Current Imaging Tunneling Spectroscopy Research Articles

Deciphering Alloy Composition in Superconducting Single-Layer FeSe1-xSx on SrTiO3(001) Substrates by Machine Learning of STM/S Data.

Scanning tunneling microscopy (STM) is a powerful technique for imaging atomic structure and inferring information on local elemental composition, chemical bonding, and electronic excitations. However, a plain visual analysis of STM images can be challenging for such determination in multicomponent alloys, particularly beyond the diluted limit due to chemical disorder and electronic inhomogeneity. One viable solution is to use machine learning to analyze STM data and identify hidden patterns and correlations. Here, we apply this approach to determine the Se/S concentration in superconducting single-layer FeSe1-xSx alloys epitaxially grown on SrTiO3(001) substrates via molecular beam epitaxy. First, the K-means clustering method is applied to identify defect-related dI/dV tunneling spectra taken by current imaging tunneling spectroscopy. Then, the Se/S ratio is calculated by analyzing the remaining spectra based on the singular value decomposition method. Such analysis provides an efficient and reliable determination of alloy composition and further reveals the correlations of nanoscale chemical inhomogeneity to superconductivity in single-layer iron chalcogenide films.

A millikelvin scanning tunneling microscope in ultra-high vacuum with adiabatic demagnetization refrigeration.

We present the design and performance of an ultra-high vacuum scanning tunneling microscope (STM) that uses adiabatic demagnetization of electron magnetic moments for controlling its operating temperature ranging between 30 mK and 1K with an accuracy of up to 7 μK rms. At the same time, high magnetic fields of up to 8T can be applied perpendicular to the sample surface. The time available for STM experiments at 50 mK is longer than 20 h, at 100 mK about 40 h. The single-shot adiabatic demagnetization refrigerator can be regenerated automatically within 7 h while keeping the STM temperature below 5K. The whole setup is located in a vibrationally isolated, electromagnetically shielded laboratory with no mechanical pumping lines penetrating its isolation walls. The 1K pot of the adiabatic demagnetization refrigeration cryostat can be operated silently for more than 20 days in a single-shot mode using a custom-built high-capacity cryopump. A high degree of vibrational decoupling together with the use of a specially designed minimalistic STM head provides outstanding mechanical stability, demonstrated by the tunneling current noise, STM imaging, and scanning tunneling spectroscopy measurements, all performed on an atomically clean Al(100) surface.

Investigating the effect of electric fields on lead halide perovskites by scanning tunneling microscopy

Lead halide perovskites have emerged as promising absorber materials over the last decade to increase the efficiency of photovoltaics beyond its current limits. However, to further optimize the performance of perovskites more detailed studies need to be performed, which allow for the correlation of film morphology and local electronic properties at the nanoscale. Here, we present a scanning tunneling microscopy (STM) approach to probe the effect of an applied electric field of a methylammonium formamidinium lead triiodide perovskite thin film on the film response by current–voltage spectroscopy, current imaging tunneling spectroscopy, differential conductance mapping, and x-ray absorption spectroscopy by means of synchrotron x-ray STM. We find a strong correlation between the measurement conditions and the obtained current–voltage characteristics when imaging under opposite bias polarities. In particular, we find similarities to already observed poling effects for lead halide perovskites, which result in either a positively or negatively charged interface due to ion and vacancy migration. Our results provide insight into the influence of measurement conditions such as bias polarity on the performance assessment of perovskite thin films by STM.

Scanning tunneling microscopy/spectroscopy study of In/In4Se3 (100) nanosystem⋆

The present paper provides the results of structural studies concerning formation of self-assembled indium deposited nanostructures on the (100) surface of In4Se3 layered semiconductor. We used to study growth orientation of indium-induced nanostructures exploiting small rates and low times of indium deposition by scanning tunneling spectroscopy (STM). We carry out our studies using In4Se3 crystals grown with rather different concentrations of the over-stoichiometric indium in the melt. It has been established that shape of subsequent indium-deposited nanostructures varies from 3D islands, in the case of low-indium-doped crystals, to elongated nanowires, for highly doped ones. Based on a high-resolution STM study, we show that self-assembled quasi-periodical nanowires are oriented along the c -axis of (100) In4Se3 surface. The observed nanostructures have metallic origin as it was acquired by the current imaging tunneling spectroscopy (CITS) studies. We considered that formation of different-shaped indium-deposited nanostructures is powered by concentration of indium nuclei on furrowed (100) In4Se3 surface, which is modulated by the degree of the over-stoichiometric indium during crystal growth subsequently intercalated into the interlayer gap.

