Local Contact Potential Difference Research Articles

Atomic force microscopy observation of surface morphologies and measurements of local contact potential differences of amorphous solid water samples deposited at 15 and 100 K.

We use an ultra-high vacuum cryogenic atomic force microscope to investigate the surface morphology of amorphous solid water (ASW) prepared by oblique deposition of water vapor onto Si(111)7 × 7 substrates at temperatures of 15 and 100 K. Height-height correlation function analysis of topographic images suggests that ASW at 15 K has a columnar structure and that the typical diameter of the column is 5-10 nm. At 100 K, the typical diameter is 10-30 nm, although columnar features are less prominent. The surface roughness (i.e., deviation of the height) is greater at 15 K than at 100 K, indicating that the surface at 100 K exhibits a relatively flat morphology. This result implies that transient diffusion of deposited water molecules affects the surface morphology at 100 K. In addition, measurements of the local contact potential difference between the tip and the ASW surface suggest that the magnitude of the negative surface potential at the microscopic scale, which is attributed to spontaneous polarisation, cannot simply be scaled by the thickness of ASW as predicted in previous experiments with Kelvin probes.

Measurement of distribution of charge adsorbed on Au<i><sub>x</sub></i>/Si(111)-7×7 surface on an atomic scale in ultra-high vacuum

The physicochemical properties of Au atoms adsorbed on the surface on an atomic scale play a very important role in preparing nanodevices and surface catalysis. In this paper, we use frequency modulated Kelvin probe force microscopy (FM-KPFM)to study the multi-bit adsorbed charge distribution of Au on the surface of Si(111)-(7×7) at room temperature. Firstly, the surface topography and local contact potential difference (LCPD) of Au at different adsorption sites in Si(111)-(7×7) are successfully obtained by using home-made ultra-high vacuum Kelvin probe force microscopy. Secondly, we analyze the atomic characteristics of specific atomic positions of Au/Si(111)-(7×7) by force spectroscopy and potential difference, and realize the atomic identification . The adsorption characteristics of Au/Si(111)-(7×7) surface charge transfer and Au are explained by combining differential charge density calculations. The results show that Au atom adsorption mainly is in the form of single atom and cluster . Specifically, the Au cluster is adsorbed at the three central positions of Si(111)-(7×7) in a hexagonal structure of six atoms. Individual Au atoms are adsorbed to the positions of central adatoms of Si(111)-(7×7). At the same time, through the measurement of potential difference, it is known that a single Au atom and Au cluster lose electrons, presenting a positive electrical characteristic. The results of surface differential charge density show that Au undergoes charge transfer during adsorption, losing part of the charge, which locally reduces the work function at the position of the adsorbed atom. In the range of distances where short-range forces, local contact potential energy differences and differential charge densities change, the theoretical results and experimental results are in reasonable agreement.

Effect of amorphous calcium phosphate coatings on tribological properties of titanium grade 4 in protein-free artificial saliva

Progress in dental implant prosthetics largely depends on developing new biomaterials and understanding the complex processes of their tissue adaptation. The related tribological wear phenomena within the dental system determine the durability and quality of the newly developed dental biomaterials. This paper presents an assessment of the tribological wear of the amorphous calcium phosphate (ACP) coatings on the commercially pure titanium Grade 4 (CpTi G4) substrate subjected to sandblasting and autoclaving in artificial saliva. The ACP coatings were produced using electrochemically assisted deposition (ECAD). The tribological properties were studied in a reciprocating motion in the system of ball-on-disc in protein-free artificial saliva. The surface morphology and chemical composition was characterized using the SEM and EDS method, respectively. The surface wettability was tested using the sitting drop in the air. It was found that the presence of the ECAD-derived ACP coating increases surface roughness, local contact potential difference, surface wettability, and resistance to tribological wear of CpTi G4 substrate significantly improving its service life. The tribological wear of CpTi G4/ACP occurred according to the three-body abrasion wear mechanism, in which artificial saliva played a key role as a biological lubricant.

