If perovskite solar cells (PSCs) with high power conversion efficiencies (PCEs) are to be commercialized, they must achieve long-term stability, which is usually assessed with accelerated degradation tests. One of the persistent obstacles for PSCs has been successfully passing the damp-heat test (85°C and 85% relative humidity), which is the standard for verifying the stability of commercial photovoltaic (PV) modules. We fabricated damp heat–stable PSCs by tailoring the dimensional fragments of two-dimensional perovskite layers formed at room temperature with oleylammonium iodide molecules; these layers passivate the perovskite surface at the electron-selective contact. The resulting inverted PSCs deliver a 24.3% PCE and retain >95% of their initial value after >1000 hours at damp-heat test conditions, thereby meeting one of the critical industrial stability standards for PV modules.

We report on bulk-heterojunction (BHJ) organic photovoltaics (OPVs) based on the self-assembled monolayer (SAM) 2PACz as a hole-selective interlayer functionalized directly onto the indium tin oxide (ITO) anode. The 2PACz is found to change the work function of ITO while simultaneously affecting the morphology of the BHJ deposited atop. Cells with PM6:N3 BHJ and ITO-2PACz anode exhibit a power conversion efficiency (PCE) of 16.6%, which is greater than that measured for bare ITO (6.45%) and ITO/PEDOT:PSS (15.94%) based devices. The enhanced performance is attributed to lower contact-resistance, reduced bimolecular recombination losses, and improved charge transport within the BHJ. Importantly, the ITO-2PACz-based OPVs show dramatically improved operational stability when compared with PEDOT:PSS-based cells. When the ITO-2PACz anode is combined with the ternary PM6:BTP-eC9:PC 71 BM BHJ, the resulting cells exhibit a maximum PCE of 18.03%, highlighting the potential of engineered SAMs for use in hole-selective contacts in high-performance OPVs.

The short exciton diffusion length associated with most classical organic semiconductors used in organic photovoltaics (5-20 nm) imposes severe limits on the maximum size of the donor and acceptor domains within the photoactive layer of the cell. Identifying materials that are able to transport excitons over longer distances can help advancing our understanding and lead to solar cells with higher efficiency. Here, we measure the exciton diffusion length in a wide range of nonfullerene acceptor molecules using two different experimental techniques based on photocurrent and ultrafast spectroscopy measurements. The acceptors exhibit balanced ambipolar charge transport and surprisingly long exciton diffusion lengths in the range of 20 to 47 nm. With the aid of quantum-chemical calculations, we are able to rationalize the exciton dynamics and draw basic chemical design rules, particularly on the importance of the end-group substituent on the crystal packing of nonfullerene acceptors.

Molecular doping has recently been shown to improve the operating characteristics of organic photovoltaics (OPVs). Here, we prepare neutral Diquat (DQ) and use it as n-dopant to improve the performance of state-of-the-art OPVs. Adding DQ in ternary bulk-heterojunction (BHJ) cells based of PM6:Y6:PC 71 BM is found to consistently increase their power conversion efficiency (PCE) from 16.7 to 17.4%. Analyses of materials and devices reveal that DQ acts as n-type dopant and morphology modifier for the BHJ leading to observable changes in its surface topography. The resulting n-doped BHJs exhibit higher optical absorption coefficients, balanced ambipolar transport, longer carrier lifetimes and suppressed bimolecular recombination, which are ultimately responsible for the increased PCE. The use of DQ was successfully extended to OPVs based on PM6:BTP-eC9:PC 71 BM for which a maximum PCE of 18.3% (uncertified) was achieved. Our study highlights DQ as a promising dopant for application in next generation organic solar cells.

