Richard A. J. Woolley

Near-field Raman spectroscopy of biological nanomaterials by in situ laser-induced synthesis of tip-enhanced Raman spectroscopy tips

We report a new approach in tip-enhanced Raman spectroscopy (TERS) in which TERS-active tips with enhancement factors of ∼10(-5)× can be rapidly (1-3 min) produced in situ by laser-induced synthesis of silver nanoparticles at the tip apex. The technique minimizes the risks of tip contamination and damage during handling and provides in situ feedback control, which allows the prediction of the tip performance. We show that TERS tips produced by this technique enable the measurement of spatially resolved TERS spectra of self-assembled peptide nanotubes with a spatial resolution of ∼20  nm.

Automated probe microscopy via evolutionary optimization at the atomic scale

We describe the development and application of an imaging protocol, which evolves a scanning probe’s atomic structure in parallel with automated optimization of the scan parameters. Our protocol coerces the system into a state that produces a specific atomic resolution image type without human involvement.

Identifying passivated dynamic force microscopy tips on H:Si(100)

The chemical reactivity of the tip plays a central role in image formation in dynamic force microscopy, but in very many cases the state of the probe is a key experimental unknown. We show here that an H-terminated and thus chemically unreactive tip can be readily identified via characteristic imaging and spectroscopic (F(z)) signatures, including, in particular, contrast inversion, on hydrogen-passivated Si(100). We determine the tip apex termination by comparing site-specific difference force curves with the results of density functional theory, providing a clear protocol for the identification of chemically unreactive tips on silicon surfaces.

Dewetting of Au nanoparticle assemblies

Atomic force microscopy measurements as a function of annealing temperature, time of exposure to a high relative humidity environment, and scan duration/parameters have been used to ascertain the stability of assemblies of thiol-passivated Au nanoparticles on silicon substrates. Striking changes in the morphology of self-organised nanoparticle patterns are observed following the exposure of samples to atmospheres with a relative humidity of 80%. The nanoparticle film dewets the underlying silicon substrate on exposure to water, forming locally thicker regions. Time-lapse imaging shows that the dewetting proceeds via layer-by-layer growth, and there is no evidence for classical coarsening mechanisms involving self-similar film morphologies. Annealing at temperatures between 100 °C and 160 °C produces a rather different dewetting effect for the highest temperatures and/or annealing times, where significant nanoparticle sintering promotes the break-up of the two-dimensional assembly. The morphology of the initial 2D film plays a key role in determining the time scale on which annealing promotes nanoparticle dewetting. Dewetting can also be induced by a scanning probe such that localised (micron-scale) areas of the nanoparticle assembly can be converted from 2D to 3D character.

Automated extraction of single H atoms with STM: tip state dependency

The atomistic structure of the tip apex plays a crucial role in performing reliable atomic-scale surface and adsorbate manipulation using scanning probe techniques. We have developed an automated extraction routine for controlled removal of single hydrogen atoms from the H:Si(100) surface. The set of atomic extraction protocols detect a variety of desorption events during scanning tunneling microscope (STM)-induced modification of the hydrogen-passivated surface. The influence of the tip state on the probability for hydrogen removal was examined by comparing the desorption efficiency for various classifications of STM topographs (rows, dimers, atoms, etc). We find that dimer-row-resolving tip apices extract hydrogen atoms most readily and reliably (and with least spurious desorption), while tip states which provide atomic resolution counter-intuitively have a lower probability for single H atom removal.

In-situ fabrication of gold nanoparticle functionalized probes for tip-enhanced Raman spectroscopy by dielectrophoresis

We report the use of dielectrophoresis to fabricate in-situ probes for tip-enhanced Raman spectroscopy (TERS) based on Au nanoparticles. A typical conductive atomic force microscope (AFM) was used to functionalize iridium-coated conductive silicon probes with Au nanoparticles of 10-nm diameter. Suitable TERS probes can be rapidly produced (30 to 120 s) by applying a voltage of 10 Vpp at a frequency of 1 MHz. The technique has the advantage that the Au-based probes are ready for immediate use for TERS measurements, minimizing the risks of tip contamination and damage during handling. Scanning electron microscopy and energy dispersive x-ray spectroscopy were used to confirm the quality of the probes, and used samples of p-ATP monolayers on silver substrates were used to demonstrate experimentally TERS measurements.

Scanning probe image wizard: a toolbox for automated scanning probe microscopy data analysis

We describe SPIW (scanning probe image wizard), a new image processing toolbox for SPM (scanning probe microscope) images. SPIW can be used to automate many aspects of SPM data analysis, even for images with surface contamination and step edges present. Specialised routines are available for images with atomic or molecular resolution to improve image visualisation and generate statistical data on surface structure.

A compact combined ultrahigh vacuum scanning tunnelling microscope (UHV STM) and near-field optical microscope

We have designed and constructed a hybrid scanning near-field optical microscope (SNOM)–scanning tunnelling microscope (STM) instrument which operates under ultrahigh vacuum (UHV) conditions. Indium tin oxide (ITO)-coated fibre-optic tips capable of high quality STM imaging and tunnelling spectroscopy are fabricated using a simple and reliable method which foregoes the electroless plating strategy previously employed by other groups. The fabrication process is reproducible, producing robust tips which may be exchanged under UHV conditions. We show that controlled contact with metal surfaces considerably enhances the STM imaging capabilities of fibre-optic tips. Light collection (from the cleaved back face of the ITO-coated fibre-optic tip) and optical alignment are facilitated by a simple two-lens arrangement where the in-vacuum collimation/collection lens may be adjusted using a slip-stick motor. A second in-air lens focuses the light (which emerges from the UHV system as a parallel beam) onto a cooled CCD spectrograph or photomultiplier tube. The application of the instrument to combined optical and electronic spectroscopy of Au and GaAs surfaces is discussed.

Combining nanoscale manipulation with macroscale relocation of single quantum dots

Summary We have controllably positioned, with nanometre precision, single CdSe quantum dots referenced to a registration template such that the location of a given nanoparticle on a macroscopic (≈1 cm2) sample surface can be repeatedly revisited. The atomically flat sapphire substrate we use is particularly suited to optical measurements of the isolated quantum dots, enabling combined manipulation–spectroscopy experiments on a single particle. Automated nanoparticle manipulation and imaging routines have been developed so as to facilitate the rapid assembly of specific nanoparticle arrangements.