Low-temperature Ultrahigh-vacuum Scanning Tunneling Microscope Research Articles

Back focal plane imaging for light emission from a tunneling junction in a low-temperature ultrahigh-vacuum scanning tunneling microscope.

We report the design and realization of the back focal plane (BFP) imaging for the light emission from a tunnel junction in a low-temperature ultrahigh-vacuum (UHV) scanning tunneling microscope (STM). To achieve the BFP imaging in a UHV environment, a compact "all-in-one" sample holder is designed and fabricated, which allows us to integrate the sample substrate with the photon collection units that include a hemisphere solid immersion lens and an aspherical collecting lens. Such a specially designed holder enables the characterization of light emission both within and beyond the critical angle and also facilitates the optical alignment inside a UHV chamber. To test the performance of the BFP imaging system, we first measure the photoluminescence from dye-doped polystyrene beads on a thin Ag film. A double-ring pattern is observed in the BFP image, arising from two kinds of emission channels: strong surface plasmon coupled emissions around the surface plasmon resonance angle and weak transmitted fluorescence maximized at the critical angle, respectively. Such an observation also helps to determine the emission angle for each image pixel in the BFP image and, more importantly, proves the feasibility of our BFP imaging system. Furthermore, as a proof-of-principle experiment, electrically driven plasmon emissions are used to demonstrate the capability of the constructed BFP imaging system for STM induced electroluminescence measurements. A single-ring pattern is obtained in the BFP image, which reveals the generation and detection of the leakage radiation from the surface plasmon propagating on the Ag surface. Further analyses of the BFP image provide valuable information on the emission angle of the leakage radiation, the orientation of the radiating dipole, and the plasmon wavevector. The UHV-BFP imaging technique demonstrated here opens new routes for future studies on the angular distributed emission and dipole orientation of individual quantum emitters in UHV.

Preface to the special issue dedicated to Professor Richard P. Van Duyne (1945–2019)

Preface to the special issue dedicated to Professor Richard P. Van Duyne (1945–2019)

Self-Assembly of Metallo-Supramolecules with Dissymmetrical Ligands and Characterization by Scanning Tunneling Microscopy.

Asymmetrical and dissymmetrical structures are widespread and play a critical role in nature and life systems. In the field of metallo-supramolecular assemblies, it is still in its infancy for constructing artificial architectures using dissymmetrical building blocks. Herein, we report the self-assembly of supramolecular systems based on two dissymmetrical double-layered ligands. With the aid of ultra-high-vacuum, low-temperature scanning tunneling microscopy (UHV-LT-STM), we were able to investigate four isomeric structures corresponding to four types of binding modes of ligand LA with two major conformations complexes A. The distribution of isomers measured by STM and total binding energy of each isomer obtained by density functional theory (DFT) calculations suggested that the most abundant isomer could be the most stable one with highest total binding energy. Finally, through shortening the linker between inner and outer layers and the length of arms, the arrangement of dissymmetrical ligand LB could be controlled within one binding mode corresponding to the single conformation for complexes B.

Synthesis of Metallopolymers and Direct Visualization of the Single Polymer Chain.

During the past few decades, the study of the single polymer chain has attracted considerable attention with the goal of exploring the structure-property relationship of polymers. It still, however, remains challenging due to the variability and low atomic resolution of the amorphous single polymer chain. Here, we demonstrated a new strategy to visualize the single metallopolymer chain with a hexameric or trimeric supramolecule as a repeat unit, in which Ru(II) with strong coordination and Fe(II) with weak coordination were combined together in a stepwise manner. With the help of ultrahigh-vacuum, low-temperature scanning tunneling microscopy (UHV-LT-STM) and scanning tunneling spectroscopy (STS), we were able to directly visualize both Ru(II) and Fe(II), which act as staining reagents on the repeat units, thus providing detailed structural information for the single polymer chain. As such, the direct visualization of the single random polymer chain is realized to enhance the characterization of polymers at the single-molecule level.

