N-Heterocyclic Olefin Type Ionic Liquid with Innate Soft Lewis-Base Character as an Effective Additive for Hybrid Quasi-2D and 3D Perovskite Solar Cells

In optimizing perovskites with ionic liquid (IL), the comparative study on Lewis acid-base (LAB) and hydrogen-bonding (HB) interactions between IL and perovskite is lacking. Herein, methyl is substituted for hydrogen on 2-position of imidazolium ring of N-heterocyclic carbene (NHC) type IL IdH to weaken HB interactions, and the resulting N-heterocyclic olefin (NHO) type IL IdMe with softer Lewis base character is studied in both hybrid quasi-2D (Q-2D) and 3D perovskites. It is revealed that IdMe participates in constructing high-quality Q-2D perovskite (n = 4) and provides stronger passivation for 3D perovskite compared with IdH. Power conversion efficiency (PCE) of Q-2D PEA₂MA₃Pb₄I₁₃ perovskite solar cells (PVSCs) is boosted to 17.68% from 14.03%. PCE and device stability of 3D PVSCs enhances simultaneously. Both theoretical simulations and experimental results show that LAB interactions between NHO and Pb²⁺ take the primary optimization effects on perovskite. The success of engineering LAB interactions also offers inspiration to develop novel ILs for high-performance PVSCs.     

High Performance Inverted RbCsFAPbI3 Perovskite Solar Cells Based on Interface Engineering and Defects Passivation

Lead halide-based perovskites solar cells (PSCs) are intriguing candidates for photovoltaic technology due to their high efficiency, low cost, and simple fabrication processes. Currently, PSCs with efficiencies of >25% are mainly based on methylammonium (MA)-free and bromide (Br) free, formamide lead iodide (FAPbI₃)-based perovskites, because MA is thermally unstable due to its volatile nature and Br incorporation will induce blue shift in the absorption spectrum. Therefore, MA-free, Br-free formamidine-based perovskites are drawing huge research attention in recent years. The hole transporting layer (HTL) is crucial in fabricating highly efficient and stable inverted p-i-n structured PSCs by enhancing charge extraction, lowering interfacial recombination, and altering band alignment, etc. Here, this work employs a NiO_x/PTAA bi-layer HTL combined with GuHCl (guanidinium hydrochloride) additive engineering and PEAI (phenylethylammonium iodide) passivation strategy to optimize the charge carrier dynamics and tune defects chemistry in the MA-free, Br-free RbCsFAPbI₃-based perovskite absorber, which boosts the device efficiency up to 22.78%. Additionally, the device retains 95% of its initial performance under continuous 1 sun equivalent LED light illumination at 45 °C for up to 500 h.     

Ideal Bandgap Organic–Inorganic Hybrid Perovskite Solar Cells

Extremely high power conversion efficiencies (PCEs) of ≈20–22% are realized through intensive research and development of 1.5–1.6 eV bandgap perovskite absorbers. However, development of ideal bandgap (1.3–1.4 eV) absorbers is pivotal to further improve PCE of single junction perovskite solar cells (PVSCs) because of a better balance between absorption loss of sub‐bandgap photons and thermalization loss of above‐bandgap photons as demonstrated by the Shockley–Queisser detailed balanced calculation. Ideal bandgap PVSCs are currently hindered by the poor optoelectronic quality of perovskite absorbers and their PCEs have stagnated at <15%. In this work, through systematic photoluminescence and photovoltaic analysis, a new ideal bandgap (1.35 eV) absorber composition (MAPb_0.5Sn_0.5(I_0.8Br_0.2)₃) is rationally designed and developed, which possesses lower nonradiative recombination states, band edge disorder, and Urbach energy coupled with a higher absorption coefficient, which yields a reduced V_oc,loss (0.45 V) and improved PCE (as high as 17.63%) for the derived PVSCs. This work provides a promising platform for unleashing the complete potential of ideal bandgap PVSCs and prospects for further improvement.     

