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Electronic technologies critically rely on the ability to broadly dope the active semiconductor; yet the promising class of halide perovskite semiconductors so far does not allow for significant control over carrier type (p- or n-) and density. The molecular doping approach offers important opportunities for generating free carriers through charge transfer. In this work, we demonstrate effective p-doping of MAPb 0.5 Sn 0.5 I 3 films using the molecular dopant F4TCNQ as a grain boundary coating, offering a conductivity and hole density tuning range of up to five orders of magnitude, associated with a 190 meV Fermi level down-shift. While charge transfer between MAPb 0.5 Sn 0.5 I 3 and F4TCNQ appears efficient, dopant ionization decreases with increasing Pb content, highlighting the need for appropriate energy offset between host and dopant molecule. Finally, we show that electrical p-doping impacts the perovskite optoelectronic properties, with a hole recombination lifetime increase of over one order of magnitude, suggesting passivation of deep traps. 

While progress has been made in the design of organic semiconductors (OSCs) with improved transport properties, the understanding of the mechanisms involved is still limited, hindering further development. In this study, the interplay between structural order and transport considering one single OSC, analogous to past research on silicon is investigated. Rubrene (C₄₂H₂₈) is selected as it spans transport mechanisms from thermally activated hopping in its amorphous form to band‐like in highly ordered crystals in the orthorhombic polymorph. Transport characterizations including variable temperature conductivity, advanced Hall effect, and magnetoresistance measurements are performed on rubrene films with varying levels of order (polycrystalline vs amorphous), crystal phase (orthorhombic vs triclinic), and morphologies (platelet‐like vs spherulitic grains). A conductivity tuning range over four orders of magnitude between polycrystalline (platelet‐like) orthorhombic and amorphous films is reported. As observed in silicon, transport in polycrystalline orthorhombic rubrene is limited by energy barriers at grain boundaries. Additionally, a gradual transition from predominantly band‐like to predominantly hopping transport with increasing disorder, reminiscent of observations in silicon is shown. Nevertheless, OSCs differ from covalently bonded silicon by their weak intermolecular interaction. This study highlights that molecular packing must be optimized in OSCs to favor advantageous π‐orbital overlap and optimized transport properties.

 

In a quest for Pb-free perovskites suitable for solar energy applications, Cs 2 TiBr 6 has recently been reported as a promising compound, with appropriate optical and electrical properties as well as high stability under environmental stresses. In this study, we pursue investigation on this compound, demonstrating phase pure Cs 2 TiBr 6 powder formation using solution synthesis and providing complementary experimental characterization and theoretical calculations. An experimental absorption onset of around 2.0 eV is extracted and a weak broad photoluminescence is measured. Density functional theory calculations predict an indirect bandgap, parity-forbidden for both the direct and indirect transitions, which explains the weak and Stokes shifted luminescence. Additionally, we highlight the strong instability of Cs 2 TiBr 6 powder in ambient atmosphere. Therefore, our experimental results supported by theoretical calculations differ from previous results and raise doubts on the suitability of Cs 2 TiBr 6 in its pristine form for solar energy applications. 

With power conversion efficiencies now exceeding 25%, hybrid perovskite solar cells require deeper understanding of defects and processing to further approach the Shockley‐Queisser limit. One approach for processing enhancement and defect reduction involves additive engineering—, e.g., addition of MASCN (MA = methylammonium) and excess PbI₂have been shown to modify film grain structure and improve performance. However, the underlying impact of these additives on transport and recombination properties remains to be fully elucidated. In this study, a newly developed carrier‐resolved photo‐Hall (CRPH) characterization technique is used that gives access to both majority and minority carrier properties within the same sample and over a wide range of illumination conditions. CRPH measurements on n‐type MAPbI₃films reveal an order of magnitude increase in carrier recombination lifetime and electron density for 5% excess PbI₂added to the precursor solution, with little change noted in electron and hole mobility values. Grain size variation (120–2100 nm) and MASCN addition induce no significant change in carrier‐related parameters considered, highlighting the benign nature of the grain boundaries and that excess PbI₂must predominantly passivate bulk defects rather than defects situated at grain boundaries. This study offers a unique picture of additive impact on MAPbI₃optoelectronic properties as elucidated by the new CRPH approach.