Hybrid lead halide perovskites have emerged as promising active materials for photovoltaic cells. Although superb efficiencies have been achieved, it is widely recognized that long-term stability is a key challenge intimately determining the future development of perovskite-based photovoltaic technology. Herein, we present reversible and irreversible photodecomposition reactions of methylammonium lead iodide (MAPbI3). Simulated sunlight irradiation and temperature (40–80 °C) corresponding to solar cell working conditions lead to three degradation pathways: (1) CH3NH2 + HI (identified as the reversible path), (2) NH3 + CH3I (the irreversible or detrimental path), and (3) a reversible Pb(0) + I2(g) photodecomposition reaction. If only the reversible reactions (1) and (3) take place and reaction (2) can be avoided, encapsulated MAPbI3 can be regenerated during the off-illumination timeframe. Therefore, to further improve operational stability in hybrid perovskite solar cells, detailed understanding of how to mitigate photodegradation and thermal degradation processes is necessary. First, encapsulation of the device is necessary not only to avoid contact of the perovskite with ambient air, but also to prevent leakage of volatile products released from the perovskite. Second, careful selection of the organic cations in the compositional formula of the perovskite is necessary to avoid irreversible reactions. Third, selective contacts must be as chemically inert as possible toward the volatile released products. Finally, hybrid halide perovskite materials are speculated to undergo a dynamic formation and decomposition process; this can gradually decrease the crystalline grain size of the perovskite with time; therefore, efforts to deposit highly crystalline perovskites with large crystal sizes may fail to increase the long-term stability of photovoltaic devices.

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Photodecomposition and thermal decomposition in methylammonium halide lead perovskites and inferred design principles to increase photovoltaic device stability

The power conversion efficiency of organic–inorganic hybrid perovskite solar cells (PSCs) has been boosted to be comparable with that of commercial silicon solar cells. Although the fabrication cost of solution-processing PSCs can be lower than that of silicon solar cells, PSCs are still facing the big challenge of instability in air due to the presence of organic components in the perovskites. To obtain stable PSCs, fully replacing the A-site organic cations with pure inorganic cations is one of the promising methods. To date, many researchers have studied the inorganic PSCs with astonishing breakthroughs, and the PCE of inorganic lead-based PSCs has exceeded 17%. In this review, the recent progress of inorganic PSCs is summarized and discussed for different perovskite compositions. The challenges of inorganic PSCs are revealed, followed by the outlook of this field.

Recent progress of inorganic perovskite solar cells

Progress of Lead-Free Halide Double Perovskites

In several photovoltaic (PV) technologies, the presence of electronic defects within the semiconductor band gap limit the efficiency, reproducibility, as well as lifetime. Metal halide perovskites (MHPs) have drawn great attention because of their excellent photovoltaic properties that can be achieved even without a very strict film-growth control processing. Much has been done theoretically in describing the different point defects in MHPs. Herein, we discuss the experimental challenges in thoroughly characterizing the defects in MHPs such as, experimental assignment of the type of defects, defects densities, and the energy positions within the band gap induced by these defects. The second topic of this Review is passivation strategies. Based on a literature survey, the different types of defects that are important to consider and need to be minimized are examined. A complete fundamental understanding of defect nature in MHPs is needed to further improve their optoelectronic functionalities.

Reducing Detrimental Defects for High-Performance Metal Halide Perovskite Solar Cells.

All-inorganic perovskites are considered to be one of the most appealing research hotspots in the field of perovskite photovoltaics in the past 3 years due to their superior thermal stability compared to their organic-inorganic hybrid counterparts. The power-conversion efficiency has reached 17.06% and the number of important publications is ever increasing. Here, the progress of inorganic perovskites is systematically highlighted, covering materials design, preparation of high-quality perovskite films, and avoidance of phase instabilities. Inorganic perovskites, nanocrystals, quantum dots, and lead-free compounds are discussed and the corresponding device performances are reviewed, which have been realized on both rigid and flexible substrates. Methods for stabilization of the cubic phase of low-bandgap inorganic perovskites are emphasized, which is a prerequisite for highly efficient and stable solar cells. In addition, energy loss mechanisms both in the bulk of the perovskite and at the interfaces of perovskite and charge selective layers are unraveled. Reported approaches to reduce these charge-carrier recombination losses are summarized and complemented by methods proposed from our side. Finally, the potential of inorganic perovskites as stable absorbers is assessed, which opens up new perspectives toward the commercialization of inorganic perovskite solar cells.

