Employment of thin perovskite shells and metal halides as surface-passivants for colloidal quantum dots (CQDs) have been important, recent developments in CQD optoelectronics. These have opened the route to single-step deposited high-performing CQD solar cells. These promising architectures employ a QD hole-transporting layer (HTL) whose intrinsically shallow Fermi level (EF) restricts band-bending at maximum power-point during solar cell operation limiting charge collection. Here, we demonstrate a generalized approach to effectively balance band-edge energy levels of the main CQD absorber and charge-transport layer for these high-performance solar cells. Briefly soaking the QD HTL in a solution of the metal-organic p-dopant, molybdenum tris(1-(trifluoroacetyl)-2-(trifluoromethyl)ethane-1,2-dithiolene), effectively deepens its Fermi level, resulting in enhanced band bending at the HTL:absorber junction. This blocks the back-flow of photo-generated electrons, leading to enhanced photocurrent and fill factor compared to undoped devices. We demonstrate 9.0% perovskite-shelled and 9.5% metal-halide-passivated CQD solar cells, both achieving ca. 10% relative enhancements over undoped baselines.

Surface molecular doping of graphene has been shown to modify its work function and increase its conductivity. However, the associated shifts in work function and increases in carrier concentration are highly coupled and limited by the surface coverage of dopant molecules on graphene. Here we show that few-layer graphene (FLG) can be doped using a hybrid approach, effectively combining surface doping by larger (metal-)organic molecules, while smaller molecules, such as Br2 and FeCl3, intercalate into the bulk. Intercalation tunes the carrier concentration more effectively, whereas surface doping of intercalated FLG can be used to tune its work function without reducing the carrier mobility. This multi-modal doping approach yields a very high carrier density and tunable work function for FLG, demonstrating a new versatile platform for fabricating graphene-based contacts for electronic, optoelectronic and photovoltaic applications.

In recent years colloidal quantum dot (CQD) photovoltaics have developed rapidly because of novel device architectures and robust surface passivation schemes. Achieving controlled net doping remains an important unsolved challenge for this field. Herein we present a general molecular doping platform for CQD solids employing a library of metal–organic complexes. Low effective ionization energy and high electron affinity complexes are shown to produce n- and p-doped CQD solids. We demonstrate the obvious advantage in solar cells by p-doping the CQD absorber layer. Employing photoemission spectroscopy, we identify two doping concentration regimes: lower concentrations lead to efficient doping, while higher concentrations also cause large surface dipoles creating energy barriers to carrier flow. Utilizing the lower concentration regime, we remove midgap electrons leading to 25% enhancement in the power conversion efficiency relative to undoped cells. Given the vast number of available metal–organic complexes, this approach opens new and facile routes to tuning the properties of CQDs for various applications without necessarily resorting to new ligand chemistries.