Measurement of local contact potential difference of atomic scale Au/Si(111)-(7×7) delocalized adsorption state in room-temperature and ultra-high vacuum environment

The structural properties and local contact potential difference of Au on Si(111)-(7×7) surface are studied by the homemade ultra-high vacuum non-contact Kelvin probe force microscope. Although scanning tunneling microscopy has been widely used to study the metal- adsorbed semiconductor surfaces on an atomic scale, the tunnel current measured by scanning tunneling microscopy is easy to lead the charge states to accidentally switch in the measurement process, and it is limited only to the observation of metal and semiconductor surfaces. Kelvin probe force microscope allows us to directly measure the charges at different positions of various flat surfaces by local contact potential difference on an atomic scale, which has become a more convenient and accurate means of charge characterization. In this paper, the topography and local contact potential difference of Au adsorbed Si(111)-(7×7) surface are measured on an atomic scale by Kelvin probe force microscope at room temperature, and the corresponding adsorption model and first principle calculation are established. The differential charge density distribution of the stable adsorption position of Au/Si(111)-(7×7) is obtained, and the local contact potential energy difference relationship of the stable adsorption position of Au on Si surface is given, The mechanism of charge transfer between Au atom and Si(111)-(7×7) surface during adsorption is analyzed. The experimental results show that at room temperature, single Au atom will form triangular delocalized adsorption state in the half unit cell of Si(111)-(7×7). The delocalized adsorption state is due to the fact that the moving speed of a single Au atom in the HUC is faster than the scanning speed of Kelvin probe force microscope, and the local contact potential difference measurement of Au/Si(111)-(7×7) adsorbed surface can effectively identify Au and Si atoms. Obviously, this research is of great significance in promoting the development of surface charge precision measurement, and is expected to provide some insights into the charge properties of metal adsorbed semiconductor surfaces.

On‐Surface Synthesis of a Dicationic Diazahexabenzocoronene Derivative on the Au(111) Surface

AbstractThe atomically precise control over the size, shape and structure of nanographenes (NGs) or the introduction of heteroatom dopants into their sp2‐carbon lattice confer them valuable electronic, optical and magnetic properties. Herein, we report on the design and synthesis of a hexabenzocoronene derivative embedded with graphitic nitrogen in its honeycomb lattice, achieved via on‐surface assisted cyclodehydrogenation on the Au(111) surface. Combined scanning tunnelling microscopy/spectroscopy and non‐contact atomic force microscopy investigations unveil the chemical and electronic structures of the obtained dicationic NG. Kelvin probe force microscopy measurements reveal a considerable variation of the local contact potential difference toward lower values with respect to the gold surface, indicative of its positive net charge. Altogether, we introduce the concept of cationic nitrogen doping of NGs on surfaces, opening new avenues for the design of novel carbon nanostructures.

On-Surface Synthesis of a Dicationic Diazahexabenzocoronene Derivative on the Au(111) Surface.

The atomically precise control over the size, shape and structure of nanographenes (NGs) or the introduction of heteroatom dopants into their sp2‐carbon lattice confer them valuable electronic, optical and magnetic properties. Herein, we report on the design and synthesis of a hexabenzocoronene derivative embedded with graphitic nitrogen in its honeycomb lattice, achieved via on‐surface assisted cyclodehydrogenation on the Au(111) surface. Combined scanning tunnelling microscopy/spectroscopy and non‐contact atomic force microscopy investigations unveil the chemical and electronic structures of the obtained dicationic NG. Kelvin probe force microscopy measurements reveal a considerable variation of the local contact potential difference toward lower values with respect to the gold surface, indicative of its positive net charge. Altogether, we introduce the concept of cationic nitrogen doping of NGs on surfaces, opening new avenues for the design of novel carbon nanostructures.

