Imaging Spatial Variations of Optical Bandgaps in Perovskite Solar Cells

A fast, nondestructive, camera‐based method to capture optical bandgap images of perovskite solar cells (PSCs) with micrometer‐scale spatial resolution is developed. This imaging technique utilizes well‐defined and relatively symmetrical band‐to‐band luminescence spectra emitted from perovskite materials, whose spectral peak locations coincide with absorption thresholds and thus represent their optical bandgaps. The technique is employed to capture relative variations in optical bandgaps across various PSCs, and to resolve optical bandgap inhomogeneity within the same device due to material degradation and impurities. Degradation and impurities are found to both cause optical bandgap shifts inside the materials. The results are confirmed with micro‐photoluminescence spectroscopy scans. The excellent agreement between the two techniques opens opportunities for this imaging concept to become a quantified, high spatial resolution, large‐area characterization tool of PSCs. This development continues to strengthen the high value of luminescence imaging for the research and development of this photovoltaic technology.     

Lessons Learnt from Spatially Resolved Electro‐ and Photoluminescence Imaging: Interfacial Delamination in CH3NH3PbI3 Planar Perovskite Solar Cells upon Illumination

The influence of illumination on the long‐term performance of planar structured perovskite solar cells (PSCs) is investigated using fast and spatially resolved luminescence imaging. The authors analyze the effect of illuminated current density–voltage (J–V) and light‐soaking measurements on pristine PSCs by providing visual evidence for the spatial inhomogeneous evolution of device performance. Regions that are exposed to light initially produce stronger electroluminescence signals than surrounding unilluminated regions, mainly due to a lower contact resistance and, possibly, higher charge collection efficiency. Over a period of several days, however, these initially illuminated regions appear to degrade more quickly despite the device being stored in a dark, moisture‐ and oxygen‐free environment. Using transmission electron microscopy, this accelerated degradation is attributed to delamination between the perovskite and the titanium dioxide (TiO₂) layer. An ion migration mechanism is proposed for this delamination process, which is in accordance with previous current–voltage hysteresis observations. These results provide evidence for the intrinsic instability of CH₃NH₃PbI₃‐based devices under illumination and have major implications for the design of PSCs from the standpoint of long‐term performance and stability.     

Spatially Resolved Performance Analysis for Perovskite Solar Cells

This review explores the current state of the art in spatially resolved characterization of mixed‐halide perovskite solar cells. As the size of perovskite cells and modules continues to grow, quantification of the spatial distribution of key cell parameters will become increasingly valuable in predicting ultimate cell‐level performance and tracking process homogeneity. Here, both high resolution microscopic approaches using scanning techniques and camera‐based methods for full‐area cell and/or module analysis are discussed. The value of this local data in predicting performance losses at the cell level is particularly emphasized. Measurable physical parameters sensitive to losses of voltage, current, fill factor, and efficiency are discussed together with selected experimental results. It is demonstrated that a combination of spatially resolved cell parameter mapping/imaging can be used to quantitatively discriminate various loss contributions at high resolution. The impact and control of inhomogeneities become particularly important when upscaling from small devices to large formats compatible with industrial mass production.     

Luminescence Imaging Characterization of Perovskite Solar Cells: A Note on the Analysis and Reporting the Results

In this essay, the authors use two properly encapsulated high‐efficiency mesoscopic perovskite solar cells (PSCs), which use a state‐of‐the‐art perovskite composition (HC(NH₂)₂PbI₃)_0.85(CH₃NH₃PbBr₃)_0.15 with excess PbI₂ as the active layer, to demonstrate the potential effect of dynamical electroluminescence responses on the analysis and interpretation of PSCs electrical characteristic. The essay does not aim to determine how to overcome this issue, nor to investigate its physical/chemical origin, although tentative propositions are made; but rather, to warn researchers in the field about the interpretation and reporting the results obtained from luminescence imaging measurements and the effect of image collection timing on the results. This is a critical message since the authors predict that luminescence imaging techniques will soon become one of the key tools for PSCs characterization, both for long‐term stability assessment and fabrication process optimization.     

