Tip-Enhanced Nano-Spectroscopy, Imaging, and Control: From Single Molecules to Van Der Waals Materials

Photon-induced phenomena in molecules and other materials play a significant role in device applications as well as understanding their physical properties. While a range of device applications using organic and inorganic molecules and soft and hard materials have led striking developments in modern technologies, using bulk systems has reached the limit in their functions, performance, and regarding application range. Recently, low-dimensional systems have emerged as appealing resources for the advanced technologies based on their significantly improved functions and properties. Hence, understanding light-matter interactions at their natural length scale is of fundamental significance, in addition to the next generation device applications. This thesis demonstrates a range of new functions and behaviors of low-dimensional materials revealed and controlled by the advanced tip-enhanced near-field spectroscopy and imaging techniques exceeding the current instrumental limits. To understand the behaviors of zero-dimensional (0D) molecular systems in interacting environments, we explore new regimes in tip-enhanced Raman spectroscopy (TERS) and scanning near-field optical microscopy (SNOM), revealing the fundamental nature of single-molecule dynamics and nanoscale spatial heterogeneity of biomolecules on the cell membranes. To gain insight into intramolecular properties and dynamic processes of single molecules, we use TERS at cryogenic temperatures. From temperature-dependent line narrowing and splitting, we investigate and quantify ultrafast vibrational dephasing, intramolecular coupling, and conformational heterogeneity. Through correlation analysis of fluctuations of individual modes, we observe rotational motion and spectral fluctuations of single-molecule. We extend single-molecule spectroscopy study into in situ nano-biomolecular imaging of cancer cells by developing in-liquid SNOM. We use a new mechanical resonance control, achieving a high-Q force sensing of the near-field probe. We reveal nanoscale correlations between surface biomolecules and intracellular organelle structures through near-field imaging of the spatial distribution of EGFRs on the membrane of A431 cancer cells. In addition, to understand modified spontaneous emission properties of single quantum dots coupled strongly with localized plasmon, we perform tip-enhanced photoluminescence (TEPL) spectroscopy of the single CdSe/ZnS quantum dots on gold film. We probe and control nanoscale processes in van der Waals two-dimensional (2D) materials. To understand lattice and electronic structure as well as elastic and phonon scattering properties of grain boundaries (GBs) in large-area graphene, we perform TERS imaging. Through correlated analysis of multispectral TERS images with corresponding topography and near-field scattering image, we reveal bilayer structure of GBs in the form of twisted stacking. In addition, we determine the misorientation angles of the bilayer GBs from a detailed quantitative investigation of the Raman modes. In addition, we present a new hybrid nano-optomechanical tip-enhanced spectroscopy and imaging approach combining TERS, TEPL, and atomic force local strain manipulation to probe the heterogeneous PL responses at nanoscale defects and control the local bandgap in transition metal dichalcogenide (TMD) monolayer. We further extend this approach to probe and control the radiative emission of dark excitons and localized excitons. Based on nano-tip enhanced spectroscopy with &sim;6 &times; 105-fold PL enhancement induced by the plasmonic Purcell effect and few-fs radiative dynamics of the optical antenna tip, we can directly probe and actively modulate the dark exciton and localized exciton emissions in time (~ms) and space (&lt;15 nm) at room temperature. Lastly, to extend the range of tip-enhanced microscopy applications to nano-crystallography and nonlinear optics, we present a generalizable approach controlling the excitation polarizability for both in-plane and out-of-plane vector fields by breaking the axial symmetry of a conventional Au tip. This vector field control with the tip enables probing of nonlinear optical second harmonic generation (SHG) responses from a range of ferroic materials as well as van der Waals 2D materials. Specifically, we demonstrate SHG nano-crystallography results for MoS2 monolayer film, ferroelectric YMnO3, BaTiO3-BiFeO3 multiferroics, and PbTiO3/SrTiO3 superlattices.</p

