Future lightweight, flexible, and wearable electronics will employ visible‐light‐communication schemes to interact within indoor environments. Organic photodiodes are particularly well suited for such technologies as they enable chemically tailored optoelectronic performance and fabrication by printing techniques on thin and flexible substrates. However, previous methods have failed to address versatile functionality regarding wavelength selectivity without increasing fabrication complexity. This work introduces a general solution for printing wavelength‐selective bulk‐heterojunction photodetectors through engineering of the ink formulation. Nonfullerene acceptors are incorporated in a transparent polymer donor matrix to narrow and tune the response in the visible range without optical filters or light‐management techniques. This approach effectively decouples the optical response from the viscoelastic ink properties, simplifying process development. A thorough morphological and spectroscopic investigation finds excellent charge‐carrier dynamics enabling state‐of‐the‐art responsivities >102 mA W−1 and cutoff frequencies >1.5 MHz. Finally, the color selectivity and high performance are demonstrated in a filterless visible‐light‐communication system capable of demultiplexing intermixed optical signals.

Organic photodiodes (OPDs) are set to enhance traditional optical detection technologies and open new fields of applications, through the addition of functionalities such as wavelength tunability, mechanical flexibility, light-weight or transparency. This, in combination with printing and coating technology will contribute to the development of cost-effective production methods for optical detection systems. In this review, we compile the current progress in the development of OPDs fabricated with the help of industrial relevant coating and printing techniques. We review their working principle and their figures-of-merit (FOM) highlighting the top device performances through a comparison of material systems and processing approaches. We place particular emphasis in discussing methodologies, processing steps and architectural design that lead to improved FOM. Finally, we survey the current applications of OPDs in which printing technology have enabled technological developments while discussing future trends and needs for improvement.

Digitally printed organic photodiodes (OPDs) are of great interest for the cost-efficient additive manufacturing of single and multidevice detection systems with full freedom of design. Recently reported high-performance nonfullerene acceptors (NFAs) can address the crucial demands of future applications in terms of high operational speed, tunable spectral response, and device stability. Here, we present the first demonstration of inkjet and aerosol-jet printed OPDs based on the high-performance NFA, IDTBR, in combination with poly(3-hexylthiophene), exhibiting a spectral response up to the near-infrared (NIR) region. These digitally printed devices reach record responsivities up to 300 mA/W in the visible and NIR spectrum, competing with current commercially available technologies based on Si. Furthermore, their fast dynamic response with cutoff frequencies surpassing 2 MHz outperforms most of the state-of-the-art OPDs. The successful process translation from spin-coating to printing is highlighted by the marginal loss in performance compared to the reference devices, which reach responsivities of 400 mA/W and detection speeds of more than 4 MHz. The achieved high device performance and the industrial relevance of the developed fabrication process provide NFAs with an enormous potential for the development of printed photodetection systems.

Organic photodiodes (OPDs) are optical sensors combining high performance, lightweight mechanical flexibility, and processability from solution. Their fabrication by industrial printing techniques opens a wide range of innovative applications for emerging fields in sensing and the Internet of Things. They typically consist of printed multilayers with functionalities to absorb light, to extract charges, or to reduce detection noise. However, the printing of such device architecture poses a challenge as the deposition of a material can lead to disruption of film morphology or intermixing of materials if its solvent interacts with the previously deposited layer. This work proposes a process to print multilayers from the same solvent system utilizing the aerosol‐jet technique. By fine adjustment of the aerosol properties through the tube temperature (TTube), the drying time of poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) printed layers is significantly reduced. This allows its deposition onto a P3HT‐based bulk‐heterojunction (BHJ) without negatively affecting its performance. The additional printed P3HT layer, spatially extends the donor region of the BHJ, providing ideal hole extraction and simultaneous noise reduction by the blocking of injected electrons. This donor blocking layer (DBL) yields a noise reduction of two orders of magnitude in OPDs operated under −2 V reverse bias.

Upcoming technologies in the fields of flexible electronics require the cost-efficient fabrication of complex circuitry in a streamlined process. Digital printing techniques such as inkjet printing can enable such applications thanks to their inherent freedom of design permitting the mask-free deposition of multilayer optoelectronic devices without the need for subtracting techniques. Here we present an active matrix sensor array comprised of 100 inkjet-printed organic thin film transistors (OTFTs) and organic photodiodes (OPDs) monolithically integrated onto the same ultrathin substrate. Both the OTFTs and OPDs exhibited high-fabrication yield and state-of-the-art performance after the integration process. By scaling of the OPDs, we achieved integrated pixels with power consumptions down to 50 nW at one of the highest sensitivities reported to date for an all-organic integrated sensor. Finally, we demonstrated the application potential of the active matrix by static and dynamic spatial sensing of optical signals.