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An ultra-high-vacuum compatible X-ray chopper system has been designed, constructed and integrated into the XTIP beamline at the Advanced Photon Source at Argonne National Laboratory. The XTIP beamline can operate at soft X-ray energies from 400 eV to 1900 eV while providing a focused beam down to about 10 µm × 10 µm into the synchrotron X-ray scanning tunneling microscopy (SX-STM) endstation instrument. The X-ray chopper is a critical component for separating topographic information from chemical information in SX-STM through phase-sensitive current detection. Depending on the experimental needs, the modulation frequency can be controlled from 100 Hz to 10 kHz. In addition, the chopper system is fully bakeable and can achieve a base pressure of 10−10 mbar. Facilities for active water cooling have been designed, but passive cooling through copper braids has been shown to be sufficient at standard chopping frequencies. Using an Fe/Al2O3/CoAl(111) sample, the separation of the SX-STM current into a chemical component and a stable feedback signal is demonstrated.

Side reactions involving surface reduction play a critical role in the failure of LiNi0.8Co0.15Al0.05O2 to reach its theoretical capacity as a cathode material for Li-ion batteries. While macroscop...

A new beamline, XTIP, has been constructed at the Advanced Photon Source to deliver monochromatic soft X-rays of between 400 and 1900 eV for the emerging synchrotron X-ray scanning tunneling microscopy technique., In recent years, there have been numerous efforts worldwide to develop the synchrotron X-ray scanning tunneling microscopy (SX-STM) technique. Here, the inauguration of XTIP, the world’s first beamline fully dedicated to SX-STM, is reported. The XTIP beamline is located at Sector 4 of the Advanced Photon Source at Argonne National Laboratory. It features an insertion device that can provide left- or right-circular as well as horizontal- and vertical-linear polarization. XTIP delivers monochromatic soft X-rays of between 400 and 1900 eV focused into an environmental enclosure that houses the endstation instrument. This article discusses the beamline system design and its performance.

Synchrotron X-ray Scanning Tunneling Microscopy (SX-STM) is a novel imaging technique capable of providing real space chemically specific mapping with a potential of reaching atomic resolution. Determination of chemical composition along with ultra-high resolution imaging by SX-STM can be realized through excitation of core electrons by incident X-rays when their energy is tuned to an absorption edge of a particular atom during raster scanning, as is done in the conventional STM experiments. In this work, we provide a brief summary and the current status of SX-STM and discuss its applications for material science. In particular, we discuss instrumentation challenges associated with the SX-STM technique and present early experiments on Cu doped ZrTe3 single crystals.

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.

X-ray beam-induced damage in nanoscale metal islands was investigated. Monolayer-high Ni islands were prepared on a Cu(111) substrate. High brilliance X-rays with photon energies between 8.45 and 8.85 keV illuminated the sample for about 11 hours. In order to track changes in the morphology of the islands, the synchrotron X-ray scanning tunneling microscopy (SX-STM) technique was utilized. The result shows that X-ray illumination onto Ni islands does not induce noticeable damage. The study demonstrates that local beam-induced changes can be studied using SX-STM.

The combination of the high spatial resolution of scanning tunneling microscopy with the chemical and magnetic contrast provided by synchrotron X-rays has the potential to allow a unique characterization of advanced functional materials. While the scanning probe provides the high spatial resolution, synchrotron X-rays that produce photo-excitations of core electrons add chemical and magnetic contrast. However, in order to realize the method's full potential it is essential to maintain tunneling conditions, even while high brilliance X-rays irradiate the sample surface. Different from conventional scanning tunneling microscopy, X-rays can cause a transition of the tip out of the tunneling regime. Monitoring the reaction of the z-piezo (the element that controls the tip to sample separation) alone is not sufficient, because a continuous tip current is obtained. As a solution, an unambiguous and direct way of fingerprinting such near to far field transitions of the tip that relies on the simultaneous analysis of the X-ray-induced tip and sample current is presented. This result is of considerable importance because it opens the path to the ultimate resolution in X-ray enhanced scanning tunneling microscopy.

