Image sensors using thin-film absorbers.

Image sensors are must-have components of most consumer electronics devices. They enable portable camera systems, which find their way into billions of devices annually. Such high volumes are possible thanks to the complementary metal-oxide semiconductor (CMOS) platform, leveraging wafer-scale manufacturing. Silicon photodiodes, at the core of CMOS image sensors, are perfectly suited to replicate human vision. Thin-film absorbers are an alternative family of photoactive materials, distinguished by the layer thickness comparable with or smaller than the wavelength of interest. They allow design of imagers with functionalities beyond Si-based sensors, such as transparency or detectivity at wavelengths above Si cutoff (e.g., short-wave infrared). Thin-film image sensors are an emerging device category. While intensive research is ongoing to achieve sufficient performance of thin-film photodetectors, to our best knowledge, there have been few complete studies on their integration into advanced systems. In this paper, we will describe several types of image sensors being developed at imec, based on organic, quantum dot, and perovskite photodiode and show their figures of merit. We also discuss the methodology for selecting the most appropriate sensor architecture (integration with thin-film transistor or CMOS). Application examples based on imec proof-of-concept sensors are demonstrated to showcase emerging use cases.

A Thin-Film Pinned-Photodiode Imager Pixel with Fully Monolithic Fabrication and beyond 1Me- Full Well Capacity.

Thin-film photodiodes (TFPD) monolithically integrated on the Si Read-Out Integrated Circuitry (ROIC) are promising imaging platforms when beyond-silicon optoelectronic properties are required. Although TFPD device performance has improved significantly, the pixel development has been limited in terms of noise characteristics compared to the Si-based image sensors. Here, a thin-film-based pinned photodiode (TF-PPD) structure is presented, showing reduced kTC noise and dark current, accompanied with a high conversion gain (CG). Indium-gallium-zinc oxide (IGZO) thin-film transistors and quantum dot photodiodes are integrated sequentially on the Si ROIC in a fully monolithic scheme with the introduction of photogate (PG) to achieve PPD operation. This PG brings not only a low noise performance, but also a high full well capacity (FWC) coming from the large capacitance of its metal-oxide-semiconductor (MOS). Hence, the FWC of the pixel is boosted up to 1.37 Me- with a 5 µm pixel pitch, which is 8.3 times larger than the FWC that the TFPD junction capacitor can store. This large FWC, along with the inherent low noise characteristics of the TF-PPD, leads to the three-digit dynamic range (DR) of 100.2 dB. Unlike a Si-based PG pixel, dark current contribution from the depleted semiconductor interfaces is limited, thanks to the wide energy band gap of the IGZO channel material used in this work. We expect that this novel 4 T pixel architecture can accelerate the deployment of monolithic TFPD imaging technology, as it has worked for CMOS Image sensors (CIS).

Macroporous perovskite nanocrystal composites for ultrasensitive copper ion detection.

Accumulation of heavy metal ions, including copper ions (Cu2+), presents a serious threat to human health and to the environment. A substantial amount of research has focused on detecting such species in aqueous solutions. However, progress towards ultrasensitive and easy-to-use sensors for non-aqueous solutions is still limited. Here, we focus on the detection of copper species in hexane, realising ultra-sensitive detection through a fluorescence-based approach. To achieve this, a novel macroporous composite material has been developed featuring luminescent CsPbBr3 nanocrystals (NCs) chemically adhered to a polymerized high internal phase emulsion (polyHIPE) substrate through surface thiol groups. Due to this thiol functionality, sub-monolayer NC formation is realised, which also renders outstanding stability of the composite in the ambient environment. Copper detection is achieved through a direct solution based immersion of the CsPbBr3-(SH)polyHIPE composite, which results in concentration-dependent quenching of the NC photoluminescence. This newly developed sensor has a limit of detection (LOD) for copper as low as 1 × 10-16 M, and a wide operating window spanning 10-2 to 10-16 M. Moreover, the composite exhibits excellent selectivity among different transition metals.

Role of Molecular and Interchain Ordering in the Formation of a δ-Hole-Transporting Layer in Organic Solar Cells.

Interface engineering, especially the realization of Ohmic contacts at the interface between organic semiconductors and metal contacts, is one of the essential preconditions to achieve high-efficiency organic electronic devices. Here, the interface structures of polymer/fullerene blends are correlated with the charge extraction/injection properties of working organic solar cells. The model system-poly(3-hexylthiophene) (P3HT):phenyl-C61-butyric acid methyl ester (PCBM)-is fabricated using two different degrees of P3HT regioregularity to alter the blend interchain order and molecular packing, resulting in different device performances. Investigations by electroabsorption spectroscopy on these devices indicate a significant reduction (≈1 V) in the built-in potential with an increase in the P3HT regioregularity. This observation is also supported by a change in the work function (WF) of high regioregular polymer blends from photoelectron spectroscopy measurements. These results confirm the presence of a strong dipole layer acting as a δ-hole-transporting layer at the polymer/MoO3/Ag electrode interface. Unipolar hole-only devices show an increase in the magnitude of the hole current in high regioregular P3HT devices, suggesting an increase in the hole injection/extraction efficiency inside the device with a δ-hole-transporting layer. Microscopically, near-edge X-ray absorption fine structure spectroscopy was conducted to probe the surface microstructure in these blends, finding a highly edge-on orientation of P3HT chains in blends made with high regioregular P3HT. This edge-on orientation of P3HT chains at the interface results in a layer of oriented alkyl side chains capping the surface, which favors the formation of a dipole layer at the polymer/MoO3 interface. The increase in the charge extraction efficiency due to the formation of a δ-hole-transporting layer thus results in higher short circuit currents and fill factor values, eventually increasing the device efficiency in high regioregular P3HT devices despite a slight decrease in cell open circuit voltage. These findings emphasize the significance of WF control as a tool for improved device performance and pave the way toward interfacial optimization based on the modulation of fundamental polymer properties, such as polymer regioregularity.

