Low-temperature Scanning Probe Microscopy Research Articles

Intrinsically Patterned Two-Dimensional Transition Metal Halides.

Patterning and defect engineering are key methods for tuning the properties and enabling distinctive functionalities in two-dimensional (2D) materials. However, generating 2D periodic patterns of point defects in 2D materials, such as vacancy lattices that can serve as antidot lattices, has been elusive until now. Herein, we report on 2D transition metal dihalides epitaxially grown on metal surfaces featuring periodically assembled halogen vacancies that result in alternating coordination of the transition metal atom. Using low-temperature scanning probe microscopy and low-energy electron diffraction, we identified the structural properties of intrinsically patterned FeBr2 and CoBr2 monolayers grown epitaxially on Au(111). Density functional theory reveals that Br vacancies are facilitated by low formation energies, and the formation of a vacancy lattice results in a substantial decrease in the lattice mismatch with the underlying Au(111). We demonstrate that interfacial strain engineering presents a versatile strategy for controlled patterning in two dimensions with atomic precision over several hundred nanometers to solve a long-standing challenge of growing atomically precise antidot lattices. In particular, patterning of 2D materials containing transition metals provides a versatile method to achieve unconventional spin textures with noncollinear spin.

Advances in dry low-temperature scanning probe microscopy system development

Since the beginning of the 21st century, Scanning Probe Microscopy (SPM) has played an increasingly important role in the fields of micro- and nanoscale surface characterization, physical property measurement, and micro/nano fabrication. To provide a more stable operating environment and higher energy resolution for SPM, researchers have developed Low-Temperature Scanning Probe Microscopy (LT-SPM) systems that operate under ultra-high vacuum and low temperature conditions. Currently, most LT-SPM systems achieve temperatures around 4.2 K by supplying liquid helium-4 (<sup>4</sup>He) to continuous flow cryostats or low-temperature Dewars. However, due to the low natural abundance of <sup>4</sup>He and its rising demand, the price of liquid helium has surged dramatically, severely impacting the normal operation of <sup>4</sup>He-based low temperature equipment. To address this issue, dry (cryogen-free) refrigeration technology has emerged as a promising alternative for next-generation low-temperature systems. In this context, the integration of dry refrigeration technology with SPM to construct DRY-LT-SPM systems has become a key research focus in the field of scanning probe instruments.<br>This paper mainly discusses several reported closed-cycle DRY -LT-SPM systems, focusing on aspects such as system design, refrigeration schemes, vibration reduction methods, and overall performance. Finally, the paper summarizes the current challenges and issues faced by DRY -LT-SPM systems and explores potential future developments in this field.

Planar π-extended cycloparaphenylenes featuring an all-armchair edge topology.

The [n]cycloparaphenylenes ([n]CPPs)-n para-linked phenylenes that form a closed-loop-have attracted substantial attention due to their unique cyclic structure and highly effective para-conjugation leading to a myriad of fascinating electronic and optoelectronic properties. However, their strained topology prevents the π-extension of CPPs to convert them either into armchair nanobelts or planarized CPP macrocycles. Here we successfully tackle this long-standing challenge and present the bottom-up synthesis and characterization of atomically precise in-plane π-extended [12]CPP on Au(111) by low-temperature scanning probe microscopy and spectroscopy combined with density functional theory. The planar π-extended CPP is a nanographene with an all-armchair edge topology. The exclusive para-conjugation at the periphery yields delocalized electronic states and the planarization maximizes the overlap of p orbitals, which both reduce the bandgap compared to conventional CPPs. Calculations predict ring currents and global aromaticity in the doubly charged system. The intriguing planar ring topology and unique electronic properties make planar π-extended CPPs promising quantum materials.

