Marco Brandl

Brightly Luminescent and Color-Tunable Formamidinium Lead Halide Perovskite FAPbX3 (X = Cl, Br, I) Colloidal Nanocrystals

In the past few years, hybrid organic-inorganic and all-inorganic metal halide perovskite nanocrystals have become one of the most interesting materials for optoelectronic applications. Here, we report a facile and rapid room temperature synthesis of 15-25 nm formamidinium CH(NH2)2PbX3 (X = Cl, Br, I, or mixed Cl/Br and Br/I) colloidal nanocrystals by ligand-assisted reprecipitation (LARP). The cubic and platelet-like nanocrystals with their emission in the range of 415-740 nm, full width at half-maximum (fwhm) of 20-44 nm, and radiative lifetimes of 5-166 ns enable band gap tuning by halide composition as well as by their thickness tailoring; they have a high photoluminescence quantum yield (up to 85%), colloidal and thermodynamic stability. Combined with surface modification that prevents degradation by water, this nanocrystalline material is an ideal candidate for optoelectronic devices and applications. In addition, optoelectronic measurements verify that the photodetector based on FAPbI3 nanocrystals paves the way for perovskite quantum dot photovoltaics.

Gallium-rich Pd–Ga phases as supported liquid metal catalysts

A strategy to develop improved catalysts is to create systems that merge the advantages of heterogeneous and molecular catalysis. One such system involves supported liquid-phase catalysts, which feature a molecularly defined, catalytically active liquid film/droplet layer adsorbed on a porous solid support. In the past decade, this concept has also been extended to supported ionic liquid-phase catalysts. Here we develop this idea further and describe supported catalytically active liquid metal solutions (SCALMS). We report a liquid mixture of gallium and palladium deposited on porous glass that forms an active catalyst for alkane dehydrogenation that is resistant to coke formation and is thus highly stable. X-ray diffraction and X-ray photoelectron spectroscopy, supported by theoretical calculations, confirm the liquid state of the catalytic phase under the reaction conditions. Unlike traditional heterogeneous catalysts, the supported liquid metal reported here is highly dynamic and catalysis does not proceed at the surface of the metal nanoparticles, but presumably at homogeneously distributed metal atoms at the surface of a liquid metallic phase.

A comprehensive study on the mechanism behind formation and depletion of Cu2ZnSnS4 (CZTS) phases

High efficiency kesterite based solar cells have vigorously raised the research interests in this material. The challenge lies in understanding the formation and co-existence of more than 10 possible by-products during and after the synthesis of Cu2ZnSnS4 (CZTS) and their various different structural and electronic defects. The present contribution shows an in-depth study on the stages of formation and depletion of nanoparticulate CZTS. Employing a hot injection synthesis method, we give direct experimental evidence of the co-existence of cubic, tetragonal and defected CZTS structures and different by-products as a function of time and temperature. SEM, (HR)TEM, XRD, EDX, ICP-OES, Raman spectroscopy and UV-Vis-NIR spectroscopy have been used in order to better evaluate and interpret data for crystal structures and compositions. The obtained understanding on the formation of different phases suggests 250 °C as the most favourable synthesis temperature. Based on our study, general strategies can be developed for controlling the amount of formed phases, the by-products and the defects in kesterite and other similar multicomponent nanoparticles as well as in bulk systems.

Photoinduced degradation of methylammonium lead triiodide perovskite semiconductors

Photoinduced degradation is a critical obstacle for the real application of novel semiconductors for photovoltaic applications. In this paper, the photoinduced degradation of CH3NH3PbI3 in a vacuum and air (relative humidity 40%) is analyzed by ex situ and advanced in situ technologies. Without light illumination, CH3NH3PbI3 films slowly degrade under vacuum and air within 24 hours. However, we find that CH3NH3PbI3 converts to metallic lead (Pb0) when exposed to vacuum and light illumination. Further, a series of lead salts (e.g. PbO, Pb(OH)2 and PbCO3) are formed when CH3NH3PbI3 is degraded under environmental conditions, i.e. under the combination of light, oxygen and moisture. Photoinduced degradation is found to be determined by the environmental atmosphere as CH3NH3PbI3 films remain very stable under nitrogen conditions. The results from vacuum conditions underpin that the high volatility of the organic component (CH3NH3I) is in conflict with reaching excellent intrinsic stability due to its role in creating ion vacancies. The degradation in air suggests that both oxygen and water contribute to the fast photodecomposition of CH3NH3PbI3 into lead salts rather than water alone. Given these basic yet fundamental understandings, the design of hydrophobic capping layers becomes one prerequisite towards long-term stable perovskite-based devices.