Impact of Acceptor Fluorination on the Performance of All-Polymer Solar Cells.

Here, we systematically study the effect of fluorination on the performance of all-polymer solar cells by employing a naphthalene diimide (NDI)-based polymer acceptor with thiophene-flanked phenyl co-monomer. Fluorination of the phenyl co-monomer with either two or four fluorine units is used to create a series of acceptor polymers with either no fluorination (PNDITPhT), bifluorination (PNDITF2T), or tetrafluorination (PNDITF4T). In blends with the donor polymer PTB7-Th, fluorination results in an increase in power conversion efficiency from 3.1 to 4.6% despite a decrease in open-circuit voltage from 0.86 V (unfluorinated) to 0.78 V (tetrafluorinated). Countering this decrease in open-circuit voltage is an increase in short-circuit current from 7.7 to 11.7 mA/cm2 as well as an increase in fill factor from 0.45 to 0.53. The origin of the improvement in performance with fluorination is explored using a combination of morphological, photophysical, and charge-transport studies. Interestingly, fluorination is found not to affect the ultrafast charge-generation kinetics, but instead is found to improve charge-collection yield subsequent to charge generation, linked to improved electron mobility and improved phase separation. Fluorination also leads to improved light absorption, with the blue-shifted absorption profile of the fluorinated polymers complementing the absorption profile of the low-band gap PTB7-Th.

Correlation between Photovoltaic Performance and Interchain Ordering Induced Delocalization of Electronics States in Conjugated Polymer Blends.

In this paper we correlate the solar cell performance with bimolecular packing of donor:acceptor bulk heterojunction (BHJ) organic solar cells (OSCs), where interchain ordering of the donor molecule and its influence on morphology, optical properties, and charge carrier dynamics of BHJ solar cells are studied in detail. Solar cells that are fabricated using more ordered defect free 100% regioregular poly(3-hexylthiophene) (DF-P3HT) as the donor polymer show ca. 10% increase in the average power conversion efficiency (PCE) when compared to that of the solar cell fabricated using 92% regioregularity P3HT, referred to as rr-P3HT. EQE and UV-vis absorption spectrum show a clear increase in the 607 nm vibronic shoulder of the DF-P3HT blend suggesting better interchain ordering which was also reflected in the less Urbach energy (Eu) value for this system. The increase in ordering inside the blend has enhanced the hole-mobility which is calculated from the single carrier device J-V characteristics. Electroluminance (EL) studies on the DF-P3HT system showed a red-shifted peak when compared to rr-P3HT-based devices suggesting low CT energy states in DF-P3HT. The morphologies of the blend films are studied using AFM and grazing-incidence wide-angle X-ray scattering (GIWAXS) suggesting increase in the roughness and phase segregation which could enhance the internal scattering of the light inside the device and improvement in the crystallinity along alkyl and π-stacking direction. Hence, higher PCE, lower Eu, red-shifted EL emission, high hole-mobility, and better crystallinity suggest improved interchain ordering has facilitated a more delocalized HOMO state in DF-P3HT-based BHJ solar cells.

Impact of Fullerene Mixing Behavior on the Microstructure, Photophysics, and Device Performance of Polymer/Fullerene Solar Cells.

Here, a comprehensive study of the influence of polymer:fullerene mixing behavior on the performance, thin-film microstructure, photophysics, and device physics of polymer solar cells is presented. In particular, blends of the donor polymer PBDTTT-EFT with the acceptor PC71BM that exhibit power conversion efficiencies over 9% are investigated. Through tuning of the fullerene concentration in PBDTTT-EFT:PC71BM blends, the impact of fullerene mixing behavior is systematically investigated via a combination of synchrotron-based X-ray scattering and spectroscopy techniques. The impact of fullerene loading on photophysics and device physics is further explored with steady-state photoluminescence measurements, ultrafast transient absorption spectroscopy, and transient photovoltage measurements. In the low fullerene concentration regime (<50 wt %), most fullerene molecules are dispersed in the polymer matrix, resulting in severe geminate and nongeminate recombination due to a lack of pure fullerene aggregates and percolating pathways for charge separation and transport. In the high fullerene concentration regime (>70 wt %), large fullerene domains result in incomplete PC71BM exciton harvesting with the presence of fullerene molecules also disrupting the molecular packing of polymer crystallites. The optimum fullerene concentration of ∼60-67 wt % balances the requirements of charge generation and charge collection. These findings demonstrate that controlling the fullerene concentration in the mixed phase and optimizing the balance between pure and mixed phases are critical for maximizing the efficiency of highly mixed polymer/fullerene solar cells.