Topological Defects Induced High-Spin Quartet State in Truxene-Based Molecular Graphenoids

Topological Defects Induced High-Spin Quartet State in Truxene-Based Molecular Graphenoids

Local control of improper ferroelectric domains in YMnO3

Improper ferroelectrics are described by two order parameters: a primary one, driving a transition to long-range distortive, magnetic or otherwise non-electric order, and the electric polarization, which is induced by the primary order parameter as a secondary, complementary effect. Using low-temperature scanning probe microscopy, we show that improper ferroelectric domains in YMnO$_3$ can be locally switched by electric field poling. However, subsequent temperature changes restore the as-grown domain structure as determined by the primary lattice distortion. The backswitching is explained by uncompensated bound charges occuring at the newly written domain walls due to the lack of mobile screening charges at low temperature. Thus, the polarization of improper ferroelectrics is in many ways subject to the same electrostatics as in their proper counterparts, yet complemented by additional functionalities arising from the primary order parameter. Tailoring the complex interplay between primary order parameter, polarization, and electrostatics is therefore likely to result in novel functionalities specific to improper ferroelectrics.

Synthesis of Monolayer Blue Phosphorus Enabled by Silicon Intercalation.

The growth of entirely synthetic two-dimensional (2D) materials could further expand the library of naturally occurring layered solids and provide opportunities to design materials with finely tunable properties. Among them, the synthesis of elemental 2D materials is of particular interest as they represent the chemically simplest case and serve as a model system for exploring the on-surface synthesis mechanism. Here, a pure atomically thin blue phosphorus (BlueP) monolayer is synthesized via silicon intercalation of the BlueP-Au alloy on Au(111). The intercalation process is characterized at the atomic scale by low-temperature scanning probe microscopy and further corroborated by synchrotron radiation-based X-ray photoelectron spectroscopy measurements. The evolution of the band structures from the BlueP-Au alloy into Si-intercalated BlueP are clearly revealed by angle-resolved photoemission spectroscopy and further verified by density functional theory calculations.

Interface dipoles of Ir(ppy)3 on Cu(111).

The interplay of adsorption geometry and interface dipoles of the transition-metal complex Ir(ppy)3 on Cu(111) was studied using low-temperature scanning probe microscopy and density-functional-theory calculations. We find that the orientation of the molecule's intrinsic dipole moment with respect to the surface has a strong influence on the total energy of the different configurations, where the most stable one has the molecular dipole moment pointing out of the surface plane along the surface normal. Adsorption-induced redistribution of charges results in an additional dipole moment that also points out of the surface plane for all configurations. Submolecularly resolved maps of the resulting local contact potential difference suggest that any in-plane dipole moment is very effectively screened.

A low-temperature scanning probe microscopy system with molecular beam epitaxy and optical access.

A low-temperature ultra-high vacuum scanning probe microscopy (SPM) system with molecular beam epitaxy (MBE) capability and optical access was conceived, built, and tested in our lab. The design of the whole system is discussed here, with special emphasis on some critical parts. The SPM scanner head takes a modified Pan-type design with improved rigidity and compatible configuration to optical access and can accommodate both scanning tunneling microscope (STM) tips and tuning-fork based qPlus sensors. In the system, the scanner head is enclosed by a double-layer cold room under a bath type cryostat. Two piezo-actuated focus-lens stages are mounted on both sides of the cold room to couple light in and out. The optical design ensures the system's forward compatibility to the development of photo-assisted STM techniques. To test the system's performance, we conducted STM and spectroscopy studies. The herringbone reconstruction and atomic structure of an Au(111) surface were clearly resolved. The dI/dV spectra of an Au(111) surface were obtained at 5 K. In addition, a periodic 2D tellurium (Te) structure was grown on the Au(111) surface using MBE and the atomic structure is clearly resolved by using STM.

Iron-based trinuclear metal-organic nanostructures on a surface with local charge accumulation

Coordination chemistry relies on harnessing active metal sites within organic matrices. Polynuclear complexes—where organic ligands bind to several metal atoms—are relevant due to their electronic/magnetic properties and potential for functional reactivity pathways. However, their synthesis remains challenging; few geometries and configurations have been achieved. Here, we synthesise—via supramolecular chemistry on a noble metal surface—one-dimensional metal-organic nanostructures composed of terpyridine (tpy)-based molecules coordinated with well-defined polynuclear iron clusters. Combining low-temperature scanning probe microscopy and density functional theory, we demonstrate that the coordination motif consists of coplanar tpyʼs linked via a quasi-linear tri-iron node in a mixed (positive-)valence metal–metal bond configuration. This unusual linkage is stabilised by local accumulation of electrons between cations, ligand and surface. The latter, enabled by bottom-up on-surface synthesis, yields an electronic structure that hints at a chemically active polynuclear metal centre, paving the way for nanomaterials with novel catalytic/magnetic functionalities.