Well-Ordered Monolayer Growth of Crown-Ether Ring Molecules on Cu(111) in Ultra-High Vacuum: An STM, UPS, and DFT Study

Crown-ether (CR) ring molecules are known as host molecules for capturing guest species inside the ring. So far CR molecular films have only been grown by drop-casting a CR solution on an inert substrate in air which offers little control over the molecular structure. Here we report the successful growth of a well-ordered CR molecular array on an atomically flat and clean noble metal Cu(111) substrate at 300 K in ultra-high vacuum (UHV), using 4,4′,5,5′-tetrabromodibenzo[18] crown-6 ether (Br-CR). The adsorption, self-assembly, and electronic structures of Br-CR were studied by means of UHV low-temperature scanning tunneling microscopy and spectroscopy, low electron energy diffraction, and angle-resolved ultraviolet photoemission spectroscopy. We found that (1) the Br-CR ring, which is bent both in the crystal and gas phase, flattens upon adsorption on Cu(111). Density functional theory reveals that the two benzene groups of the molecule lie flat on the surface such as to maximize the substrate-molecule interaction. (2) The moderate molecule–substrate interaction allows thermal diffusion of the Br-CR molecules, resulting in the formation of self-assembled monolayer islands with 7 × 4 superstructure. (3) While the deposition of 0.05 ML Br-CR forms multidomain islands with disordered defects, a drastic improvement occurred at 0.25 ML, where only atomically flat single-domain islands were grown. This Br-CR flat ring cavity array could become a template for designing novel two-dimensional arrays of desired guest atoms, ions, or functionalized molecules.

Low-temperature, ultrahigh-vacuum tip-enhanced Raman spectroscopy combined with molecular beam epitaxy for in situ two-dimensional materials' studies.

Tip-enhanced Raman spectroscopy (TERS), which combines scanning probe microscopy with the Raman spectroscopy, is capable to access the local structure and chemical information simultaneously. However, the application of ambient TERS is limited by the unstable and poorly controllable experimental conditions. Here, we designed a high performance TERS system based on a low-temperature ultrahigh-vacuum scanning tunneling microscope (LT-UHV-STM) and combined with a molecular beam epitaxy (MBE) system. It can be used for growing two-dimensional (2D) materials and for in situ STM and TERS characterization. Using a 2D silicene sheet on the Ag(111) surface as a model system, we achieved an unprecedented 109 Raman single enhancement factor in combination with a TERS spatial resolution down to 0.5 nm. The results show that TERS combined with a MBE system can be a powerful tool to study low dimensional materials and surface science.

Conformation Manipulation and Motion of a Double Paddle Molecule on an Au(111) Surface.

The molecular conformation of a bisbinaphthyldurene (BBD) molecule is manipulated using a low-temperature ultrahigh-vacuum scanning tunneling microscope (LT-UHV STM) on an Au(111) surface. BBD has two binaphthyl groups at both ends connected to a central durene leading to anti/syn/flat conformers. In solution, dynamic nuclear magnetic resonance indicated the fast interexchange between the anti and syn conformers as confirmed by density functional theory calculations. After deposition in a submonolayer on an Au(111) surface, only the syn conformers were observed forming small islands of self-assembled syn dimers. The syn dimers can be separated into syn monomers by STM molecular manipulations. A flat conformer can also be prepared by using a peculiar mechanical unfolding of a syn monomer by STM manipulations. The experimental STM dI/dV and theoretical elastic scattering quantum chemistry maps of the low-lying tunneling resonances confirmed the flat conformer BBD molecule STM production. The key BBD electronic states for a step-by-step STM inelastic excitation lateral motion on the Au(111) are presented requiring no mechanical interactions between the STM tip apex and the BBD. On the BBD molecular board, selected STM tip apex positions for this inelastic tunneling excitation enable the flat BBD to move controllably on Au(111) by a step of 0.29 nm per bias voltage ramp.

The surface structures growth’s features caused by Ge adsorption on the Au(111) surface

The initial stage of the adsorption of Ge on an Au(111) surface was investigated. The growth and stability of the structures formed at the surface were studied by ultrahigh-vacuum low-temperature scanning tunneling microscopy and analyzed using density functional theory. It was established that the adsorption of single Ge atoms at the Au(111) surface at room temperature leads to the substitution of Au atoms by Ge atoms in the first surface layer. An increasing of surface coverage up to 0.2–0.4 monolayers results in the growth of an amorphous binary layer composed of intermixed Au and Ge atoms. It was shown that the annealing of the binary layer at a temperature of T s ≃ 500 K, as well as the adsorption of Ge on the Au(111) surface heated to T s ≃ 500 K for coverages up to 1 monolayer lead to a structural transition and the formation of an Au–Ge alloy at least in the first two surface layers. Based on experimental and theoretical data, it was shown that the formation of single-layer germanene on the Au(111) surface for coverages ≤1 monolayer in the temperature range of T s = 297–500 K is impossible.

