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Among several solution process photovoltaics, perovskite solar cells are evolving at an impressive pace, emerging as the most promising next‐generation photovoltaic devices. Herein, the recent developments in laser technology applicable to perovskite‐based solar devices, technological and process aspects, and an outlook on future applications are reported.

In the last decade, hybrid organic–inorganic perovskite‐based solar cells (PSCs) have shown an impressive rate of growth in performance, reaching power conversion efficiencies (PCEs) comparable with the ones exhibited by crystalline silicon devices. Recently, perovskite‐based solar modules (PSMs) have been developed, showing a similar pace in the progress of the reported PCE. Nevertheless, scaling up the dimensions of devices is not a trivial process. To this effect, different deposition and manufacturing techniques have to be implemented. Laser apparatuses have been demonstrated to be fundamental in the production of PSMs, due to the extreme precision needed for manufacturing processes. Herein, an overview of the recent progresses in the application of laser systems in the production of perovskite‐based solar devices is provided. In particular, lasers are used in small‐area PSCs to realize pulsed laser deposition procedures for the realization of perovskite layers and novel electrodes. In the field of PSMs, lasers have boosted the exploitation of substrates, minimizing the dimension of interconnection areas between the cells that form a module and providing the necessary accuracy, repeatability, and level of automation needed for the future industrialization of perovskite‐based solar technology.

The in situ reduction of parasitic Sn⁴⁺ to Sn²⁺ by metallic tin powder effectively reduces Sn⁴⁺ content and thereby decreases the trap density of the perovskite films, giving rise to a remarkably long charge carrier lifetime and favorable energy‐level alignment at the interfaces. Consequently, a high power conversion efficiency of 20.7% is achieved for low‐bandgap Pb–Sn‐alloyed perovskite solar cells.

Although the theoretical power conversion efficiency (PCE) of low‐bandgap Pb–Sn‐alloyed perovskite solar cells (PSCs) is higher than that of its conventional pure Pb counterpart, its device performance currently has been severely restricted by the large open‐circuit voltage (V _oc) loss. Herein, it is discovered that the Sn⁴⁺‐induced trap states of the perovskite film can be effectively suppressed by introducing excess Sn powder into the precursor solution (FASnI₃) to reduce the Sn⁴⁺ content. As a result, the average charge carrier lifetime of the perovskite film increases remarkably from 115 to 701 ns due to the suppressed nonradiative recombination, and the energy levels have up‐shifted by about 0.27 eV, rendering a more favorable energy‐level alignment at the interface. Ultimately, the champion PSCs using a low‐bandgap (FASnI₃)_0.6(MAPbI₃)_0.4 perovskite film with Sn⁴⁺ reduction show a high V _oc of 0.843 V corresponding to a V _oc loss as low as 0.397 eV and a high fill factor of 80.34%, leading to an impressive PCE of 20.7%, which is one of the few instances of a PCE over 20% for low‐bandgap mixed Pb–Sn PSCs to date.

Organic amine cation, GA⁺ is intentionally incorporated in MA_0.7FA_0.3PbI₃ perovskite to stiffen the inorganic Pb–I lattice, restrain the formation of iodine vacancies defects, and reduce ion diffusion. Solar cells based on this component engineering and PFN‐Br interfacial strategy demonstrate an enhanced power conversion efficiency value over 21% for SnO₂‐based planar perovskite solar cells and excellent thermal stability.

Tin oxide (SnO₂) offers its advantages in widespread applications that require efficient carrier transport. However, the usages of SnO₂ in organic solar cells are hindered because of dangling bonds on the surface of SnO₂. Herein, PFN‐Br as an interfacial layer to tailor the work function of SnO₂ is adopted, making it an ideal candidate for interfacial material in organic electronics. Meanwhile, such an efficient SnO₂/PFN‐Br electron transport layer (ETL) can also be applied to perovskite devices and achieve competitive efficiency. To eliminate current–voltage hysteresis and improve poor thermodynamic stability of perovskite solar cells (PSCs), 5 mol% of guanidinium iodide (GAI) into the (MA) _x (FA)_1 − x PbI₃ precursor solution is incorporated, enabling the formation of triple‐cation perovskite films with excellent optoelectronic quality and stability. The combination of an SnO₂/PFN‐Br ETL and GAI doping strategy finally delivers power conversion efficiencies over 21% and negligible current–voltage hysteresis in planar PSCs. These improvements arise from the strong hydrogen bonding caused by the incorporation of GA⁺. It can stiffen the inorganic Pb–I lattice of the unit cell and restrain the formation of iodine vacancies defects. Moreover, the strong hydrogen bonding can immobilize iodide ion and thus enhance the thermal stability of the corresponding device.

