Abstract: To achieve high detectivity in infrared detectors, it is critical to reduce the device noise. However, for non-crystalline semiconductors, an essential framework is missing to understand and predict the effects of disorder on the dark current. This report presents experimental and modeling studies on the noise current in exemplar organic bulk heterojunction photodiodes, with 10 donor–acceptor combinations spanning wavelength between 800 and 1600 nm. A significant reduction of the noise and higher detectivity were found in devices using non-fullerene acceptors (NFAs) in comparison to those using fullerene derivatives. The low noise in NFA blends was attributed to a sharp drop off in the distribution of bandtail states, as revealed by variable-temperature density-of-states measurements. Taking disorder into account, we developed a general physical model to explain the dependence of thermal noise on the effective bandgap and bandtail spread. The model provides theoretical targets for the maximum detectivity that can be obtained at different detection wavelengths in inherently disordered infrared photodiodes.

Infrared photodetectors are essential to many applications, including surveillance, communications, process monitoring, and biological imaging. The short-wave infrared (SWIR) spectral region (λ = 1-3 μm) is particularly powerful for health monitoring and medical diagnostics because biological tissues show low absorbance and minimal SWIR autofluorescence, enabling greater penetration depth and improved resolution in comparison with visible light. However, current SWIR photodetection technologies are largely based on epitaxially grown inorganic semiconductors, which are costly, require complex processing, and impose cooling requirements incompatible with wearable electronics. Solution-processable semiconductors are being developed for infrared detectors to enable low-cost direct deposition and facilitate monolithic integration and resolution not achievable using current technologies. In particular, organic semiconductors offer numerous advantages, including large-area and conformal coverage, temperature insensitivity, and biocompatibility, for enabling ubiquitous SWIR optoelectronics. This Account introduces recent efforts to advance the spectral response of organic photodetectors into the SWIR. High-performance visible to near-infrared (NIR) organic photodetectors have been demonstrated by leveraging the wealth of knowledge from organic solar cell research in the past decade. On the other hand, organic semiconductors that absorb in the SWIR are just emerging, and only a few organic materials have been reported that exhibit photocurrent past 1 μm. In this Account, we survey novel SWIR molecules and polymers and discuss the main bottlenecks associated with charge recombination and trapping, which are more challenging to address in narrow-band-gap photodetectors in comparison with devices operating in the visible to NIR. As we call attention to discrepancies in the literature regarding performance metrics, we share our perspective on potential pitfalls that may lead to overestimated values, with particular attention to the detectivity (signal-to-noise ratio) and temporal characteristics, in order to ensure a fair comparison of device performance. As progress is made toward overcoming challenges associated with losses due to recombination and increasing noise at progressively narrower band gaps, the performance of organic SWIR photodetectors is steadily rising, with detectivity exceeding 10¹¹ Jones, comparable to that of commercial germanium photodiodes. Organic SWIR photodetectors can be incorporated into wearable physiological monitors and SWIR spectroscopic imagers that enable compositional analysis. A wide range of potential applications include food and water quality monitoring, medical and biological studies, industrial process inspection, and environmental surveillance. There are exciting opportunities for low-cost organic SWIR technologies to be as widely deployable and affordable as today's ubiquitous cell phone cameras operating in the visible, which will serve as an empowering tool for users to discover information in the SWIR and inspire new use cases and applications.

Bulk heterojunction photodiodes are fabricated using a new donor-acceptor polymer with a near-infrared absorption edge at 1.2 μm, achieving a detectivity up to 10¹² Jones at a wavelength of 1 μm and an excellent linear dynamic range of 86 dB. The photodiode detectivity is maximized by operating at zero bias to suppress dark current, while a thin 175 nm active layer is used to facilitate charge collection without reverse bias. Analysis of the temperature dependence of the dark current and spectral response demonstrates a 2.8-fold increase in detectivity as the temperature was lowered from 44 to -12 °C, a relatively small change when compared to that of inorganic-based devices. The near-infrared photodiode shows a switching speed reaching up to 120 μs without an external bias. An application using our NIR photodiode to detect arterial pulses of a fingertip is demonstrated.

Nitrate is an important marker of water quality that can be challenging to detect in seawater due to the presence of multiple chemical interferants and high background chloride. Here, we demonstrate a compact microfluidic device that incorporates electrochemical desalination to selectively remove the interfering chloride ions and improve the detection limit of the downstream potentiometric nitrate sensor. The microfluidic platform was fabricated by a low-cost cut-and-lamination approach, and the detection mechanism was based on potentiometric measurements at an Ag/AgCl electrode coated with a nitrate-selective membrane. The sensor system achieved a detection limit of 0.5 mM with a sensitivity of 11.3 mV/dec under continuous flow.