Second-harmonic confocal microscopy of single ß-BBO nanocrystals

Abstract

In this M. Sc. thesis, we apply the Confocal Microscopy (CM) technique for optical characterization of single β–barium-borate (BBO) nanocrystals (NCs). CM can produce images by reflection and fluorescence with high signal-to-noise ratio. Our experimental setup allows the measurement of the SH polarization response to be recorded and the results can be used to determine the NCs orientation as well as to obtain information about the NL susceptibility tensor, allowing a detailed characterization of the sample. Home-synthesized BBO NCs were previously characterized by several techniques such as X-ray diffraction (XRD), High-Resolution Transmission Electronic Microscopy (HRTEM), Selected Area Electron Diffraction (SAED) and Diffuse Reflectance (DR), assuring that non-centrosymmetric and single crystalline phase have been synthesized. The NCs have average dimensions of 150 nm×15 nm×15 nm, and these needles are oriented in the direction of the crystallographic c-axis. On the other hand, the HRTEM and SAED showed the presence of defects in the needles composed of crystallites about 10 nm in size that are formed during the growth by the rotation of crystallographic planes around the c-axis. Due to symmetry properties of BBO, the technique employed in this work cannot discern rotations along the c-axis and thus, the defects are effectively irrelevant to SH CM as well to polarization dependent measurements. The experimental setup uses a mode-locked Ti:Sapphire laser (120 fs, 76 MHz, 820 nm) as a light source for a home-made inverted optical confocal microscope employing a 100X NA=1.25 objective, set under a piezo module for scanning the sample in relation to the laser focal region. A dichroic mirror serves as a beam splitter, ensuring the incidence of the laser on the sample and the transmission of the SH signal. The confocal aspect is obtained by using a 10 μm pinhole in the detection path. Spectral information is obtained with a monochromator equipped with a photomultiplier. A half-wave plate placed right before the dichroic mirror allows measurements of the SH signal as a function of the laser polarization orientation. Several images of single NCs were made by raster scanning of the sample in 2 and 3 dimensions, showing a good agreement with the corresponding imaging theory. The polarization dependence of the SH signal allowed the identification of individual particles from aggregates and the data was fitted using a model that takes into account the BBO symmetries and the optical elements in the setup. The model considers: i) the electrostatic approximation; ii) the effects of the microscope’s objective used to focus the light on the sample in epi-geometry configuration and iii) the properties of χ⁽²⁾ for the β–BBO NCs. The results constitute a proof of concept for high resolution CM of single NL emitters as well an optical characterization for BBO NCs not hitherto described in the literature.