Perovskite Solar Cell Stability in Humid Air: Partially Reversible Phase Transitions in the PbI2‐CH3NH3I‐H2O System

After rapid progress over the past five years, organic–inorganic perovskite solar cells (PSCs) currently exhibit photoconversion efficiencies comparable to the best commercially available photovoltaic technologies. However, instabilities in the materials and devices, primarily due to reactions with water, have kept PSCs from entering the marketplace. Here, laser beam induced current imaging is used to investigate the spatial and temporal evolution of the quantum efficiency of perovskite solar cells under controlled humidity conditions. Several interesting mechanistic aspects are revealed as the degradation proceeds along a four‐stage process. Three of the four stages can be reversed, while the fourth stage leads to irreversible decomposition of the photoactive perovskite material. A series of reactions in the PbI₂‐CH₃NH₃I‐H₂O system explains the interplay between the interactions with water and the overall stability. Understanding of the degradation mechanisms of PSCs on a microscopic level gives insight into improving the long‐term stability.     

Outstanding Performance of Hole‐Blocking Layer‐Free Perovskite Solar Cell Using Hierarchically Porous Fluorine‐Doped Tin Oxide Substrate

Perovskite solar cells (PSCs) are of great interest in current photovoltaic research due to their extraordinary power conversion efficiency of ≈20% and boundless potentialities. The high efficiency has been mostly obtained from TiO₂‐based PSCs, where TiO₂ is utilized as a hole‐blocking, mesoporous layer. However, trapped charges and the light‐induced photocatalytic effect of TiO₂ seriously degrade the perovskite and preclude PSCs from being immediately commercialized. Herein, a simplified PSC is successfully fabricated by eliminating the problematic TiO₂ layers, using instead a fluorine‐doped tin oxide (FTO)/perovskite/hole–conductor/Au design. Simultaneously, the sluggish charge extraction at the FTO/perovskite interface is overcome by modifying the surface of the FTO to a porous structure using electrochemical etching. This surface engineering enables a substantial increase in the photocurrent density and mitigation of the hysteretic behavior of the pristine FTO‐based PSC; a remarkable 19.22% efficiency with a low level of hysteresis is obtained. This performance is closely approaching that of conventional PSCs and may facilitate their commercialization due to improved convenience, lower cost, greater stability, and potentially more efficient mass production.     

Processing‐Performance Evolution of Perovskite Solar Cells: From Large Grain Polycrystalline Films to Single Crystals

Solution‐processable halide perovskites have emerged as strong contenders for next‐generation solar cells owing to their favorable optoelectronic properties. To maintain the efficiency momentum of perovskite solar cells (PSCs), development of advanced processing techniques, particularly for the perovskite layer, is imperative. There is a close correlation between the quality of the perovskite layer and its photophysical properties: Highly crystalline large grains with uniform morphology of the perovskite layer and their interface with charge transporters are crucial for achieving high performance. Significant efforts have been dedicated to achieve perovskite films with large grains reaching the millimeter‐scale for high‐efficiency PSCs. Recent work showcases a transition from large grain polycrystalline to single‐crystalline (SC) PSCs made possible by the facile growth of perovskite single crystals. In this review, the recent progress of the large grain polycrystalline PSCs and grain boundary‐free SC‐PSCs is reported, particularly focusing on the recent approach of depositing large‐grained perovskite layers and single crystal growth technique, that have been adopted for fabrication of efficient PSCs. In addition, prospects of SC‐PSCs and their further development in terms of efficiency, device design, scalability, and stability are discussed.     

Hot‐Substrate Deposition of Hole‐ and Electron‐Transport Layers for Enhanced Performance in Perovskite Solar Cells

Charge transport layers play an important role in determining the power conversion efficiencies (PCEs) of perovskite solar cells (PSCs). However, it has proven challenging to produce thin and compact charge transport layers via solution processing techniques. Herein, a hot substrate deposition method capable of improving the morphology of high‐coverage hole‐transport layers (HTLs) and electron‐transport layers (ETLs) is reported. PSC devices using HTLs deposited on a hot substrate show improvement in the open‐circuit voltage (V_oc) from 1.041 to 1.070 V and the PCE from 17.00% to 18.01%. The overall device performance is then further enhanced with the hot substrate deposition of ETLs as the V_oc and PCE reach 1.105 V and 19.16%, respectively. The improved performance can be explained by the decreased current leakage and series resistance, which are present in PSCs with rough and discontinuous HTLs and ETLs.     

