So-called negative capacitance seems to remain an obscure feature in the analysis of the frequency-dependent impedance of perovskite solar cells. It belongs to one of the puzzling peculiarities ...arising from the mixed ionic-electronic conductivity of this class of semiconductor. Here we show that apparently high capacitances in general (positive and negative) are not related to any capacitive feature in the sense of a corresponding charge accumulation. Instead, they are a natural consequence of slow transients mainly in forward current of the diode upon ion displacement when changing voltage. The transient current leads to a positive or negative 'capacitance' dependent on the sign of its gradient. The 'capacitance' appears so large because the associated resistance, when thinking of a resistor-capacitor element, results from another physical process, namely modified electronic charge injection and transport. Observable for a variety of devices, it is a rather universal phenomenon related to the hysteresis in the current-voltage curve.
Dye-sensitized solar cells (DSCs) have gained widespread interest because of their potential for low-cost solar energy conversion. Currently, the certified record efficiency of these solar cells is ...11.1%, and measurements of their durability and stability suggest lifetimes exceeding 10 years under operational conditions. The DSC is a photoelectrochemical system: a monolayer of sensitizing dye is adsorbed onto a mesoporous TiO2 electrode, and the electrode is sandwiched together with a counter electrode. An electrolyte containing a redox couple fills the gap between the electrodes. The redox couple is a key component of the DSC. The reduced part of the couple regenerates the photo-oxidized dye. The formed oxidized species diffuses to the counter electrode, where it is reduced. The photovoltage of the device depends on the redox couple because it sets the electrochemical potential at the counter electrode. The redox couple also affects the electrochemical potential of the TiO2 electrode through the recombination kinetics between electrons in TiO2 and oxidized redox species. This Account focuses on the special properties of the iodide/triiodide (I−/I3 −) redox couple in dye-sensitized solar cells. It has been the preferred redox couple since the beginning of DSC development and still yields the most stable and efficient DSCs. Overall, the iodide/triiodide couple has good solubility, does not absorb too much light, has a suitable redox potential, and provides rapid dye regeneration. But what distinguishes I−/I3 − from most redox mediators is the very slow recombination kinetics between electrons in TiO2 and the oxidized part of the redox couple, triiodide. Certain dyes adsorbed at TiO2 catalyze this recombination reaction, presumably by binding iodine or triiodide. The standard potential of the iodide/triiodide redox couple is 0.35 V (versus the normal hydrogen electrode, NHE), and the oxidation potential of the standard DSC-sensitizer (Ru(dcbpy)2(NCS)2) is 1.1 V. The driving force for reduction of oxidized dye is therefore as large as 0.75 V. This process leads to the largest internal potential loss in DSC devices. We expect that overall efficiencies above 15% might be achieved if half of this internal potential loss could be gained. The regeneration of oxidized dye with iodide leads to the formation of the diiodide radical (I2 −•). The redox potential of the I2 −•/I− couple must therefore be considered when determining the actual driving force for dye regeneration. The formed I2 −• disproportionates to I3 − and I−, which leads to a large loss in potential energy.
The efficiencies of perovskite solar cells have gone from single digits to a certified 22.1% in a few years’ time. At this stage of their development, the key issues concern how to achieve further ...improvements in efficiency and long-term stability. We review recent developments in the quest to improve the current state of the art. Because photocurrents are near the theoretical maximum, our focus is on efforts to increase open-circuit voltage by means of improving charge-selective contacts and charge carrier lifetimes in perovskites via processes such as ion tailoring. The challenges associated with long-term perovskite solar cell device stability include the role of testing protocols, ionic movement affecting performance metrics over extended periods of time, and determination of the best ways to counteract degradation mechanisms.
Abstract
Photoelectrochemical water splitting provides a promising solution for harvesting and storing solar energy. As the best-performing oxide photocathode, the Cu
2
O photocathode holds the ...performance rivaling that of many photovoltaic semiconductor-based photocathodes through continuous research and development. However, the state-of-the-art Cu
2
O photocathode employs gold as the back contact which can lead to considerable electron-hole recombination. Here, we present a Cu
2
O photocathode with overall improved performance, enabled by using solution-processed CuSCN as hole transport material. Two types of CuSCN with different structures are synthesized and carefully compared. Furthermore, detailed characterizations reveal that hole transport between Cu
2
O and CuSCN is assisted by band-tail states. Owing to the multiple advantages of applying CuSCN as the hole transport layer, a standalone solar water splitting tandem cell is built, delivering a solar-to-hydrogen efficiency of 4.55%. Finally, approaches towards more efficient dual-absorber tandems are discussed.
