Electrostatic tip effects in scanning probe microscopy of nanostructures.

Electrical scanning probe microscopies (SPM) use ultrasharp metallic tips to obtain nanometer spatial resolution and are a key tool for characterizing nanoscale semiconducting materials and systems. However, these tips are not passive probes; their high work functions can induce local band bending whose effects depend sensitively on the local geometry and material properties and thus are inherently difficult to quantify. We use sequential finite element simulations to first explore the magnitude and spatial distribution of charge reorganization due to tip-induced band bending (TIBB) for planar and nanostructured geometries. We demonstrate that tip-induced depletion and accumulation of carriers can be significantly modified in confined geometries such as nanowires compared to a bulk planar response. This charge reorganization is due to finite size effects that arise as the nanostructure size approaches the Debye length, with significant implications for a range of SPM techniques. We then use the reorganized charge distribution from our model to describe experimentally measured quantities, using in operando scanning microwave impedance microscopy measurements on axial p-i-n silicon nanowire devices as a specific example. By incorporating TIBB, we reveal that our experimentally observed enhancement (absence) of contrast at the p-i (i-n) junction is explained by the tip-induced accumulation (depletion) of carriers at the interface. Our results demonstrate that the inclusion of TIBB is critical for an accurate interpretation of electrical SPM measurements, and is especially important for weakly screening or low-doped materials, as well as the complex doping patterns and confined geometries commonly encountered in nanoscale systems.

Crystallographic polarity measurements in two-terminal GaN nanowire devices by lateral piezoresponse force microscopy.

Lateral piezoresponse force microscopy (L-PFM) is demonstrated as a reliable method for determining the crystallographic polarity of individual, dispersed GaN nanowires that were functional components in electrical test structures. In contrast to PFM measurements of vertically oriented (as-grown) nanowires, where a biased probe tip couples to out-of-plane deformations through the d33 piezoelectic coefficient, the L-PFM measurements in this study were implemented on horizontally oriented nanowires that coupled to shear deformations through the d15 coefficient. L-PFM phase-polarity relationships were determined experimentally using a bulk m-plane GaN sample with a known [0001] direction and further indicated that the sign of the d15 piezoelectric coefficient was negative. L-PFM phase images successfully revealed the in-plane [0001] orientation of self-assembed GaN nanowires as part of a growth polarity study and results were validated against scanning transmission electron microscopy lattice images. Combined characterization of electrical properties and crystallographic polarity was also implemented for two-terminal GaN/Al0.1Ga0.9N/GaN nanowires devices, demonstrating L-PFM measurements as a viable tool for assessing correlations between device rectification and polarization-induced band bending.

Imaging Carrier Inhomogeneities in Ambipolar Tellurene Field Effect Transistors.

The development of van der Waals (vdW) homojunction devices requires materials with narrow bandgaps and simultaneously high hole and electron mobilities for bipolar transport, as well as methods to image and study spatial variations in carrier type and associated conductivity with nanometer spatial resolution. Here, we demonstrate the general capability of near-field scanning microwave microscopy (SMM) to image and study the local carrier type and associated conductivity in operando by studying ambiploar field-effect transistors (FETs) of the 1D vdW material tellurium in 2D form. To quantitatively understand electronic variations across the device, we produce nanometer-resolved maps of the local carrier equivalence backgate voltage. We show that the global device conductivity minimum determined from transport measurements does not arise from uniform carrier neutrality but rather from the continued coexistence of p-type regions at the device edge and n-type regions in the interior of our micrometer-scale devices. This work both underscores and addresses the need to image and understand spatial variations in the electronic properties of nanoscale devices.

Electronic and Morphological Inhomogeneities in Pristine and Deteriorated Perovskite Photovoltaic Films.

We perform scanning microwave microscopy (SMM) to study the spatially varying electronic properties and related morphology of pristine and degraded methylammonium lead-halide (MAPI) perovskite films fabricated under different ambient humidity. We find that higher processing humidity leads to the emergence of increased conductivity at the grain boundaries but also correlates with the appearance of resistive grains that contain PbI2. Deteriorated films show larger and increasingly insulating grain boundaries as well as spatially localized regions of reduced conductivity within grains. These results suggest that while humidity during film fabrication primarily benefits device properties due to the passivation of traps at the grain boundaries and self-doping, it also results in the emergence of PbI2-containing grains. We further establish that MAPI film deterioration under ambient conditions proceeds via the spatially localized breakdown of film conductivity, both at grain boundaries and within grains, due to local variations in susceptibility to deterioration. These results confirm that PbI2 has both beneficial and adverse effects on device performance and provide new means for device optimization by revealing spatial variations in sample conductivity as well as morphological differences in resistance to sample deterioration.

Microwave near-field imaging of two-dimensional semiconductors.