The real-space observation of magnetic structure using scanning probe microscopy (SPM) methods or synchrotron-based microscopy continues to have a tremendous impact on our understanding of functional magnetic materials. However, although SPM methods provide high spatial resolution, they lack direct chemical contrast and the ability to quantify magnetic moments. X-ray microscopy, on the other hand, can provide chemical as well as magnetic sensitivity, but the spatial resolution is limited.

A tunneling smart tip of a synchrotron X-ray scanning tunneling microscope provides simultaneously localized topographic, elemental and magnetic information., Localized spectroscopy with simultaneous topographic, elemental and magnetic information is presented. A synchrotron X-ray scanning tunneling microscope has been employed for the local study of the X-ray magnetic circular dichroism at the Fe L 2,3-edges of a thin iron film grown on Cu(111). Polarization-dependent X-ray absorption spectra have been obtained through a tunneling smart tip that serves as a photoelectron detector. In contrast to conventional spin-polarized scanning tunneling microscopy, X-ray excitations provide magnetic contrast even with a non-magnetic tip. Intensity variations in the photoexcited tip current point to chemical variations within a single magnetic Fe domain.

Magnetism at buried interfaces plays a crucial role in many emerging phenomena, but detection of interfacial magnetism in close proximity to a surface with elemental and chemical sensitivity is a challenging task. Here, we use low temperature synchrotron x-ray scanning tunneling microscopy to investigate x-ray magnetic circular dichroism and the near edge x-ray absorption fine structure of La0.67Sr0.33MnO3-LaNiO3 superlattices. In stark contrast to the weak magnetic signal of Mn when the La0.67Sr0.33MnO3 layers are located on top, a robust x-ray magnetic circular dichroism signal is detected when they are buried underneath the LaNiO3 layers. The near edge x-ray absorption fine structure reveals the valence states of manganese, while the oxygen K-edge x-ray absorption spectra show an increase in hole formation, indicating a cogent charge transfer at the LaNiO3/La0.67Sr0.33MnO3 interface. This work demonstrates that scanning tunneling microscopy can be extended to the synchrotron X-ray study of buried interfaces by controlling the tip-sample separation in the nanometer regime.

High-speed beam choppers are a crucial part of time-resolved x-ray studies as well as a necessary component to enable elemental contrast in synchrotron x-ray scanning tunneling microscopy (SX-STM). However, many chopper systems are not capable of operation in vacuum, which restricts their application to x-ray studies with high photon energies, where air absorption does not present a significant problem. To overcome this limitation, we present a fully ultra-high vacuum (UHV) compatible chopper system capable of operating at variable chopping frequencies up to 4 kHz. The lightweight aluminum chopper disk is coated with Ti and Au films to provide the required beam attenuation for soft and hard x-rays with photon energies up to about 12 keV. The chopper is used for lock-in detection of x-ray enhanced signals in SX-STM.

We have investigated the growth of Co nanoparticles on {theta}-Al{sub 2}O{sub 3}/CoAl(1 0 0) by means of Auger electron spectroscopy (AES), high-resolution electron energy loss spectroscopy (EELS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). Due to Volmer--Weber growth, Co forms particles with a mean diameter of approximately 2.5 nm and height of 0.8 nm. Even on the entirely covered oxide, there is no Ostwald ripening and Co particles stay structurally isolated. The nanoparticles exhibit a small size distribution and tend to form chains, as predetermined by the streak structure of the oxide template. For sufficient high coverages Co-core-CoO-shell nanoparticles may be evidenced, which is explained as a result of surfactant oxygen. The nanostructured particles may open the door to numerous applications, such as in catalysis and magnetoelectronic applications, where large areas of ordered nanodots are desired.