An excellent antioxidant, tea polyphenol (TP), is introduced to a CsPb_0.5Sn_0.5I₂Br precursor solution to obtain high‐efficiency inorganic PSCs. TP can not only retard the oxidation of Sn²⁺ but also regulate the formation of Pb/Sn binary perovskite films, leading to a reduced density of defects. The corresponding device demonstrates power conversion efficiency as high as 8.10% with high stability.

Implementation of inorganic perovskite compounds and reduction toxicity of lead are important for developing sustainable and renewable photovoltaic power generation. The inorganic Pb/Sn binary metal halide perovskites offer a perfect opportunity for tuning optical bandgap and thus hold significant potential in emerging technologies such as solar cells. However, an easy oxidation of Sn²⁺ to Sn⁴⁺ has become one of the main issues for achieving efficient and stable Sn‐based perovskite solar cells (PSCs). Herein, an effective method for stabilizing CsPb_0.5Sn_0.5I₂Br is proposed to realize high‐efficiency PSCs via antioxidant tea polyphenol (TP). It is found that TP can not only slow down the oxidation of Sn²⁺ but also regulate perovskite film crystallization during the formation of perovskite films via coordination interaction, leading to a reduced density of defects and an enlarged open‐circuit voltage. The resultant perovskite solar cell using CsPb_0.5Sn_0.5I₂Br (TP) with an all‐inorganic mesoscopic framework of FTO/c‐TiO₂/m‐TiO₂/Al₂O₃/NiO/carbon achieves an impressive power conversion efficiency of 8.10% with high stability.

In this review, the recent developments in understanding the structural evolution of halide perovskites during both formation and degradation using in situ and operando X‐ray scattering techniques are discussed. The benefit of this experimental approach in contrast to ex situ characterization is highlighted and emphasis is laid on the encouraging progress made in terms of upscaling and stability.

Abstract

This review provides an update on the progress in understanding formation and degradation mechanisms in halide perovskites for photovoltaic applications, as supported by in situ and operando X‐ray scattering techniques. The value of these real‐time analyses is particularly high for gaining insights into the structural evolution during crystal formation and decomposition upon exposure to external stress factors. This type of analysis reveals the pathways between starting and end points of a process rather than being limited to comparing states before and after the process. Special attention is put on the successful efforts toward upscaling including deposition techniques that are compatible to roll‐to‐roll processing. These processes are realized using fast annealing procedures. The development of these processes strongly benefited from in situ studies exploring the direct transition from precursor to perovskite without going through observable crystalline intermediate phases. A particular focus of this review is the benefit of using in situ and operando X‐ray scattering techniques to better understand and ultimately improve device stability. The difference between structural stability of thin films and structural stability under device operation is highlighted, convincingly demonstrating the indispensability of operando studies.

This work investigates the effect of applied stack pressure on lithium metal containing all‐solid‐state batteries. Using characterization techniques to probe failure mechanisms, it is found that above a critical stack pressure, the cells will eventually and predictably fail. Ultimately, determining an optimal stack pressure is crucial to allow Li metal cycling at room temperature.

Abstract

All‐solid‐state batteries are expected to enable batteries with high energy density with the use of lithium metal anodes. Although solid electrolytes are believed to be mechanically strong enough to prevent lithium dendrites from propagating, various reports today still show cell failure due to lithium dendrit growth at room temperature. While cell parameters such as current density, electrolyte porosity, and interfacial properties have been investigated, mechanical properties of lithium metal and the role of applied stack pressure on the shorting behavior are still poorly understood. Here, failure mechanisms of lithium metal are investigated in all‐solid‐state batteries as a function of stack pressure, and in situ characterization of the interfacial and morphological properties of the buried lithium is conducted in solid electrolytes. It is found that a low stack pressure of 5 MPa allows reliable plating and stripping in a lithium symmetric cell for more than 1000 h, and a Li | Li₆PS₅Cl | LiNi_0.80Co_0.15Al_0.05O₂ full cell, plating more than 4 µm of lithium per charge, is able to cycle over 200 cycles at room temperature. These results suggest the possibility of enabling the lithium metal anode in all‐solid‐state batteries at reasonable stack pressures.