Optimizing new generations of two-dimensional devices based on van der Waals materials will require techniques capable of measuring variations in electronic properties in situ and with nanometer spatial resolution. We perform scanning microwave microscopy (SMM) imaging of single layers of MoS2 and n- and p-doped WSe2. By controlling the sample charge carrier concentration through the applied tip bias, we are able to reversibly control and optimize the SMM contrast to image variations in electronic structure and the localized effects of surface contaminants. By further performing tip bias-dependent point spectroscopy together with finite element simulations, we distinguish the effects of the quantum capacitance and determine the local dominant charge carrier species and dopant concentration. These results underscore the capability of SMM for the study of 2D materials to image, identify, and study electronic defects.

Control of plasmon emission and dynamics at the transition from classical to quantum coupling.

With nanosecond radiative lifetimes, quenching dominates over enhancement for conventional fluorescence emitters near metal interfaces. We explore the fundamentally distinct behavior of photoluminescence (PL) with few-femtosecond radiative lifetimes of a coupled plasmonic emitter. Controlling the emitter-surface distance with subnanometer precision by combining atomic force and scanning tunneling distance control, we explore the unique behavior of plasmon dynamics at the transition from long-range classical resonant energy transfer to quantum coupling. Because of the ultrafast radiative plasmon emission, classical quenching is completely suppressed. Field-enhanced behavior dominates until the onset of quantum coupling dramatically reduces emission intensity and field enhancement, as verified in concomitant tip-enhanced Raman measurements. The entire distance behavior from tens of nanometers to subnanometers can be described using a phenomenological rate equation model and highlights the new degrees of freedom in radiation control enabled by an ultrafast radiative emitter near surfaces.

Phase-resolved surface plasmon interferometry of graphene.

The surface plasmon polaritons (SPPs) of graphene reflect the microscopic spatial variations of underlying electronic structure and dynamics. Here, we excite and image the graphene SPP response in phase and amplitude by near-field interferometry. We develop an analytic cavity model that can self-consistently describe the SPP response function for edge, grain boundary, and defect SPP reflection and scattering. The derived SPP wave vector, damping, and carrier mobility agree with the results from more complex models. Spatial variations in the Fermi level and associated variations in dopant concentration reveal a nanoscale spatial inhomogeneity in the reduced conductivity at internal boundaries. The additional SPP phase information thus opens a new degree of freedom for spatial and spectral graphene SPP tuning and modulation for optoelectronics applications.

GaN nanowire coated with atomic layer deposition of tungsten: a probe for near-field scanning microwave microscopy.

GaN nanowires were coated with tungsten by means of atomic layer deposition. These structures were then adapted as probe tips for near-field scanning microwave microscopy. These probes displayed a capacitive resolution of ~0.03 fF, which surpasses that of a commercial Pt tip. Upon imaging of MoS2 sheets with both the Pt and GaN nanowire tips, we found that the nanowire tips were comparatively immune to surface contamination and far more durable than their Pt counterparts.

Nano-chemical infrared imaging of membrane proteins in lipid bilayers.

The spectroscopic characterization of biomolecular structures requires nanometer spatial resolution and chemical specificity. We perform full spatio-spectral imaging of dried purple membrane patches purified from Halobacterium salinarum with infrared vibrational scattering-type scanning near-field optical microscopy (s-SNOM). Using near-field spectral phase contrast based on the Amide I resonance of the protein backbone, we identify the protein distribution with 20 nm spatial resolution and few-protein sensitivity. This demonstrates the general applicability of s-SNOM vibrational nanospectroscopy, with potential extension to a wide range of biomolecular systems.

Adaptive Channel-State-Information Feedback in Integrated Sensing and Communication Systems.

Efficient design of integrated sensing and communication systems can minimize signaling overhead by reducing the size and/or rate of feedback in reporting channel state information (CSI). To minimize the signaling overhead when performing sensing operations at the transmitter, this paper proposes a procedure to reduce the feedback rate. We consider a threshold-based sensing measurement and reporting procedure, such that the CSI is transmitted only if the channel variation exceeds a threshold. However, quantifying the channel variation, determining the threshold, and recovering sensing information with a lower feedback rate are still open problems. In this paper, we first quantify the channel variation by considering several metrics including the Euclidean distance, time-reversal resonating strength, and frequency-reversal resonating strength. We then design an algorithm to adaptively select a threshold, minimizing the feedback rate, while guaranteeing sufficient sensing accuracy by reconstructing high-quality signatures of human movement. To improve sensing accuracy with irregular channel measurements, we further propose two reconstruction schemes, which can be easily employed at the transmitter in case there is no feedback available from the receiver. Finally, the sensing performance of our scheme is extensively evaluated through real and synthetic channel measurements, considering channel estimation and synchronization errors. Our results show that the amount of feedback can be reduced by 50% while maintaining good sensing performance in terms of range and velocity estimations. Moreover, in contrast to other schemes, we show that the Euclidean distance metric is better able to capture various human movements with high channel variation values.