Molecular doping is often used in organic semiconductors to tune their (opto)electronic properties. Despite its versatility, however, its application in organic photovoltaics (OPVs) remains limited and restricted to p‐type dopants. In an effort to control the charge transport within the bulk‐heterojunction (BHJ) of OPVs, the n‐type dopant benzyl viologen (BV) is incorporated in a BHJ composed of the donor polymer PM6 and the small‐molecule acceptor IT‐4F. The power conversion efficiency (PCE) of the cells is found to increase from 13.2% to 14.4% upon addition of 0.004 wt% BV. Analysis of the photoactive materials and devices reveals that BV acts simultaneously as n‐type dopant and microstructure modifier for the BHJ. Under optimal BV concentrations, these synergistic effects result in balanced hole and electron mobilities, higher absorption coefficients and increased charge‐carrier density within the BHJ, while significantly extending the cells' shelf‐lifetime. The n‐type doping strategy is applied to five additional BHJ systems, for which similarly remarkable performance improvements are obtained. OPVs of particular interest are based on the ternary PM6:Y6:PC71BM:BV(0.004 wt%) blend for which a maximum PCE of 17.1%, is obtained. The effectiveness of the n‐doping strategy highlights electron transport in NFA‐based OPVs as being a key issue.

Electronic doping in organic materials has remained an elusive concept for several decades. It drew considerable attention in the early days in the quest for organic materials with high electrical conductivity, paving the way for the pioneering work on pristine organic semiconductors (OSCs) and their eventual use in a plethora of applications. Despite this early trend, however, recent strides in the field of organic electronics have been made hand in hand with the development and use of dopants to the point that are now ubiquitous. Here, we give an overview of all important advances in the area of doping of organic semiconductors and their applications. We first review the relevant literature with particular focus on the physical processes involved, discussing established mechanisms but also newly proposed theories. We then continue with a comprehensive summary of the most widely studied dopants to date, placing particular emphasis on the chemical strategies toward the synthesis of molecules with improved functionality. The processing routes toward doped organic films and the important doping−processing−nanostructure relationships, are also discussed. We conclude the review by highlighting how doping can enhance the operating characteristics of various organic devices.

Molecular doping of organic semiconductors creates Coulombically bound charge and counterion pairs through a charge-transfer process. However, their Coulomb interactions and strategies to mitigate their effects have been rarely addressed. Here, we report that the number of free charges and thermoelectric properties are greatly enhanced by overcoming the Coulomb interaction in an n-doped conjugated polymer. Poly­(2,2′-bithiazolothienyl-4,4′,10,10′-tetracarboxydiimide) (PDTzTI) and the benchmark N2200 are n-doped by tetrakis (dimethylamino) ethylene (TDAE) for thermoelectrics. Doped PDTzTI exhibits ∼10 times higher free-charge density and 500 times higher conductivity than doped N2200, leading to a power factor of 7.6 μW m–1 K–2 and ZT of 0.01 at room temperature. Compared to N2200, PDTzTI features a better molecular ordering and two-dimensional charge delocalization, which help overcome the Coulomb interaction in the doped state. Consequently, free charges are more easily generated from charge–counterion pairs. This work provides a strategy for improving n-type thermoelectrics by tackling electrostatic interactions.

The ‘phonon-glass electron-crystal’ concept has triggered most of the progress that has been achieved in inorganic thermoelectrics in the past two decades. Organic thermoelectric materials, unlike their inorganic counterparts, exhibit molecular diversity, flexible mechanical properties and easy fabrication, and are mostly ‘phonon glasses’. However, the thermoelectric performances of these organic materials are largely limited by low molecular order and they are therefore far from being ‘electron crystals’. Here, we report a molecularly n-doped fullerene derivative with meticulous design of the side chain that approaches an organic ‘PGEC’ thermoelectric material. This thermoelectric material exhibits an excellent electrical conductivity of >10 S cm−1 and an ultralow thermal conductivity of <0.1 Wm−1K−1, leading to the best figure of merit ZT = 0.34 (at 120 °C) among all reported single-host n-type organic thermoelectric materials. The key factor to achieving the record performance is to use ‘arm-shaped’ double-triethylene-glycol-type side chains, which not only offer excellent doping efficiency (~60%) but also induce a disorder-to-order transition upon thermal annealing. This study illustrates the vast potential of organic semiconductors as thermoelectric materials.