Research on compositional engineering can realize power conversion efficiency (PCE) over 25%. Interfacial engineering along with optimal perovskite solar cell device structure is expected to lead to stable and theoretical PCE over 30%.

Abstract

Discovery of the 9.7% efficiency, 500 h stable solid‐state perovskite solar cell (PSC) in 2012 triggered off a wave of perovskite photovoltaics. As a result, a certified power conversion efficiency (PCE) of 25.2% was recorded in 2019. Publications on PSCs have increased exponentially since 2012 and the total number of publications reached over 13 200 as of August 2019. PCE has improved by developing device structures from mesoscopic sensitization to planar p‐i‐n (or n‐i‐p) junction and by changing composition from MAPbI₃ to FAPbI₃‐based mixed cations and/or mixed anion perovskites. Long‐term stability has been significantly improved by interfacial engineering with hydrophobic materials or the 2D/3D concept. Although small area cells exhibit superb efficiency, scale‐up technology is required toward commercialization. In this review, research direction toward large‐area, stable, high efficiency PSCs is emphasized. For large‐area perovskite coating, a precursor solution is equally important as coating methods. Precursor engineering and formulation of the precursor solution are described. For hysteresis‐less, stable, and higher efficiency PSCs, interfacial engineering is one of the best ways as defects can be effectively passivated and thereby nonradiative recombination is efficiently reduced. Methodologies are introduced to minimize interfacial and grain boundary recombination.

Highly efficient and stable perovskite solar cells are fabricated utilizing perovskite/Ag‐graphene in the active layer and SrTiO₃/Al₂O₃‐graphene in the electron transport layer. This composites‐based device not only improves charge transport and thermal‐ and photostability but also suppresses moisture penetration, ion migration, and recombination, resulting in remarkable long‐term stability, sustaining ≈93% of initial power conversion efficiency over 300 d under ambient conditions.

Abstract

For practical use of perovskite solar cells (PSCs) the instability issues of devices, attributed to degradation of perovskite molecules by moisture, ions migration, and thermal‐ and light‐instability, have to be solved. Herein, highly efficient and stable PSCs based on perovskite/Ag‐reduced graphene oxide (Ag‐rGO) and mesoporous Al₂O₃/graphene (mp‐AG) composites are reported. The mp‐AG composite is conductive with one‐order of magnitude higher mobility than mp‐TiO₂ and used for electron transport layer (ETL). Compared to the mp‐TiO₂ ETL based cells, the champion device based on perovskite/Ag‐rGO and SrTiO₃/mp‐AG composites shows overall a best performance (i.e., V _OC = 1.057 V, J _SC = 25.75 mA cm⁻², fill factor (FF) = 75.63%, and power conversion efficiency (PCE) = 20.58%). More importantly, the champion device without encapsulation exhibits not only remarkable thermal‐ and photostability but also long‐term stability, retaining 97–99% of the initial values of photovoltaic parameters and sustaining ≈93% of initial PCE over 300 d under ambient conditions.

A novel design for all‐inorganic perovskite solar cells with a modified electron transporting layer facilitates excellent thermal‐air stability. This study demonstrates a dynamic‐hot air method with Mn²⁺ incorporated CsPbI₂Br perovskite based on low temperature processed MgZnO which enables higher thermal‐air stability.

Abstract

The high thermal stability and facile synthesis of CsPbI₂Br all‐inorganic perovskite solar cells (AI‐PSCs) have attracted tremendous attention. As far as electron‐transporting layers (ETLs) are concerned, low temperature processing and reduced interfacial recombination centers through tunable energy levels determine the feasibility of the perovskite devices. Although the TiO₂ is the most popular ETL used in PSCs, its processing temperature and moderate electron mobility hamper the performance and feasibility. Herein, the highly stable, low‐temperature processed MgZnO nanocrystal‐based ETLs for dynamic hot‐air processed Mn²⁺ incorporated CsPbI2Br AI‐PSCs are reported. By holding its regular planar “n–i–p” type device architecture, the MgZnO ETL and poly(3‐hexylthiophene‐2,5‐diyl) hole transporting layer, 15.52% power conversion efficiency (PCE) is demonstrated. The thermal‐stability analysis reveals that the conventional ZnO ETL‐based AI‐PSCs show a serious instability and poor efficiency than the Mg²⁺ modified MgZnO ETLs. The photovoltaic and stability analysis of this improved photovoltaic performance is attributed to the suitable wide‐bandgap, low ETL/perovskite interface recombination, and interface stability by Mg²⁺ doping. Interestingly, the thermal stability analysis of the unencapsulated AI‐PSCs maintains >95% of initial PCE more than 400 h at 85 °C for MgZnO ETL, revealing the suitability against thermal degradation than conventional ZnO ETL.

