to remove. In-situ doping of nanostructures is especially common for bottom-up grown nanostructures but problems associated with concentration gradients and morphology changes are commonly experienced. Monolayer doping (MLD) has been shown to satisfy the requirements for extended defect-free, conformal and controllable doping on many materials ranging from traditional silicon and germanium devices to emerging replacement materials such as III-V compounds but challenges still remain, especially with regard to metrology and surface chemistry at such small feature sizes. This article summarises and critically assesses developments over the last number of years regarding the application of gas and solution phase techniques to dope silicon-, germanium- and III-V-based materials and nanostructures to obtain shallow diffusion depths coupled with high carrier concentrations and abrupt junctions