We prepared MoS 2 monolayers on Au nanodot (ND) and nanohole (NH) arrays. Both these sample arrays exhibited enhanced photoluminescence intensity compared with that of a bare SiO 2 /Si substrate. The reflectance spectra of MoS 2 /ND and MoS 2 /NH had clear features originating from excitation of localized surface plasmon and propagating surface plasmon polaritons. Notably, the surface photovoltages (SPV) of these hybrid plasmonic nanostructures had opposite polarities, indicating negative and positive charging at MoS 2 /ND and MoS 2 /NH, respectively. Surface potential maps, obtained by Kelvin probe force microscopy, suggested that the potential gradient led to a distinct spatial distribution of photo-generated charges in these two samples under illumination. Furthermore, the local density of photo-generated excitons, as predicted from optical simulations, explained the SPV spectra of MoS 2 /ND and MoS 2 /NH. We show that the geometric configuration of the plasmonic nanostructures modified the polarity of photo-generated excess charges in MoS 2 . These findings point to a useful means of optimizing optoelectronic characteristics and improving the performance of MoS 2 -based plasmonic devices.

Dilute donor organic solar cells (OSCs) are a promising technology to circumvent the trade‐off between open‐circuit voltage (Voc) and short‐circuit current density (Jsc). The origin of hole transport in OSCs with donor concentrations below the percolation threshold is diversely discussed in the community. Herein, both hole back transfer and long‐range hopping (tunneling) are analyzed as possible mechanisms of photocurrent in small molecule dilute donor OSCs using kinetic Monte Carlo (kMC) simulations. In contrast to previous kMC studies, the driving force for exciton dissociation is accounted for. As a study system, nitrogen‐bridged terthiophene (NBTT) molecules in a [6,6]‐phenyl‐C70‐butyric acid methyl ester (PC71BM) matrix are investigated. The simulations show that hole back transfer from the small molecule donor to the fullerene matrix explains the measured concentration dependences of the photocurrents as well as the Jsc dependence on the light intensity for donor concentrations below 5 wt%. For 5 wt%, distances between NBTT molecules decrease to reasonable ranges that long‐range hopping or tunneling cannot be discounted. Compared with polymer donors, larger hole localization is observed. The results emphasize that the barrier for hole back transfer is not only due to the highest occupied molecular orbital (HOMO) offset, but also by hole localization.

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We performed frequency-modulated (AC) and steady-state (DC) surface photovoltage spectroscopy (SPS) measurements on a bilayer structure consisting of an organic semiconductor (P3HT, P3HT:PC61BM, or PFBT2Se2Th:PC71BM) on top of a ZnO electron-transport layer. The AC spectra overlap with the absorption spectra of the organic layer, providing evidence that AC SPS corresponds to band-to-band transitions. The DC spectra are generally broader than the AC spectra, with responses extended below the absorption edge. Thus, DC SPS also probes transitions between band states and trap states within the band gap in addition to band-to-band transitions. When a hole-transport layer (HTL) is deposited on top of the organic layer, the DC spectra of P3HT and P3HT:PC61BM are narrower than those without the HTL, suggesting that the sub-band gap states exist at the surface of these organic semiconductors. In contrast, PFBT2Se2Th:PC71BM does not show signature of surface states or optically active trap states in the band gap. External quantum efficiency and capacitance measurements are employed to explain the nature of sub-band gap states that contribute to surface photovoltage signals and the differences between the two bulk heterojunction systems.

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