Recent Progress on Hole‐Transporting Materials for Emerging Organometal Halide Perovskite Solar Cells

In less than three years, the photovoltaic community has witnessed a rapid emergence of a new class of solid‐state heterojunction solar cells based on solution‐processable organometal halide perovskite absorbers. The energy conversion efficiency of solid‐state perovskite solar cells (PSCs) has been quickly increased to a certified value of 20.1% by the end of 2014 because of their unique characteristics, such as a broad spectral absorption range, large absorption coefficient, high charge carrier mobility and diffusion length. Here, the focus is specifically on recent developments of hole‐transporting materials (HTMs) in PSCs, which are essential components for achieving high solar cell efficiencies. Some fundamentals with regard to PSCs are first presented, including the history of PSCs, device architectures and general operational principles of PSCs as well as various techniques developed for the fabrications of uniform and dense perovskite complexes. A broad range of the state‐of‐the‐art HTMs being used in PSCs are then discussed in detail. Finally, an outlook on the design of more efficient HTMs for highly efficient PSCs is addressed.     

Progress in Tandem Solar Cells Based on Hybrid Organic–Inorganic Perovskites

Owing to their high efficiency, low‐cost solution‐processability, and tunable bandgap, perovskite solar cells (PSCs) made of hybrid organic‐inorganic perovskite (HOIP) thin films are promising top‐cell candidates for integration with bottom‐cells based on Si or other low‐bandgap solar‐cell materials to boost the power conversion efficiency (PCE) beyond the Shockley‐Quiesser (S‐Q) limit. In this review, recent progress in such tandem solar cells based on the emerging PSCs is summarized and reviewed critically. Notable achievements for different tandem solar cell configurations including mechanically‐stacked, optical coupling, and monolithically‐integrated with PSCs as top‐cells are described in detail. Highly‐efficient semitransparent PSC top‐cells with high transmittance in near‐infrared (NIR) region are critical for tandem solar cells. Different types of transparent electrodes with high transmittance and low sheet‐resistance for PSCs are reviewed, which presents a grand challenge for PSCs. The strategies to obtain wide‐bandgap PSCs with good photo‐stability are discussed. The PCE reduction due to reflection loss, parasitic absorption, electrical loss, and current mismatch are analyzed to provide better understanding of the performance of PSC‐based tandem solar cells.     

Progress of Surface Science Studies on ABX3‐Based Metal Halide Perovskite Solar Cells

ABX₃ type metal halide perovskite solar cells (PSCs) have shown efficiencies over 25%, rocketing toward their theoretical limit. To gain the full potential of PSCs relies on the understanding of the device working mechanisms and recombination, the material quality, and the match of energy levels in the device stacks. In this review, the importance of designing PSCs from the viewpoint of surface/interface science studies is presented. For this purpose, recent case studies are discussed to demonstrate how probing of local heterogeneities (e.g., grains, grain boundaries, atomic structure, etc.) in perovskites by surface science techniques can help correlate material properties and PSC device performance. At the solar cell device level with active areas larger than millimeter scale, the ensemble average measurement techniques can characterize the overall average properties of perovskite films as well as their adjacent layers and provide clues to understand better the solar cell parameters. How generation and healing of electronic defects in perovskite films limit the device efficiency, reproducibility, and stability, and induce the time‐dependent transient behavior in the current‐voltage curves are also the central focus of this review. On the basis of these studies, strategies to further improve efficiency and stability, as well as reducing hysteresis are presented.     

Solvent Engineering Boosts the Efficiency of Paintable Carbon‐Based Perovskite Solar Cells to Beyond 14%

Carbon‐based hole transport material (HTM)‐free perovskite solar cells (PSCs) have shown much promise for practical applications because of their high stability and low cost. However, the efficiencies of this kind of PSCs are still relatively low, especially for the simplest paintable carbon‐based PSCs, in comparison with the organic HTM‐based PSCs. This can be imputed to the perovskite deposition methods that are not very suitable for this kind of devices. A solvent engineering strategy based on two‐step sequential method is exploited to prepare a high‐quality perovskite layer for the paintable carbon‐based PSCs in which the solvent for CH₃NH₃I (MAI) solution at the second step is changed from isopropanol (IPA) to a mixed solvent of IPA/Cyclohexane (CYHEX). This mixed solvent not only accelerates the conversion of PbI₂ to CH₃NH₃PbI₃ but also suppresses the Ostwald ripening process resulting in a high‐quality perovskite layer, e.g., pure phase, even surface, and compact capping layer. The paintable carbon‐based PSCs fabricated from IPA/CYHEX solvent exhibits a considerable enhancement in photovoltaic performance and performance reproducibility in comparison with that from pure IPA, especially on fill factor (FF), owing mainly to the better contact of perovskite/carbon interface, lower trap density in perovskite, higher light absorption ability, and faster charge transport of perovskite layer. As a result, the highest power conversion efficiency (PCE) of 14.38% is obtained, which is a record value for carbon‐based HTM‐free PSCs. Furthermore, a PCE of as high as 10% is achieved for the large area device (1 cm²), also the highest of its kind.     