We have employed Auger electron spectroscopy (AES), high resolution electron energy loss spectroscopy (EELS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM) to investigate the growth of an Al2O3 film on CoAl(1 0 0). While exposure to oxygen at room temperature leads to the formation of amorphous alumina, subsequent annealing at higher temperatures results in the growth of well-ordered θ-Al2O3. Well-ordered Al2O3 films are also formed by oxidation at temperatures of 800 K and above. The oxide is characterized by Fuchs–Kliewer modes at around 430, 630, 780 and 920 cm−1. Oxide islands grow in two sets of domains perpendicular to each other. Under ultra-high vacuum conditions, self-limiting thickness of the oxide layer (9–10 A) has been found. The band gap of the θ-Al2O3 film on CoAl(1 0 0) is 4.3–4.5 eV.

The oxidation of a CoAl(1 0 0) surface at 300 K was studied by means of Auger electron spectroscopy, high resolution electron energy loss spectroscopy (EELS), low energy electron diffraction and scanning tunneling microscopy (STM). For an exposure ⩽0.3 L, the oxygen atoms are chemisorbed on the CoAl(1 0 0) surface, while for a larger O2 exposure the oxidation of the surface sets in. For an exposure ⩾300 L the surface is entirely covered with amorphous Al2O3 (a-Al2O3) whereas the Co atoms seem to be unaffected. The EEL spectra of a-Al2O3 exhibit Fuchs–Kliewer modes at around 640 and 890 cm−1. The thickness of the a-Al2O3 film is estimated to be 7.1 ± 0.7 A. The STM images show that the oxide grows as large islands which cover the whole surface. The band gap of the ultra-thin a-Al2O3 film on CoAl(1 0 0) is found to be 3.2 eV and thus it is strongly diminished with respect to the bulk value.

We use a nanofabricated scanning tunneling microscope tip as a detector to investigate local X-ray induced tunneling and electron emission from a single cobalt nanocluster on a Au(111) surface. The tip-detector is positioned a few angstroms above the nanocluster, and ramping the incident X-ray energy across the Co photoabsorption K-edge enables the detection of element specific electrons. Atomic-scale spatial dependent changes in the X-ray absorption cross section are directly measured by taking the X-ray induced current as a function of X-ray energy. From the measured sample and tip currents, element specific X-ray induced current components can be separated and thereby the corresponding yields for the X-ray induced processes of the single cobalt nanocluster can be determined. The detection of element specific synchrotron X-ray induced electrons of a single nanocluster opens an avenue for materials characterization on a one particle at-a-time basis.

By using synchrotron X-rays as a probe and a nanofabricated smart tip of a tunneling microscope as a detector, we have achieved chemical fingerprinting of individual nickel clusters on a Cu(111) surface at 2 nm lateral resolution, and at the ultimate single-atomic height sensitivity. Moreover, by varying the photon energy, we have succeeded to locally measure photoionization cross sections of just a single Ni nanocluster, which opens new exciting opportunities for chemical imaging of nanoscale materials.

In order to achieve elemental and chemical sensitivity in scanning tunneling microscopy (STM), synchrotron x-rays have been applied to excite core-level electrons during tunneling. The x-ray photo-excitations result in tip currents that are superimposed onto conventional tunneling currents. While carrying important physical information, the varying x-ray induced currents can destabilize the feedback loop causing it to be unable to maintain a constant tunneling current, sometimes even causing the tip to retract fully or crash. In this paper, we report on an easy-to-implement filter circuit that can separate the x-ray induced currents from conventional tunneling currents, thereby allowing simultaneous measurements of topography and chemical contrasts. The filter and the schematic presented here can also be applied to other variants of light-assisted STM such as laser STM.

The effect of a local external electric field on the barrier potential of a tunneling gap is studied utilizing an emerging technique, synchrotron x-ray scanning tunneling microscopy. Here, we demonstrate that the shape of the potential barrier in the tunneling gap can be altered by a localized external electric field, generated by voltages placed on the metallic outer shield of a nanofabricated coaxial metal-insulator-metal tip, resulting in a controlled linear modulation of the tunneling current. Experiments at hard and soft x-ray synchrotron beamlines reveal that both the chemical contrast and magnetic contrast signals measured by the tip can be drastically enhanced, resulting in improved local detection of chemistry and magnetization at the surface.

