Organic photodetectors (OPDs) possessing broadband/narrowband photodetection capability and gain have great potential in integrated optoelectronics products. In this work, OPDs with a device structure of ITO/poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)/thick active layer/semitransparent Al electrode exhibit the extraordinary functions, gain and bidirectional photodetection capability with tunable spectral response range. For the binary OPDs with poly(3‐hexylthiophene‐2,5‐diyl) (P3HT):[6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) (100:1, wt/wt) as active layer, the OPDs exhibit narrowband response from 620 to 700 nm with full‐width at half maximum (FWHM) of ≈30 nm under bottom illumination condition and broadband response from 300 to 700 nm under top illumination condition, respectively. To further confirm and optimize the extraordinary functions of OPDs, ternary devices are fabricated with P3HT:poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dit‐hiophene‐co‐3‐fluor‐othieno[3,4‐b]thiophene‐2‐carboxylate] (PTB7‐Th):PC71BM (50:50:1, wt/wt) as active layer. The narrowband response can be adjusted to near infrared (NIR) region from 760 to 860 nm. The broadband response can be extended to NIR region with response range from 300 to 860 nm. Meanwhile, external quantum efficiency (EQE) spectral shape of the ternary OPDs becomes flatter under top illumination condition and can be kept constant under different bias. The ternary OPDs exhibit similar EQE values of ≈2000% and specific detectivity larger than 1011 Jones at −50 V bias under bottom and top illumination conditions.
A series of photomultiplication (PM)-type polymer photodetectors (PPDs) were fabricated with polymer poly(3-hexylthiophene)-[6,6]-phenyl-C71-butyric acid methyl ester (P3HT-PC71BM) (100:1, w/w) as the active layers, the only difference being the self-assembly time of the active layers for adjusting the P3HT molecular arrangement. The grazing incidence X-ray diffraction (GIXRD) results exhibit that P3HT molecular arrangement can be adjusted between face-on and edge-on structures by controlling the self-assembly time. The champion EQE value of PPDs, based on the active layers without the self-assembly process, arrives at 6380% under 610 nm light illumination at -10 V bias, corresponding to the face-on molecular arrangement of P3HT in the active layers. The EQE values of PPDs were markedly decreased to 1600%, along with the self-assembly time up to 12 min, which should be attributed to the variation of absorption and hole transport ability of the active layers induced by the change of P3HT molecular arrangement. This finding provides an effective strategy for improving the performance of PM-type PPDs by adjusting the molecular arrangement, in addition to the enhanced trap-assisted charge-carrier tunneling injection.
A series of polymer photodetectors (PPDs) are fabricated based on P3HT as an electron donor and fullerene-free material DC-IDT2T as an electron acceptor. The only difference among these PPDs is the P3HT:DC-IDT2T doping weight ratios from 2 : 1 to 150 : 1. The PPDs with P3HT:DC-IDT2T (100 : 1, w/w) as the active layers exhibit champion external quantum efficiency (EQE) of 28 000% and 4000% corresponding to 390 nm and 750 nm light illumination at -20 V bias, respectively. The photomultiplication (PM) phenomenon should be attributed to the enhanced hole tunneling injection due to the interfacial band bending, which is induced by the trapped electrons in DC-IDT2T near the Al cathode. The high EQE value in the long wavelength range is due to the effect of DC-IDT2T photon harvesting and exciton dissociation on the interfacial trap-assisted hole tunneling injection. Meanwhile, the PPDs with DC-IDT2T as the electron acceptor exhibit superior stability compared with the PPDs with PC71BM as the electron acceptor.
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