Nanoscale investigation of enhanced electron field emission for silver ion implanted/post-annealed ultrananocrystalline diamond films

Silver (Ag) ions are implanted in ultrananocrystalline diamond (UNCD) films to enhance the electron field emission (EFE) properties, resulting in low turn-on field of 8.5 V/μm with high EFE current density of 6.2 mA/cm2 (at an applied field of 20.5 V/μm). Detailed nanoscale investigation by atomic force microscopy based peak force-controlled tunneling atomic force microscopy (PF-TUNA) and ultra-high vacuum scanning tunneling microscopy (STM) based current imaging tunneling spectroscopy (CITS) reveal that the UNCD grain boundaries are the preferred electron emission sites. The two scanning probe microscopic results supplement each other well. However, the PF-TUNA measurement is found to be better for explaining the local electron emission behavior than the STM-based CITS technique. The formation of Ag nanoparticles induced abundant sp2 nanographitic phases along the grain boundaries facilitate the easy transport of electrons and is believed to be a prime factor in enhancing the conductivity/EFE properties of UNCD films. The nanoscale understanding on the origin of electron emission sites in Ag-ion implanted/annealed UNCD films using the scanning probe microscopic techniques will certainly help in developing high-brightness electron sources for flat-panel displays applications.

Anomalous hexagonal superstructure of aluminum oxide layer grown on NiAl(110) surface

A modified method for the fabrication of a highly crystallized layer of aluminum oxide on a NiAl(110) surface is reported. The fabrication method involves the multistep selective oxidation of aluminum atoms on a NiAl(110) surface resulting from successive oxygen deposition and annealing. The surface morphology and local electronic structure of the novel aluminum oxide layer were investigated by high-resolution imaging using scanning tunneling microscopy (STM) and current imaging tunneling spectroscopy. In contrast to the standard fabrication method of aluminum oxide on a NiAl(110) surface, the proposed method produces an atomically flat surface exhibiting a hexagonal superstructure. The superstructure exhibits a slightly distorted hexagonal array of close-packed bright protrusions with a periodicity of 4.5 ± 0.2 nm. Atomically resolved STM imaging of the aluminum oxide layer reveals a hexagonal arrangement of dark contrast spots with a periodicity of 0.27 ± 0.02 nm. On the basis of the atomic structure of the fabricated layer, the formation of α-Al2O3(0001) on the NiAl(110) surface is suggested.

Straight imaging and mechanism behind grain boundary electron emission in Pt-doped ultrananocrystalline diamond films

A detailed scanning tunneling microscopic (STM) investigation is carried out to directly image and understand the mechanism behind enhanced conductivity and electron field emission (EFE) properties for platinum (Pt) ion doped/post-annealed ultrananocrystalline diamond (UNCD) films. Straight imaging of conducting/non-conducting sites is mapped by dynamic scanning tunneling microscopy (D–STM). Energy dissipation mapping and the local current–voltage measurements illustrate that grain boundaries are the conducting/emitting sites. Further, this fact is supported by the high resolution current imaging tunneling spectroscopy (CITS). The formation of abundant conducting sp2 nanographitic phases along the diamond grain boundaries, confirmed from transmission electron microscopic examinations, is believed to be the genuine factor that helps for the easy transport of electrons and hence enhanced the conductivity/emission properties. The fabrication of these films with high conductivity and superior EFE properties is a direct and simple approach which opens up new prospects in flat panel displays and high brightness electron sources. Moreover, we expect the energy dissipation associated with assisted tunneling process of electrons from the tip of STM to sample surface, can be a very useful technique for imaging heterostructured semiconducting surfaces due to their electrical conductivity differences in nanometer scale, which can explain many physical and chemical properties.