High Electron Affinity Enables Fast Hole Extraction for Efficient Flexible Inverted Perovskite Solar Cells

Inverted perovskite solar cells (PSCs) with low‐temperature processed hole transporting materials (HTMs) suffer from poor performance due to the inferior hole‐extraction capability at the HTM/perovskite interfaces. Here, molecules with controlled electron affinity enable a HTM with conductivity improved by more than ten times and a decreased energy gap between the Fermi level and the valence band from 0.60 to 0.24 eV, leading to the enhancement of hole‐extraction capacity by five times. As a result, the 3,6‐difluoro‐2,5,7,7,8,8‐hexacyanoquinodimethane molecules are used for the first time enhancing open‐circuit voltage (V_oc) and fill factor (FF) of the PSCs, which enable rigid‐and flexible‐based inverted perovskite devices achieving highest power conversion efficiencies of 22.13% and 20.01%, respectively. This new method significantly enhances the V_oc and FF of the PSCs, which can be widely combined with HTMs based on not only NiO_x but also PTAA, PEDOTT:PSS, and CuSCN, providing a new way of realizing efficient inverted PSCs.     

Long‐Lasting Nanophosphors Applied to UV‐Resistant and Energy Storage Perovskite Solar Cells

Recently, considerable progress is achieved in lab prototype perovskite solar cells (PSCs); however, the stability of outdoor applications of PSCs remains a challenge due to the high sensitivity of perovskite material under moist and ultraviolet (UV) light conditions. In this work, the UV photostability of PSC devices is improved by incorporating a photon downshifting layer—SrAl₂O₄: Eu²⁺, Dy³⁺ (SAED)—prepared using the pulsed laser deposition approach. Light‐induced deep trap states in the photoactive layer are depressed, and UV light‐induced device degradation is inhibited after the SAED modification. Optimized power conversion efficiency (PCE) of 17.8% is obtained through the enhanced light harvesting and reduced carrier recombination provided by SAED. More importantly, a solar energy storage effect due to the long‐persistent luminescence of SAED is obtained after light illumination is turned off. The introduction of downconverting material with long‐persistent luminescence in PSCs not only represents a new strategy to improve PCE and light stability by photoconversion from UV to visible light but also provides a new paradigm for solar energy storage.     

A Review on Additives for Halide Perovskite Solar Cells

Additives are widely adopted for efficient, stable, and hysteresis‐free perovskite solar cells and play an important role in various breakthroughs of perovskite solar cells (PSCs). Herein the various additives adopted for PSCs are reviewed and their functioning mechanism and influence on device performance is described. The main roles of additives, modulating morphology of perovskite films, stabilizing phase of formamidinium (FA) and cesium (Cs)‐based perovskites, adjusting energy level alignment in PSCs, suppressing nonradiative recombination in perovskites, eliminating hysteresis, enhancing operational stability of PSCs, are summarized.     

Diffraction‐Grated Perovskite Induced Highly Efficient Solar Cells through Nanophotonic Light Trapping

Achieving light harvesting is crucial for the efficiency of the solar cell. Constructing optical structures often can benefit from micro‐nanophotonic imprinting. Here, a simple and facile strategy is developed to introduce a large area grating structure into the perovskite‐active layer of a solar cell by utilizing commercial optical discs (CD‐R and DVD‐R) and achieve high photovoltaic performance. The constructed diffraction grating on the perovskite active layer realizes nanophotonic light trapping by diffraction and effectively suppresses carrier recombination. Compared to the pristine perovskite solar cells (PSCs), the diffraction‐grating perovskite devices with DVD obtain higher power conversion efficiency and photocurrent density, which are improved from 16.71% and 21.67 mA cm^?2 to 19.71% and 23.11 mA cm^?2. Moreover, the stability of the PSCs with diffraction‐grating‐structured perovskite active layer is greatly enhanced. The method can boost photonics merge into the remarkable perovskite materials for various applications.     