Femtosecond nanofocusing with full optical waveform control.

The simultaneous nanometer spatial confinement and femtosecond temporal control of an optical excitation has been a long-standing challenge in optics. Previous approaches using surface plasmon polariton (SPP) resonant nanostructures or SPP waveguides have suffered from, for example, mode mismatch, or possible dependence on the phase of the driving laser field to achieve spatial localization. Here we take advantage of the intrinsic phase- and amplitude-independent nanofocusing ability of a conical noble metal tip with weak wavelength dependence over a broad bandwidth to achieve a 10 nm spatially and few-femtosecond temporally confined excitation. In combination with spectral pulse shaping and feedback on the second-harmonic response of the tip apex, we demonstrate deterministic arbitrary optical waveform control. In addition, the high efficiency of the nanofocusing tip provided by the continuous micro- to nanoscale mode transformation opens the door for spectroscopy of elementary optical excitations in matter on their natural length and time scales and enables applications from ultrafast nano-opto-electronics to single molecule quantum coherent control.

Nanoscale Photoexcited Carrier Dynamics in Perovskites.

The optoelectronic properties of lead halide perovskite thin films can be tuned through compositional variations and strain, but the associated nanocrystalline structure makes it difficult to untangle the link between composition, processing conditions, and ultimately material properties and degradation. Here, we study the effect of processing conditions and degradation on the local photoconductivity dynamics in [(CsPbI3)0.05(FAPbI3)0.85(MAPbBr3)0.15] and (FA0.7Cs0.3PbI3) perovskite thin films using temporally and spectrally resolved microwave near-field microscopy with a temporal resolution as high as 5 ns and a spatial resolution better than 50 nm. For the latter FACs formulation, we find a clear effect of the process annealing temperature on film morphology, stability, and spatial photoconductivity distribution. After exposure of samples to ambient conditions and illumination, we find spectral evidence of halide segregation-induced degradation below the instrument resolution limit for the mixed halide formulation, while we find a clear spatially inhomogeneous increase in the carrier lifetime for the FACs formulation annealed at 180 °C.

Nano-optical investigations of the metal-insulator phase behavior of individual VO(2) microcrystals.

Despite the relatively simple stoichiometry and structure of VO(2), many questions regarding the nature of its famous metal-insulator transition (MIT) remain unresolved. This is in part due to the prevailing use of polycrystalline film samples and the limited spatial resolution in most studies, hindering access to and control of the complex phase behavior and its inevitable spatial inhomogeneities. Here, we investigate the MIT and associated nanodomain formation in individual VO(2) microcrystals subject to substrate stress. We employ symmetry-selective polarization Raman spectroscopy to identify crystals that are strain-stabilized in either the monoclinic M1 or M2 insulating phase at room-temperature. Raman measurements are further used to characterize the phase dependence on temperature, identifying the appearance of the M2 phase during the MIT. The associated formation and spatial evolution of rutile (R) metallic domains is studied with nanometer-scale spatial resolution using infrared scattering-scanning near-field optical microscopy (s-SNOM). We deduce that even for small crystals of VO(2), the MIT is influenced by the competition between the R, M1, and M2 crystal phases with their different lattice constants subjected to the external substrate-induced stress. The results have important implications for the interpretation of the investigations of conventional polycrystalline thin films where the mutual interaction of constituent crystallites may affect the nature of the MIT in VO(2).

Near-field localization in plasmonic superfocusing: a nanoemitter on a tip.

Focusing light to subwavelength dimensions has been a long-standing desire in optics but has remained challenging, even with new strategies based on near-field effects, polaritons, and metamaterials. The adiabatic propagation of surface plasmon polaritons (SPP) on a conical taper as proposed theoretically has recently emerged as particularly promising to obtain a nanoconfined light source at the tip. Employing grating-coupling of SPPs onto gold tips, we demonstrate plasmonic nanofocusing into a localized excitation of approximately 20 nm in size and investigate its near- and far-field behavior. For cone angles of approximately 10-20 degrees , the breakdown of the adiabatic propagation conditions is found to be localized at or near the apex region with approximately 10 nm radius. Despite an asymmetric side-on SPP excitation, the apex far-field emission with axial polarization characteristics representing a radially symmetric SPP mode in the nanofocus confirms that the conical tip acts as an effective mode filter with only the fundamental radially symmetric TM mode (m = 0) propagating to the apex. We demonstrate the use of these tips as a source for nearly background-free scattering-type scanning near-field optical microscopy (s-SNOM).

Signal limitations in tip-enhanced Raman scattering: the challenge to become a routine analytical technique.

