Absence of Nonlocal Manipulation of Oxygen Atoms Inserted below the Si(111)-7×7 Surface.

The injection of electrons from the scanning tunneling microscope tip can be used to perform nanoscale chemistry and study hot electron transport through surfaces. While nonlocal manipulation has been demonstrated primarily for aromatic adsorbates, here we confirm that oxygen atoms bonded to the Si(111) surface can also be nonlocally manipulated, and we fit the measured manipulation data to a single channel decay model. Unlike aromatic adsorption systems, oxygen atoms also insert below the surface of silicon. Although the inserted oxygen can be manipulated when the tip is directly over the relevant silicon adatom, it is not possible to induce nonlocal manipulation of inserted oxygen atoms at the same bias. We attribute this to the electrons injected at +4 eV initially relaxing to couple to the highest available surface state at +3.4 eV before laterally transporting through the surface. With a manipulation threshold of 3.8 eV for oxygen inserted into silicon, once carriers have undergone lateral transport, they do not possess enough energy to manipulate and remove oxygen atoms inserted beneath the surface of silicon. This result confirms that nonlocal nanoscale chemistry using the scanning tunneling microscope tip is dependent not only on the energy required for atomic manipulation, but also on the energy of the available surface states to carry the electrons to the manipulation site.

Investigation into the effects of surface stripping ZnO nanosheets.

ZnO nanosheets are polycrystalline nanostructures that are used in devices including solar cells and gas sensors. However, for efficient and reproducible device operation and contact behaviour the conductivity characteristics must be controlled and surface contaminants removed. Here we use low doses of argon bombardment to remove surface contamination and make reproducible lower resistance contacts. Higher doses strip the surface of the nanosheets altering the contact type from near-ohmic to rectifying by removing the donor-type defects, which photoluminescence shows to be concentrated in the near-surface. Controlled doses of argon treatments allow nanosheets to be customised for device formation.

XPS investigation of titanium contact formation to ZnO nanowires.

Ti is often used to form an initial Ohmic interface between ZnO and Au due to its low work function, and the TiO2/ZnO heterojunction is also of great importance for many practical applications of nanoparticles. Here, Ti has been controllably deposited onto hydrothermally grown ZnO nanowires and the formation of metal-semiconductor contact has been investigated using x-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectroscopy and scanning electron microscopy. XPS results showed that that the Ti initially reacts with surface oxygen species to form TiO2, and further deposition results in the formation of oxides with oxidation state numbers lower than four, and eventually metallic Ti on top of the TiO2. The formation of TiC was also observed. XPS showed that the onset of metallic Ti coincided with a Zn 3p core level shift to lower binding energy, indicating upwards band bending and the formation of a rectifying contact. Annealing caused a near-complete conversion of the metallic Ti to TiO2 and caused the Zn 3p to shift back to its original higher binding energy, resulting in downwards band bending and a more Ohmic contact. PL measurements showed that the optical properties of the nanowires are not affected by the contact formation.

Nondestructive Method for Mapping Metal Contact Diffusion in In2O3 Thin-Film Transistors.

The channel width-to-length ratio is an important transistor parameter for integrated circuit design. Contact diffusion into the channel during fabrication or operation alters the channel width and this important parameter. A novel methodology combining atomic force microscopy and scanning Kelvin probe microscopy (SKPM) with self-consistent modeling is developed for the nondestructive detection of contact diffusion on active devices. Scans of the surface potential are modeled using physically based Technology Computer Aided Design (TCAD) simulations when the transistor terminals are grounded and under biased conditions. The simulations also incorporate the tip geometry to investigate its effect on the measurements due to electrostatic tip-sample interactions. The method is particularly useful for semiconductor- and metal-semiconductor interfaces where the potential contrast resulting from dopant diffusion is below that usually detectable with scanning probe microscopy.

Effects of Vacuum Annealing on the Conduction Characteristics of ZnO Nanosheets.

ZnO nanosheets are a relatively new form of nanostructure and have demonstrated potential as gas-sensing devices and dye sensitised solar cells. For integration into other devices, and when used as gas sensors, the nanosheets are often heated. Here we study the effect of vacuum annealing on the electrical transport properties of ZnO nanosheets in order to understand the role of heating in device fabrication. A low cost, mass production method has been used for synthesis and characterisation is achieved using scanning electron microscopy (SEM), photoluminescence (PL), auger electron spectroscopy (AES) and nanoscale two-point probe. Before annealing, the measured nanosheet resistance displayed a non-linear increase with probe separation, attributed to surface contamination. Annealing to 300 °C removed this contamination giving a resistance drop, linear probe spacing dependence, increased grain size and a reduction in the number of n-type defects. Further annealing to 500 °C caused the n-type defect concentration to reduce further with a corresponding increase in nanosheet resistance not compensated by any further sintering. At 700 °C, the nanosheets partially disintegrated and the resistance increased and became less linear with probe separation. These effects need to be taken into account when using ZnO nanosheets in devices that require an annealing stage during fabrication or heating during use.

The effects of surface stripping ZnO nanorods with argon bombardment.

ZnO nanorods are used in devices including field effects transistors, piezoelectric transducers, optoelectronics and gas sensors. However, for efficient and reproducible device operation and contact behaviour, surface contaminants must be removed or controlled. Here we use low doses of argon bombardment to remove surface contamination and make reproducible lower resistance contacts. Higher doses strip the surface of the nanorods allowing intrinsic surface measurements through a cross section of the material. Photoluminescence finds that the defect distribution is higher at the near-surface, falling away in to the bulk. Contacts to the n-type defect-rich surface are near-Ohmic, whereas stripping away the surface layers allows more rectifying Schottky contacts to be formed. The ability to select the contact type to ZnO nanorods offers a new way to customize device behaviour.

Controlling the Electrical Transport Properties of Nanocontacts to Nanowires.

The ability to control the properties of electrical contacts to nanostructures is essential to realize operational nanodevices. Here, we show that the electrical behavior of the nanocontacts between free-standing ZnO nanowires and the catalytic Au particle used for their growth can switch from Schottky to Ohmic depending on the size of the Au particles in relation to the cross-sectional width of the ZnO nanowires. We observe a distinct Schottky to Ohmic transition in transport behavior at an Au to nanowire diameter ratio of 0.6. The current-voltage electrical measurements performed with a multiprobe instrument are explained using 3-D self-consistent electrostatic and transport simulations revealing that tunneling at the contact edge is the dominant carrier transport mechanism for these nanoscale contacts. The results are applicable to other nanowire materials such as Si, GaAs, and InAs when the effects of surface charge and contact size are considered.