High‐Performance Flexible Perovskite Solar Cells via Precise Control of Electron Transport Layer

Flexible perovskite solar cells (f‐PSCs) have attracted great attention due to their promising commercial prospects. However, the performance of f‐PSCs is generally worse than that of their rigid counterparts. Herein, it is found that the unsatisfactory performance of planar heterojunction (PHJ) f‐PSCs can be attributed to the undesirable morphology of electron transport layer (ETL), which results from the rough surface of the flexible substrate. Precise control over the thickness and morphology of ETL tin dioxide (SnO₂) not only reduces the reflectance of the indium tin oxide (ITO) on polyethylene 2,6‐naphthalate (PEN) substrate and enhances photon collection, but also decreases the trap‐state densities of perovskite films and the charge transfer resistance, leading to a great enhancement of device performance. Consequently, the f‐PSCs, with a structure of PEN/ITO/SnO₂/perovskite/Spiro‐OMeTAD/Ag, exhibit a power conversion efficiency (PCE) up to 19.51% and a steady output of 19.01%. Furthermore, the f‐PSCs show a robust bending resistance and maintain about 95% of initial PCE after 6000 bending cycles at a bending radius of 8 mm, and they present an outstanding long‐term stability and retain about 90% of the initial performance after >1000 h storage in air (10% relative humidity) without encapsulation.     

Inorganic Halide Perovskite Solar Cells: Progress and Challenges

All‐inorganic perovskite semiconductors have recently drawn increasing attention owing to their outstanding thermal stability. Although all‐inorganic perovskite solar cells (PSCs) have achieved significant progress in recent years, they still fall behind their prototype organic–inorganic counterparts owing to severe energy losses. Therefore, there is considerable interest in further improving the performance of all‐inorganic PSCs by synergic optimization of perovskite films and device interfaces. This review article provides an overview of recent progress in inorganic PSCs in terms of lead‐based and lead‐free composition. The physical properties of all‐inorganic perovskite semiconductors as well as the hole/electron transporting materials are discussed to unveil the important role of composition engineering and interface modification. Finally, a discussion of the prospects and challenges for all‐inorganic PSCs in the near future is presented.     

Cold Antisolvent Bathing Derived Highly Efficient Large‐Area Perovskite Solar Cells

Scaling large‐area solar cells is in high demand for the commercialization of perovskite solar cells (PSCs) with a high power‐conversion efficiency (PCE). However, few roll‐to‐roll‐compatible deposition methods for the formation of highly oriented uniform perovskite films are reported. Herein, a facile cold antisolvent bathing approach compatible with large‐area fabrication is introduced. The wet precursor films are submerged in a cold antisolvent bath at 0 °C, and the retarded nucleation and growth kinetics allow highly oriented perovskite to be grown along the [110] and [220] directions, perpendicular to the substrate. The high degree of the preferred crystal orientation benefits the effective charge extraction and reduces the amount of inter‐ and intra‐grain defects inside the perovskite films, improving the PCE from 16.48% (ambient‐bathed solar cell) to 18.50% (cold‐bathed counterpart). The cold antisolvent bathing method is employed for the fabrication of large‐area (8 × 10 cm²) PSCs with uniform photovoltaic device parameters, thereby verifying the scale‐up capability of the method.     

High‐Efficiency CsPbI2Br Perovskite Solar Cells with Dopant‐Free Poly(3‐hexylthiophene) Hole Transporting Layers

CsPbI₂Br is emerging as a promising all‐inorganic material for perovskite solar cells (PSCs) due to its more stable lattice structure and moisture resistance compared to CsPbI₃, although its device performance is still much behind this counterpart. Herein, a preannealing process is developed and systematically investigated to achieve high‐quality CsPbI₂Br films by regulating the nucleation and crystallization of perovskite. The preannealing temperature and time are specifically optimized for a dopant‐free poly(3‐hexylthiophene) (P3HT)‐based device to target dopant‐induced drastic performance degradation for spiro‐OMeTAD‐based devices. The resulting P3HT‐based device exhibits comparable power conversion efficiency (PCE) to spiro‐OMeTAD‐based devices but much enhanced ambient stability with over 95% PCE after 1300 h. A diphenylamine derivative is introduced as a buffer layer to improve the energy‐level mismatch between CsPbI₂Br and P3HT. A record‐high PCE of 15.50% for dopant‐free P3HT‐based CsPbI₂Br PSCs is achieved by alleviating the open‐circuit voltage loss with the buffer layer. These results demonstrate that the preannealing processing together with a suitable buffer layer are applicable strategies for developing dopant‐free P3HT PSCs with high efficiency and stability.