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.     

Correlating Phase Behavior with Photophysical Properties in Mixed‐Cation Mixed‐Halide Perovskite Thin Films

Mixed cation perovskites currently achieve very promising efficiency and operational stability when used as the active semiconductor in thin‐film photovoltaic devices. However, an in‐depth understanding of the structural and photophysical properties that drive this enhanced performance is still lacking. Here the prototypical mixed‐cation mixed‐halide perovskite (FAPbI₃)_0.85(MAPbBr₃)_0.15 is explored, and temperature‐dependent X‐ray diffraction measurements that are correlated with steady state and time‐resolved photoluminescence data are presented. The measurements indicate that this material adopts a pseudocubic perovskite α phase at room temperature, with a transition to a pseudotetragonal β phase occurring at ≈260 K. It is found that the temperature dependence of the radiative recombination rates correlates with temperature‐dependent changes in the structural configuration, and observed phase transitions also mark changes in the gradient of the optical bandgap. The work illustrates that temperature‐dependent changes in the perovskite crystal structure alter the charge carrier recombination processes and photoluminescence properties within such hybrid organic–inorganic materials. The findings have significant implications for photovoltaic performance at different operating temperatures, as well as providing new insight on the effect of alloying cations and halides on the phase behavior of hybrid perovskite materials.     

Localized Traps Limited Recombination in Lead Bromide Perovskites

Traps exert an omnipotent influence over the performance of halide perovskite optoelectronic devices. A clear understanding of the origin and nature of the traps in halide perovskites is the key to controlling them and realizing optimal devices. Herein, the role of localized traps on the optical properties of lead bromide perovskite films is investigated. In the low‐temperature orthorhombic phase of CH₃NH₃PbBr₃ perovskite, band‐edge carrier dynamics exhibit a power‐law decay due to the presence of structural‐disorder‐induced localized traps, which has a depth of ≈40 meV. The continuous distribution of these localized traps gives rise to a broad sub‐band‐gap emission that becomes more prominent in thicker films with a larger trap density. The presence of this emission only from the hybrid organic–inorganic perovskites points to the vital role of organic dipoles in localized trap states formation. This study explicates the nature of these localized traps as well as their nontrivial role in carrier recombination kinetics, which is of fundamental importance in perovskites optoelectronics.     

Soft Template‐Controlled Growth of High‐Quality CsPbI3 Films for Efficient and Stable Solar Cells

The unfavorable morphology and inefficient utilization of phase transition reversibility have limited the high‐temperature‐processed inorganic perovskite films in both efficiency and stability. Here, a simple soft template‐controlled growth (STCG) method is reported by introducing (adamantan‐1‐yl)methanammonium to control the nucleation and growth rate of CsPbI₃ crystals, which gives rise to pinhole‐free CsPbI₃ film with a grain size on a micrometer scale. The STCG‐based CsPbI₃ perovskite solar cell exhibits a power conversion efficiency of 16.04% with significantly reduced defect densities and charge recombination. More importantly, an all‐inorganic solar cell with the architecture fluorine‐doped tin oxide (FTO)/NiO_x/STCG‐CsPbI₃/ZnO/indium‐doped tin oxide (ITO) is successfully fabricated to demonstrate its real advantage in thermal stability. By suppressing the inductive effect of defects during the phase transition and utilizing the unique reversibility of the phase transition for the high‐temperature‐processed CsPbI₃ film, the all‐inorganic solar cell retains 90% of its initial efficiency after 3000 h of continuous light soaking and heating.     