A micro-SQUID with dispersive readout for magnetic scanning microscopy

We have designed and characterized a micro-SQUID with dispersive readout for use in low temperature scanning probe microscopy systems. The design features a capacitively shunted RF SQUID with a tunable resonance frequency from 5 to 12 GHz, micrometer spatial resolution, and integrated superconducting coils for local application of magnetic fields. The SQUID is operated as a nonlinear oscillator with a flux- and power-dependent resonance frequency. Measurements for device characterization and noise benchmarking were carried out at 4 K. The measured flux noise above 10 kHz at 4 K is 80 nΦ0 Hz−1∕2 at a bandwidth of 200 MHz. Estimations suggest that one can benefit from parametric gain based on inherent nonlinearity of the Josephson junction and reduce the flux noise to 30 nΦ0Hz–1∕2 at 100 mK, which corresponds to 10.6 μBHz–1∕2 for a magnetic moment located at the center of the pickup loop.

Atomic species recognition on oxide surfaces using low temperature scanning probe microscopy

In scanning probe microscopy (SPM), the chemical properties and sharpness of the tips of the cantilever greatly influence the scanning of a sample surface. Variation in the chemical properties of the sharp tip apex can induce transformation of the SPM images. In this research, we explore the relationship between the tip and the structure of a sample surface using dynamic atomic force microscopy (AFM) on a Cu(110)-O surface under ultra-high vacuum (UHV) at low temperature (78K). We observed two different c(6×2) phase types in which super-Cu atoms show as a bright spot when the tip apex is of O atoms and O atoms show as a bright spot when the tip apex is of Cu atoms. We also found that the electronic state of the tip has a serious effect on the resolution and stability of the sample surface, and provide an explanation for these phenomena. This technique can be used to identify atom species on sample surfaces, and represents an important development in the SPM technique.

An ultra-compact, high-throughput molecular beam epitaxy growth system.

We present a miniaturized molecular beam epitaxy (miniMBE) system with an outer diameter of 206 mm, optimized for flexible and high-throughput operation. The three-chamber system, used here for oxide growth, consists of a sample loading chamber, a storage chamber, and a growth chamber. The growth chamber is equipped with eight identical effusion cell ports with linear shutters, one larger port for either a multi-pocket electron beam evaporator or an oxygen plasma source, an integrated cryoshroud, retractable beam-flux monitor or quartz-crystal microbalance, reflection high energy electron diffraction, substrate manipulator, main shutter, and quadrupole mass spectrometer. The system can be combined with ultrahigh vacuum (UHV) end stations on synchrotron and neutron beamlines, or equivalently with other complex surface analysis systems, including low-temperature scanning probe microscopy systems. Substrate handling is compatible with most UHV surface characterization systems, as the miniMBE can accommodate standard surface science sample holders. We introduce the design of the system, and its specific capabilities and operational parameters, and we demonstrate the epitaxial thin film growth of magnetoelectric Cr2O3 on c-plane sapphire and ferrimagnetic Fe3O4 on MgO (001).

Transport through a single donor in p-type silicon

Single phosphorus donors in silicon are promising candidates as qubits in the solid state. Here, we present low temperature scanning probe microscopy and spectroscopy measurements of individual phosphorus dopants deliberately placed in p-type silicon ∼1 nm below the surface. The ability to image individual dopants combined with scanning tunnelling spectroscopy allows us to directly study the transport mechanism through the donor. We show that for a single P donor, transport is dominated by a minority carrier recombination process with the surrounding p-type matrix. The understanding gained will underpin future studies of atomically precise mapping of donor-donor interactions in silicon.

ChemInform Abstract: Single‐Molecule Chemistry and Physics Explored by Low‐Temperature Scanning Probe Microscopy

AbstractReview: 107 refs.