Open-loop amplitude-modulation Kelvin probe force microscopy operated in single-pass PeakForce tapping mode.

The open-loop (OL) variant of Kelvin probe force microscopy (KPFM) provides access to the voltage response of the electrostatic interaction between a conductive atomic force microscopy (AFM) probe and the investigated sample. The measured response can be analyzed a posteriori, modeled, and interpreted to include various contributions from the probe geometry and imaged features of the sample. In contrast to this, the currently implemented closed-loop (CL) variants of KPFM, either amplitude-modulation (AM) or frequency-modulation (FM), solely report on their final product in terms of the tip–sample contact potential difference. In ambient atmosphere, both CL AM-KPFM and CL FM-KPFM work at their best during the lift part of a two-pass scanning mode to avoid the direct contact with the surface of the sample. In this work, a new OL AM-KPFM mode was implemented in the single-pass scan of the PeakForce Tapping (PFT) mode. The topographical and electrical components were combined in a single pass by applying the electrical modulation only in between the PFT tip–sample contacts, when the AFM probe separates from the sample. In this way, any contact and tunneling discharges are avoided and, yet, the location of the measured electrical tip–sample interaction is directly affixed to the topography rendered by the mechanical PFT modulation at each tap. Furthermore, because the detailed response of the cantilever to the bias stimulation was recorded, it was possible to analyze and separate an average contribution of the cantilever to the determined local contact potential difference between the AFM probe and the imaged sample. The removal of this unwanted contribution greatly improved the accuracy of the AM-KPFM measurements to the level of the FM-KPFM counterpart.

Towards understanding micro-galvanic activities in localised corrosion of AA2099 aluminium alloy

The micro-galvanic interactions between Cu-Fe-Mn-Li-containing aluminides and the alloy matrix of aluminium alloy AA2099 during chloride-induced corrosion were investigated in-situ with real-time monitoring of the local contact potential difference (VCPD) using the scanning Kelvin probe force microscopy (SKPFM) at controlled relative humidities. The aluminides showed noble potentials and were able to ennoble their neighbouring matrix sites when a cluster of aluminides surrounded the matrix. The matrix, hence, adopted a more positive VCPD, towards that of the aluminides. The anode-to-cathode ratio changed throughout the corrosion exposure and was seen to show a dynamic character. Much higher local VCPD activities were recorded during the earliest stages of corrosion, when the Al-Li AA2099 surface was first exposed to high humidities, than in later RH cycles; a phenomenon not seen in other aluminium alloys.

Work function difference of naphthyl end-capped oligothiophene in different crystal alignments studied by Kelvin probe force microscopy

The performance of organic semiconductor devices is strongly affected by the interface energetics at the junctions between the constituent materials. A large group of organic semiconductors consists of rodlike small molecules that crystallize upon deposition with a molecular orientation dependent on the specifics of the molecule–molecule and molecule–substrate interactions. By means of Kelvin probe force microscopy (KPFM), this work studies naphthyl end-capped oligothiophene, 5,50-bis(naphth-2-yl)-2,20-bithiophene (NaT2), deposited on samples of pristine SiO 2 and samples of graphene-covered SiO 2 . The crystal molecular orientation of NaT2 is dependent on the substrate on which it is deposited. On SiO 2 , the NaT2 molecules are predominately upright standing, forming crystallites with distinct terrace heights of 2 . 0 ± 0 . 1 nm . Measurements indicate formation of an initial wetting layer in the NaT2- SiO 2 system for the upright standing molecules. When deposited on graphene, the molecules additionally form fibrous structures with heights of 10 − 115 nm consisting of molecules lying down (face-on orientation). Using KPFM, a difference in the local contact potential difference (CPD) of upright standing NaT2 and face-on oriented structures on graphene is measured to be − 0 . 16 ± 0 . 04 V , indicating a work function difference between the two system configurations, which is confirmed through Density Functional Theory calculations. • The work function of a molecule is affected by its orientation on the substrate. • KPFM measures the contact potential difference that is related to the work function. • KPFM can distinguish different orientations of NaT2 on graphene- SiO 2 substrate. • DFT reveals that the electron distribution causes the difference in work function.

