Isotopic effects on in-plane hyperbolic phonon polaritons in MoO3.

Hyperbolic phonon polaritons (HPhPs), hybrids of light and lattice vibrations in polar dielectric crystals, empower nanophotonic applications by enabling the confinement and manipulation of light at the nanoscale. Molybdenum trioxide (α-MoO3) is a naturally hyperbolic material, meaning that its dielectric function deterministically controls the directional propagation of in-plane HPhPs within its reststrahlen bands. Strategies such as substrate engineering, nano- and heterostructuring, and isotopic enrichment are being developed to alter the intrinsic die ectric functions of natural hyperbolic materials and to control the confinement and propagation of HPhPs. Since isotopic disorder can limit phonon-based processes such as HPhPs, here we synthesize isotopically enriched 92MoO3 (92Mo: 99.93 %) and 100MoO3 (100Mo: 99.01 %) crystals to tune the properties and dispersion of HPhPs with respect to natural α-MoO3, which is composed of seven stable Mo isotopes. Real-space, near-field maps measured with the photothermal induced resonance (PTIR) technique enable comparisons of inplane HPhPs in α-MoO3 and isotopically enriched analogues within a reststrahlen band (≈820 cm-1 to ≈ 972 cm-1). Results show that isotopic enrichment (e.g., 92MoO3 and 100MoO3) alters the dielectric function, shifting the HPhP dispersion (HPhP angular wavenumber × thickness vs IR frequency) by ≈-7% and ≈ +9 %, respectively, and changes the HPhP group velocities by ≈ ±12 %, while the lifetimes (≈ 3 ps) in 92MoO3 were found to be slightly improved (≈ 20 %). The latter improvement is attributed to a decrease in isotopic disorder. Altogether, isotopic enrichment was found to offer fine control over the properties that determine the anisotropic in-plane propagation of HPhPs in α-MoO3, which is essential to its implementation in nanophotonic applications.

Atomic-Scale Insights into the Interlayer Characteristics and Oxygen Reactivity of Bilayer Borophene.

Bilayer (BL) two-dimensional boron (i.e., borophene) has recently been synthesized and computationally predicted to have promising physical properties for a variety of electronic and energy technologies. However, the fundamental chemical properties of BL borophene that form the foundation of practical applications remain unexplored. Here, we present atomic-level chemical characterization of BL borophene using ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS). UHV-TERS identifies the vibrational fingerprint of BL borophene with angstrom-scale spatial resolution. The observed Raman spectra are directly correlated with the vibrations of interlayer boron-boron bonds, validating the three-dimensional lattice geometry of BL borophene. By virtue of the single-bond sensitivity of UHV-TERS to oxygen adatoms, we demonstrate the enhanced chemical stability of BL borophene compared to its monolayer counterpart by exposure to controlled oxidizing atmospheres in UHV. In addition to providing fundamental chemical insight into BL borophene, this work establishes UHV-TERS as a powerful tool to probe interlayer bonding and surface reactivity of low-dimensional materials at the atomic scale.

Chemically identifying single adatoms with single-bond sensitivity during oxidation reactions of borophene.

The chemical interrogation of individual atomic adsorbates on a surface significantly contributes to understanding the atomic-scale processes behind on-surface reactions. However, it remains highly challenging for current imaging or spectroscopic methods to achieve such a high chemical spatial resolution. Here we show that single oxygen adatoms on a boron monolayer (i.e., borophene) can be identified and mapped via ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS) with ~4.8 Å spatial resolution and single bond (B-O) sensitivity. With this capability, we realize the atomically defined, chemically homogeneous, and thermally reversible oxidation of borophene via atomic oxygen in UHV. Furthermore, we reveal the propensity of borophene towards molecular oxygen activation at room temperature and phase-dependent chemical properties. In addition to offering atomic-level insights into the oxidation of borophene, this work demonstrates UHV-TERS as a powerful tool to probe the local chemistry of surface adsorbates in the atomic regime with widespread utilities in heterogeneous catalysis, on-surface molecular engineering, and low-dimensional materials.