Low Temperature Synthesis of Stable γ‐CsPbI3 Perovskite Layers for Solar Cells Obtained by High Throughput Experimentation

The structural phases and optoelectronic properties of coevaporated CsPbI₃ thin films with a wide range of [CsI]/[PbI₂] compositional ratios are investigated using high throughput experimentation and gradient samples. It is found that for CsI‐rich growth conditions, CsPbI₃ can be synthesized directly at low temperature into the distorted perovskite γ‐CsPbI₃ phase without detectable secondary phases. In contrast, PbI₂‐rich growth conditions are found to lead to the non‐perovskite δ‐phase. Photoluminescence spectroscopy and optical‐pump THz‐probe mapping show carrier lifetimes larger than 75 ns and charge carrier (sum) mobilities larger than 60 cm² V^?1 s^?1 for the γ‐phase, indicating their suitability for high efficiency solar cells. The dependence of the carrier mobilities and luminescence peak energy on the Cs‐content in the films indicates the presence of Schottky defect pairs, which may cause the stabilization of the γ‐phase. Building on these results, p–i–n type solar cells with a maximum efficiency exceeding 12% and high shelf stability of more than 1200 h are demonstrated, which in the future could still be significantly improved, judging on their bulk optoelectronic properties.     

The Rise of Textured Perovskite Morphology: Revolutionizing the Pathway toward High‐Performance Optoelectronic Devices

Halide perovskite materials have achieved overwhelming success in various optoelectronic applications, especially perovskite solar cells and perovskite‐based light‐emitting diodes (P‐LEDs), owing to their outstanding optical and electric properties. It is widely believed that flat and mirror‐like perovskite films are imperative for achieving high device performance, while the potential of other perovskite morphologies, such as the emerging textured perovskite, is overlooked, which leaves plenty of room for further breakthroughs. Compared to flat and mirror‐like perovskites, textured perovskites with unique structures, e.g., coral‐like, maze‐like, column‐like or quasi‐core@shell assemblies, are more efficient at light harvesting and charge extraction, thus revolutionizing the pathways toward ultrahigh performance in perovskite‐based optoelectronic devices. Employing a textured perovskite morphology, the record of external quantum efficiency for P‐LEDs is demonstrated as 21.6%. In this research news, recent progress in the utilization of textured perovskite is summarized, with the emphasis on the preparation strategies and prominent optoelectronic properties. The impact of the textured morphology on light harvesting, carrier dynamic management, and device performance is highlighted. Finally, the challenges and great potential of employing these innovative morphologies in fabricating more efficient optoelectronic devices, or creating a new energy harvesting and conversion regime are also provided.     

Inkjet‐Printed Micrometer‐Thick Perovskite Solar Cells with Large Columnar Grains

Transferring the high power conversion efficiencies (PCEs) of spin‐coated perovskite solar cells (PSCs) on the laboratory scale to large‐area photovoltaic modules requires a significant advance in scalable fabrication methods. Digital inkjet printing promises scalable, material, and cost‐efficient deposition of perovskite thin films on a wide range of substrates and in arbitrary shapes. In this work, high‐quality inkjet‐printed triple‐cation (methylammonium, formamidinium, and cesium) perovskite layers with exceptional thicknesses of >1 µm are demonstrated, enabling unprecedentedly high PCEs > 21% and stabilized power output efficiencies > 18% for inkjet‐printed PSCs. In‐depth characterization shows that the thick inkjet‐printed perovskite thin films deposited using the process developed herein exhibit a columnar crystal structure, free of horizontal grain boundaries, which extend over the entire thickness. A thin film thickness of around 1.5 µm is determined as optimal for PSC for this process. Up to this layer thickness X‐ray photoemission spectroscopy analysis confirms the expected stoichiometric perovskite composition at the surface and shows strong deviations and inhomogeneities for thicker thin films. The micrometer‐thick perovskite thin films exhibit remarkably long charge carrier lifetimes, highlighting their excellent optoelectronic characteristics. They are particularly promising for next‐generation inkjet‐printed perovskite solar cells, photodetectors, and X‐ray detectors.     

