Perovskite-Perovskite Homojunctions via Compositional Doping.

One of the most important properties of semiconductors is the possibility of controlling their electronic behavior via intentional doping. Despite the unprecedented progress in the understanding of hybrid metal halide perovskites, extrinsic doping of perovskite remains nearly unexplored and perovskite-perovskite homojunctions have not been reported. Here we present a perovskite-perovskite homojunction obtained by vacuum deposition of stoichiometrically tuned methylammonium lead iodide (MAPI) films. Doping is realized by adjusting the relative deposition rates of MAI and PbI2, obtaining p-type (MAI excess) and n-type (MAI defect) MAPI. The successful stoichiometry change in the thin films is confirmed by infrared spectroscopy, which allows us to determine the MA content in the films. We analyzed the resulting thin-film junction by cross-sectional scanning Kelvin probe microscopy (SKPM) and found a contact potential difference (CPD) of 250 mV between the two differently doped perovskite layers. Planar diodes built with the perovskite-perovskite homojunction show the feasibility of our approach for implementation in devices.

Impact of Bi3+ Heterovalent Doping in Organic-Inorganic Metal Halide Perovskite Crystals.

Intrinsic organic-inorganic metal halide perovskites (OIHP) based semiconductors have shown wide applications in optoelectronic devices. There have been several attempts to incorporate heterovalent metal (e.g., Bi3+) ions in the perovskites in an attempt to induce electronic doping and increase the charge carrier density in the semiconductor. It has been reported that inclusion of Bi3+ decreases the band gap of the material considerably. However, contrary to the earlier conclusions, despite a clear change in the appearance of the crystal as observed by eye, here we show that the band gap of MAPbBr3 crystals does not change due the presence of Bi3+ in the growth solution. An increased density of states in the band gap and use of very thick samples for transmission measurements, erroneously give the impression of a band gap shift. These sub band gap states also act as nonradiative recombination centers in the crystals.

High-Performance Electron Injection Layers with a Wide Processing Window from an Amidoamine-Functionalized Polyfluorene.

In this work, we present organic light-emitting diodes (OLEDs) utilizing a novel amidoamine-functionalized polyfluorene (PFCON-C) as an electron injection layer (EIL). PFCON-C consists of a polyfluorene backbone to which multiple tertiary amine side chains are connected via an amide group. The influence of molecular characteristics on electronic performance and morphological properties was tested and compared to that of the widely used, literature known amino-functionalized polyfluorene (PFN) and polyethylenimine (PEI). PFCON-C reduces the turn-on voltage (VON) of poly(p-phenylene vinylene) (PPV)-based OLEDs from ∼5 to ∼3 V and increases the maximum power efficiency from <2 to >5 lm W(-1) compared to that of PFN. As a result of its semiconducting backbone, PFCON-C is significantly less sensitive to the processing parameters than PEI, and comparable power efficiencies are achieved for devices where thicknesses of PFCON-C are between 15 and 35 nm. Atomic force microscopy (AFM) measurements indicate that the presence of nonpolar side chains in the EIL material is important for its film-forming behavior, while Kelvin probe measurements suggest that the amount of amine groups in the side chains influences the work-function shift induced by the EIL material. These results are used to suggest strategies for the design of polymeric electron injection layers.

Infrared Spectroscopic Study of Vibrational Modes in Methylammonium Lead Halide Perovskites.

The organic cation and its interplay with the inorganic lattice underlie the exceptional optoelectronic properties of organo-metallic halide perovskites. Herein we report high-quality infrared spectroscopic measurements of methylammonium lead halide perovskite (CH3NH3Pb(I/Br/Cl)3) films and single crystals at room temperature, from which the dielectric function in the investigated spectral range is derived. Comparison with electronic structure calculations in vacuum of the free methylammonium cation allows for a detailed peak assignment. We analyze the shifts of the vibrational peak positions between the different halides and infer the extent of interaction between organic moiety and the surrounding inorganic cage. The positions of the NH3(+) stretching vibrations point to significant hydrogen bonding between the methylammonium and the halides for all three perovskites.