Self-Assembly Formation of M-Type Enantiomer of 2,13-Bis(hydroxymethyl)[7]-thiaheterohelicene Molecules on Au(111) Surface Investigated by STM/CITS

Adsorption of the M-type enantiomer of 2,13-bis(hydroxymethyl)[7]-thiaheterohelicene molecules deposited on Au(111) was investigated by scanning tunneling microscopy (STM) and current imaging tunneling spectroscopy (CITS). We observed preferential adsorption at step edges, fcc regions, and fcc elbow regions of the herringbone reconstruction at a low coverage after molecular deposition onto a substrate maintained at 150 ± 20 K. Surprisingly, after molecular deposition onto a substrate maintained at 355 ± 20 K, highly ordered islands exhibiting molecular self-assembly surrounded by disordered areas were observed. The islands consist of self-assembled zigzagged twin rows with the preferential direction tilted clockwise and anticlockwise from the ⟨112⟩ direction of the Au(111) substrate by an angle of 12 ± 2°. A detailed statistical analysis of the twin rows indicated that the unit cell lattice vectors a and b have lengths of 2.4 and 4.4 nm, respectively, with an angle between them of 77°. We postulate an ad...

Correlating the Local Defect-Level Density with the Macroscopic Composition and Energetics of Chalcopyrite Thin-Film Surfaces.

The unusual defect chemistry of polycrystalline Cu(In,Ga)Se2 (CIGSe) thin films is a main issue for a profound understanding of recombination losses in chalcopyrite thin-film solar cells. Especially, impurity-driven passivation of electronic levels due to point defects segregating at the surface and at grain boundaries is extensively debated. By combining current imaging tunneling spectroscopy with photoelectron spectroscopy, the local defect-level density and unusual optoelectronic grain-boundary properties of this material are correlated with the macroscopic energy levels and surface composition. Vacuum annealing of different CIGSe materials provides evidence that Na diffusion from the glass substrate does not affect the surface defect passivation or grain-boundary properties of standard Cu-poor materials. Furthermore, we find no major impact on the observed thermally activated dipole compensation or the accompanying change in surface band bending (up to 0.6 eV) due to Na. In contrast, Cu-rich CIGSe shows an opposing surface defect chemistry with only minor heat-induced band bending. Our results lead to a comprehensive picture, where the highly desirable type inversion at the p/n interface in standard chalcopyrite thin-film solar cells is dominated by band bending within the CIGSe absorber rather than the result of Na impurities or an n-type defect phase segregating at the interface. This is in accordance with recent studies suggesting a surface reconstruction as the origin for Cu depletion and band-gap widening at the surface of chalcopyrite thin films.

Research Update: Spatially resolved mapping of electronic structure on atomic level by multivariate statistical analysis

Atomic level spatial variability of electronic structure in Fe-based superconductor FeTe0.55Se0.45 (Tc = 15 K) is explored using current-imaging tunneling-spectroscopy. Multivariate statistical analysis of the data differentiates regions of dissimilar electronic behavior that can be identified with the segregation of chalcogen atoms, as well as boundaries between terminations and near neighbor interactions. Subsequent clustering analysis allows identification of the spatial localization of these dissimilar regions. Similar statistical analysis of modeled calculated density of states of chemically inhomogeneous FeTe1−xSex structures further confirms that the two types of chalcogens, i.e., Te and Se, can be identified by their electronic signature and differentiated by their local chemical environment. This approach allows detailed chemical discrimination of the scanning tunneling microscopy data including separation of atomic identities, proximity, and local configuration effects and can be universally applicable to chemically and electronically inhomogeneous surfaces.

Direct observation and mechanism for enhanced field emission sites in platinum ion implanted/post-annealed ultrananocrystalline diamond films

Enhanced electron field emission (EFE) properties for ultrananocrystalline diamond (UNCD) films upon platinum (Pt) ion implantation and subsequent post-annealing processes is reported, viz., low turn-on field of 4.17 V/μm with high EFE current density of 5.08 mA/cm2 at an applied field of 7.0 V/μm. Current imaging tunneling spectroscopy (CITS) mode in scanning tunneling spectroscopy directly revealed the increased electron emission sites density for Pt ion implanted/post-annealed UNCD films than the pristine one. The high resolution CITS mapping and local current–voltage characteristic curves demonstrated that the electrons are dominantly emitted from the diamond grain boundaries and Pt nanoparticles.

Effects of temperature and ammonia flow rate on the chemical vapour deposition growth of nitrogen-doped graphene.