Tip-Enhanced Raman Spectroscopic Imaging of Individual Carbon Nanotubes with Subnanometer Resolution.

Individual carbon nanotubes (CNTs) have been investigated by tip-enhanced Raman spectroscopy (TERS) using silver tips on the Ag(111) substrate with a low-temperature ultrahigh-vacuum scanning tunneling microscope. Thanks to the strong and highly localized plasmonic field offered by the silver nanogap, the spatial resolution of TERS on CNTs is driven down to about 0.7 nm. Such a high spatial resolution allows to visualize in real space the spatial extent of the defect-induced D-band scattering, to track the strain-induced spectral evolution, and to resolve the spectral differences between the inner and the outer sides of a bent CNT, all at the nanometer scale.

Effect of surface defects and few-atomic steps on the local density of states of the atomically-clean surface of Bi2Se3 topological insulator

The results of ultra-high vacuum low-temperature scanning-tunneling microscopy (STM) and spectroscopy (STS) of atomically clean (111) surface of the topological insulator Bi$_2$Se$_3$ are presented. We observed several types of new subsurface defects whose location and charge correspond to p-type conduction of grown crystals. The sign of the thermoelectric effect also indicates p-type conduction. STM and STS measurements demonstrate that the chemical potential is always located inside the bulk band gap. We also observed changes in the local density of states in the vicinity of the quintuple layer steps at the studied surface. This changes correspond either to the shift of the Dirac cone position or to the shift of the chemical potential near the step edge.

Scanning tunneling microscopy/spectroscopy of picene thin films formed on Ag(111).

Using ultrahigh-vacuum low-temperature scanning tunneling microscopy and spectroscopy combined with first principles density functional theory calculations, we have investigated structural and electronic properties of pristine and potassium (K)-deposited picene thin films formed in situ on a Ag(111) substrate. At low coverages, the molecules are uniformly distributed with the long axis aligned along the [112̄] direction of the substrate. At higher coverages, ordered structures composed of monolayer molecules are observed, one of which is a monolayer with tilted and flat-lying molecules resembling a (11̄0) plane of the bulk crystalline picene. Between the molecules and the substrate, the van der Waals interaction is dominant with negligible hybridization between their electronic states; a conclusion that contrasts with the chemisorption exhibited by pentacene molecules on the same substrate. We also observed a monolayer picene thin film in which all molecules were standing to form an intermolecular π stacking. Two-dimensional delocalized electronic states are found on the K-deposited π stacking structure.

Coverage-Dependent Structures of Cobalt−Phthalocyanine Molecules Adsorbed on Cu(001) Surface

The morphologies, self-assembly structures, and stability of cobalt-phthalocyanines (CoPc) molecules adsorbed on Cu(001) with coverage ranging from 0.2 monolayer (ML) to 1.6 ML are investigated by ultrahigh-vacuum low-temperature scanning tunneling microscopy (UHV LT-STM) at liquid nitrogen temperature. Upon increasing the deposition of CoPc molecules various structures, such as isolated adsorption, quasi-hexagonal structure, square root(29) x square root(29) structure, are well characterized by the corresponding high-resolution STM images. The CoPc-CoPc intermolecular interaction and CoPc-substrate interfacial interaction dominate the structural evolutions. For the coverage higher than 1 ML, CoPc molecules preferentially locate on top of the molecules underneath and organize into square root(58) x square root(58) structure. As more and more CoPc molecules adsorb on the first layer, in some square root(58) x square root(58) regions molecular insertion leads to the formation of the square root(29) x square root(29) domain to effectively decrease the energy of the whole system.