The power conversion efficiency of inorganic perovskite solar cells (PSCs) is still low compared with hybrid PSCs. The use of lithium fluoride on SnO₂ and PbCl₂ additive in perovskite is reported for reducing the charge recombination; 18.64% efficiency of CsPbI_3–x Br _x solar cells is demonstrated; and the devices show over than 1000 h light soaking stability.

Abstract

Cesium‐based inorganic perovskite solar cells (PSCs) are promising due to their potential for improving device stability. However, the power conversion efficiency of the inorganic PSCs is still low compared with the hybrid PSCs due to the large open‐circuit voltage (V _OC) loss possibly caused by charge recombination. The use of an insulated shunt‐blocking layer lithium fluoride on electron transport layer SnO₂ for better energy level alignment with the conduction band minimum of the CsPbI_{3‐ x} Br _x and also for interface defect passivation is reported. In addition, by incorporating lead chloride in CsPbI_{3‐ x} Br _x precursor, the perovskite film crystallinity is significantly enhanced and the charge recombination in perovksite is suppressed. As a result, optimized CsPbI_{3‐ x} Br _x PSCs with a band gap of 1.77 eV exhibit excellent performance with the best V _OC as high as 1.25 V and an efficiency of 18.64%. Meanwhile, a high photostability with a less than 6% efficiency drop is achieved for CsPbI_{3‐ x} Br _x PSCs under continuous 1 sun equivalent illumination over 1000 h.

A near‐infrared (NIR)‐harvesting perovskite solar cell with a power‐conversion efficiency of 21.6% and an operational half‐life of 1900 h is achieved by directly incorporating a multifunctional organic semiconductor that both extends light absorption and passivates defects in the perovskite active layer.

Abstract

Typical lead‐based perovskites solar cells show an onset of photogeneration around 800 nm, leaving plenty of spectral loss in the near‐infrared (NIR). Extending light absorption beyond 800 nm into the NIR should increase photocurrent generation and further improve photovoltaic efficiency of perovskite solar cells (PSCs). Here, a simple and facile approach is reported to incorporate a NIR‐chromophore that is also a Lewis‐base into perovskite absorbers to broaden their photoresponse and increase their photovoltaic efficiency. Compared with pristine PSCs without such an organic chromophore, these solar cells generate photocurrent in the NIR beyond the band edge of the perovskite active layer alone. Given the Lewis‐basic nature of the organic semiconductor, its addition to the photoactive layer also effectively passivates perovskite defects. These films thus exhibit significantly reduced trap densities, enhanced hole and electron mobilities, and suppressed illumination‐induced ion migration. As a consequence, perovskite solar cells with organic chromophore exhibit an enhanced efficiency of 21.6%, and substantively improved operational stability under continuous one‐sun illumination. The results demonstrate the potential generalizability of directly incorporating a multifunctional organic semiconductor that both extends light absorption and passivates surface traps in perovskite active layers to yield highly efficient and stable NIR‐harvesting PSCs.

A δ‐CsPbI₃ intermediate phase growth (IPG)‐assisted sequential deposition strategy is developed in this work, which not only achieves controllable Cs⁺ incorporation and enlarged perovskite grains, but also manipulates the crystallization, modulates the bandgap, and improves the stability of the final perovskite film. This CsPbI₃‐IPG is a facile and effective strategy to obtain large‐grain Cs⁺ incorporated perovskite films via sequential deposition.