We doped graphene in situ during synthesis from methane and ammonia on copper in a low-pressure chemical vapour deposition system, and investigated the effect of the synthesis temperature and ammonia concentration on the growth. Raman and X-ray photoelectron spectroscopy was used to investigate the quality and nitrogen content of the graphene and demonstrated that decreasing the synthesis temperature and increasing the ammonia flow rate results in an increase in the concentration of nitrogen dopants up to ca. 2.1% overall. However, concurrent scanning electron microscopy studies demonstrate that decreasing both the growth temperature from 1000 to 900 °C and increasing the N/C precursor ratio from 1/50 to 1/10 significantly decreased the growth rate by a factor of six overall. Using scanning tunnelling microscopy we show that the nitrogen was incorporated mainly in substitutional configuration, while current imaging tunnelling spectroscopy showed that the effect of the nitrogen on the density of states was visible only over a few atom distances.

High resolution scanning tunneling microscopy of a 1D coordination polymer with imidazole-based N,N,O ligands on HOPG.

Novel κ(3) -N,N,O ligands tend to form 1D coordination polymer strands. Deposition of 1D structures on highly oriented pyrolytic graphite (HOPG) was achieved from diluted solutions and polymer strands have been studied on HOPG by AFM/STM. Single strands were mapped by STM and their electronic properties were subsequently characterized by current imaging tunneling spectroscopy (CITS). Periodic density functional calculations simulating a polymer strand deposited on a HOPG surface are in agreement with the zig-zag structure indicated by experimental findings. Both the observed periodicity and the Zn-Zn distances can be reproduced in the simulations. Van der Waals interactions were found to play a major role for the geometry of the isolated polymer strand, for the adsorption geometry on HOPG, as well as for the adsorption energy.

Imaging of buried phosphorus nanostructures in silicon using scanning tunneling microscopy

We demonstrate the locating and imaging of single phosphorus atoms and phosphorus dopant nanostructures, buried beneath the Si(001) surface using scanning tunneling microscopy. The buried dopant nanostructures have been fabricated in a bottom-up approach using scanning tunneling microscope lithography on Si(001). We find that current imaging tunneling spectroscopy is suited to locate and image buried nanostructures at room temperature and with residual surface roughness present. From these studies, we can place an upper limit on the lateral diffusion during encapsulation with low-temperature Si molecular beam epitaxy.

Direct observation and mechanism for enhanced electron emission in hydrogen plasma-treated diamond nanowire films.

The effect of hydrogen plasma treatment on the electrical conductivity and electron field emission (EFE) properties for diamond nanowire (DNW) films were systematically investigated. The DNW films were deposited on silicon substrate by N2-based microwave plasma-enhanced chemical vapor deposition process. Transmission electron microscopy depicted that DNW films mainly consist of wirelike diamond nanocrystals encased in a nanographitic sheath, which formed conduction channels for efficient electron transport and hence lead to excellent electrical conductivity and EFE properties for these films. Hydrogen plasma treatment initially enhanced the electrical conductivity and EFE properties of DNW films and then degraded with an increase in treatment time. Scanning tunneling spectroscopy in current imaging tunneling spectroscopy mode clearly shows significant increase in local emission sites in 10 min hydrogen plasma treated diamond nanowire (DNW10) films as compared to the pristine films that is ascribed to the formation of graphitic phase around the DNWs due to the hydrogen plasma treatment process. The degradation in EFE properties of extended (15 min) hydrogen plasma-treated DNW films was explained by the removal of nanographitic phase surrounding the DNWs. The EFE process of DNW10 films can be turned on at a low field of 4.2 V/μm and achieved a high EFE current density of 5.1 mA/cm(2) at an applied field of 8.5 V/μm. Moreover, DNW10 films with high electrical conductivity of 216 (Ω cm)(-1) overwhelm that of other kinds of UNCD films and will create a remarkable impact to diamond-based electronics.

Enhanced Electron Field Emission Properties of Conducting Ultrananocrystalline Diamond Films after Cu and Au Ion Implantation

The effects of Cu and Au ion implantation on the structural and electron field emission (EFE) properties of ultrananocrystalline diamond (UNCD) films were investigated. High electrical conductivity of 186 (Ω•cm)(-1) and enhanced EFE properties with low turn-on field of 4.5 V/μm and high EFE current density of 6.70 mA/cm(2) have been detected for Au-ion implanted UNCD (Au-UNCD) films that are superior to those of Cu-ion implanted UNCD (Cu-UNCD) ones. Transmission electron microscopic investigations revealed that Au-ion implantation induced a larger proportion of nanographitic phases at the grain boundaries for the Au-UNCD films in addition to the formation of uniformly distributed spherically shaped Au nanoparticles. In contrast, for Cu-UNCD films, plate-like Cu nanoparticles arranged in the row-like pattern were formed, and only a smaller proportion of nanographite phases along the grain boundaries was induced. From current imaging tunneling spectroscopy and local current-voltage curves of scanning tunneling spectroscopic measurements, it is observed that the electrons are dominantly emitted from the grain boundaries. Consequently, the presence of nanosized Au particles and the induction of abundant nanographitic phases in the grain boundaries of Au-UNCD films are believed to be the authentic factors, ensuing in high electrical conductivity and outstanding EFE properties of the films.