Scanning Tunneling Microscopy Imaging and Spectroscopy of a Single Viologen Molecule

A low-temperature ultrahigh-vacuum scanning tunneling microscope (UHV-STM) was used to image viologen (N-methyl-N'-di (8-mercaptooctyl)-4,4'-bipyridinium; HSC8VC8SH) molecules and to perform local spectroscopic measurements on these molecules. Self-assembly of viologen molecules was conducted on Au (111), which had been thermally deposited onto freshly cleaved, heated mica. Here, we demonstrate a novel SAM matrix appropriate for the isolation of viologen molecules composed of octanethiol (C8) in which HSC8VC8SH was inserted at defects in the molecular lattice. The isolated single molecules of viologen inserted in the SAM matrix were observed as protrusions in STM topography using a constant current mode. STM images at 298 K showed protrusions with a topographic height of about 2.71 nm (HSC8VC8SH) with viologen molecules that self-assembled on the substrate. The current-voltage (I-V) characteristics were measured while the electrical properties of the formed monolayer were scanned using scanning tunneling spectroscopy (STS). We found the high peak current-like rectification at +1.14 V (HSC8VC8SH). The rectification ratios, RR = J (at +2.5 V)/J (at -2.5 V), are in the range of 4.47.

A low-temperature ultrahigh-vacuum scanning tunneling microscope with rotatable magnetic field

We present a new design of a low-temperature ultrahigh-vacuum (UHV) scanning tunneling microscope setup with a combination of a solenoid and a split-pair magnet. The scanning tunneling microscope can be operated at temperatures down to 8 K and in a rotatable magnetic field of up to 1 T. Magnetic fields of up to 7 T perpendicular and 2 T parallel to the sample surface can be applied. The UHV part of the system allows in situ preparation and low energy electron diffraction/Auger analysis of samples. First topographic and spectroscopic measurements on p-InAs(110) are presented.

STM imaging and spectroscopy of single copperphthalocyanine molecules

A low-temperature ultrahigh-vacuum scanning tunneling microscope (STM) is used to image individual copperphthalocyanine (CuPc) molecules and to perform local spectroscopic measurements on these molecules. Evaporation of CuPc on liquid-nitrogen-cooled graphite substrates leads to nonclustered individual molecules at random positions. STM images at 35 K show protrusions with a height of about 0.2 nm and a diameter of about 1.0 nm, consistent with CuPc molecules that lie flat on the substrate. Current-voltage curves acquired with the STM tip positioned over CuPc show a pronounced peak in dI/dV vs V at a tip voltage of 0.4 ± 0.1 V. This is attributed to resonant tunneling through a molecular level of CuPc.

Atomic resolution in photon emission induced by a scanning tunneling microscope.

A low-temperature ultrahigh-vacuum scanning tunneling microscope (STM) is used to excite photon emission from Au(110) surfaces. In the detected photon intensity the (1 \ifmmode\times\else\texttimes\fi{} 2) reconstruction of the Au surface is clearly resolved. This first observation of atomic resolution in STM-induced photon emission is interpreted in terms of local variations of the electromagnetic interaction of tip and sample occurring at constant tunneling current. Similar effects are expected to affect other scanning probe methods, in particular those involving photons.

Spectroscopy of a single adsorbed atom.

We have used a low-temperature ultrahigh-vacuum scanning tunneling microscope to perform atomically localized spectroscopic measurements on single Fe atoms adsorbed onto the Pt(111) surface. Using a simple tunneling model, we are able to quantitatively deconvolute the tip and adatom local densities of states (LDOS) from the dI/dV spectra. We find that a resonance occurs in the adatom LDOS that is centered 0.5 eV above the Fermi energy. This feature has a width of approximately 0.6 eV, and occurs only when the tip is within angstroms (laterally) of the center of an Fe adatom

Field emission current-voltage curves as a diagnostic for scanning tunneling microscope tips

The current-voltage ( I–V) characteristics of a low-temperature ultrahigh-vacuum scanning tunneling microscope (STM) tip positioned >100 Å from a planar surface have been recorded. We find curvature in the Fowler-Nordheim plots (log 10( I/V 2) versus 1/ V) due to the tip-plane geometry as has been predicted theoretically. In addition, oscillations and sharp breaks in these I–V curves are observed over a wide voltage range, 50–1000 V. These I–V curves are used to characterize the STM tips prior to tunneling.