Multi-Channel Exploration of O Adatom on TiO2(110) Surface by Scanning Probe Microscopy.

We studied the O2 dissociated state under the different O2 exposed temperatures with atomic resolution by scanning probe microscopy (SPM) and imaged the O adatom by simultaneous atomic force microscopy (AFM)/scanning tunneling microscopy (STM). The effect of AFM operation mode on O adatom contrast was investigated, and the interaction of O adatom and the subsurface defect was observed by AFM/STM. Multi-channel exploration was performed to investigate the charge transfer between the adsorbed O and the TiO2(110) by obtaining the frequency shift, tunneling current and local contact potential difference at an atomic scale. The tunneling current image showed the difference of the tunneling possibility on the single O adatom and paired O adatoms, and the local contact potential difference distribution of the O-TiO2(110) surface institutively revealed the charge transfer from TiO2(110) surface to O adatom. The experimental results are expected to be helpful in investigating surface/interface properties by SPM.

Direct study of the electrical properties of PC12 cells and hippocampal neurons by EFM and KPFM.

Electrical related properties play important roles in biological structures and functions. Herein, the capacitance gradient and local contact potential difference (CPD) of cell bodies and processes of PC12 cells (representative cells of the sympathetic nervous system), hippocampal neurons (representative cells of the central nervous system) and spines were investigated by Electrostatic Force Microscopy (EFM) and Kelvin Probe Force Microscopy (KPFM) at high lateral spatial resolution directly. The results demonstrate that the capacitance gradients of cell bodies, processes and spines of PC12 cells and hippocampal neurons are very close (in the range of 19–23 zF nm−1) and fit well with the theoretical calculation results (21.7 zF nm−1). This indicates that the differences of nerve signal activities and functions of the sympathetic and central nervous systems are not related to the electric polarization properties. The CPD of cell bodies and processes of PC12 cells is smaller than that of hippocampal neurons. The CPD of spines is much more negative than that of the cell bodies and processes. These results reveal that the surface potential is closely related to the neural signal transduction functions, and spines play vital roles in neural signal transmission. This work indicates the similarity (capacitance gradient) and differences (surface potential) of the electrical properties between the sympathetic and central nervous systems for the first time. The methods and results of this work are useful in the further study of the electrical properties in cellular activities and physiological processes.

Laser-Based Texturing of Graphene to Locally Tune Electrical Potential and Surface Chemistry.

A simple procedure of producing three-dimensional blisters of graphene through irradiation of the visible range laser by Raman spectrometer has been presented. Fabrication of different volumes of the blisters and their characterization were carried out with Raman spectroscopy by tuning the irradiation dose. The produced blisters showed a consistency in altitude and a remarkable change in functionality, adhesion force map and local contact potential difference as compared to untreated monolayer graphene and naturally occurred graphene nanobubbles. Nevertheless, bilayer graphene is unaffected in the applied laser doses. The laser irradiation led to lattice expansion of carbon atoms and introduced oxygenic functional groups with the structural disorder. The internal pressure of the gaseous molecules was evaluated by monitoring the shape of the graphene blisters and nanobubbles. High-resolution Raman mapping showed the impact of laser-affected area and the defect density (nd) is reported as a function of displacement. Our results reveal ease of applicability of the Raman laser for the imaging and texturing of graphene pointing toward the possibility of the desirable and cost-effective laser writing at the submicron scale by tuning photochemistry of graphene which is pivotal for numerous applications.

Measurement and Manipulation of the Charge State of an Adsorbed Oxygen Adatom on the Rutile TiO2(110)-1×1 Surface by nc-AFM and KPFM.

