We propose, simulate, and experimentally validate a new mechanical detection method to analyze atomic force microscopy (AFM) cantilever motion that enables noncontact discrimination of transient events with ~100 ns temporal resolution without the need for custom AFM probes, specialized instrumentation, or expensive add-on hardware. As an example application, we use the method to screen thermally annealed poly(3-hexylthiophene):phenyl-C(61)-butyric acid methyl ester photovoltaic devices under realistic testing conditions over a technologically relevant performance window. We show that variations in device efficiency and nanoscale transient charging behavior are correlated, thereby linking local dynamics with device behavior. We anticipate that this method will find application in scanning probe experiments of dynamic local mechanical, electronic, magnetic, and biophysical phenomena.

Controversy has long surrounded the question of whether spontaneous lateral demixing of membranes into coexisting liquid phases can organize proteins and lipids on micron scales within unperturbed, living cells. A clear answer hinges on observation of hallmarks of a reversible phase transition. Here, by directly imaging micron-scale membrane domains of yeast vacuoles both in vivo and cell free, we demonstrate that the domains arise through a phase separation mechanism. The domains are large, have smooth boundaries, and can merge quickly, consistent with fluid phases. Moreover, the domains disappear above a distinct miscibility transition temperature (T) and reappear below T, over multiple heating and cooling cycles. Hence, large-scale membrane organization in living cells under physiologically relevant conditions can be controlled by tuning a single thermodynamic parameter.

We study local photooxidation and trap formation in all-polymer bulk-heterojunction organic photovoltaics (OPVs) using both time-resolved electrostatic force microscopy (trEFM) and conventional scanning Kelvin probe microscopy (SKPM). We create electron-trapping defects at known locations by locally photooxidizing blends of poly[(9,9′-dioctylfluorene-alt-(bis(N,N′-(4-butylphenyl))-bis(N,N′-phenyl-1,4-phenylenediamine)] and poly[9,9′-dioctylfluorene-alt-1,4-benzothiadiazole]. We then compare the local surface photovoltage shifts measured via SKPM and the changes in local photoinduced charging rates measured via trEFM with changes in the performance of macroscopic photodiodes that have been exposed to similar photooxidation. We find that the trEFM charging rate images can identify local photooxidation and trap formation with much better sensitivity than conventional SKPM images. In addition, the changes in the trEFM charging rates correlate well with the external quantum efficiencies of the macroscopic photodiodes. In contrast, the SKPM images not only are less sensitive to trap formation but also show a more complicated response. We conclude that trEFM is well suited to studying local trap formation in organic solar cells and caution that SKPM data by itself can be difficult to interpret on OPV films, especially when materials have been exposed to photooxidation.

We show that local structural variation affects the rate of aging in nanostructured polymer solar cells by comparing time-resolved electrostatic force microscopy (trEFM) and conventional device measurements on model polymer blends. Specifically, we study photovoltaic devices made from 1:1 blends of the polyfluorene copolymers poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylene-diamine) (PFB) and poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT). We photooxidize these films in situ using 365, 405, and 455 nm illumination under ambient conditions, with the wavelengths chosen to preferentially excite the different components. During photooxidation, we observe a faster loss of photocurrent generation from F8BT-rich domains, leaving the PFB-rich phases to show higher photoresponse even at wavelengths absorbed predominantly by F8BT. We propose that this effect is due to the more rapid degradation of PFB hole-transport pathways in the F8BT-rich regions, resulting in a loss of percolation pathways for hole transport in the F8BT-rich phase.

Hallmarks of Reversible Phase Separation in Living, Unperturbed Cell Membranes