Letter pubs.acs.org/NanoLett
Improved Superresolution Imaging Using Telegraph Noise in Organic Semiconductor Nanoparticles Yifei Jiang,† Muskendol Novoa,† Teeranan Nongnual,† Rhonda Powell,‡ Terri Bruce,‡ and Jason McNeill*,† †
Department of Chemistry and ‡Clemson Light Imaging Facility, Clemson University, Clemson, South Carolina 29634, United States S Supporting Information *
ABSTRACT: Small semiconductor structures often exhibit “telegraph noise”. If the number of charge carriers is small, then spontaneous changes in the number of carriers can lead to abrupt switching between two or more discrete levels, leading to burst noise or popcorn noise in transistors. We have observed similar behavior in the fluorescence of organic semiconductor nanoparticles, where typical carrier populations are often less than ∼10 carriers per nanoparticle. Spontaneous changes in the number of charges results in abrupt switching between 2 or more fluorescence intensity levels, because the charges act as highly efficient fluorescence quenchers. The equilibrium number of charges is determined by competition between a photodriven ionization process and spontaneous recombination. Doping with redox-active molecules also affects the balance. Nanoparticles of the conjugated polymer PFBT doped with the fullerene derivative PCBM, rapidly establish a fluctuating steady-state population of tens of hole polaron charge carriers, sufficient to nearly completely suppress nanoparticle fluorescence. However, fluctuations in the number of charges lead to occasional bursts of fluorescence. This spontaneous photoswitching phenomenon can be exploited for superresolution imaging. The repeated, spontaneous generation of short, intense bursts of fluorescence photons results in a localization precision of ∼0.6 nm, about 4 times better than typical resolution obtained by localization of dye molecules. KEYWORDS: Superresolution imaging, 1 nm resolution, conjugated polymer nanoparticles, hole polaron
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polymer systems.16−19 Nanoparticles of the conjugated polymer poly[9,9-dioctylfluorenyl-2,7-diyl)-co-1,4-benzo-{2,1′-3}-thiadiazole)] (PFBT) doped with the fullerene derivative phenylC61-butyric acid methyl ester (PCBM), rapidly establish a large population of hole polaron charge carriers, sufficient to nearly completely suppress nanoparticle fluorescence. However, fluctuations in the number of charges lead to occasional bursts of fluorescence, which is similar to the random telegraph signal noise observed in semiconductor devices.20 The repeated, spontaneous generation of short, intense bursts of fluorescence photons (3−5 × 104 photons detected per switching event, on average) are roughly 1−2 orders of magnitude brighter than those of photoswitching dye molecules, resulting in a localization precision of ∼0.6 nm, about 4 times better than the typical resolution obtained by localization of dye molecules.21 Nanoparticles of the conjugated polymer PFBT doped with various percentages of PCBM were prepared using nanoprecipitation method described previously.22−24 The size distribution of the nanoparticles was determined using atomic force microscope (AFM) and dynamic light scattering (DLS) (see SI for AFM images and particle size distributions). No significant difference in particle size was observed throughout the doping range (Figure 1b). The typical particle sizes
n recent years, driven by the interest of studying cellular structures and processes beyond the diffraction limit, superresolution imaging techniques have undergone rapid growth. Various photophysical processes, such as, photoactivation,1 photoswitching,2 stimulated emission,3 and intersystem crossing,4 have been utilized to overcome the diffraction limit. The development of superresolution fluorescent probes, including photoactivatable proteins,1,5 photoswitchable dyes,6,7 proteins,8,9 and nanoparticles10,11 have improved the spatial resolution of optical microscope to
