New generation hole transporting materials for Perovskite solar cells: Amide-based small-molecules with nonconjugated backbones

State-of-the-art perovskite-based solar cells employ expensive, organic hole transporting materials (HTMs) such as Spiro-OMeTAD that, in turn, limits the commercialization of this promising technology. Herein an HTM (EDOT-Amide-TPA) is reported in which a functional amide-based backbone is introduced, which allows this material to be synthesized in a simple condensation reaction with an estimated cost of <$5 g−1. When employed in perovskite solar cells, EDOT-Amide-TPA demonstrates stabilized power conversion efficiencies up to 20.0% and reproducibly outperforms Spiro-OMeTAD in direct comparisons. Time resolved microwave conductivity measurements indicate that the observed improvement originates from a faster hole injection rate from the perovskite to EDOT-Amide-TPA. Additionally, the devices exhibit an improved lifetime, which is assigned to the coordination of the amide bond to the Li-additive, offering a novel strategy to hamper the migration of additives. It is shown that, despite the lack of a conjugated backbone, the amide-based HTM can outperform state-of-the-art HTMs at a fraction of the cost, thereby providing a novel set of design strategies to develop new, low-cost HTMs

Direct-indirect character of the bandgap in methylammonium lead iodide perovskite.

Metal halide perovskites such as methylammonium lead iodide (CH3NH3PbI3) are generating great excitement due to their outstanding optoelectronic properties, which lend them to application in high-efficiency solar cells and light-emission devices. However, there is currently debate over what drives the second-order electron-hole recombination in these materials. Here, we propose that the bandgap in CH3NH3PbI3 has a direct-indirect character. Time-resolved photo-conductance measurements show that generation of free mobile charges is maximized for excitation energies just above the indirect bandgap. Furthermore, we find that second-order electron-hole recombination of photo-excited charges is retarded at lower temperature. These observations are consistent with a slow phonon-assisted recombination pathway via the indirect bandgap. Interestingly, in the low-temperature orthorhombic phase, fast quenching of mobile charges occurs independent of the temperature and photon excitation energy. Our work provides a new framework to understand the optoelectronic properties of metal halide perovskites and analyse spectroscopic data

Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals

Metal halide perovskites are generating enormous excitement for use in solar cells and light-emission applications, but devices still show substantial non-radiative losses. Here, we show that by combining light and atmospheric treatments, we can increase the internal luminescence quantum efficiencies of polycrystalline perovskite films from 1% to 89%, with carrier lifetimes of 32 μs and diffusion lengths of 77 μm, comparable with perovskite single crystals. Remarkably, the surface recombination velocity of holes in the treated films is 0.4 cm/s, approaching the values for fully passivated crystalline silicon, which has the lowest values for any semiconductor to date. The enhancements translate to solar cell power-conversion efficiencies of 19.2%, with a near-instant rise to stabilized power output, consistent with suppression of ion migration. We propose a mechanism in which light creates superoxide species from oxygen that remove shallow surface states. The work reveals an industrially scalable post-treatment capable of producing state-of-the-art semiconducting films.S.D.S. has received funding from the European Union's Seventh Framework Program (Marie Curie Actions) under REA grant number PIOF-GA-2013-622630. This work made use of the Shared Experimental Facilities supported in part by the MRSEC Program of the National Science Foundation (NSF) under award number MDR – 1419807. R.B. acknowledges support from the MIT Undergraduate Research Opportunities Program (UROP). A.O. acknowledges support from the NSF under grant no. 1605406 (EP/L000202). D.G. acknowledges the China Scholarship Council for funding, file no. 201504910812. The authors acknowledge funding from the Engineering and Physical Sciences Research Council (EPSRC) under EP/P02484X/1 and the Programme Grant EP/M005143/1. M.S.I. and C.E. acknowledge support from the EPSRC Program grant on Energy Materials (EP/KO16288) and the Archer HPC/MCC Consortium (EP/L000202). E.M.H. gratefully acknowledges the Netherlands Organization for Scientific Research (NWO) Echo number 712.014.007 for funding. The work was also partially supported by Eni S.p.A. via the Eni-MIT Solar Frontiers Center. The authors thank Mengfei Wu and Marc Baldo for access to an integrating sphere, Jay Patel and Michael Johnston for EQE verifications, and Eli Yablonovitch and Luis Pazos-Outón for helpful discussion

The effect of thermal treatment on the morphology and charge carrier dynamics in a polythiophene-fullerene bulk heterojunction

The influence of various thermal treatment steps on the morphology and the photoconductive properties of a non-contacted, 50 nm thick blend (50:50 wt.-%) of [6,6]-phenyl C61-butyric acid methyl ester (PCBM) and poly(3-hexyl thiophene) (P3HT) spin-coated from chloroform has been studied using transmission electron microscopy (TEM) and the electrodeless time-resolved microwave conductivity technique. After annealing the film for 5 min at 80 ?C, TEM images show the formation of crystalline fibrils of P3HT due to a more ordered packing of the polymer chains. The thermal treatment results in a large increase of the photoconductivity, due to an enhancement of the hole mobility in these crystalline P3HT domains from 0.0056 cm2 V-1 s -1 for the non-annealed sample to 0.044 cm2 V-1 s -1 for the sample annealed at 80 ?C. In contrast, the temporal shape of the photoconductivity, with typical decay half-times, 1/2, of 1 s for the lowest excitation intensities, is unaffected by the temperature treatment. Further annealing of the sample at 130 ?C results in the formation of three different substructures within the heterojunction: a PCBM:P3HT blend with PCBM-rich clusters, a region depleted of PCBM, and large PCBM single crystals. Only a minor increase in the amplitude, but a tenfold rise of the decay time of the photoconductivity, is observed. This is explained by the formation of PCBM-rich clusters and large PCBM single crystals, resulting in an increased diffusional escape probability for mobile charge carriers and hence reduced recombinatio