For the first time, the charge states of adsorbed oxygen adatoms on the rutile TiO2(110)-1×1 surface are successfully measured and deliberately manipulated by a combination of noncontact atomic force microscopy and Kelvin probe force microscopy at 78 K under ultrahigh vacuum and interpreted by extensive density functional theory modeling. Several kinds of single and double oxygen adatom species are clearly distinguished and assigned to three different charge states: Oad-/2Oad-, Oad2-/2Oad2-, and Oad--Oad2-, i.e., formal charges of either one or two electrons per atom. Because of the strong atomic-scale image contrast, these states are clearly resolved. The observations are supported by measurements of the short-range force and local contact potential difference as a function of the tip-sample distance as well as simulations. Comparison with the simulations suggests subatomic resolution by allowing us to resolve the rotated oxygen p orbitals. In addition, we manage to reversibly switch the charge states of the oxygen adatoms between the Oad- and Oad2- states, both individually and next to another oxygen, by modulating the frequency shift at constant positive voltage during both charging and discharging processes, i.e., by the tip-induced electric field of one orientation. This work provides a novel route for the investigation of the charge state of the adsorbates and opens up novel prospects for studying transition-metal-oxide-based catalytic reactions.

Elemental Identification by Combining Atomic Force Microscopy and Kelvin Probe Force Microscopy.

There are currently no experimental techniques that combine atomic-resolution imaging with elemental sensitivity and chemical fingerprinting on single molecules. The advent of using molecular-modified tips in noncontact atomic force microscopy (nc-AFM) has made it possible to image (planar) molecules with atomic resolution. However, the mechanisms responsible for elemental contrast with passivated tips are not fully understood. Here, we investigate elemental contrast by carrying out both nc-AFM and Kelvin probe force microscopy (KPFM) experiments on epitaxial monolayer hexagonal boron nitride (hBN) on Ir(111). The hBN overlayer is inert, and the in-plane bonds connecting nearest-neighbor boron and nitrogen atoms possess strong covalent character and a bond length of only ∼1.45 Å. Nevertheless, constant-height maps of both the frequency shift Δf and the local contact potential difference exhibit striking sublattice asymmetry. We match the different atomic sites with the observed contrast by comparison with nc-AFM image simulations based on the density functional theory optimized hBN/Ir(111) geometry, which yields detailed information on the origin of the atomic-scale contrast.

KPFM/AFM imaging on TiO2(110) surface in O2 gas

We have carried out high-speed imaging of the topography and local contact potential difference (LCPD) on rutile TiO2(110) in O2 gas by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We succeeded in KPFM/AFM imaging with atomic resolution at 1 frame min−1 and observed the adsorbate on a hydroxylated TiO2(110) surface. The observed adsorbate is considered to be oxygen adatoms (Oa), hydroperoxyls (HO2), or terminal hydroxyls (OHt). After adsorption, changes in the topography and the LCPD of the adsorbate were observed. This phenomenon is thought to be caused by the charge transfer of the adsorbate. This technique has the potential to observe catalytic behavior with atomic resolution.

A full monolayer of superoxide: oxygen activation on the unmodified Ca3Ru2O7(001) surface.

Activating the O2 molecule is at the heart of a variety of technological applications, most prominently in energy conversion schemes including solid oxide fuel cells, electrolysis, and catalysis. Perovskite oxides, both traditionally-used and novel formulations, are the prime candidates in established and emerging energy devices. This work shows that the as-cleaved and unmodified CaO-terminated (001) surface of Ca3Ru2O7, a Ruddlesden-Popper perovskite, supports a full monolayer of superoxide ions, O2-, when exposed to molecular O2. The electrons for activating the molecule are transferred from the subsurface RuO2 layer. Theoretical calculations using both, density functional theory (DFT) and more accurate methods (RPA), predict the adsorption of O2- with Eads = 0.72 eV and provide a thorough analysis of the charge transfer. Non-contact atomic force microscopy (nc-AFM) and scanning tunnelling microscopy (STM) are used to resolve single molecules and confirm the predicted adsorption structures. Local contact potential difference (LCPD) and X-ray photoelectron spectroscopy (XPS) measurements on the full monolayer of O2- confirm the negative charge state of the molecules. The present study reports the rare case of an oxide surface without dopants, defects, or low-coordinated sites readily activating molecular O2.