Chemically imaging nanostructures formed by the covalent assembly of molecular building blocks on a surface with ultrahigh vacuum tip-enhanced Raman spectroscopy.

Surface-bound reactions have become a viable method to develop nanoarchitectures through bottom-up assembly with near atomic precision. However, the bottom-up fabrication of nanostructures on surfaces requires careful consideration of the intrinsic properties of the precursors and substrate as well as the complex interplay of any interactions that arise in the heterogeneous two-dimensional (2D) system. Therefore, it becomes necessary to consider these systems with characterization methods sensitive to such properties with suitable spatial resolution. Here, low temperature ultrahigh vacuum scanning tunneling microscopy (STM) and tip-enhanced Raman spectroscopy (TERS) were used to investigate the formation of 2D covalent networks via coupling reactions of tetra(4-bromophenyl)porphyrin (Br4TPP) molecules on a Ag(100) substrate. Through the combination of STM topographic imaging and TERS vibrational fingerprints, the conformation of molecular precursors on the substrate was understood. Following the thermally activated coupling reaction, STM and TERS imaging confirm the covalent nature of the 2D networks and suggest that the apparent disorder arises from molecular flexibility.

Controlling Localized Plasmons via an Atomistic Approach: Attainment of Site-Selective Activation inside a Single Molecule.

Chemical reactions such as bond dissociation and formation assisted by localized surface plasmons (LSPs) of noble metal nanostructures hold promise in solar-to-chemical energy conversion. However, the precise control of localized plasmons to activate a specific moiety of a molecule, in the presence of multiple chemically equivalent parts within a single molecule, is scarce due to the relatively large lateral distribution of the plasmonic field. Herein, we report the plasmon-assisted dissociation of a specific molecular site (C-Si bond) within a polyfunctional molecule adsorbed on a Cu(100) surface in the scanning tunneling microscope (STM) junction. The molecular site to be activated can be selected by carefully positioning the tip and bringing the tip extremely close to the molecule (atomistic approach), thereby achieving plasmonic nanoconfinement at the tip apex. Furthermore, multiple reactive sites are activated in a sequential manner at the sub-molecular scale, and different sets of products are created and visualized by STM topography and density functional theory (DFT) modeling. The illustration of site-selective activation achieved by localized surface plasmons implies the realization of molecular-scale resolution for bond-selected plasmon-induced chemistry.

Angstrom-Scale Spectroscopic Visualization of Interfacial Interactions in an Organic/Borophene Vertical Heterostructure.

Two-dimensional boron monolayers (i.e., borophene) hold promise for a variety of energy, catalytic, and nanoelectronic device technologies due to the unique nature of boron-boron bonds. To realize its full potential, borophene needs to be seamlessly interfaced with other materials, thus motivating the atomic-scale characterization of borophene-based heterostructures. Here, we report the vertical integration of borophene with tetraphenyldibenzoperiflanthene (DBP) and measure the angstrom-scale interfacial interactions with ultrahigh-vacuum tip-enhanced Raman spectroscopy (UHV-TERS). In addition to identifying the vibrational signatures of adsorbed DBP, TERS reveals subtle ripples and compressive strains of the borophene lattice underneath the molecular layer. The induced interfacial strain is demonstrated to extend in borophene by ∼1 nm beyond the molecular region by virtue of 5 Šchemical spatial resolution. Molecular manipulation experiments prove the molecular origins of interfacial strain in addition to allowing atomic control of local strain with magnitudes as small as ∼0.6%. In addition to being the first realization of an organic/borophene vertical heterostructure, this study demonstrates that UHV-TERS is a powerful analytical tool to spectroscopically investigate buried and highly localized interfacial characteristics at the atomic scale, which can be applied to additional classes of heterostructured materials.

