Correlating light-induced deep defects and phase segregation in mixed-halide perovskites

Mixed-halide perovskites are highly promising materials for tandem solar cells. The phenomenon of phase segregation, however hinders their application. Here, we combine Fourier-Transform photocurrent spectroscopy with photoluminescence and current density-voltage (J-V) measurements to study the effect of light soaking on such materials and devices. At first, we observe a gradual formation of an I-rich phase, which correlates with an increase in deep defect level concentration. We attribute these deep defects to charged iodide interstitials and associate phase segregation with iodide migration through interstitial positions. Upon further light soaking, the second less I-rich phase forms, while the deep level concentration simultaneously decreases. An empirical model describing the phase segregation mechanism is proposed to rationalize these observations. Further, we point to an important role of grain size in determining the degree and terminal phase of segregation.

A low-cost spiro[fluorene-9,9 '-xanthene]-based hole transport material for highly efficient solid-state dye-sensitized solar cells and perovskite solar cells

Dongqin Bi, Ming Cheng, Michael Graetzel, Ulf Anders Hagfeldt, Peng Liu

A low-cost spiro[fluorene-9,9'-xanthene] (SFX) based organic hole transport material (HTM) termed X60 was designed and synthesized using a two-step synthetic route. Devices with X60 as HTM showed high power conversion efficiencies (PCEs) amounting to 7.30% in solid-state dye-sensitized solar cells (ssDSCs) and 19.84% in perovskite solar cells (PSCs), under 100 mW cm(-2) AM1.5G solar illumination. To the best of our knowledge, this is the first example of an easily synthesized spiro-structured HTM that shows comparable performance with respect to the well-known HTM Spiro-OMeTAD in both ssDSCs and PSCs. Furthermore, the facile synthesis of X60 from commercially available starting materials makes this HTM very promising for large-scale industrial production in the future.

Royal Society of Chemistry2016

Nanoparticle sensitisation of solid-state nanocrystalline solar cell

Robert Plass

Over the past fifteen years dye-sensitised nanocrystalline solar cells have been the subject of intense research and development efforts. These systems provide a technically and economically credible alternative to classical p-n junction solar cells, reaching over 10 % certified efficiency under standard solar illumination conditions (AM 1.5, 1000 W/m2). Recently, the liquid electrolyte, commonly used in these dye-sensitised solar cells, could successfully be replaced by a novel solid hole-conducting material (spiro-OMeTAD). The absence of volatile solvents and corrosive components like iodine presents a clear advantage of these solid-state devices over their photoelectrochemical counterparts. Yet, their maximum overall efficiency of about 3 % clearly lacks behind the performance features of classical dye-sensitized solar cells. The objective of this work is the replacement of the usually used sensitiser (transition metal complexes and organic dyes) by quantum-dots. It was motivated by the possibility to achieve panchromatic light absorption due to the size-dependent properties of the quantum-dots. Some studies have been published using quantum-dots of inorganic low-bandgap semiconductors as sensitisers for mesoporous wide bandgap semiconductor electrodes in conjunction with liquid electrolytes. These systems often suffer from corrosion and photo-corrosion mainly due to the aggressive nature of the electrolyte employed. Solid-state organic-inorganic heterojunctions might provide the desired environment for quantum-dot sensitisation, as the environment is much less aggressive. A large variety of inorganic quantum-dot materials like PbS, CdS, PbSe and CdSe were scrutinized for their use as sensitisers. All particles were synthesised in situ on the TiO2 surface using two different techniques: dip-coating and chemical bath deposition. Lead sulphide was the most investigated due to its superior photovoltaic characteristics. High Resolution Transmission Electron Microscopy (HRTEM) of PbS sensitised TiO2 electrodes fabricated via dip-coating clearly showed the distinct particles on the surface of the semiconductor. The electron transfer dynamics following optical excitation of quantum-dot sensitized TiO2/spiro-OMeTAD heterojunctions were thoroughly studied. Fluorescence spectroscopy was used to prove the possible electron injection from the PbS into the TiO2. Nanosecond laser spectroscopy was applied to monitor the interfacial recombination of the injected electron and the oxidised hole-conductor. Femtosecond laser spectroscopy allowed measuring the ultra-fast kinetics in the system, including electron trapping, exciton recombination and PbS regeneration. An overall efficiency of 0.5 % at 0.1 sun (AM 1.5) has been reached with such systems. Chemical bath deposition (CBD) of PbS leads to the formation of a layer rather than distinct particles on the TiO2. Solar cells fabricated via CBD exhibited open-circuit voltages which were generally 100 mV higher then those of comparable devices made via dip-coating. The PbS layer acts as blocking layer, hindering the contact between TiO2 and the hole-conductor. This technique allowed achieving devices highly linear with respect to the illumination power. Different strategies were pursued to impede interfacial recombination, among which the introduction of self-assembled monolayers at the interface between the organic and inorganic phases was proven to be the most efficient. Nanosecond laser spectroscopy showed a strong decrease of the interfacial recombination kinetic rates in the presence of hexadecylmalonic acid or decylphosphonic acid monolayers. Short-circuit currents could be raised by a factor two to four using such type of molecules. The overall efficiency of the device could be strongly increased, reaching 1 % at 0.1 Sun (AM 1.5). CBD was also used to deposit PbSe and CdSe layers at the surface of TiO2. Fluorescence spectroscopy was used to probe electron injection from CdSe quantum dots to TiO2. Generally it was observed that metal sulfides were more efficient in sensitizing TiO2/OMeTAD heterojunctions then the respective selenides.

EPFL2004

Formate as Anti-Oxidation Additives for Pb-Free FASnI(3) Perovskite Solar Cells

Jaeki Jeong, Jinhyun Kim, Jiyoun Seo

Pb-free Sn-based perovskite solar cells (PSCs) have significant potential for application in photovoltaic devices because oftheir suitable bandgap, low exciton binding energy, high carrier mobility, and long diffusion length. However, their performance is hampered by several issues. Sn-based perovskites are highly susceptible to oxidation, which induces a high concentration of defects and degrades the chemical stability of the perovskite crystals. Herein, the anion formate (HCOO-) can effectively suppress the oxidation of Sn in the pure formamidinium tin triiodide (FASnI(3)) perovskite without using A-site cationic additives. Moreover, the presence of formate results in a uniform pinhole-free perovskite film with a low trap density, reduced charge carrier recombination, and improved charge extraction. Density functional theory calculations show that formate-treated FASnI(3) has improved stability against oxidative Sn degradation. The formate-treated PSC achieves a power conversion efficiency of 12.11% at a high open-circuit voltage of 0.71 V. The device exhibits improved stability in ambient air in which it maintained over 80% of its initial power conversion efficiency after 180 min because oxidation is inhibited owing to the strong interaction between Sn and formate.

WILEY-V C H VERLAG GMBH2022

Nanoparticle sensitisation of solid-state nanocrystalline solar cell

Robert Plass

EPFL2004