Tip-enhanced strong coupling spectroscopy, imaging, and control of a single quantum emitter

Optical cavities can enhance and control light-matter interactions. This level of control has recently been extended to the nanoscale with single emitter strong coupling even at room temperature using plasmonic nanostructures. However, emitters in static geometries, limit the ability to tune the coupling strength or to couple different emitters to the same cavity. Here, we present tip-enhanced strong coupling (TESC) with a nanocavity formed between a scanning plasmonic antenna tip and the substrate. By reversibly and dynamically addressing single quantum dots, we observe mode splitting up to 160 meV and anticrossing over a detuning range of ~100 meV, and with subnanometer precision over the deep subdiffraction-limited mode volume. Thus, TESC enables previously inaccessible control over emitter-nanocavity coupling and mode volume based on near-field microscopy. This opens pathways to induce, probe, and control single-emitter plasmon hybrid quantum states for applications from optoelectronics to quantum information science at room temperature

Growth Kinetics and Optical Properties of CsPbBr3 Perovskite Nanocrystals

We synthesized CsPbBr3 perovskite nanocrystals (NCs) at different reaction temperatures and tracked their growth kinetics on the basis of their optical properties and estimated size. The energies of the absorption and fluorescence (FL) peaks with increasing reaction temperature for the CsPbBr3 perovskite NCs were tuned within the regions of 2.429-2.570 eV and 2.391-2.469 eV, respectively, depending on size of the NCs (9.9-12.5 nm). The Stokes shifts of CsPbBr3 perovskite NCs with increasing NC size decreased from 101 meV to 38 meV. The full-width at half-maximum of the FL peaks for the CdSe NCs decreased from 150 meV to 90 meV because of the improved size uniformity of the CsPbBr3 perovskite NCs. The energy spacing of CsPbBr3 perovskite NCs synthesized at various reaction temperatures was calculated from Tauc plots; this information is critical for determining the bandgap energy and enables the size of the CsPbBr3 perovskite NCs to be estimated using the effective mass approximation

Comparison of standard-setting methods for the Korean Radiological Technologist Licensing Examination: Angoff, Ebel, bookmark, and Hofstee

Purpose This study aimed to compare the possible standard-setting methods for the Korean Radiological Technologist Licensing Examination, which has a fixed cut score, and to suggest the most appropriate method. Methods Six radiological technology professors set standards for 250 items on the Korean Radiological Technologist Licensing Examination administered in December 2016 using the Angoff, Ebel, bookmark, and Hofstee methods. Results With a maximum percentile score of 100, the cut score for the examination was 71.27 using the Angoff method, 62.2 using the Ebel method, 64.49 using the bookmark method, and 62 using the Hofstee method. Based on the Hofstee method, an acceptable cut score for the examination would be between 52.83 and 70, but the cut score was 71.27 using the Angoff method. Conclusion The above results suggest that the best standard-setting method to determine the cut score would be a panel discussion with the modified Angoff or Ebel method, with verification of the rated results by the Hofstee method. Since no standard-setting method has yet been adopted for the Korean Radiological Technologist Licensing Examination, this study will be able to provide practical guidance for introducing a standard-setting process

Wide-gap photoluminescence control of quantum dots through atomic interdiffusion and bandgap renormalization

Bandgap and photoluminescence (PL) energy control of epitaxially grown II-VI quantum dots (QDs) are highly desirable for applications in optoelectronic devices, yet little work has been reported. Here, we present a wide tunability of PL emission for CdTe/ZnTe QDs through an impurity-free vacancy disordering method. To induce compressive stress at the dielectric layer/ZnTe interface, a SiO2 film is deposited onto the samples, followed by rapid thermal annealing to induce atomic interdiffusion. After the heat treatment, the PL spectra of the intermixed QDs show pronounced blueshifts in peak energy as large as similar to 200 meV because of the reduced bandgap renormalization and decreased quantum confinement effects in addition to the dominant atomic interdiffusion effect. In addition, we present a thorough investigation on the modified physical properties of the intermixed QDs, including their lattice structure, thermal escape energy, and carrier dynamics, through quantitative X-ray and optical characterizations