Abstract

Cs/FA/MA triple cation perovskite films have been well developed in the antisolvent dripping method, attributable to its outstanding photovoltaic and stability performances. However, a facile and effective strategy is still lacking for fabricating high‐quality large‐grain triple cation perovskite films via sequential deposition method a, which is one of the key technologies for high efficiency perovskite solar cells. To address this issue, a δ‐CsPbI₃ intermediate phase growth (CsPbI₃‐IPG) assisted sequential deposition method is demonstrated for the first time. The approach not only achieves incorporation of controllable cesium into (FAPbI₃)_1–x (MAPbBr₃)_x perovskite, but also enlarges the perovskite grains, manipulates the crystallization, modulates the bandgap, and improves the stability of final perovskite films. The photovoltaic performances of the devices based on these Cs/FA/MA perovskite films with various amounts of the δ‐CsPbI₃ intermediate phase are investigated systematically. Benefiting from moderate cesium incorporation and intermediate phase‐assisted grain growth, the optimized Cs/FA/MA perovskite solar cells exhibit a significantly improved power conversion efficiency and operational stability of unencapsulated devices. This facile strategy provides new insights into the compositional engineering of triple or quadruple cation perovskite materials with enlarged grains and superior stability via a sequential deposition method.

Although high power conversion efficiency of up to 23.3% is certified for perovskite solar cells (PSCs), it is still far from the theoretical Shockley–Queisser limit efficiency (30.5%). Nonradiative recombination and charge back transfer at interfaces are mainly responsible for conversion loss. Interface engineering is the most important approach toward the theoretical efficiency in PSCs.

Abstract

Organic–inorganic hybrid perovskite materials are receiving increasing attention and becoming star materials on account of their unique and intriguing optical and electrical properties, such as high molar extinction coefficient, wide absorption spectrum, low excitonic binding energy, ambipolar carrier transport property, long carrier diffusion length, and high defects tolerance. Although a high power conversion efficiency (PCE) of up to 22.7% is certified for perovskite solar cells (PSCs), it is still far from the theoretical Shockley–Queisser limit efficiency (30.5%). Obviously, trap‐assisted nonradiative (also called Shockley–Read–Hall, SRH) recombination in perovskite films and interface recombination should be mainly responsible for the above efficiency distance. Here, recent research advancements in suppressing bulk SRH recombination and interface recombination are systematically investigated. For reducing SRH recombination in the films, engineering perovskite composition, additives, dimensionality, grain orientation, nonstoichiometric approach, precursor solution, and post‐treatment are explored. The focus herein is on the recombination at perovskite/electron‐transporting material and perovskite/hole‐transporting material interfaces in normal or inverted PSCs. Strategies for suppressing bulk and interface recombination are described. Additionally, the effect of trap‐assisted nonradiative recombination on hysteresis and stability of PSCs is discussed. Finally, possible solutions and reasonable prospects for suppressing recombination losses are presented.

The properties of excitons and photogenerated charge carriers in metal halide perovskites (MHPs) are explored. The properties of excitons including the exciton binding energy, exciton dynamics, and exciton–photon and exciton–phonon coupling, are discussed. The properties of photogenerated free charge carriers in MHPs such as diffusion length, mobility, and recombination are described. A brief review of recent applications is also demonstrated.

Abstract

Metal halide perovskites (MHPs) have recently attracted great attention from the scientific community due to their excellent photovoltaic performance as well as their tremendous potential for other optoelectronic applications such as light‐emitting diodes, lasers, and photodetectors. Despite the rapid progress in device applications, a solid understanding of the photophysical properties behind the device performance is highly desirable for MHPs. Here, the properties of excitons and photogenerated charge carriers in MHPs are explored. The unique dielectric constant properties, crystal–liquid duality, and fundamental optical processes of MHPs are first discussed. The properties of excitons and related phenomena in MHPs are then detailed, including the exciton binding energy determined by various methods and their influence factors, exciton dynamics, exciton–photon coupling and related applications, and exciton–phonon coupling in MHPs. The properties of photogenerated free charge carriers in MHPs such as the carrier diffusion length, mobility, and recombination are described. Recent progress in various applications is also demonstrated. Finally, a conclusion and perspectives of future studies for MHPs are presented.

Inorganic and layered perovskites have broadened research paradigm for a range of optoelectronic devices. Their unique electronic and photophysical properties show that they are an excellent material, leading forefronts of solar cells, light‐emitting diodes, photodetectors, lasers, and beyond. An overview of key research activities for these devices is provided and challenges for their future research are identified.