Enhancing electrical conductivity and electron field emission properties of ultrananocrystalline diamond films by copper ion implantation and annealing

Copper ion implantation and subsequent annealing at 600 °C achieved high electrical conductivity of 95.0 (Ωcm)−1 for ultrananocrystalline diamond (UNCD) films with carrier concentration of 2.8 × 1018 cm−2 and mobility of 6.8 × 102 cm2/V s. Transmission electron microscopy examinations reveal that the implanted Cu ions first formed Cu nanoclusters in UNCD films, which induced the formation of nanographitic grain boundary phases during annealing process. From current imaging tunneling spectroscopy and local current-voltage curves of scanning tunneling spectroscopic measurements, it is observed that the electrons are dominantly emitted from the grain boundaries. Consequently, the nanographitic phases presence in the grain boundaries formed conduction channels for efficient electron transport, ensuing in excellent electron field emission (EFE) properties for copper ion implanted/annealed UNCD films with low turn-on field of 4.80 V/μm and high EFE current density of 3.60 mA/cm2 at an applied field of 8.0 V/μm.

Study on the Microstructure and Electrical Properties of Boron and Sulfur Codoped Diamond Films Deposited Using Chemical Vapor Deposition

The atomic‐scale microstructure and electron emission properties of boron and sulfur (denoted as B‐S) codoped diamond films grown on high‐temperature and high‐pressure (HTHP) diamond and Si substrates were investigated using atom force microscopy (AFM), scanning tunneling microscopy (STM), secondary ion mass spectroscopy (SIMS), and current imaging tunneling spectroscopy (CITS) measurement techniques. The films grown on Si consisted of large grains with secondary nucleation, whereas those on HTHP diamond are composed of well‐developed polycrystalline facets with an average size of 10–50 nm. SIMS analyses confirmed that sulfur was successfully introduced into diamond films, and a small amount of boron facilitated sulfur incorporation into diamond. Large tunneling currents were observed at some grain boundaries, and the emission character was better at the grain boundaries than that at the center of the crystal. The films grown on HTHP diamond substrates were much more perfect with higher quality than the films deposited on Si substrates. The local I-V characteristics for films deposited on Si or HTHP diamond substrates indicate n‐type conduction.

Multidimensional SPM applied for nanoscale conductance mapping

Abstract

The induction of nanographitic phase on Fe coated diamond films for the enhancement in electron field emission properties

A thin layer of iron coating and subsequent post-annealing (Fe-coating/post-annealing) is seen to significantly enhance the electron field emission (EFE) properties of ultrananocrystalline diamond (UNCD) films. The best EFE properties, with a turn on field (E0) of 1.98 V/μm and current density (Je) of 705 μA/cm2 at 7.5 V/μm, are obtained for the films, which were Fe-coated/post-annealed at 900 °C in H2 atmosphere. The mechanism behind the enhanced EFE properties of Fe coated/post-annealed UNCD films are explained by the microstructural analysis which shows formation of nanographitic phase surrounding the Fe (or Fe3C) nanoparticles. The role of the nanographitic phase in improving the emission sites of Fe coated/post-annealed UNCD films is clearly revealed by the current imaging tunneling spectroscopy (CITS) images. The CITS images clearly show significant increase in emission sites in Fe-coated/post-annealed UNCD films than the as-deposited one. Enhanced emission sites are mostly seen around the boundaries of the Fe (or Fe3C) nanoparticles which were formed due to the Fe-coating/post-annealing processes. Moreover, the Fe-coating/post-annealing processes enhance the EFE properties of UNCD films more than that on the microcrystalline diamond films. The authentic factor, resulting in such a phenomenon, is attributed to the unique granular structure of the UNCD films. The nano-sized and uniformly distributed grains of UNCD films, resulted in markedly smaller and densely populated Fe-clusters, which, in turn, induced more finer and higher populated nano-graphite clusters.