Tip-enhanced photoluminescence nano-spectroscopy and nano-imaging

Photoluminescence (PL), a photo-excited spontaneous emission process, provides a wealth of optical and electronic properties of materials, which enable microscopic and spectroscopic imaging, biomedical sensing and diagnosis, and a range of photonic device applications. However, conventional far-field PL measurements have limitations in sensitivity and spatial resolution, especially to investigate single nano-materials or nano-scale dimension of them. In contrast, tip-enhanced photoluminescence (TEPL) nano-spectroscopy provides an extremely high sensitivity with &lt;10 nm spatial resolution, which allows the desired nano-scale characterizations. With outstanding and unique optical properties, low-dimensional quantum materials have recently attracted much attention, and TEPL characterizations, i. e., probing and imaging, and even control at the nanoscale, have been extensively studied. In this review, we discuss the fundamental working mechanism of PL enhancement by plasmonic tip, and then highlight recent advances in TEPL studies for low-dimensional quantum materials. Finally, we discuss several remaining challenges of TEPL nano-spectroscopy and nano-imaging, such as implementation in non-ambient media and in situ environments, limitations in sample structure, and control of near-field polarization, with perspectives of the approach and its applications

Conformational heterogeneity of molecules physisorbed on a gold surface at room temperature

A quantitative single-molecule tip-enhanced Raman spectroscopy (TERS) study at room temperature remained a challenge due to the rapid structural dynamics of molecules exposed to air. Here, we demonstrate the hyperspectral TERS imaging of single or a few brilliant cresyl blue (BCB) molecules at room temperature, along with quantitative spectral analyses. Robust chemical imaging is enabled by the freeze-frame approach using a thin Al2O3 capping layer, which suppresses spectral diffusions and inhibits chemical reactions and contamination in air. For the molecules resolved spatially in the TERS image, a clear Raman peak variation up to 7.5 cm(-1) is observed, which cannot be found in molecular ensembles. From density functional theory-based quantitative analyses of the varied TERS peaks, we reveal the conformational heterogeneity at the single-molecule level. This work provides a facile way to investigate the single-molecule properties in interacting media, expanding the scope of single-molecule vibrational spectroscopy studies. Tip-enhanced vibrational spectroscopy at room temperature is complicated by molecular conformational dynamics, photobleaching, contaminations, and chemical reactions in air. This study demonstrates that a sub-nm protective layer of Al2O3 provides robust conditions for probing single-molecule conformations

Current Trends in the Epidemiological and Pathological Characteristics of Gastrointestinal Stromal Tumors in Korea, 2003-2004

Despite remarkable progress in understanding and treating gastrointestinal stromal tumors (GISTs) during the past two decades, the pathological characteristics of GISTs have not been made clear yet. Furthermore, concrete diagnostic criteria of malignant GISTs are still uncertain. We collected pathology reports of 1,227 GISTs from 38 hospitals in Korea between 2003 and 2004 and evaluated the efficacy of the NIH and AFIP classification schemes as well as the prognostic factors among pathologic findings. The incidence of GISTs in Korea is about 1.6 to 2.2 patients per 100,000. Extra-gastrointestinal GISTs (10.1%) are more common in Korea than in Western countries. In univariate analysis, gender, age, tumor location, size, mitosis, tumor necrosis, vascular and mucosal invasions, histologic type, CD34 and s-100 protein expression, and classifications by the NIH and AFIP criteria were found to be significantly correlated with patient's survival. However, the primary tumor location, stage and classification of the AFIP criteria were prognostically significant in predicting patient's survival in multivariate analysis. The GIST classification based on original tumor location, size, and mitosis is more efficient than the NIH criteria in predicting patient's survival, but the mechanism still needs to be clarified through future studies