Understanding Film Formation Morphology and Orientation in High Member 2D Ruddlesden–Popper Perovskites for High‐Efficiency Solar Cells

2D Ruddlesden–Popper (RP) perovskites have recently emerged as promising candidates for hybrid perovskite photovoltaic cells, realizing power‐conversion efficiencies (PCEs) of over 10% with technologically relevant stability. To achieve solar cell performance comparable to the state‐of‐the‐art 3D perovskite cells, it is highly desirable to increase the conductivity and lower the optical bandgap for enhanced near‐IR region absorption by increasing the perovskite slab thickness. Here, the use of the 2D higher member (n = 5) RP perovskite (n‐butyl‐NH₃)₂(MeNH₃)₄Pb₅I₁₆ in depositing highly oriented thin films from dimethylformamide/dimethylsulfoxide mixtures using the hot‐casting method is reported. In addition, they exhibit superior environmental stability over thin films of their 3D counterpart. These films are assembled into high‐efficiency solar cells with an open‐circuit voltage of ≈1 V and PCE of up to 10%. This is achieved by fine‐tuning the solvent ratio, crystal growth orientation, and grain size in the thin films. The enhanced performance of the optimized devices is ascribed to the growth of micrometer‐sized grains as opposed to more typically obtained nanometer grain size and highly crystalline, densely packed microstructures with the majority of the inorganic slabs preferentially aligned out of plane to the substrate, as confirmed by X‐ray diffraction and grazing‐incidence wide‐angle X‐ray scattering mapping.     

A Bottom‐Up Approach toward All‐Solution‐Processed High‐Efficiency Cu(In,Ga)S2 Photocathodes for Solar Water Splitting

The development of solution‐processable routes to prepare efficient photoelectrodes for water splitting is highly desirable to reduce manufacturing costs. Recently, sulfide chalcopyrites (Cu(In,Ga)S₂) have attracted attention as photocathodes for hydrogen evolution owing to their outstanding optoelectronic properties and their band gap—wider than their selenide counterparts—which can potentially increase the attainable photovoltage. A straightforward and all‐solution‐processable approach for the fabrication of highly efficient photocathodes based on Cu(In,Ga)S₂ is reported for the first time. It is demonstrated that semiconductor nanocrystals can be successfully employed as building blocks to prepare phase‐pure microcrystalline thin films by incorporating different additives (Sb, Bi, Mg) that promote the coalescence of the nanocrystals during annealing. Importantly, the grain size is directly correlated to improved charge transport for Sb and Bi additives, but it is shown that secondary effects can be detrimental to performance even with large grains (for Mg). For optimized electrodes, the sequential deposition of thin layers of n‐type CdS and TiO₂ by solution‐based methods, and platinum as an electrocatalyst, leads to stable photocurrents saturating at 8.0 mA cm^–2 and onsetting at ≈0.6 V versus RHE under AM 1.5G illumination for CuInS₂ films. Electrodes prepared by our method rival the state‐of‐the‐art performance for these materials.     

Effect of Precursor Solution Aging on the Crystallinity and Photovoltaic Performance of Perovskite Solar Cells

Perovskite materials due to their exceptional photophysical properties are beginning to dominate the field of thin‐film optoelectronic devices. However, one of the primary challenges is the processing‐dependent variability in the properties, thus making it imperative to understand the origin of such variations. Here, it is discovered that the precursor solution aging time before it is cast into a thin film, is a subtle but a very important factor that dramatically affects the overall thin‐film formation and crystallinity and therein factors such as grain growth, phase purity, surface uniformity, trap state density, and overall solar cell performance. It is shown that progressive aging of the precursor promotes efficient formation of larger seeds after the fast nucleation of a large density of small seeds. The hot‐casting method then leads to the growth of large grains in uniform thin‐films with excellent crystallinity validated using scanning microscopy images and X‐ray diffraction patterns. The high‐quality films cast from aged solution is ideal for thin‐film photovoltaic device fabrication with reduced shunt current and good charge transport. This observation is a significant step toward achieving highly crystalline thin‐films with reliability in device performance and establishes the subtle but dramatic effect of solution aging before fabricating perovskite thin‐films.     