Abstract

Organic–inorganic halide perovskites are making breakthroughs in a range of optoelectronic devices. Reports of >23% certified power conversion efficiency in photovoltaic devices, external quantum efficiency >21% in light‐emitting diodes (LEDs), continuous‐wave lasing and ultralow lasing thresholds in optically pumped lasers, and detectivity in photodetectors on a par with commercial GaAs rivals are being witnessed, making them the fastest ever emerging material technology. Still, questions on their toxicity and long‐term stability raise concerns toward their market entry. The intrinsic instability in these materials arises due to the organic cation, typically the volatile methylamine (MA), which contributes to hysteresis in the current–voltage characteristics and ion migration. Alternative inorganic substitutes to MA, such as cesium, and large organic cations that lead to a layered structure, enhance structural as well as device operational stability. These perovskites also provide a high exciton binding energy that is a prerequisite to enhance radiative emission yield in LEDs. The incorporation of inorganic and layered perovskites, in the form of polycrystalline films or as single‐crystalline nanostructure morphologies, is now leading to the demonstration of stable devices with excellent performance parameters. Herein, key developments made in various optoelectronic devices using these perovskites are summarized and an outlook toward stable yet efficient devices is presented.

The photochemistry of halide‐related defects affects the optoelectronic properties of lead–halide perovskite semiconductors and their reactivity to external stimuli such as light and environmental molecules.

Abstract

The presence of various types of chemical interactions in metal‐halide perovskite semiconductors gives them a characteristic “soft” fluctuating structure, prone to a wide set of defects. Understanding of the nature of defects and their photochemistry is summarized, which leverages the cooperative action of density functional theory investigations and accurate experimental design. This knowledge is used to describe how defect activity determines the macroscopic properties of the material and related devices. Finally, a discussion of the open questions provides a path towards achieving an educated prediction of device operation, necessary to engineer reliable devices.

Rapid advancement of perovskite solar cells confronts the challenges of reliable measurement, which is important for data analysis and results reproduction. Major measurement methods and the key factors affecting evaluation are summarized. A measurement proposal is provided to help researchers obtain reliable measurement results close to those certified by public test centers.

Abstract

Perovskite solar cells (PSCs) have undergone an incredibly fast development and attracted intense attention worldwide owing to their high efficiency and low‐cost fabrication. However, it is challenging to make a reliable measurement of PSCs, which creates great difficulty for researchers to compare and reproduce published results. Herein, the major measurement methods and key factors affecting evaluation of PSCs are summarized, such as hysteresis in current–voltage measurement, calibration of solar simulators for less mismatch in spectra and light intensity, and the area for the calculation of current density and power conversion efficiency. PSCs are also compared with n–i–p or p–i–n structures that exhibit different feedback under the same measurement methods. Finally, a measurement proposal is provided to help researchers obtain reliable measurement results close to those certified by public test centers.

The latest breakthroughs in interface and defect engineering as applied to metal halide perovskite solar cells and light‐emitting diodes (LEDs) are reviewed in order to shed light on their necessity and importance in tuning the optoelectronic properties of devices in an attempt to realize the best‐performing solar cells and LEDs.

Abstract

Metal halide perovskites have been in the limelight in recent years due to their enormous potential for use in optoelectronic devices, owing to their unique combination of properties, such as high absorption coefficient, long charge‐carrier diffusion lengths, and high defect tolerance. Perovskite‐based solar cells and light‐emitting diodes (LEDs) have achieved remarkable breakthroughs in a comparatively short amount of time. As of writing, a certified power conversion efficiency of 22.7% and an external quantum efficiency of over 10% have been achieved for perovskite solar cells and LEDs, respectively. Interfaces and defects have a critical influence on the properties and operational stability of metal halide perovskite optoelectronic devices. Therefore, interface and defect engineering are crucial to control the behavior of the charge carriers and to grow high quality, defect‐free perovskite crystals. Herein, a comprehensive review of various strategies that attempt to modify the interfacial characteristics, control the crystal growth, and understand the defect physics in metal halide perovskites, for both solar cell and LED applications, is presented. Lastly, based on the latest advances and breakthroughs, perspectives and possible directions forward in a bid to transcend what has already been achieved in this vast field of metal halide perovskite optoelectronic devices are discussed.

Low‐toxicity tin‐based perovskites have excellent optical and electrical properties, and are a good alternative for lead‐based perovskites. However, the performance and stability of tin‐based perovskites are not comparable. The properties of tin‐based perovskite films and the performance of tin‐based perovskite solar cells are reviewed. The current challenges and a future outlook for Sn‐based perovskites are discussed.