The combination of high-brilliance synchrotron radiation with scanning tunneling microscopy opens the path to high-resolution imaging with chemical, electronic, and magnetic contrast. Here, the design and experimental results of an in-situ synchrotron enhanced x-ray scanning tunneling microscope (SXSTM) system are presented. The system is designed to allow monochromatic synchrotron radiation to enter the chamber, illuminating the sample with x-ray radiation, while an insulator-coated tip (metallic tip apex open for tunneling, electron collection) is scanned over the surface. A unique feature of the SXSTM is the STM mount assembly, designed with a two free-flex pivot, providing an angular degree of freedom for the alignment of the tip and sample with respect to the incoming x-ray beam. The system designed successfully demonstrates the ability to resolve atomic-scale corrugations. In addition, experiments with synchrotron x-ray radiation validate the SXSTM system as an accurate analysis technique for the study of local magnetic and chemical properties on sample surfaces. The SXSTM system's capabilities have the potential to broaden and deepen the general understanding of surface phenomena by adding elemental contrast to the high-resolution of STM.

The combination of synchrotron x-rays with scanning tunneling microscopy provides a promising new path towards the imaging of nanoscale structures with chemical, electronic, and magnetic contrast. While a scanning probe provides the high spatial resolution measuring x-ray magnetic circular dichroism allows the direct quantification of magnetic moments. This capability has the potential to broaden and deepen the general understanding of nanomagnetism.

The achievement of nanometer spatial resolution with direct elemental selectivity would have a tremendous impact on our ability to probe and understand complex phenomena occurring at the nanoscale. The combination of synchrotron-based X-ray spectroscopy with the high spatial resolution of scanning tunneling microscopy (STM) has the potential to help attain this goal. In this chapter we show how synchrotron X-ray-enhanced scanning tunneling microscopy (SXSTM) has evolved from the very early days of photo-assisted STM to become a promising spectroscopy and imaging technique in nanoscience and nanotechnology. The basic principles of SXSTM are discussed accompanied by a presentation of recent experiments.

The combination of synchrotron radiation with scanning tunneling microscopy provides a promising new concept for chemical imaging of nanoscale structures. It employs detection of local x‐ray absorption, which directly yields chemical, electronic, and magnetic sensitivity. The study of the tip current in the far field (800 nm tip/sample separation) shows that insulator‐coated tips have to be considered in order to reduce the background from stray photoelectron. A picture of the different channels contributing to the x‐ray enhanced STM process is proposed. If during electron tunneling the sample is illuminated with monochromatic x‐rays, characteristic absorption will arise, and core electrons are excited, which might modulate the conventional tunnel current and facilitate chemical imaging at the nanoscale.

Utilizing a combination of the in situ magneto-optical Kerr effect and scanning tunneling microscopy and spectroscopy measurements, we show that the (100) surface of the B2 bulk paramagnetic CoAl is an excellent representation of a two-dimensional ferromagnet. The order-parameter critical exponent beta=0.22 +/- 0.02 is determined, which is the universal signature of a finite-size two-dimensional XY behavior. The Curie temperature is found to be T-c=90 K. The magnetism can be explained by the appearance of Co antisite atoms at the surface.

The ability to position a sharp probe in close proximity to a sample while the surface is illuminated by synchrotron x-rays opens a path to localized spectroscopy and imaging with chemical and magnetic contrast. We have employed a scanning tunneling microscope for the local study of synchrotron x-ray magnetic circular dichroism of micron-sized NiFe rings. Spectra have been obtained by an insulator-coated tip positioned about 200 nm over the sample surface. A negative sample bias is required in order to enhance the dichroism signal at the tip.

Detection of x-ray-enhanced electrons emitted by synchrotron radiation with the tip of a scanning tunneling microscope has the potential to open a path to high-resolution microscopy with chemical sensitivity. Nonresonant photoejected electrons typically yield a current background of a few hundred picoamperes at a bare tip. Coating the tip with an insulating boron nitride film can effectively reduce this background. In this configuration, we have quantitatively studied the bias dependent photoelectron collection for tip/sample separations of 400–1600nm, where quantum mechanical tunneling does not contribute.