On-surface formation of metal-organic coordination networks with C⋯Ag⋯C and C=O⋯Ag interactions assisted by precursor self-assembly.

Surface-bound reactions are commonly employed to develop nanoarchitectures through bottom-up assembly. Precursor molecules are carefully designed, and surfaces are chosen with the intention to fabricate low-dimensional extended networks, which can include one-dimensional and two-dimensional structures. The inclusion of functional groups can offer the opportunity to utilize unique chemistry to further tune the bottom-up method or form novel nanostructures. Specifically, carbonyl groups open up new avenues for on-surface coordination chemistry. Here, the self-assembly and formation of an organometallic species via the thermally induced reaction of 3,6-dibromo-9,10-phenanthrenequinone (DBPQ) molecules were studied on Ag(100) and Ag(110). Low-temperature ultrahigh vacuum scanning tunneling microscopy revealed the room temperature formation of self-assemblies defined by hydrogen and halogen bonds on Ag(100). Following a thermal anneal to 300 °C, DBPQ on Ag(100) was found to form metal-organic coordination networks composed of a combination of organometallic species characteristics of Ullmann-like coupling reactions and carbonyl complexes. On Ag(110), the C-Br bonds were found to readily dissociate at room temperature, resulting in the formation of disordered organometallic species.

Optical scanning tunneling microscopy based chemical imaging and spectroscopy.

Through coupling optical processes with the scanning tunneling microscope (STM), single-molecule chemistry and physics have been investigated at the ultimate spatial and temporal limit. Electrons and photons can be used to drive interactions and reactions in chemical systems and simultaneously probe their characteristics and consequences. In this review we introduce and review methods to couple optical imaging and spectroscopy with scanning tunneling microscopy. The integration of the STM and optical spectroscopy provides new insights into individual molecular adsorbates, surface-supported molecular assemblies, and two-dimensional materials with subnanoscale resolution, enabling the fundamental study of chemistry at the spatial and temporal limit. The inelastic scattering of photons by molecules and materials, that results in unique and sensitive vibrational fingerprints, will be considered with tip-enhanced Raman spectroscopy. STM-induced luminescence examines the intrinsic luminescence of organic adsorbates and their energy transfer and charge transfer processes with their surroundings. We also provide a survey of recent efforts to probe the dynamics of optical excitation at the molecular level with scanning tunneling microscopy in the context of light-induced photophysical and photochemical transformations.

Tip-enhanced Raman spectroscopy: Chemical analysis with nanoscale to angstrom scale resolution.

Tip-enhanced Raman spectroscopy (TERS), a cutting-edge near-field spectroscopic tool, provides invaluable chemical insight with impressive spatial resolution in chemistry-related fields such as molecular and catalytic systems, surface science, two-dimensional materials, and biochemistry. High-resolution TERS, in particular, which has advanced exceptionally in the last five years, provides a unique opportunity to scrutinize single molecules individually. Here, this perspective places emphasis on the basic concepts and recent experimental findings of this state-of-the-art research and concludes with a glimpse of future prospects.

The Expanding Frontiers of Tip-Enhanced Raman Spectroscopy.

Fundamental understanding of chemistry and physical properties at the nanoscale enables the rational design of interface-based systems. Surface interactions underlie numerous technologies ranging from catalysis to organic thin films to biological systems. Since surface environments are especially prone to heterogeneity, it becomes crucial to characterize these systems with spatial resolution sufficient to localize individual active sites or defects. Spectroscopy presents as a powerful means to understand these interactions, but typical light-based techniques lack sufficient spatial resolution. This review describes the growing number of applications for the nanoscale spectroscopic technique, tip-enhanced Raman spectroscopy (TERS), with a focus on developments in areas that involve measurements in new environmental conditions, such as liquid, electrochemical, and ultrahigh vacuum. The expansion into unique environments enables the ability to spectroscopically define chemistry at the spatial limit. Through the confinement and enhancement of light at the apex of a plasmonic scanning probe microscopy tip, TERS is able to yield vibrational fingerprint information of molecules and materials with nanoscale resolution, providing insight into highly localized chemical effects.