Interfacial Passivation of the p‐Doped Hole‐Transporting Layer Using General Insulating Polymers for High‐Performance Inverted Perovskite Solar Cells

Organic–inorganic lead halide perovskite solar cells (PVSCs), as a competing technology with traditional inorganic solar cells, have now realized a high power conversion efficiency (PCE) of 22.1%. In PVSCs, interfacial carrier recombination is one of the dominant energy‐loss mechanisms, which also results in the simultaneous loss of potential efficiency. In this work, for planar inverted PVSCs, the carrier recombination is dominated by the dopant concentration in the p‐doped hole transport layers (HTLs), since the F4‐TCNQ dopant induces more charge traps and electronic transmission channels, thus leading to a decrease in open‐circuit voltages (V_OC). This issue is efficiently overcome by inserting a thin insulating polymer layer (poly(methyl methacrylate) or polystyrene) as a passivation layer with an appropriate thickness, which allows for increases in the V_OC without significantly sacrificing the fill factor. It is believed that the passivation layer attributes to the passivation of interfacial recombination and the suppression of current leakage at the perovskite/HTL interface. By manipulating this interfacial passivation technique, a high PCE of 20.3% is achieved without hysteresis. Consequently, this versatile interfacial passivation methodology is highly useful for further improving the performance of planar inverted PVSCs.     

Interface Engineering for All‐Inorganic CsPbI2Br Perovskite Solar Cells with Efficiency over 14%

In this work, a SnO₂/ZnO bilayered electron transporting layer (ETL) aimed to achieve low energy loss and large open‐circuit voltage (V_oc) for high‐efficiency all‐inorganic CsPbI₂Br perovskite solar cells (PVSCs) is introduced. The high‐quality CsPbI₂Br film with regular crystal grains and full coverage can be realized on the SnO₂/ZnO surface. The higher‐lying conduction band minimum of ZnO facilitates desirable cascade energy level alignment between the perovskite and SnO₂/ZnO bilayered ETL with superior electron extraction capability, resulting in a suppressed interfacial trap‐assisted recombination with lower charge recombination rate and greater charge extraction efficiency. The as‐optimized all‐inorganic PVSC delivers a high V_oc of 1.23 V and power conversion efficiency (PCE) of 14.6%, which is one of the best efficiencies reported for the Cs‐based all‐inorganic PVSCs to date. More importantly, decent thermal stability with only 20% PCE loss is demonstrated for the SnO₂/ZnO‐based CsPbI₂Br PVSCs after being heated at 85 °C for 300 h. These findings provide important interface design insights that will be crucial to further improve the efficiency of all‐inorganic PVSCs in the future.     

A 0D/3D Heterostructured All‐Inorganic Halide Perovskite Solar Cell with High Performance and Enhanced Phase Stability

Although organic–inorganic hybrid perovskite solar cells (PVSCs) have achieved dramatic improvement in device efficiency, their long‐term stability remains a major concern prior to commercialization. To address this issue, extensive research efforts are dedicated to exploiting all‐inorganic PVSCs by using cesium (Cs)‐based perovskite materials, such as α‐CsPbI₃. However, the black‐phase CsPbI₃ (cubic α‐CsPbI₃ and orthorhombic γ‐CsPbI₃ phases) is not stable at room temperature, and it tends to convert to the nonperovskite δ‐CsPbI₃ phase. Here, a simple yet effective approach is described to prepare stable black‐phase CsPbI₃ by forming a heterostructure comprising 0D Cs₄PbI₆ and γ‐CsPbI₃ through tuning the stoichiometry of the precursors between CsI and PbI. Such heterostructure is manifested to enable the realization of a stable all‐inorganic PVSC with a high power conversion efficiency of 16.39%. This work provides a new perspective for developing high‐performance and stable all‐inorganic PVSCs.     

Matching Charge Extraction Contact for Wide‐Bandgap Perovskite Solar Cells

Efficient wide‐bandgap (WBG) perovskite solar cells are needed to boost the efficiency of silicon solar cells to beyond Schottky–Queisser limit, but they suffer from a larger open circuit voltage (V_OC) deficit than narrower bandgap ones. Here, it is shown that one major limitation of V_OC in WBG perovskite solar cells comes from the nonmatched energy levels of charge transport layers. Indene‐C60 bisadduct (ICBA) with higher‐lying lowest‐unoccupied‐molecular‐orbital is needed for WBG perovskite solar cells, while its energy‐disorder needs to be minimized before a larger V_OC can be observed. A simple method is applied to reduce the energy disorder by isolating isomer ICBA‐tran3 from the as‐synthesized ICBA‐mixture. WBG perovskite solar cells with ICBA‐tran3 show enhanced V_OC by 60 mV, reduced V_OC deficit of 0.5 V, and then a record stabilized power conversion efficiency of 18.5%. This work points out the importance of matching the charge transport layers in perovskite solar cells when the perovskites have a different composition and energy levels.     

