Functionalization of lamellar molybdenum disulphide nanocomposite with gold nanoparticles

This work explores the functionalization of an organic-inorganic MoS2 lamellar compound, prepared by a Chemical Liquid Deposition Method (CLD), that has an interlamellar distance of ~5.2 nm, using clusters of gold nanoparticles. The gold nanoparticles have a mean diameter of 1.2 nm, a stability of ~85 days, and a zeta potential measured to be ζ = -6.8 mV (solid). The nanoparticles are localized in the hydrophilic zones, defined by the presence of amine groups of the surfactant between the lamella of MoS2. SEM, TEM, EDAX and electron diffraction provide conclusive evidence of the interlamellar insertion of the gold nanoparticles in the MoS2.

Single-crystal micro/nanostructures and thin films of lamellar molybdenum oxide by solid-state pyrolysis of organometallic derivatives of a cyclotriphosphazene

The solid-state pyrolysis of organometallic derivatives of a cyclotriphosphazene is demonstrated to be a new, simple and versatile solid-state templating method for obtaining single-crystal micro- and nanocrystals of transition and valve metal oxides. The technique, when applied to Mo-containing organometallics N3P3[OC6H4CH2CN·Mo(CO)5]6 and N3P3[OC6H4CH2CN·Mo(CO)4 py]6, results in stand-alone and surface-deposited lamellar MoO3 single crystals, as determined by electron and atomic force microscopies and X-ray diffraction. The size and morphology of the resulting crystals can be tuned by the composition of the precursor. X-ray photoelectron and infrared spectroscopies indicate that the deposition of highly lamellar MoO3 directly on an oxidized (400 nm SiO2) surface or (100) single-crystal silicon surfaces yields a layered uniphasic single-crystal film formed by cluster diffusion on the surface during pyrolysis of the metal-carbonyl derivatives. For MoO3 in its layered form, this provides a new route to an important intercalation material for high energy density battery materials.

Fabrication of sub-10 nm lamellar structures by solvent vapour annealing of block copolymers

Fabrication of nanoscale patterns through the bottom-up approach of self-assembly of phase-separated block copolymers (BCP) holds promise for nanoelectronics applications. For lithographic applications, it is useful to vary the morphology of BCPs by monitoring various parameters to make “from lab to fab” a reality. Here I report on the solvent annealing studies of lamellae forming polystyrene-blockpoly( 4-vinylpyridine) (PS-b-P4VP). The high Flory-Huggins parameter (χ = 0.34) of PS-b-P4VP makes it an ideal BCP system for self-assembly and template fabrication in comparison to other BCPs. Different molecular weights of symmetric PS-b-P4VP BCPs forming lamellae patterns were used to produce nanostructured thin films by spin-coating from mixture of toluene and tetrahydrofuran(THF). In particular, the morphology change from micellar structures to well-defined microphase separated arrangements is observed. Solvent annealing provides a better alternative to thermal treatment which often requires long annealing periods. The choice of solvent (single and dual solvent exposure) and the solvent annealing conditions have significant effects on the morphology of films and it was found that a block neutral solvent was required to realize vertically aligned PS and P4VP lamellae. Here, we have followed the formation of microdomain structures with time development at different temperatures by atomic force microscopy (AFM). The highly mobilized chains phase separate quickly due to high Flory-Huggins (χ) parameter. Ultra-small feature size (~10 nm pitch size) nanopatterns were fabricated by using low molecular weight PSb- P4VP (PS and P4VP blocks of 3.3 and 3.1 kg mol-1 respectively). However, due to the low etch contrast between the blocks, pattern transfer of the BCP mask is very challenging. To overcome the etch contrast problem, a novel and simple in-situ hard mask technology is used to fabricate the high aspect ratio silicon nanowires. The lamellar structures formed after self-assembly of phase separated PS-b-P4VP BCPs were used to fabricate iron oxide nanowires which acted as hard mask material to facilitate the pattern transfer into silicon and forming silicon nanostructures. The semiconductor and optical industries have shown significant interest in two dimensional (2D) molybdenum disulphide (MoS2) as a potential device material due to its low band gap and high mobility. However, current methods for its synthesis are not ‘fab’ friendly and require harsh environments and processes. Here, I also report a novel method to prepare MoS2 layered structures via self-assembly of a PS-b-P4VP block copolymer system. The formation of the layered MoS2 was confirmed by XPS, Raman spectroscopy and high resolution transmission electron microscopy.

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.

Study of the kinetics and mechanism of rapid self-assembly in block copolymer thin films during solvo-microwave annealing

Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high- lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during "solvo-microwave" annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 degrees C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during "solvo-microwave" annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O-2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.

The morphology of ordered block copolymer patterns as probed by high resolution imaging

The microphase separation of block copolymer (BCP) thin films can afford a simple and cost-effective means to studying nanopattern surfaces, and especially the fabrication of nanocircuitry. However, because of complex interface effects and other complications, their 3D morphology, which is often critical for application, can be more complex than first thought. Here, we describe how emerging microscopic methods may be used to study complex BCP patterns and reveal their rich detail. These methods include helium ion microscopy (HIM) and high resolution x-section transmission electron microscopy (XTEM), and complement conventional secondary electron and atomic force microscopies (SEM and TEM). These techniques reveal that these structures are quite different to what might be expected. We illustrate the advances in the understanding of BCP thin film morphology in several systems, which result from this characterization. The systems described include symmetric, lamellar forming polystyrene-b-polymethylmethacrylate (PS-b-PMMA), cylinder forming polystyrene-b-polydimethylsiloxane (PS-b-PDMS), as well as lamellar and cylinder forming patterns of polystyrene-b-polyethylene oxide (PS-b-PEO) and polystyrene-b-poly-4-vinylpyridine (PS-b-P4VP). Each of these systems exhibits more complex arrangements than might be first thought. Finding and developing techniques whereby complex morphologies, particularly at very small dimensions, can be determined is critical to the practical use of these materials in many applications. The importance of quantifying these complex morphologies has implications for their use in integrated circuit manufacture, where they are being explored as alternative pattern forming methods to conventional UV lithography.