Ligand-assisted thickness tailoring of highly luminescent colloidal CH3NH3PbX3 (X = Br and I) perovskite nanoplatelets

Quantum size-confined CH3NH3PbX3 (X = Br and I) perovskite nanoplatelets with remarkably high photoluminescence quantum yield (up to 90%) were synthesized by ligand-assisted re-precipitation. Thickness-tunability was realized by varying the oleylamine and oleic acid ligand ratio. This method allows tailoring the nanoplatelet thickness by adjusting the number of unit cell monolayers. Broadly tunable emission wavelengths (450-730 nm) are achieved via the pronounced quantum size effect without anion-halide mixing.

Low-Temperature Solution-Processed Kesterite Solar Cell Based on in Situ Deposition of Ultrathin Absorber Layer

The production of high-performance, solution-processed kesterite Cu2ZnSn(Sx,Se1-x)4 (CZTSSe) solar cells typically relies on high-temperature crystallization processes in chalcogen-containing atmosphere and often on the use of environmentally harmful solvents, which could hinder the widespread adoption of this technology. We report a method for processing selenium free Cu2ZnSnS4 (CZTS) solar cells based on a short annealing step at temperatures as low as 350 °C using a molecular based precursor, fully avoiding highly toxic solvents and high-temperature sulfurization. We show that a simple device structure consisting of ITO/CZTS/CdS/Al and comprising an extremely thin absorber layer (∼110 nm) achieves a current density of 8.6 mA/cm(2). Over the course of 400 days under ambient conditions encapsulated devices retain close to 100% of their original efficiency. Using impedance spectroscopy and photoinduced charge carrier extraction by linearly increasing voltage (photo-CELIV), we demonstrate that reduced charge carrier mobility is one limiting parameter of low-temperature CZTS photovoltaics. These results may inform less energy demanding strategies for the production of CZTS optoelectronic layers compatible with large-scale processing techniques.

Correction to Brightly Luminescent and Color-Tunable Formamidinium Lead Halide Perovskite FAPbX3 (X = Cl, Br, I) Colloidal Nanocrystals

Formamidinium Lead Halide Perovskite FAPbX3 (X = Cl, Br, I) Colloidal Nanocrystals Ievgen Levchuk,* Andres Osvet, Xiaofeng Tang, Marco Brandl, Jose ́ Darío Perea, Florian Hoegl, Gebhard J. Matt, Rainer Hock, Miroslaw Batentschuk, and Christoph J. Brabec Nano Lett. 2017, 17 (5), pp 2765−2770. DOI:10.1021/acs.nanolett.6b04781 O page 2766, line 25 (left side) of the main text, “rapidly injected a DMF solution of PbX2 and MAX” should be “rapidly injected a DMF solution of PbX2 and FAX”. Addition/Correction

Deciphering the role of impurities in methylammonium iodide and their impact on the performance of perovskite solar cells(Conference Presentation)

Solution based perovskite solar cell fabrication typically involves rather complex processing sequences to yield highest performance. While most studies concentrate on the exploration of processing conditions, we have investigated the purity levels of common perovskite precursor solutions and found a number of impurities which are most critically controlling the crystallization of perovskites. Moreover, we identified these impurities at different level of concentrations is all commercially available precursors. In detail, we present a detailed chemical study on the nature of the various impurities in CH3NH3I and explored their impact on the crystal formation. The detrimental role of the impurities is best demonstrated by comparing perovskite solar cell devices fabricated from impurity free precursors vs precursors containing different concentrations of impurities. Most interestingly, we revealed that a certain concentration of impurities is detrimental to facilitate the growth of large grained crystals. This study gives valuable insight into the rate determining steps of perovskite crystal growth and provides the basis for developing reliable and reproducible high performance recipes for Perovskite solar cell processing.

Organometallic perovskites for optoelectronic applications(Conference Presentation)

Organometallic halide perovskites CH3NH3BX3 (B= Pb, Sn, Ge; X = I, Br, Cl) have become one of the most promising semiconductors for solar cell applications, reaching power conversion efficiencies beyond 20%. Improving our ability to harness the full potential of organometal halide perovskites requires the development of more reliable synthesis routines of well defined, reproducible and defect free reference systems allowing to study the fundamental photo-physical processes. In this study we present size and band gap engineering for organo-lead perovskites crystallites with various shapes and sizes ranging from the 5 nm regime all the way to 1 cm. Colloidal nano-crystals, micro-crystlline particles as well as single crystals are demonstrated with excellent purity and control in shape and size are demonstrated. The structural, optical and photo-physical properties of these reference materials are investigated and analyzed as function of their size and shape.