Hysteresis‐Free 1D Network Mixed Halide‐Perovskite Semitransparent Solar Cells

The morphology of hybrid organic–inorganic perovskite films is known to strongly affect the performance of perovskite‐based solar cells. CH₃NH₃PbI_3‐xCl_x (MAPbI_3‐xCl_x) films have been previously fabricated with 100% surface coverage in glove boxes. In ambient air, fabrication generally relies on solvent engineering to obtain compact films. In contrast, this work explores the potential of altering the perovskites microstructure for solar cell engineering. This work starts with CH₃NH₃PbI_3‐xCl_x, films with grain morphology carefully controlled by varying the deposition speed during the spin‐coating process to fabricate efficient and partially transparent solar cells. Devices produced with a CH₃NH₃PbI_3‐xCl_x film and a compact thick top gold electrode reach a maximum efficiency of 10.2% but display a large photocurrent hysteresis. As it is demonstrated, the introduction of different concentrations of bromide in the precursor solution addresses the hysteresis issues and turns the film morphology into a partially transparent interconnected network of 1D microstructures. This approach leads to semitransparent solar cells with negligible hysteresis and efficiencies up to 7.2%, while allowing average transmission of 17% across the visible spectrum. This work demonstrates that the optimization of the perovskites composition can mitigate the hysteresis effects commonly attributed to the charge trapping within the perovskite film.     

Nonconfinement Structure Revealed in Dion–Jacobson Type Quasi‐2D Perovskite Expedites Interlayer Charge Transport

Dion–Jacobson (DJ) type 2D perovskites with a single organic cation layer exhibit a narrower distance between two adjacent inorganic layers compared to the corresponding Ruddlesden–Popper perovskites, which facilitates interlayer charge transport. However, the internal crystal structures in 2D DJ perovskites remain elusive. Herein, in a p‐xylylenediamine (PDMA)‐based DJ perovskite bearing bifunctional NH₃⁺ spacer, the compression from confinement structure (inorganic layer number, n = 1, 2) to nonconfinement structure (n > 3) with the decrease of PDMA molar ratio is unraveled. Remarkably, the nonconfined perovskite displays shorter spacing between 2D quantum wells, which results in a lower exciton binding energy and hence promotes exciton dissociation. The significantly diminishing quantum confinement promotes interlayer charge transport leading to a maximum photovoltaic efficiency of ≈11%. Additionally, the tighter interlayer packing arising from the squeezing of inorganic octahedra gives rise to enhanced ambient stability.     

Fluorinated 2D Lead Iodide Perovskite Ferroelectrics

Hybrid perovskite materials are famous for their great application potential in photovoltaics and optoelectronics. Among them, lead‐iodide‐based perovskites receive great attention because of their good optical absorption ability and excellent electrical transport properties. Although many believe the ferroelectric photovoltaic effect (FEPV) plays a crucial role for the high conversion efficiency, the ferroelectricity in CH₃NH₃PbI₃ is still under debate, and obtaining ferroelectric lead iodide perovskites is still challenging. In order to avoid the randomness and blindness in the conventional method of searching for perovskite ferroelectrics, a design strategy of fluorine modification is developed. As a demonstration, a nonpolar lead iodide perovskite is modified and a new 2D fluorinated layered hybrid perovskite material of (4,4‐difluorocyclohexylammonium)₂PbI₄, 1 , is obtained, which possesses clear ferroelectricity with controllable spontaneous polarization. The direct bandgap of 2.38 eV with strong photoluminescence also guarantees the direct observation of polarization‐induced FEPV. More importantly, the 2D structure and fluorination are also expected to achieve both good stability and charge transport properties. 1 is not only a 2D fluorinated lead iodide perovskite with confirmed ferroelectricity, but also a great platform for studying the effect of ferroelectricity and FEPV in the context of lead halide perovskite solar cells and other optoelectronic applications.     