Tuning properties of carbon surfaces functionalized with amino-ended dendron layers by exploring their supramolecular interactions

An effective tailoring of carbon surfaces functionalized with a first-generation amino-ended dendrons was achieved by a simple self-assembly strategy. The morphology, as well as the viscoelastic and electrical properties of the modified surfaces were characterized at a micro-nanoscale level, by Cyclic Voltammetry (CV), Electrochemical Impedance Spectroscopy (EIS), Atomic Force Microscopy (AFM) and Kelvin Probe Force Microscopy (KPFM). Thermodynamic parameters of the adsorption were investigated by EIS, studying the blocking properties of the modified surfaces towards the redox conversion of [Fe(CN)6]3−/[Fe(CN)6]4−. AFM images were used to characterize the topography of the modified surfaces and also their viscoelastic properties by the acquisition of phase images. π-π stacking interactions between dendrons and the carbon surface control the aggregation at low coverages, while forces of intermolecular Hydrogen-bond among dendrons appear at high coverages leading to more compact regions. The implications of the amino-ended dendron layer on the electrical properties of the modified surface have been analyzed through KPFM in comparison with nitro-ended dendron films, showing a decrease of the local contact potential difference after the incorporation of molecules having electron-donor (−NH2) functional groups, in contrast with the increase showed for molecules with electron-acceptor (−NO2) ones.

Surface potential modeling and reconstruction in Kelvin probe force microscopy

Kelvin probe force microscopy (KPFM) measurement has been extensively applied in metallic, semiconductor and organic electronic or photovoltaic devices, to characterize the local contact potential difference or surface potential of the samples at the nanoscale. Here, a comprehensive modeling of surface potential in KPFM is established, from the well-known single capacitance model to a precise electrodynamic model, considering the long range property of the electrostatic force in KPFM. The limitations and relations of different models are also discussed. Besides, the feedback condition of the KPFM system is reconsidered and modified, showing that the influence of the cantilever has been overestimated by about 20% in previous reports. Afterwards, the surface potential of charged Si-nanocrystals is reconstructed based on the electrodynamic model, and the calculated surface charge density is very consistent with the macroscopic capacitance–voltage (C–V) measurement. A deep understanding and correct reconstruction of surface potential is crucial to the quantitative analysis of KPFM results.

FM-AFM/KPFMによるルチル型TiO2(110)表面上の局所接触電位差に関する研究

FM-AFM/KPFMによるルチル型TiO2(110)表面上の局所接触電位差に関する研究

A scanning probe mounted on a field-effect transistor: Characterization of ion damage in Si

We have examined the capabilities of a Tip-On-Gate of Field-Effect Transistor (ToGoFET) probe for characterization of FIB-induced damage in Si surface. A ToGoFET probe is the SPM probe which the Field Effect Transistor(FET) is embedded at the end of a cantilever and a Pt tip was mounted at the gate of FET. The ToGoFET probe can detect the surface electrical properties by measuring source-drain current directly modulated by the charge on the tip. In this study, a Si specimen whose surface was processed with Ga+ ion beam was prepared. Irradiation and implantation with Ga+ ions induce highly localized modifications to the contact potential. The FET embedded on ToGoFET probe detected the surface electric field profile generated by schottky contact between the Pt tip and the sample surface. Experimentally, it was shown that significant differences of electric field due to the contact potential barrier in differently processed specimens were observed using ToGOFET probe. This result shows the potential that the local contact potential difference can be measured by simple working principle with high sensitivity.