X-Ray, Ultraviolet, and Visible Light Induced Energy Level Realignment

The article processing charge was funded by the Open Access Publication Fund of Humboldt-Universität zu Berlin.The electronic properties of metal halide perovskites (MHPs) are crucial for achieving the full potential of MHPs-based optoelectronic devices, and they are extensively studied by photoelectron spectroscopy (PES). However, there are numerous complexities during PES measurements, which can result in inconsistent experimental data or even misinterpretation of results. Here, it is demonstrated that in the presence of charge selective junctions with MHPs, significant electronic energy level realignment can occur during PES measurements due to the sample excitation with high-energy photons used in PES, amounting up to over 0.8 eV in the present case. This is caused by unbalanced charge carrier accumulation within the perovskite due to the charge-selective interface. X-ray photoelectron spectroscopy further reveals that photoexcitation due to bremsstrahlung, as produced in commonly employed twin-anode lab-sources, can readily produce sizable photoinduced shifts of core levels of MHPs films, whereas monochromatized X-ray lab-sources (irradiation flux reduced by >50 times by eliminating the bremsstrahlung) induce negligible shifts within the range of presently applied anode powers. The data and measurement conditions presented here are intended to enable others to obtain reliable MHP electronic property information from PES measurements.Peer Reviewe

Narrow bandgap Metal halide perovskites for all-perovskite tandem photovoltaics

All-perovskite tandem solar cells are attracting considerable interest in photovoltaics research, owing to their potential to surpass the theoretical efficiency limit of single-junction cells, in a cost-effective sustainable manner. Thanks to the bandgap-bowing effect, mixed tin−lead (Sn−Pb) perovskites possess a close to ideal narrow bandgap for constructing tandem cells, matched with wide-bandgap neat lead-based counterparts. The performance of all-perovskite tandems, however, has yet to reach its efficiency potential. One of the main obstacles that need to be overcome is the─oftentimes─low quality of the mixed Sn−Pb perovskite films, largely caused by the facile oxidation of Sn(II) to Sn(IV), as well as the difficult-to-control film crystallization dynamics. Additional detrimental imperfections are introduced in the perovskite thin film, particularly at its vulnerable surfaces, including the top and bottom interfaces as well as the grain boundaries. Due to these issues, the resultant device performance is distinctly far lower than their theoretically achievable maximum efficiency. Robust modifications and improvements to the surfaces of mixed Sn−Pb perovskite films are therefore critical for the advancement of the field. This Review describes the origins of imperfections in thin films and covers efforts made so far toward reaching a better understanding of mixed Sn−Pb perovskites, in particular with respect to surface modifications that improved the efficiency and stability of the narrow bandgap solar cells. In addition, we also outline the important issues of integrating the narrow bandgap subcells for achieving reliable and efficient all-perovskite double- and multi-junction tandems. Future work should focus on the characterization and visualization of the specific surface defects, as well as tracking their evolution under different external stimuli, guiding in turn the processing for efficient and stable single-junction and tandem solar cell devices

On the Origin of the Ideality Factor in Perovskite Solar Cells

The measurement of the ideality factor (n id) is a popular tool to infer the dominant recombination type in perovskite solar cells (PSC). However, the true meaning of its values is often misinterpreted in complex multilayered devices such as PSC. In this work, the effects of bulk and interface recombination on the n id are investigated experimentally and theoretically. By coupling intensity‐dependent quasi‐Fermi level splitting measurements with drift diffusion simulations of complete devices and partial cell stacks, it is shown that interfacial recombination leads to a lower n id compared to Shockley–Read–Hall (SRH) recombination in the bulk. As such, the strongest recombination channel determines the n id of the complete cell. An analytical approach is used to rationalize that n id values between 1 and 2 can originate exclusively from a single recombination process. By expanding the study over a wide range of the interfacial energy offsets and interfacial recombination velocities, it is shown that an ideality factor of nearly 1 is usually indicative of strong first‐order non‐radiative interface recombination and that it correlates with a lower device performance. It is only when interface recombination is largely suppressed and bulk SRH recombination dominates that a small n id is again desirable