Simultaneous Contact and Grain‐Boundary Passivation in Planar Perovskite Solar Cells Using SnO2‐KCl Composite Electron Transport Layer

The performance of perovskite solar cells is sensitive to detrimental defects, which are prone to accumulate at the interfaces and grain boundaries of bulk perovskite films. Defect passivation at each region will lead to reduced trap density and thus less nonradiative recombination loss. However, it is challenging to passivate defects at both the grain boundaries and the bottom charge transport layer/perovskite interface, mainly due to the solvent incompatibility and complexity in perovskite formation. Here SnO₂‐KCl composite electron transport layer (ETL) is utilized in planar perovskite solar cells to simultaneously passivate the defects at the ETL/perovskite interface and the grain boundaries of perovskite film. The K and Cl ions at the ETL/perovskite interface passivate the ETL/perovskite contact. Meanwhile, K ions from the ETL can diffuse through the perovskite film and passivate the grain boundaries. An enhancement of open‐circuit voltage from 1.077 to 1.137 V and a corresponding power conversion efficiency increasing from 20.2% to 22.2% are achieved for the devices using SnO₂‐KCl composite ETL. The composite ETL strategy reported herein provides an avenue for defect passivation to further increase the efficiency of perovskite solar cells.     

Vacuum‐Assisted Growth of Low‐Bandgap Thin Films (FA0.8MA0.2Sn0.5Pb0.5I3) for All‐Perovskite Tandem Solar Cells

All‐perovskite multijunction photovoltaics, combining a wide‐bandgap (WBG) perovskite top solar cell (E_G ≈1.6–1.8 eV) with a low‐bandgap (LBG) perovskite bottom solar cell (E_G < 1.3 eV), promise power conversion efficiencies (PCEs) >33%. While the research on WBG perovskite solar cells has advanced rapidly over the past decade, LBG perovskite solar cells lack PCE as well as stability. In this work, vacuum‐assisted growth control (VAGC) of solution‐processed LBG perovskite thin films based on mixed Sn–Pb perovskite compositions is reported. The reported perovskite thin films processed by VAGC exhibit large columnar crystals. Compared to the well‐established processing of LBG perovskites via antisolvent deposition, the VAGC approach results in a significantly enhanced charge‐carrier lifetime. The improved optoelectronic characteristics enable high‐performance LBG perovskite solar cells (1.27 eV) with PCEs up to 18.2% as well as very efficient four‐terminal all‐perovskite tandem solar cells with PCEs up to 23%. Moreover, VAGC leads to promising reproducibility and potential in the fabrication of larger active‐area solar cells up to 1 cm².     

On the Effect of the Amorphous Silicon Microstructure on the Grain Size of Solid Phase Crystallized Polycrystalline Silicon

In this paper the effect of the microstructure of remote plasma‐deposited amorphous silicon films on the grain size development in polycrystalline silicon upon solid‐phase crystallization is reported. The hydrogenated amorphous silicon films are deposited at different microstructure parameter values R* (which represents the distribution of SiH_x bonds in amorphous silicon), at constant hydrogen content. Amorphous silicon films undergo a phase transformation during solid‐phase crystallization and the process results in fully (poly‐)crystallized films. An increase in amorphous film structural disorder (i.e., an increase in R*), leads to the development of larger grain sizes (in the range of 700–1100 nm). When the microstructure parameter is reduced, the grain size ranges between 100 and 450 nm. These results point to the microstructure parameter having a key role in controlling the grain size of the polycrystalline silicon films and thus the performance of polycrystalline silicon solar cells.     

