Eva L. Unger

Hysteresis and transient behavior in current–voltage measurements of hybrid-perovskite absorber solar cells

Hybrid organo-metal halide perovskites are an exciting new class of solar absorber materials and have exhibited a rapid increase in solar cell efficiencies throughout the past two years to over 17% in both meso-structured and thin-film device architectures. We observe slow transient effects causing hysteresis in the current–voltage characterization of these devices that can lead to an over- or underestimation of the solar cell device efficiency. We find that the current–voltage (IV) measurement scan direction, measurement delay time, and light and voltage bias conditions prior to measurement can all have a significant impact upon the shape of the measured IV light curves and the apparent device efficiency. We observe that hysteresis-free light IV curves can be obtained at both extremely fast and slow voltage scan rates but only in the latter case are quasi-steady-state conditions achieved for a valid power conversion efficiency measurement. Hysteretic effects are also observed in devices utilizing alternative selective contacts but differ in magnitude and time scale, suggesting that the contact interfaces have a big effect on transients in perovskite-absorber devices. The transient processes giving rise to hysteresis are consistent with a polarization response of the perovskite absorber that results in changes in the photocurrent extraction efficiency of the device. The strong dependence of the hysteresis on light and voltage biasing conditions in thin film devices for a period of time prior to the measurement suggests that photo-induced ion migration may additionally play an important role in device hysteresis. Based on these observations, we provide recommendations for correct measurement and reporting of IV curves for perovskite solar cell devices.

Silicon-Naphthalo/Phthalocyanine-Hybrid Sensitizer for Efficient Red Response in Dye-Sensitized Solar Cells

Introduction of a naphthalocyanine moiety to phthalocyanine allows for a gradual red shift of the absorption spectrum in the resulting chromophore. Using silicon as a core atom allows for the introduction of additional siloxane side chains which mitigate dye aggregation. A dye-sensitized solar cell with this hybrid sensitizer exhibits a broad and flat IPCE of 80% between 600 and 750 nm and high photocurrent densities of 19.0 mA/cm(2).

Melt-infiltration of spiro-OMeTAD and thermal instability of solid-state dye-sensitized solar cells

A method for achieving complete pore-filling in solid-state dye-sensitized solar cells termed melt-infiltration is presented: after the customary solution-processed deposition of spiro-OMeTAD, the device is heated above the glass transition temperature of spiro-OMeTAD to soften the material and allow capillary action to pull additional spiro-OMeTAD from the overlayer reservoir into the pores. The pore-filling fraction increases from 60-65% to 90-100% as a result of melt-infiltration. The organic D-π-A dye used in this study is found to withstand the thermal treatment without performance loss, unlike ruthenium-based dyes. Through our experiments, we find that the 4-tert-butylpyridine (tBP) additive, commonly used in dye-sensitized solar cells, evaporates from the device during heat treatment at temperatures as low as 85 °C. This significantly impacts device performance, potentially excluding its use in commercial applications, and demonstrates the need for a more thermally stable tBP alternative. Melt-infiltration is expected to be a viable method for achieving complete pore-filling in systems where volatile additives are not required for operation.

It Takes Two to Tango—Double-Layer Selective Contacts in Perovskite Solar Cells for Improved Device Performance and Reduced Hysteresis

Solar cells made from inorganic-organic perovskites have gradually approached market requirements as their efficiency and stability have improved tremendously in recent years. Planar low-temperature processed perovskite solar cells are advantageous for possible large-scale production but are more prone to exhibiting photocurrent hysteresis, especially in the regular n-i-p structure. Here, a systematic characterization of different electron selective contacts with a variety of chemical and electrical properties in planar n-i-p devices processed below 180 °C is presented. The inorganic metal oxides TiO2 and SnO2, the organic fullerene derivatives C60, PCBM, and ICMA, as well as double-layers with a metal oxide/PCBM structure are used as electron transport materials (ETMs). Perovskite layers deposited atop the different ETMs with the herein applied fabrication method show a similar morphology according to scanning electron microscopy. Further, surface photovoltage spectroscopy measurements indicate comparable perovskite absorber qualities on all ETMs, except TiO2, which shows a more prominent influence of defect states. Transient photoluminescence studies together with current-voltage scans over a broad range of scan speeds reveal faster charge extraction, less pronounced hysteresis effects, and higher efficiencies for devices with fullerene compared to those with metal oxide ETMs. Beyond this, only double-layer ETM structures substantially diminish hysteresis effects for all performed scan speeds and strongly enhance the power conversion efficiency up to a champion stabilized value of 18.0%. The results indicate reduced recombination losses for a double-layer TiO2/PCBM contact design: First, a reduction of shunt paths through the fullerene to the ITO layer. Second, an improved hole blocking by the wide band gap metal oxide. Third, decreased transport losses due to an energetically more favorable contact, as implied by photoelectron spectroscopy measurements. The herein demonstrated improvements of multilayer selective contacts may serve as a general design guideline for perovskite solar cells.

Highly soluble energy relay dyes for dye-sensitized solar cells

High solubility is a requirement for energy relay dyes (ERDs) to absorb a large portion of incident light and significantly improve the efficiency of dye-sensitized solar cells (DSSCs). Two benzonitrile-soluble ERDs, BL302 and BL315, were synthesized, characterized, and resulted in a 65% increase in the efficiency of TT1-sensitized DSSCs. The high solubility (180 mM) of these ERDs allows for absorption of over 95% of incident light at their peak wavelength. The overall power conversion efficiency of DSSCs with BL302 and BL315 was found to be limited by their energy transfer efficiency of approximately 70%. Losses due to large pore size, dynamic collisional quenching of the ERD, energy transfer to desorbed sensitizing dyes and static quenching by complex formation were investigated and it was found that a majority of the losses are caused by the formation of statically quenched ERDs in solution.