Single-molecule chemistry and physics explored by low-temperature scanning probe microscopy

It is well known that scanning probe techniques such as scanning tunnelling microscopy (STM) and atomic force microscopy (AFM) routinely offer atomic scale information on the geometric and the electronic structure of solids. Recent developments in STM and especially in non-contact AFM have allowed imaging and spectroscopy of individual molecules on surfaces with unprecedented spatial resolution, which makes it possible to study chemistry and physics at the single molecule level. In this feature article, we first review the physical concepts underlying image contrast in STM and AFM. We then focus on the key experimental considerations and use selected examples to demonstrate the capabilities of modern day low-temperature scanning probe microscopy in providing chemical insight at the single molecule level.

11]Anthrahelicene on InSb(001) c(8×2): A Low‐Temperature Scanning Probe Microscopy Study

The adsorption of individual [11]anthrahelicene molecules and their self-assembly into monolayer islands on an InSb(001) c(8×2) reconstructed surface is studied with low-temperature scanning probe microscopy. A racemic mixture is deposited on atomically flat terraces of InSb at room temperature. At lower coverage, the molecules tend to decorate atomic step edges of the substrate. At higher coverage, [11]anthrahelicene molecules form 2D islands. A quasi-hexagonal ordering of molecules within the layer is identified. Furthermore, it is shown that molecules adsorb with the helical axis almost perpendicular to the substrate. Interference between tunneling through the molecular layer and directly through space is reported. Finally, experimental results are compared to those of theoretical calculations.

Gradiometric micro-SQUID susceptometer for scanning measurements of mesoscopic samples

We have fabricated and characterized micro-SQUID susceptometers for use in low-temperature scanning probe microscopy systems. The design features the following: a 4.6 mum diameter pickup loop; an integrated field coil to apply a local field to the sample; an additional counterwound pickup-loop/field-coil pair to cancel the background signal from the applied field in the absence of the sample; modulation coils to allow setting the SQUID at its optimum bias point (independent of the applied field), and shielding and symmetry that minimizes coupling of magnetic fields into the leads and body of the SQUID. We use a SQUID series array preamplifier to obtain a system bandwidth of 1 MHz. The flux noise at 125 mK is approximately 0.25 mu Phi 0/ sqrt Hz above 10 kHz, with a value of 2.5 mu Phi 0/ sqrt Hz at 10 Hz. The nominal sensitivity to electron spins located at the center of the pickup loop is approximately 200 muB/ sqrt Hz above 10 kHz, in the white-noise frequency region.

A reverse pendulum bath cryostat design suitable for low temperature scanning probe microscopy

A new low temperature, ultrahigh vacuum cryostat design has been developed for atomic force and scanning tunnelling microscopy measurements. A microscope can be operated at 5 K in ultrahigh vacuum. The microscope body is thermally connected to a reverse pendulum and completely surrounded by a radiation shield. The design allows in situ dosing and irradiation of the sample as well as for easy access of tip and sample. The temperature performance and the vibrational properties of the reverse pendulum design are demonstrated in detail. A brief overview of low temperature instrumentation in scanning probe microscopy is given.

Low-temperature scanning probe microscopy of surface and subsurface charges

The operation of a cryogenic scanning force microscope is demonstrated with a sensitivity of about 50 fN/Hz at 5 kHz modulation. This microscope is used as an electrometer in noncontact mode in order to map the local electrostatic forces and capacitance of several nanostructures at 4.2 K. Capacitance imaging of nanostructured surfaces with subatto-Farad resolution is demonstrated.

GaAs/AlGaAs self-sensing cantilevers for low temperature scanning probe microscopy

We have fabricated scanning probe microscope cantilevers with dimensions 65×11.4×0.25 μm3 and 3×2×0.129 μm3 from GaAs/Al0.3Ga0.7As heterostructures containing two-dimensional electron gases. Deflection is measured by an integrated field-effect transistor (FET) that senses strain via the piezoelectric effect and provides a low noise, low power displacement readout. We present images of a 200 nm mica grating taken with the large cantilever having a deflection (force) noise 10 Å/√Hz (19 pN/√Hz) at T=2.2 K. The small cantilever has a resonant frequency of 11 MHz, a FET gate charge noise of 0.001 e/√Hz, and is projected to have a deflection (force) noise of 0.002 Å/√Hz (1 pN/√Hz) at T=4.2 K.