Kelvin Probe Force Microscopy Experiments Research Articles

Exploring the Local Optoelectronic Properties of ALD Grown TiO2 Photoelectrode-Coatings with Atomic Force Microscopy Methods

Photoelectrochemical cells (PECs) hold great promise as an environmentally friendly method of converting sunlight into valuable fuels. However, the semiconductor components of PEC photoelectrodes are susceptible to corrosion under photoelectrochemical conditions.In order to protect the surface of these semiconductors from degradation, a thin overlayer of Titanium dioxide (TiO2) is often applied by atomic layer deposition (ALD). In addition to their protecting function, the physicochemical properties of these thin films significantly affect the overall performance of the device. The local nano-scale optoelectronic characteristics, which considerably influence their macroscopic properties, have rarely been reported in the literature.AFM methods constitute a powerful tool to investigate photo-induced charge separation, charge transport and recombination on photoelectrode surfaces with nanometer resolution.In this context, we have employed Tunneling Conductive AFM (TUNA) and Kelvin Probe Force Microscopy (KPFM) in the dark and under illumination to investigate the surface of ALD-grown TiO2. The synthesis conditions determine the morphology, which has a strong impact on the local optoelectronic properties. TUNA measurements reveal higher photogenerated currents on the grain and facet boundaries, showing that these regions can be favorable conduction pathways. Based on KPFM experiments we can quantify the more efficient photo-induced charge separation on the crystalline TiO2 inclusions, which generate a significant surface photopotential (~450 mV) upon UV-illumination. Categorization of different regions of surface topography based on morphology allows us to analyze the evolution of surface potential over time and extract localized time constants for carrier dynamic processes on the films. This spatially resolved information provides valuable insight to guide the development of macroscopically stable and efficient photoelectrodes through the engineering of microstructure at the nano scale.

Accurate determination of band tail properties in amorphous semiconductor thin film with Kelvin probe force microscopy

The disordered microscopic structure of amorphous semiconductors causes the formation of band tails in the density of states (DOS) that strongly affect charge transport properties. Such band tail properties are crucial for understanding and optimizing thin-film device performance with immense relevance for large area electronics. Among the available techniques to measure the DOS, Kelvin Probe Force Microscopy (KPFM) is exceptional as it enables precise local electronic investigations combined with microscopic imaging. However, a model to interpret KPFM spectroscopy data on amorphous semiconductors of finite thickness is lacking. To address this issue, we provide an analytical solution to the Poisson equation for a metal–insulator–semiconductor junction interacting with the atomic force microscope tip. The solution enables us to fit experimental data for semiconductors with finite thickness and to obtain DOS parameters, such as band tail width, doping density, and flat band potential. To demonstrate our method, we perform KPFM experiments on Indium–Gallium–Zinc Oxide (IGZO) thin-film transistors (IGZO-TFTs). DOS parameters compare well with values obtained with photocurrent spectroscopy. We demonstrate the relevance of the developed method by investigating the impact of ionizing radiation on DOS parameters and TFT performance. Our results provide clear evidence that the observed shift in threshold voltage is caused by static charge in the gate dielectric, leading to a shift in flat band potential. Band-tails and doping density are not affected by the radiation. The developed methodology can be easily translated to different semiconductor materials and paves the way for quantitative microscopic mapping of local DOS parameters in thin-film devices.

Surface potential extraction from electrostatic and Kelvin-probe force microscopy images

A comprehensive comparison study of electrostatic force microscopy (EFM) and Kelvin probe force microscopy (KPFM) is conducted in this manuscript. First, it is theoretically demonstrated that for metallic or semiconductor samples, both the EFM and KPFM signals are a convolution of the sample surface potential with their respective transfer functions. Then, an equivalent point-mass model describing cantilever deflection under distributed loads is developed to reevaluate the cantilever influence on detection signals, and it is shown that the cantilever has no influence on the EFM signal, while it will affect the KPFM signal intensity but not change the resolution. Finally, EFM and KPFM experiments are carried out, and the surface potential is extracted from the EFM and KPFM images by deconvolution processing, respectively. The extracted potential intensity is well consistent with each other and the detection resolution also complies with the theoretical analysis. Our work is helpful to perform a quantitative analysis of EFM and KPFM signals, and the developed point-mass model can also be used for other cantilever beam deflection problems.

Effects of Pb Intercalation on the Structural and Electronic Properties of Epitaxial Graphene on SiC.

The effects of Pb intercalation on the structural and electronic properties of epitaxial single-layer graphene grown on SiC(0001) substrate are investigated using scanning tunneling microscopy (STM), noncontact atomic force microscopy, Kelvin probe force microscopy (KPFM), X-ray photoelectron spectroscopy, and angle-resolved photoemission spectroscopy (ARPES) methods. The STM results show the formation of an ordered moiré superstructure pattern induced by Pb atom intercalation underneath the graphene layer. ARPES measurements reveal the presence of two additional linearly dispersing π-bands, providing evidence for the decoupling of the buffer layer from the underlying SiC substrate. Upon Pb intercalation, the Si 2p core level spectra show a signature for the existence of PbSi chemical bonds at the interface region, as manifested in a shift of 1.2 eV of the bulk SiC component toward lower binding energies. The Pb intercalation gives rise to hole-doping of graphene and results in a shift of the Dirac point energy by about 0.1 eV above the Fermi level, as revealed by the ARPES measurements. The KPFM experiments have shown that decoupling of the graphene layer by Pb intercalation is accompanied by a work function increase. The observed increase in the work function is attributed to the suppression of the electron transfer from the SiC substrate to the graphene layer. The Pb intercalated structure is found to be stable in ambient conditions and at high temperatures up to 1250 °C. These results demonstrate that the construction of a graphene-capped Pb/SiC system offers a possibility of tuning the graphene electronic properties and exploring intriguing physical properties such as superconductivity and spintronics.

Doping graphene thin films with metallic nanoparticles: Experiment and theory

Precise doping of graphene at nanoscale resolution is vital for a number of applications in nanoelectronics and sustainable energy. Although large metallic contacts are presumed to move the Fermi level of graphene above or below the Dirac point, little has been done to study these effects when graphene is in contact with nanoscale metallic objects of specific sizes and concentrations and to investigate if such phenomena are associated with some forms of doping as in conventional semiconductors. As a case study we determine here the local effect of copper nanoparticles (Cu-NPs) on the Fermi energy of graphene domains in large-area graphene thin films. Tight-binding calculations corroborate our Kelvin-probe force microscopy experiments indicating that the Fermi level shifts in the presence of Cu-NPs (corresponding to 0.2 eV at 20% graphene area coverage by Cu) which break the electron-hole symmetry of graphene due to its weak Van der Waals interactions with Cu even in the absence of chemical bonding and charge transfer, in contrast to previous predictions for large and flat metallic contacts.