Scanning Angle Raman Spectroscopy of Poly(3-hexylthiophene)-Based Films on Indium Tin Oxide, Gold, and Sapphire Surfaces

Interest in realizing conjugated polymer-based films with controlled morphology for efficient electronic devices, including photovoltaics, requires a parallel effort to characterize these films. Scanning angle (SA) Raman spectroscopy is applied to measure poly(3-hexylthiophene) (P3HT):phenyl–C61–butyric acid methyl ester (PCBM)-blend morphology on sapphire, gold, and indium tin oxide interfaces, including functional organic photovoltaic devices. Nonresonant SA Raman spectra are collected in seconds with signal-to-noise ratios that exceed 80, which is possible due to the reproducible SA signal enhancement. Raman spectra are collected as the incident angle of the 785 nm excitation laser is precisely varied upon a prism/sample interface from approximately 35 to 70°. The width of the ∼1447 cm–1 thiophene C═C stretch is sensitive to P3HT order, and polymer order varied depending on the underlying substrate. This demonstrates the importance of performing the spectroscopic measurements on substrates and configurations used in the functioning devices, which is not a common practice. The experimental measurements are modeled with calculations of the interfacial mean square electric field to determine the distance dependence of the SA Raman signal. SA Raman spectroscopy is a versatile method applicable whenever the chemical composition, structure, and thickness of interfacial polymer layers need to be simultaneously measured

Subdiffraction, Luminescence-Depletion Imaging of Isolated, Giant, CdSe/CdS Nanocrystal Quantum Dots

Subdiffraction spatial resolution luminescence depletion imaging was performed with giant CdSe/14CdS nanocrystal quantum dots (g-NQDs) dispersed on a glass slide. Luminescence depletion imaging used a Gaussian shaped excitation laser pulse overlapped with a depletion pulse, shaped into a doughnut profile, with zero intensity in the center. Luminescence from a subdiffraction volume is collected from the central portion of the excitation spot, where no depletion takes place. Up to 92% depletion of the luminescence signal was achieved. An average full width at half-maximum of 40 ± 10 nm was measured in the lateral direction for isolated g-NQDs at an air interface using luminescence depletion imaging, whereas the average full width at half-maximum was 450 ± 90 nm using diffraction-limited, confocal luminescence imaging. Time-gating of the luminescence depletion data was required to achieve the stated spatial resolution. No observable photobleaching of the g-NQDs was present in the measurements, which allowed imaging with a dwell time of 250 ms per pixel to obtain images with a high signal-to-noise ratio. The mechanism for luminescence depletion is likely stimulated emission, stimulated absorption, or a combination of the two. The g-NQDs fulfill a need for versatile, photostable tags for subdiffraction imaging schemes where high laser powers or long exposure times are used