Effect of the Preparation Procedure on the Morphology of Thin TiO2 Films and Their Device Performance in Small-Molecule Bilayer Hybrid Solar Cells

Flat titanium dioxide films, to be used as the acceptor layer in bilayer hybrid solar cell devices, were prepared by spray-pyrolysis and by spin-casting. Both preparation methods resulted in anatase titania films with similar optical and electronic properties but considerably different film morphologies. Spray pyrolysis resulted in dense TiO₂ films grown onto and affected by the surface roughness of the underlying conducting glass substrates. The spin-casting preparation procedure resulted in nanoporous titania films. Hybrid solar cell devices with varying layer thickness of the small-molecule semiconducting dye TDCV-TPA were investigated. Devices built with spray-pyrolyzed titania substrates yielded conversion efficiencies up to 0.47%. Spin-cast titania substrates exhibited short circuits for thin dye layer thickness. For thicker dye layers the performance of these devices was up to 0.6% due to the higher interfacial area for charge separation of these nanoporous TiO₂ substrates.

Defect-induced local variation of crystal phase transition temperature in metal-halide perovskites

Solution-processed organometal halide perovskites are hybrid crystalline semiconductors highly interesting for low-cost and efficient optoelectronics. Their properties are dependent on the crystal structure. Literature shows a variety of crystal phase transition temperatures and often a spread of the transition over tens of degrees Kelvin. We explain this inconsistency by demonstrating that the temperature of the tetragonal-to-orthorhombic phase transition in methylammonium lead triiodide depends on the concentration and nature of local defects. Phase transition in individual nanowires was studied by photoluminescence microspectroscopy and super-resolution imaging. We propose that upon cooling from 160 to 140 K, domains of the crystal containing fewer defects stay in the tetragonal phase longer than highly defected domains that readily transform to the high bandgap orthorhombic phase at higher temperatures. The existence of relatively pure tetragonal domains during the phase transition leads to drastic photoluminescence enhancement, which is inhomogeneously distributed across perovskite microcrystals.Understanding crystal phase transition in materials is of fundamental importance. Using luminescence spectroscopy and super-resolution imaging, Dobrovolsky et al. study the transition from the tetragonal to orthorhombic crystal phase in methylammonium lead triiodide nanowires at low temperature.

Transformation from crystalline precursor to perovskite in PbCl 2 -derived MAPbI 3

Understanding the formation chemistry of metal halide perovskites is key to optimizing processing conditions and realizing enhanced optoelectronic properties. Here, we reveal the structure of the crystalline precursor in the formation of methylammonium lead iodide (MAPbI3) from the single-step deposition of lead chloride and three equivalents of methylammonium iodide (PbCl2 + 3MAI) (MA = CH3NH3). The as-spun film consists of crystalline MA2PbI3Cl, which is composed of one-dimensional chains of lead halide octahedra, coexisting with disordered MACl. We show that the transformation of precursor into perovskite is not favored in the presence of MACl, and thus the gradual evaporation of MACl acts as a self-regulating mechanism to slow the conversion. We propose the stable precursor phase enables dense film coverage and the slow transformation may lead to improved crystal quality. This enhanced chemical understanding is paramount for the rational control of film deposition and the fabrication of superior optoelectronic devices.The existence of a crystalline precursor is key to perovskite film formation, but the precise chemistry of the precursor and its transformation into perovskite are poorly understood. Here, the authors identify the crystal structure and conversion chemistry of the precursor for PbCl2-derived methylammonium lead iodide perovskites.

CsxFA1–xPb(I1–yBry)3 Perovskite Compositions: the Appearance of Wrinkled Morphology and its Impact on Solar Cell Performance

1 Helmholtz-Zentrum Berlin für Materialien und Energi e GmbH; a Young Investigator Group Perovskite Tandem Solar Cells, b Institute of Silicon Photovoltaics, c Young Investigator Group Hybrid Materials Formation and Scaling, d Young Investigator Group Nano-SIPPE, Kekuléstraße 5, 12489 Berlin, Germany. 2 Fraunhofer Institute for Solar Energy Systems ISE, Heidenhofstr. 2, 79110 Freiburg, Germany. 3 University of Potsdam, Institute of Physics and As tronomy, Karl-Liebknecht-Str. 24-25, 14476 Potsdam-Golm, Germany. 4 Departamento de Ciencias, Sección Física, Pontifici a Universidad Católica del Perú, Av. Universitaria 1801, Lima 32, Peru.

Research Update: Recombination and open-circuit voltage in lead-halide perovskites

The high open-circuit voltage and the slow recombination in lead-halide perovskite solar cells has been one of the main contributors to their success as photovoltaic materials. Here, we review the knowledge on recombination in perovskite-based solar cells, compare the situation with silicon solar cells, and introduce the parameters used to describe recombination and open-circuit voltage losses in solar cells. We first discuss the effect of lifetimes and surface recombination velocities on photovoltaic performance before we study the microscopic origin of charge-carrier lifetimes. The lifetimes depend on defect positions and densities and on the kinetic prefactors that control the phonon-assisted interaction between the extended states in the conduction and valence band and the localized defect states. We finally argue that the key to understand the long lifetimes and high open-circuit voltages is a combination of a low density of deep defects and a slow dissipation of energy via multiphonon processes due to the low phonon energies in the lead-halide perovskites.