Internal electric fields control triplet formation in halide perovskite-sensitized photon upconverters

Halide perovskite-based photon upconverters utilize perovskite thin films to sensitize triplet exciton formation in a small-molecule layer, driving triplet-triplet annihilation upconversion. Despite having excellent carrier mobility, these systems suffer from inefficient triplet formation at the perovskite/annihilator interface. We studied triplet formation in formamidinium-methylammonium lead iodide/rubrene bilayers using photoluminescence and surface photovoltage methods. By studying systems constructed on glass as well as hole-selective substrates, comprising self-assembled layers of the carbazole derivative 2PACz ([2-(9H-carbazol-9-yl)ethyl]phosphonic acid) on indium-doped tin oxide, we saw how changes in the carrier dynamics induced by the hole-selective substrate perturbed triplet formation at the perovskite/rubrene interface. We propose that an internal electric field, caused by hole transfer at the perovskite/rubrene interface, strongly affects triplet exciton formation, accelerating exciton-forming electron-hole encounters at the interface but also limiting the hole density in rubrene at high excitation densities. Controlling this field is a promising path to improving triplet formation in perovskite/annihilator upconverters

Spectral Dependence of the Internal Quantum Efficiency of Organic Solar Cells: Effect of Charge Generation Pathways

The conventional picture of photocurrent generation in organic solar cells involves photoexcitation of the electron donor, followed by electron transfer to the acceptor via an interfacial charge-transfer state (Channel I). It has been shown that the mirror-image process of acceptor photoexcitation leading to hole transfer to the donor is also an efficient means to generate photocurrent (Channel II). The donor and acceptor components may have overlapping or distinct absorption characteristics. Hence, different excitation wavelengths may preferentially activate one channel or the other, or indeed both. As such, the internal quantum efficiency (IQE) of the solar cell may likewise depend on the excitation wavelength. We show that several model high-efficiency organic solar cell blends, notably PCDTBT:PC70BM and PCPDTBT:PC60/70BM, exhibit flat IQEs across the visible spectrum, suggesting that charge generation is occurring either via a dominant single channel or via both channels but with comparable efficiencies. In contrast, blends of the narrow optical gap copolymer DPP-DTT with PC70BM show two distinct spectrally flat regions in their IQEs, consistent with the two channels operating at different efficiencies. The observed energy dependence of the IQE can be successfully modeled as two parallel photodiodes, each with its own energetics and exciton dynamics but both having the same extraction efficiency. Hence, an excitation-energy dependence of the IQE in this case can be explained as the interplay between two photocurrent-generating channels, without recourse to hot excitons or other exotic processes

Charge Transport Layers Limiting the Efficiency of Perovskite Solar Cells: How To Optimize Conductivity, Doping, and Thickness

Perovskite solar cells (PSCs) are one of the main research topics of the photovoltaic community; with efficiencies now reaching up to 24%, PSCs are on the way to catching up with classical inorganic solar cells. However, PSCs have not yet reached their full potential. In fact, their efficiency is still limited by nonradiative recombination, mainly via trap-states and by losses due to the poor transport properties of the commonly used transport layers (TLs). Indeed, state-of-the-art TLs (especially if organic) suffer from rather low mobilities, typically within 10-5 and 10-2 cm2 V-1 s-1, when compared to the high mobilities, 1-10 cm2 V-1 s-1, measured for perovskites. This work presents a comprehensive analysis of the effect of the mobility, thickness, and doping density of the transport layers based on combined experimental and modeling results of two sets of devices made of a solution-processed high-performing triple-cation (PCE ≈ 20%). The results are also cross-checked on vacuum-processed MAPbI3 devices. From this analysis, general guidelines on how to optimize a TL are introduced and especially a new and simple formula to easily calculate the amount of doping necessary to counterbalance the low mobility of the TLs