Impact of PbI2 Passivation and Grain Size Engineering in CH3NH3PbI3 Solar Absorbers as Revealed by Carrier‐Resolved Photo‐Hall Technique

With power conversion efficiencies now exceeding 25%, hybrid perovskite solar cells require deeper understanding of defects and processing to further approach the Shockley‐Queisser limit. One approach for processing enhancement and defect reduction involves additive engineering—, e.g., addition of MASCN (MA = methylammonium) and excess PbI₂ have been shown to modify film grain structure and improve performance. However, the underlying impact of these additives on transport and recombination properties remains to be fully elucidated. In this study, a newly developed carrier‐resolved photo‐Hall (CRPH) characterization technique is used that gives access to both majority and minority carrier properties within the same sample and over a wide range of illumination conditions. CRPH measurements on n‐type MAPbI₃ films reveal an order of magnitude increase in carrier recombination lifetime and electron density for 5% excess PbI₂ added to the precursor solution, with little change noted in electron and hole mobility values. Grain size variation (120–2100 nm) and MASCN addition induce no significant change in carrier‐related parameters considered, highlighting the benign nature of the grain boundaries and that excess PbI₂ must predominantly passivate bulk defects rather than defects situated at grain boundaries. This study offers a unique picture of additive impact on MAPbI₃ optoelectronic properties as elucidated by the new CRPH approach.     

Is Excess PbI2 Beneficial for Perovskite Solar Cell Performance?

Unreacted lead iodide is commonly believed to be beneficial to the efficiency of methylammonium lead iodide perovskite based solar cells, since it has been proposed to passivate the defects in perovskite grain boundaries. However, it is shown here that the presence of unreacted PbI₂ results in an intrinsic instability of the film under illumination, leading to the film degradation under inert atmosphere and faster degradation upon exposure to illumination and humidity. The perovskite films without lead iodide have improved stability, but lower efficiency due to inferior film morphology (smaller grain size, the presence of pinholes). Optimization of the deposition process resulted in PbI₂‐free perovskite films giving comparable efficiency to those with excess PbI₂ (14.2 ± 1.3% compared to 15.1 ± 0.9%) Thus, optimization of the deposition process for PbI₂‐free films leads to dense, pinhole‐free, large grain size perovskite films which result in cells with high efficiency without detrimental effects on the film photostability caused by excess PbI₂. However, it should be noted that for encapsulated devices illuminated through the substrate (fluorine‐doped tin oxide glass, TiO₂ film), film photostability is not a key factor in the device degradation.     

Light Absorption and Recycling in Hybrid Metal Halide Perovskite Photovoltaic Devices

The production of highly efficient single‐ and multijunction metal halide perovskite (MHP) solar cells requires careful optimization of the optical and electrical properties of these devices. Here, precise control of CH₃NH₃PbI₃ perovskite layers is demonstrated in solar cell devices through the use of dual source coevaporation. Light absorption and device performance are tracked for incorporated MHP films ranging from ≈67 nm to ≈1.4 µm thickness and transfer‐matrix optical modeling is utilized to quantify optical losses that arise from interference effects. Based on these results, a device with 19.2% steady‐state power conversion efficiency is achieved through incorporation of a perovskite film with near‐optimum predicted thickness (≈709 nm). Significantly, a clear signature of photon reabsorption is observed in perovskite films that have the same thickness (≈709 nm) as in the optimized device. Despite the positive effect of photon recycling associated with photon reabsorption, devices with thicker (>750 nm) MHP layers exhibit poor performance owing to competing nonradiative charge recombination in a “dead‐volume” of MHP. Overall, these findings demonstrate the need for fine control over MHP thickness to achieve the highest efficiency cells, and accurate consideration of photon reabsorption, optical interference, and charge transport properties.     

Emerging Conductive Atomic Force Microscopy for Metal Halide Perovskite Materials and Solar Cells

Metal halide perovskite materials, benefiting from a combination of outstanding optoelectronic properties and low‐cost solution‐preparation processes, show tremendous potential for optoelectronics and photovoltaics. However, the nanoscale inhomogeneities of the electronic properties of perovskite materials cause a number of difficulties, such as recombination, stability, and hysteresis, all of which seriously restrict device performance. Scanning probe microscopy, as a high‐resolution imaging technique, has been widely used to connect local properties and micro‐area morphologies to overall device performance. Conductive atomic force microscopy (C‐AFM) can realize a real‐space visualization of topography coupled with optoelectronic properties on a microscopic scale and thereby is uniquely suited to probe the local effects of perovskite materials and devices. The fundamental principles, alternative operation modes, and development of C‐AFM are comprehensively reviewed, and applications in perovskite solar cells (PSCs) for electronic transport behavior, ion migration and hysteresis, ferroelectric polarization, and facet orientation investigation are discussed. A comprehensive understanding and summary of up‐to‐date applications in PSCs is beneficial to further fully exploit the potential of such an emerging technique, so as to provide a novel and effective approach for perovskite materials analysis.     