Abstract

The tremendous interest focused on organic–inorganic halide perovskites since 2012 derives from their unique optical and electrical properties, which make them excellent photovoltaic materials. Pb‐based halide perovskite solar cells, in particular, currently stand at a record efficiency of ≈23%, fulfilling their potential toward commercialization. However, because of the toxicity concerns of Pb‐based perovskite solar cells, their market prospects are hindered. In principle, Pb can be replaced with other less‐toxic, environmentally benign metals. Sn‐based perovskites are thus the far most promising alternative due to their very similar and perhaps even superior semiconductor characteristics. After years of effort invested in Sn‐based halide perovskites, sufficient breakthroughs have finally been achieved that make them the next runners up to the Pb halide perovskites. To help the reader better understand the nature of Sn‐based halide perovskites, their optical and electrical properties are systematically discussed. Recent progress in Sn‐based perovskite solar cells, focusing mainly on film fabrication methods and different device architectures, and highlighting roadblocks to progress and opportunities for future work are reviewed. Finally, a brief overview of mixed Sn/Pb‐based systems with their anomalous yet beneficial optical trends are discussed. The current challenges and a future outlook for Sn‐based perovskites are discussed.

Although high power conversion efficiency of up to 23.3% is certified for perovskite solar cells (PSCs), it is still far from the theoretical Shockley–Queisser limit efficiency (30.5%). Nonradiative recombination and charge back transfer at interfaces are mainly responsible for conversion loss. Interface engineering is the most important approach toward the theoretical efficiency in PSCs.

Abstract

Organic–inorganic hybrid perovskite materials are receiving increasing attention and becoming star materials on account of their unique and intriguing optical and electrical properties, such as high molar extinction coefficient, wide absorption spectrum, low excitonic binding energy, ambipolar carrier transport property, long carrier diffusion length, and high defects tolerance. Although a high power conversion efficiency (PCE) of up to 22.7% is certified for perovskite solar cells (PSCs), it is still far from the theoretical Shockley–Queisser limit efficiency (30.5%). Obviously, trap‐assisted nonradiative (also called Shockley–Read–Hall, SRH) recombination in perovskite films and interface recombination should be mainly responsible for the above efficiency distance. Here, recent research advancements in suppressing bulk SRH recombination and interface recombination are systematically investigated. For reducing SRH recombination in the films, engineering perovskite composition, additives, dimensionality, grain orientation, nonstoichiometric approach, precursor solution, and post‐treatment are explored. The focus herein is on the recombination at perovskite/electron‐transporting material and perovskite/hole‐transporting material interfaces in normal or inverted PSCs. Strategies for suppressing bulk and interface recombination are described. Additionally, the effect of trap‐assisted nonradiative recombination on hysteresis and stability of PSCs is discussed. Finally, possible solutions and reasonable prospects for suppressing recombination losses are presented.

Halide perovskites exhibit extraordinary properties of slow hot‐carrier cooling, long‐range hot‐carrier transport, and efficient hot‐carrier extraction, and are capable of unlocking disruptive high‐efficiency hot‐carrier photovoltaics which will overcome the Shockley–Queisser limit. The intricate photophysical mechanisms behind the novel phenomena are distilled, an engineering and developmental toolkit is assembled, and the challenges and opportunities in this fledging area are examined.

Abstract

Rapid hot‐carrier cooling is a major loss channel in solar cells. Thermodynamic calculations reveal a 66% solar conversion efficiency for single junction cells (under 1 sun illumination) if these hot carriers are harvested before cooling to the lattice temperature. A reduced hot‐carrier cooling rate for efficient extraction is a key enabler to this disruptive technology. Recently, halide perovskites emerge as promising candidates with favorable hot‐carrier properties: slow hot‐carrier cooling lifetimes several orders of magnitude longer than conventional solar cell absorbers, long‐range hot‐carrier transport (up to ≈600 nm), and highly efficient hot‐carrier extraction (up to ≈83%). This review presents the developmental milestones, distills the complex photophysical findings, and highlights the challenges and opportunities in this emerging field. A developmental toolbox for engineering the slow hot‐carrier cooling properties in halide perovskites and prospects for perovskite hot‐carrier solar cells are also discussed.

The ultraslow cooling of hot carriers in a hybrid lead halide perovskite is intimately related to its dielectric function, which is responsible for the order‐of‐magnitude decrease in the Coulomb potential on the sub‐picosecond timescale. This dynamic screening reduces hot‐carrier scattering with longitudinal optical phonons, leading to partial retention of excess electronic energy on longer timescales.