The formation of crystalline P3HT fibrils upon annealing of a PCBM : P3HT bulk heterojunction

The influence of a, thermal treatment on the morphology, redox and the photoconductive properties of a non-contacted, 50 nm thick blend film (50:50 wt.%) of [6,6]-phenyl C-61-butyric acid methyl ester ('PCBM') and poly(3-hexyl thiophene) ('P3HT') spin-coated from chloroform, has been investigated. To this end, transmission electron microscopy (TEM), electrochemistry and the time-resolved microwave conductivity (TRMC) techniques were applied. After annealing the film for 5 min at 80 degrees C, TEM images show the formation of crystalline fibrils consisting of P3HT with a more ordered packing of the polymer chains, which is also reflected in the changes observed in the optical spectrum. Cyclic voltammograms show a 0.2 V positive shift of the oxidation potential of the polymer in the blend upon annealing. Furthermore, a large increase of the photoconductivity, due to an enhancement of the hole mobility in these crystalline P3HT domains from 0.0056 cm(2)/s for the non-annealed sample to 0.044 cm(2)/Vs after annealing is observed. In contrast, the temporal shape of the photoconductivity, with typical decay half-timers tau(1/2) of 1 mu s for the lowest excitation intensities, is unaffected by the temperature treatment. We suggest that after photoinduced charge separation the positive charge carriers are localized on the crystalline fibrils. Non-ordered regions around these crystalline fibrils act as energetic barriers for the positive charge carriers. The release time of the holes will be the rate limiting step for recombination or trapping of the photoinduced charge carriers. (c) 2005 Elsevier B.V All tights reserved

Tetrahedral n-type materials: Efficient quenching of the excitation of p-type polymers in amorphous films

Tetrahedral naphthalenediimide compound 1 has been synthesized as an example of a new class of amorphous n-type materials, in which the nondirectionality obtained by its shape is decoupled from its optoelectronic properties. 1 forms bicontinuous films with p-type polymers and effectively quenches the excited state, yielding long-lived mobile charge carriers on pulsed illuminatio

Direct-indirect character of the bandgap in methylammonium lead iodide perovskite.

Metal halide perovskites such as methylammonium lead iodide (CH3NH3PbI3) are generating great excitement due to their outstanding optoelectronic properties, which lend them to application in high-efficiency solar cells and light-emission devices. However, there is currently debate over what drives the second-order electron-hole recombination in these materials. Here, we propose that the bandgap in CH3NH3PbI3 has a direct-indirect character. Time-resolved photo-conductance measurements show that generation of free mobile charges is maximized for excitation energies just above the indirect bandgap. Furthermore, we find that second-order electron-hole recombination of photo-excited charges is retarded at lower temperature. These observations are consistent with a slow phonon-assisted recombination pathway via the indirect bandgap. Interestingly, in the low-temperature orthorhombic phase, fast quenching of mobile charges occurs independent of the temperature and photon excitation energy. Our work provides a new framework to understand the optoelectronic properties of metal halide perovskites and analyse spectroscopic data

Metal Halide Perovskite Polycrystalline Films Exhibiting Properties of Single Crystals

Metal halide perovskites are generating enormous excitement for use in solar cells and light-emission applications, but devices still show substantial non-radiative losses. Here, we show that by combining light and atmospheric treatments, we can increase the internal luminescence quantum efficiencies of polycrystalline perovskite films from 1% to 89%, with carrier lifetimes of 32 μs and diffusion lengths of 77 μm, comparable with perovskite single crystals. Remarkably, the surface recombination velocity of holes in the treated films is 0.4 cm/s, approaching the values for fully passivated crystalline silicon, which has the lowest values for any semiconductor to date. The enhancements translate to solar cell power-conversion efficiencies of 19.2%, with a near-instant rise to stabilized power output, consistent with suppression of ion migration. We propose a mechanism in which light creates superoxide species from oxygen that remove shallow surface states. The work reveals an industrially scalable post-treatment capable of producing state-of-the-art semiconducting films.S.D.S. has received funding from the European Union's Seventh Framework Program (Marie Curie Actions) under REA grant number PIOF-GA-2013-622630. This work made use of the Shared Experimental Facilities supported in part by the MRSEC Program of the National Science Foundation (NSF) under award number MDR – 1419807. R.B. acknowledges support from the MIT Undergraduate Research Opportunities Program (UROP). A.O. acknowledges support from the NSF under grant no. 1605406 (EP/L000202). D.G. acknowledges the China Scholarship Council for funding, file no. 201504910812. The authors acknowledge funding from the Engineering and Physical Sciences Research Council (EPSRC) under EP/P02484X/1 and the Programme Grant EP/M005143/1. M.S.I. and C.E. acknowledge support from the EPSRC Program grant on Energy Materials (EP/KO16288) and the Archer HPC/MCC Consortium (EP/L000202). E.M.H. gratefully acknowledges the Netherlands Organization for Scientific Research (NWO) Echo number 712.014.007 for funding. The work was also partially supported by Eni S.p.A. via the Eni-MIT Solar Frontiers Center. The authors thank Mengfei Wu and Marc Baldo for access to an integrating sphere, Jay Patel and Michael Johnston for EQE verifications, and Eli Yablonovitch and Luis Pazos-Outón for helpful discussion