Abstract Metal halide perovskites have achieved great success in photovoltaic applications during the last few years. The solar to electrical power conversion efficiency (PCE) of perovskite solar ...cells has been rapidly improved from 3.9% to certified 22.7% due to the extensive efforts on film deposition methods, composition and device engineering. Further investigation on eliminating the defect states in perovskite absorbers is necessary to push forward the PCE of perovskite solar cells approaching the Shockley-Queisser limit. In this review, we summarize the defect properties in perovskite films and present methodologies to control the defects density, including the growth of large size crystals, photo-curing method, grain boundary and surface passivation, and modification of the substrates. We also discuss the defects-related stability and hysteresis issues and highlight the current challenges and opportunities in defects control of perovskite films.
To advance the progress of photoelectrolysis, various promising devices integrated with p- and n-type photocatalysts and dye sensitized photoelectrodes have been systematically studied. This review ...discusses, from theory to practice, an integration strategy for state-of-the-art dye sensitized solar cells (DSSCs) with potential p- and n-type photo-electrocatalysts or directly with dye sensitized photoanodes and cathodes for hydrogen and oxygen production through water splitting. Thorough insight into the theoretical approach which systematically drives the photoelectrolysis reaction directly or in a coupled mode, with diverse configurations of DSSCs and other photovoltaic (PV) cells, is crucial to understand the underlying fundamental concepts and elucidate trends in such reactions, and will serve as a guide to design new electrocatalysts and their integration with new PV devices, while simultaneously underlining major gaps that are required to address the challenges. Likewise, challenges, opportunities and frontiers in tandem and hybrid perovskite electrolysis processes are also discoursed in the present tutorial review. We illustrate our analysis by encompassing these integrated systems to photo-electrolysis, artificial photosynthesis such as CO
2
conversion into value-added chemical reduction-products, where advancements in new catalysts and solution-processed inexpensive PV devices can certainly enrich the overall performance of the renewable production of solar fuels, including solar driven carbonaceous fuels.
This review from theory to practice discusses the principles and designs of dye-sensitized semiconductor photoelectrodes for water splitting and electrolysis reactions.
Hybrid halide perovskite solar cells (PSCs) giving over 22 % power conversion efficiencies (PCEs) have attracted considerable attention. Although perovskite plays a significant role in the operation ...of PSCs, the fundamental theories associated with perovskites have not been resolved in spite of the increase in research. In this Minireview, we assess the current understanding, based on the first‐principles calculations, of structural and electronic properties, defects, ionic diffusion, and shift current for CH3NH3PbI3 perovskite, and the effect of ionic transport on the hysteresis of current–voltage curves in PSCs. The shift current connected to the possible presence of ferroelectricity is also discussed. The current state‐of‐the‐art and some open questions regarding PSCs are also highlighted, and the benefits, challenges, and potentials of perovskite for use in PSCs are stressed.
Better by calculation: First principles calculations of CH3NH3PbI3, including structural and electronic properties, defects, ionic diffusion, and shift current, can provide valuable support for further developing perovskite solar cells (PSCs).
Metal halide perovskite absorber materials are about to emerge as a high-efficiency photovoltaic technology. At the same time, they are suitable for high-throughput manufacturing characterized by a ...low energy input and abundant low-cost materials. However, a further optimization of their efficiency, stability and reliability demands a more detailed optoelectronic characterization and understanding of losses including their evolution with time. In this work, we analyze perovskite solar cells with different architectures (planar, mesoporous, HTL-free), employing temperature dependent measurements (current–voltage, light intensity, electroluminescence) of the ideality factor to identify dominating recombination processes that limit the open-circuit voltage ( V oc ). We find that in thoroughly-optimized, high- V oc (≈1.2 V) devices recombination prevails through defects in the perovskite. On the other hand, irreversible degradation at elevated temperature is caused by the introduction of broad tail states originating from an external source ( e.g. metal electrode). Light-soaking is another effect decreasing performance, though reversibly. Based on FTPS measurements, this degradation is attributed to the generation of surface defects becoming a new source of non-radiative recombination. We conclude that improving long-term stability needs to focus on adjacent layers, whereas a further optimization of efficiency of top-performing devices requires understanding of the defect physics of the nanocrystalline perovskite absorber. Finally, our work provides guidelines for the design of further dedicated studies to correctly interpret the diode ideality factor and decrease recombination losses.
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•Transition metal complexes as p-type dopants in perovskite solar cells is reviewed.•TMC-based hole-transporting materials in PSCs are discussed in detail.•Metal phthalocyanines and ...porphyrins are promising HTMs to be further explored.
In the past few years, the photovoltaic community has witnessed a fast growth of inorganic-organic hybrid perovskite solar cells (PSCs) due to their exceptional power conversion efficiencies with a certified record value exceeding 25%, which rivals the established commercial solar cell technologies. In the state-of-the-art PSCs, a hole-transporting layer (HTL) typically consisting of an active hole-transporting material (HTM) and some additives or dopants, takes the responsibility of transporting the photo-generated holes from the perovskite to the selective contact electrode, and is a key component for achieving high-performance and stable PSCs. In this review article, recent advances in the development of transition metal complexes in HTLs for PSCs including HTMs and p-type dopants are presented.
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