The fundamental parameters and limitations that determine the signal strength in tip-enhanced Raman scattering (TERS) are discussed. A semiquantitative analysis of the Raman signal expected in different experimental geometries and with different sample systems is presented, taking into account experimental parameters including Fresnel factor, numerical aperture of the illumination and collection optics, detection efficiency, and the Raman scattering cross section of the material. A top/side-on illumination geometry is essential for the study of nontransparent samples. It can yield the highest signal levels when strong tip-sample coupling using a metallic substrate provides large field enhancement. In contrast, axial/through-sample illumination is limited to transparent sample materials. Although conceptually simpler in experimental implementation and despite high numerical aperture signal collection efficiency, signals are generally weaker due to limited field enhancement. Crystalline solids with small Raman cross sections and dense molecular/biological systems with unavoidable far-field background provide the biggest challenge for TERS analysis yet at the same time hold the most exciting outstanding scientific questions TERS has the potential to answer.

Spatially Resolved Persistent Photoconductivity in MoS2-WS2 Lateral Heterostructures.

The optical and electronic properties of 2D semiconductors are intrinsically linked via the strong interactions between optically excited bound species and free carriers. Here we use near-field scanning microwave microscopy (SMM) to image spatial variations in photoconductivity in MoS2-WS2 lateral multijunction heterostructures using photon energy-resolved narrowband illumination. We find that the onset of photoconductivity in individual domains corresponds to the optical absorption onset, confirming that the tightly bound excitons in transition metal dichalcogenides can nonetheless dissociate into free carriers. These photogenerated carriers are most likely n-type and are seen to persist for up to days. Informed by finite element modeling we reveal that they can increase the carrier density by up to 200 times. This persistent photoconductivity appears to be dominated by contributions from the multilayer MoS2 domains, and we attribute the flake-wide response in part to charge transfer across the heterointerface. Spatial correlation of our SMM imaging with photoluminescence (PL) mapping confirms the strong link between PL peak emission photon energy, PL intensity, and the local accumulated charge. This work reveals the spatially and temporally complex optoelectronic response of these systems and cautions that properties measured during or after illumination may not reflect the true dark state of these materials but rather a metastable charged state.

Near-Field Control and Imaging of Free Charge Carrier Variations in GaN Nanowires.

Despite their uniform crystallinity, the shape and faceting of semiconducting nanowires (NWs) can give rise to variations in structure and associated electronic properties. Here we develop a hybrid scanning probe-based methodology to investigate local variations in electronic structure across individual n-doped GaN NWs integrated into a transistor device. We perform scanning microwave microscopy (SMM), which we combine with scanning gate microscopy (SGM) to determine the free-carrier SMM signal contribution and image local charge carrier density variations. In particular, we find significant variations in free carriers across NWs, with a higher carrier density at the wire facets. By increasing the local carrier density through tip-gating, we find that the tip injects current into the NW with strongly localized current when positioned over the wire vertices. These results suggest that the strong variations in electronic properties observed within NWs have significant implications for device design and may lead to new paths to optimization.

Light on the Tip of a Needle: Plasmonic Nanofocusing for Spectroscopy on the Nanoscale.

The efficiency of plasmonic nanostructures as optical antennas to concentrate optical fields to the nanoscale has been limited by intrinsically short dephasing times and small absorption cross sections. We discuss a new optical antenna concept based on surface plasmon polariton (SPP) nanofocusing on conical noble metal tips to achieve efficient far- to near-field transformation of light from the micro- to the nanoscale. The spatial separation of the launching of propagating SPPs from their subsequent apex confinement with high energy concentration enables background-free near-field imaging, tip-enhanced Raman scattering, and nonlinear nanospectroscopy. The broad bandwidth and spectral tunability of the nanofocusing mechanism in combination with frequency domain pulse shaping uniquely allow for the spatial confinement of ultrashort laser pulses and few-femtosecond spatiotemporal optical control on the nanoscale. This technique not only extends powerful nonlinear and ultrafast spectroscopies to the nanoscale but can also generate fields of sufficient intensity for electron emission and higher harmonic generation.

Optical nanocrystallography with tip-enhanced phonon Raman spectroscopy.

Conventional phonon Raman spectroscopy is a powerful experimental technique for the study of crystalline solids that allows crystallography, phase and domain identification on length scales down to approximately 1 microm. Here we demonstrate the extension of tip-enhanced Raman spectroscopy to optical crystallography on the nanoscale by identifying intrinsic ferroelectric domains of individual BaTiO(3) nanocrystals through selective probing of different transverse optical phonon modes in the system. The technique is generally applicable for most crystal classes, and for example, structural inhomogeneities, phase transitions, ferroic order and related finite-size effects occurring on nanometre length scales can be studied with simultaneous symmetry selectivity, nanoscale sensitivity and chemical specificity.