Review on Recent Progress of All-Inorganic Metal Halide Perovskites and Solar Cells.

https://pubs.rsc.org/en/content/articlepdf/2017/cc/c7cc01538k

In situ investigation of degradation at organometal halide perovskite surfaces by X-ray photoelectron spectroscopy at realistic water vapour pressure

Air-stable caesium tin iodide double perovskite (Cs2SnI6) thin films have been fabricated via aerosol-assisted chemical vapour deposition (AACVD). We compare the properties of the double perovskite films made using AACVD with those made by the widely used spin-coating method. Films with purer crystalline phase (less CsI impurity) and far better stability in ambient air can be obtained by AACVD compared with spin coating. The AACVD-grown Cs2SnI6 films retain high phase purity for at least ∼100 days aging in air with negligible CsI impurities detected over this time, as determined by X-ray diffraction. The films exhibit an optical band gap energy (Eg) of ca. 1.3 eV and a homogeneous morphology with the expected nominal stoichiometry within error, as probed by energy-dispersive X-ray spectroscopy. Overall, the characteristics of the Cs2SnI6 films are highly process-dependent, e.g. they are influenced by the presence of hydroiodic acid (HI) in the precursor solution. Without HI addition, an iodine-deficient film with more CsI is produced, which also exhibits a larger Eg of ca. 1.6 eV. In addition to bulk properties, we utilise X-ray photoelectron spectroscopy (XPS) to scrutinise the surface characteristics in detail. We find excess Sn and I located at the surfaces. This can be attributed to the presence of SnI4 from the deposition precursor vapour. Furthermore, following aging in air, an increase in CsI impurity for the AACVD (+HI)-grown film is observed, along with a reduction in SnI4 at the surfaces. Near-ambient pressure XPS (NAP-XPS) is used to examine the surface stability of AACVD (+HI)-grown films on exposure to O2 and H2O. No enhancement in the amount of CsI impurity is observed after both H2O vapour (9 mbar) and O2 (5 mbar) exposure. Nevertheless, the concentrations of tin and iodine change after exposure, suggesting that SnI4 protects Cs2SnI6 from degradation. This passivation effect of SnI4 on Cs2SnI6 surfaces is proposed to explain the additional stability of Cs2SnI6 fabricated via AACVD.

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Ambient-air-stable inorganic Cs2SnI6 double perovskite thin films via aerosol-assisted chemical vapour deposition

Although multiple-material additive manufacturing has progressed rapidly over the last few years, little progress has been made so far on the additive manufacturing of metal/polymer hybrid components due to significantly different material properties. In this study, we investigated the printing of hybrid metal (Cu10Sn) and polymer (PA11) objects through a proprietary multiple-material laser powder bed fusion (LPBF) system. Powder materials were delivered to the build platform through an ultrasonic vibration-assisted dispensing system. Several 2D Cu10Sn/PA11 structures were printed and demonstrated. The scientific mechanism underlying how the interaction between Cu10Sn and PA11 during laser scanning affected printing quality is discussed. In addition, the roughness of the printed Cu10Sn top surface was improved tenfold with the addition of small amount of PA11 powder. Finally, several 3D components consisting of hybrid stainless steel (SS 316 L), copper (Cu10Sn), and polymer (PA11) including entangling structures were printed and discussed. Potential applications of this technology are discussed.

Additive manufacturing of hybrid metal/polymer objects via multiple-material laser powder bed fusion

https://pubs.rsc.org/en/content/articlepdf/2021/cc/d0cc02957b

Jack Chun Ren Ke

Papers

In situ investigation of degradation at organometal halide perovskite surfaces by X-ray photoelectron spectroscopy at realistic water vapour pressure

Ambient-air-stable inorganic Cs2SnI6 double perovskite thin films via aerosol-assisted chemical vapour deposition

Additive manufacturing of hybrid metal/polymer objects via multiple-material laser powder bed fusion

Bioinspired scaffolds that sequester lead ions in physically damaged high efficiency perovskite solar cells.

A novel ternary nanocomposite for improving the cycle life and capacitance of polypyrrole