Antimony (V) Complex Halides: Lead‐Free Perovskite‐Like Materials for Hybrid Solar Cells

Using bromoantimonate (V) (N‐EtPy)[SbBr₆] as an example, it is demonstrated that ABX₆ compounds can form perovskite‐like 3D crystalline frameworks with short interhalide contacts, enabling advanced optoelectronic characteristics of these materials. The designed compound shows an impressive performance in planar junction solar cells delivering external quantum efficiency of ≈80% and power conversion efficiency of ≈4%, thus being comparable with the conventional perovskite material MAPbBr₃. The discovery of the first perovskite‐like compound ABX₆ exhibiting good photovoltaic performance opens wide opportunities for rational design of novel perovskite‐like semiconductor materials for advanced electronic and photovoltaic applications.     

Lewis‐Adduct Mediated Grain‐Boundary Functionalization for Efficient Ideal‐Bandgap Perovskite Solar Cells with Superior Stability

State‐of‐the‐art perovskite solar cells (PSCs) have bandgaps that are invariably larger than 1.45 eV, which limits their theoretically attainable power conversion efficiency. The emergent mixed‐(Pb, Sn) perovskites with bandgaps of 1.2–1.3 eV are ideal for single‐junction solar cells according to the Shockley–Queisser limit, and they have the potential to deliver higher efficiency. Nevertheless, the high chemical activity of Sn(II) in these perovskites makes it extremely challenging to control their physical properties and chemical stability, thereby leading to PSCs with relatively low PCE and stability. In this work, the authors employ the Lewis‐adduct SnF₂·3FACl additive in the solution‐processing of ideal‐bandgap halide perovskites (IBHPs), and prepare uniform large‐grain perovskite thin films containing continuously functionalized grain boundaries with the stable SnF₂ phase. Such Sn(II)‐rich grain‐boundary networks significantly enhance the physical properties and chemical stability of the IBHP thin films. Based on this approach, PSCs with an ideal bandgap of 1.3 eV are fabricated with a promising efficiency of 15.8%, as well as enhanced stability. The concept of Lewis‐adduct‐mediated grain‐boundary functionalization in IBHPs presented here points to a new chemical route for approaching the Shockley–Queisser limit in future stable PSCs.     

Crystallinity Preservation and Ion Migration Suppression through Dual Ion Exchange Strategy for Stable Mixed Perovskite Solar Cells

The mixed perovskite (FAPbI₃)_1?x (MAPbBr₃)_x , prepared by directly mixing different perovskite components, suffers from phase competition and a low‐crystallinity character, resulting in instability, despite the high efficiency. In this study, a dual ion exchange (DIE) method is developed by treating as‐prepared FAPbI₃ with methylammonium brodide (MABr)/tert‐butanol solution. The converted perovskite thin film shows an optimized absorption edge at 800 nm after reaction time control, and the high crystallinity can be preserved after MABr incorporation. More importantly, it is found that the threshold electrical field to initiate ion migration is greatly increased in DIE perovskite thin film because excess MABr on the surface can effectively heal structural defects located on grain boundaries during the ion exchange process. It contributes to the over‐one‐month moisture stability under ≈65% room humidity (RH) and greatly enhanced light stability for the bare perovskite film. As a result of preserved high crystallinity and simultaneous grain boundary passivation, the perovskite solar cells fabricated by the DIE method demonstrate reliable reproducibility with an average power conversion efficiency (PCE) of 17% and a maximum PCE of 18.1%, with negligible hysteresis.