Direct observation of the geometric isomer selectivity of a reaction controlled via adsorbed bromine.

Methods to improve the specificity of stereoselective reactions are paramount to the viability of reaction-based processes. Surface-bound methods are a powerful means to carry out reactions with selectivity in the pursuit of specific products or nanoarchitectures through bottom-up assembly. The Ullmann-like coupling reaction has come to represent one of the most useful methods to form two-dimensional structures through covalent couplings of aromatic molecules following the dissociation of an aryl carbon-halide bond. The leaving halogen atoms are proven to remain adsorbed on the surface and can be deleterious to the fabrication of larger conjugated superstructures. However, on Au(100) we have found the leaving halogen atoms generate a new adsorbate surface that leads to geometric isomer selectivity compared to the unmodified metal surface. The covalent coupling of 3,6-dibromo-phenanthrenequinone (DBPQ) was studied and leaving bromine atoms were found to form self-assembled islands and modify the reconstruction of Au(100). Subsequently, the coupling reaction yielded total selectivity towards a radical trans dimer when surrounded by bromine atoms, while only cis dimers were observed on the undecorated Au surface. This selectivity induced by bromine networks on the surface ultimately results in another potent way to control the stereoselectivity of surface-bound coupling reactions.

Probing surface mediated configurations of nonplanar regioisomeric adsorbates using ultrahigh vacuum tip-enhanced Raman spectroscopy.

The ability to directly probe the adsorption configurations of organic regioisomeric molecules, specifically nonplanar isomers, on well-defined substrates holds promise to revolutionize fields dependent on nanoscale processes, such as catalysis, surface science, nanotechnology and modern day electronic applications. Herein, the adsorption configurations and surface sensitive interactions of two nonplanar regioisomer, trans- and cis-tetrakispentafluorophenylporphodilactone (trans- and cis-H2F20TPPDL), molecules on (100) surfaces of Ag, Cu and Au were studied and investigated using high resolution scanning tunneling microscopy (STM), combined with ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS). Depending on molecule-substrate interactions, similar "phenyl-up" configurations were observed for these molecules on Ag(100) and Au(100), while a "phenyl-flat" configuration was discovered on a Cu(100) surface. With the help of surface selection rules of TERS, we explain the spectral discrepancies recorded on the Ag and Cu substrate. Furthermore, the intermolecular interactions were addressed using STM analysis on these surfaces after the configurations were determined by TERS. This study sheds light on the distinct configurations of regioisomeric porphodilactone systems (at interfaces) for near-infrared (NIR) photosensitizers and molecular electronics in the near future.

Angstrom Scale Chemical Analysis of Metal Supported Trans- and Cis-Regioisomers by Ultrahigh Vacuum Tip-Enhanced Raman Mapping.

Real space chemical analysis of two structurally very similar components, that is, regioisomers lies at the heart of heterogeneous catalysis reactions, modern-age electronic devices, and various other surface related problems in surface science and nanotechnology. One of the big challenges in surface chemistry is to identify different surface adsorbed molecules and analyze their chemical properties individually. Herein, we report a topological and chemical analysis of two regioisomers, trans- and cis-tetrakispentafluorophenylporphodilactone ( trans- and cis-H2F20TPPDL) molecules by high-resolution scanning tunneling microscopy, and ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS). Both isomeric structures are investigated individually on Ag(100) at liquid nitrogen temperature. Following that, we have successfully distinguished these two regioisomeric molecules simultaneously through TERS with an angstrom scale (8 Å) spatial resolution. Also, the two-component organic heterojunction has been characterized at large scale using high-resolution two-dimensional mapping. Combined with time-dependent density functional theory simulations, we explain the TERS spectral discrepancies for both isomers in the fingerprint region.