Work-function-controlled operation mode transition between photodiode and photoconductor modes in organic photodetectors

The organic photodetectors (OPDs) can be proposed in two different ways: a photodiode system or a photoconductor type, where the external quantum efficiency (EQE) cannot exceed 100% in the former one but it can in the latter one. Whether the electrode-active layer contacts can inject at least one kind of carriers is the critical factor to determine the specific photodetector type. Therefore, the role of electrode/semiconductor contacts in the OPDs needs to be fully understood. In this work, we demonstrate the high performance OPDs based on PTB7:PC71BM bulk heterojunction with the different top metal electrodes (Ag, Au, Al) by incorporating the PFN modified ITO electrode. Ultraviolet photoelectron spectroscopy shows that the work function of ITO is effectively reduced from 4.7 eV to 4.1 eV due to the PFN dipole layer. Combined with current density-voltage characteristics and the EQE, the results indicate the devices show different working modes: a photodiode or photoconductor type OPDs. For the Ag or Au electrode device, the photogenerated charges can rapidly transport to the corresponding electrodes and then to be collected under reverse bias, which meets the photodiode type. However, the Al electrode device with more than 100% EQE presents the photoconductor mode, which is contributed to that the photogenerated charges accumulate around the interface between the PFN layer and the active layer, and then create a tunneling charge injection under reverse bias. Although both the proposed photodiode and photoconductor devices exhibit large signal-to-noise ratio (104∼105), fast response (∼μs), and low working voltage (−0.5 V), these two type devices show their unique strengths due to the different working modes. The photodiode devices have higher detectivity (more than 1013 Jones) and broader linear dynamic range (over 120 dB), while the photoconductor ones possess more than 100% EQE and the better responsivity (0.56 A/W). This work may pave a way to obtain the desirable working mode of the photodetectors by simply tuning the electrode work function.