Abstract

Among the exceptional properties of lead halide perovskites (LHPs) is the ultraslow cooling of hot carriers. Carrier densities below the Mott density for large polarons (≤ ≈10¹⁸ cm⁻³) are focused on here. As in other semiconductors, a nascent hot electron distribution initially cools down via emission of longitudinal optical (LO) phonons on the 10⁻¹⁴–10⁻¹³ s timescale. What distinguishes LHPs from conventional semiconductors is the exceptionally efficient screening in the former. The dielectric screening in LHPs on the 10⁻¹³ s timescale results in an order‐of‐magnitude reduction in the Coulomb potential upon the formation of a large polaron, likely with ferroelectric‐like local ordering. Further LO‐phonon emission is inhibited, and this leads to partial retention of hot electron energy on the 10⁻¹² s timescale, more so in hybrid LHPs than in their all‐inorganic counterparts. Further cooling of hot polarons occurs on the 10⁻¹⁰ s timescale, and this can be attributed to the slow diffusion of heat out of the large polaron volume due to the low thermal conductivity of LHPs. Like other carrier properties, slow hot carrier cooling in LHPs can be intimately related to efficient screening in a soft, anharmonic, and dynamically disordered lattice.

Lead‐halide perovskites have demo‐nstrated rapid rises in optoelectronic device performance, which directly links to their efficient luminescence properties. The current understanding of the physics of light emission in perovskites is discussed, along with current outstanding challenges and opportunities to push device performances beyond existing technologies.

Abstract

Light emission is a critical property that must be maximized and controlled to reach the performance limits in optoelectronic devices such as photovoltaic solar cells and light‐emitting diodes. Halide perovskites are an exciting family of materials for these applications owing to uniquely promising attributes that favor strong luminescence in device structures. Herein, the current understanding of the physics of light emission in state‐of‐the‐art metal‐halide perovskite devices is presented. Photon generation and management, and how these can be further exploited in device structures, are discussed. Key processes involved in photoluminescence and electroluminescence in devices as well as recent efforts to reduce nonradiative losses in neat films and interfaces are discussed. Finally, pathways toward reaching device efficiency limits and how the unique properties of perovskites provide a tremendous opportunity to significantly disrupt both the power generation and lighting industries are outlined.

The high‐performing single‐junction organic solar cell blend, PM6:Y6, is examined to obtain an in‐depth understanding of the voltage losses, and charge recombination and extraction dynamics. The devices exhibit remarkable extraction coupled with moderate recombination losses. This behavior can most likely be credited to a beneficial morphology as evidenced by atomically resolved ¹⁹F magic‐angle‐spinning solid‐state NMR analysis.

Abstract

The highly efficient single‐junction bulk‐heterojunction (BHJ) PM6:Y6 system can achieve high open‐circuit voltages (V _OC) while maintaining exceptional fill‐factor (FF) and short‐circuit current (J _SC) values. With a low energetic offset, the blend system is found to exhibit radiative and non‐radiative recombination losses that are among the lower reported values in the literature. Recombination and extraction dynamic studies reveal that the device shows moderate non‐geminate recombination coupled with exceptional extraction throughout the relevant operating conditions. Several surface and bulk characterization techniques are employed to understand the phase separation, long‐range ordering, as well as donor:acceptor (D:A) inter‐ and intramolecular interactions at an atomic‐level resolution. This is achieved using photo‐conductive atomic force microscopy, grazing‐incidence wide‐angle X‐ray scattering, and solid‐state ¹⁹F magic‐angle‐spinning NMR spectroscopy. The synergy of multifaceted characterization and device physics is used to uncover key insights, for the first time, on the structure–property relationships of this high‐performing BHJ blend. Detailed information about atomically resolved D:A interactions and packing reveals that the high performance of over 15% efficiency in this blend can be correlated to a beneficial morphology that allows high J _SC and FF to be retained despite the low energetic offset.

In article number https://doi.org/10.1002/adma.2019044941904494, Yueh‐Lin Loo and co‐workers demonstrate a near‐infrared‐harvesting perovskite solar cell with enhanced power‐conversion efficiency as high as 21.6% and improved stability, with an operational half‐life of 1900 h, by directly incorporating a multifunctional organic semiconductor that both extends light absorption and passivates defects in the perovskite active layers. This work provides a promising approach to prepare highly efficient and stable perovskites solar cells and opens a new application field for the rational design of narrow‐bandgap organic semiconductors.