Fine Multi‐Phase Alignments in 2D Perovskite Solar Cells with Efficiency over 17% via Slow Post‐Annealing

Layered Ruddlesden–Popper (RP) phase (2D) halide perovskites have attracted tremendous attention due to the wide tunability on their optoelectronic properties and excellent robustness in photovoltaic devices. However, charge extraction/transport and ultimate power conversion efficiency (PCE) in 2D perovskite solar cells (PSCs) are still limited by the non‐eliminable quantum well effect. Here, a slow post‐annealing (SPA) process is proposed for BA₂MA₃Pb₄I₁₃ (n = 4) 2D PSCs by which a champion PCE of 17.26% is achieved with simultaneously enhanced open‐circuit voltage, short‐circuit current, and fill factor. Investigation with optical spectroscopy coupled with structural analyses indicates that enhanced crystal orientation and favorable alignment on the multiple perovskite phases (from the 2D phase near bottom to quasi‐3D phase near top regions) is obtained with SPA treatment, which promotes carrier transport/extraction and suppresses Shockley–Read–Hall charge recombination in the solar cell. As far as it is known, the reported PCE is so far the highest efficiency in RP phase 2D PSCs based on butylamine (BA) spacers (n = 4). The SPA‐processed devices exhibit a satisfactory stability with <4.5% degradation after 2000 h under N₂ environment without encapsulation. The demonstrated process strategy offers a promising route to push forward the performance in 2D PSCs toward realistic photovoltaic applications.     

SrCl2 Derived Perovskite Facilitating a High Efficiency of 16% in Hole‐Conductor‐Free Fully Printable Mesoscopic Perovskite Solar Cells

Despite the breakthrough of over 22% power conversion efficiency demonstrated in organic–inorganic hybrid perovskite solar cells (PVSCs), critical concerns pertaining to the instability and toxicity still remain that may potentially hinder their commercialization. In this study, a new chemical approach using environmentally friendly strontium chloride (SrCl₂) as a precursor for perovskite preparation is demonstrated to result in enhanced device performance and stability of the derived hole‐conductor‐free printable mesoscopic PVSCs. The CH₃NH₃PbI₃ perovskite is chemically modified by introducing SrCl₂ in the precursor solution. The results from structural, elemental, and morphological analyses show that the incorporation of SrCl₂ affords the formation of CH₃NH₃PbI₃(SrCl₂)_x perovskites endowed with lower defect concentration and better pore filling in the derived mesoscopic PVSCs. The optimized compositional CH₃NH₃PbI₃(SrCl₂)_0.1 perovskite can substantially enhance the photovoltaic performance of the derived hole‐conductor‐free device to 15.9%, outperforming the value (13.0%) of the pristine CH₃NH₃PbI₃ device. More importantly, the stability of the device in ambient air under illumination is also improved.     

Compositional Control in 2D Perovskites with Alternating Cations in the Interlayer Space for Photovoltaics with Efficiency over 18%

2D perovskites stabilized by alternating cations in the interlayer space (ACI) represent a very new entry as highly efficient semiconductors for solar cells approaching 15% power conversion efficiency (PCE). However, further improvements will require understanding of the nature of the films, e.g., the thickness distribution and charge‐transfer characteristics of ACI quantum wells (QWs), which are currently unknown. Here, efficient control of the film quality of ACI 2D perovskite (GA)(MA)_nPb_nI_3n+1 (〈n〉 = 3) QWs via incorporation of methylammonium chloride as an additive is demonstrated. The morphological and optoelectronic characterizations unambiguously demonstrate that the additive enables a larger grain size, a smoother surface, and a gradient distribution of QW thickness, which lead to enhanced photocurrent transport/extraction through efficient charge transfer between low‐n and high‐n QWs and suppressed nonradiative charge recombination. Therefore, the additive‐treated ACI perovskite film delivers a champion PCE of 18.48%, far higher than the pristine one (15.79%) due to significant improvements in open‐circuit voltage and fill factor. This PCE also stands as the highest value for all reported 2D perovskite solar cells based on the ACI, Ruddlesden–Popper, and Dion–Jacobson families. These findings establish the fundamental guidelines for the compositional control of 2D perovskites for efficient photovoltaics.     

Dual Interfacial Design for Efficient CsPbI2Br Perovskite Solar Cells with Improved Photostability

A synergic interface design is demonstrated for photostable inorganic mixed‐halide perovskite solar cells (PVSCs) by applying an amino‐functionalized polymer (PN4N) as cathode interlayer and a dopant‐free hole‐transporting polymer poly[5,5′‐bis(2‐butyloctyl)‐(2,2′‐bithiophene)‐4,4′‐dicarboxylate‐alt‐5,5′‐2,2′‐bithiophene] (PDCBT) as anode interlayer. First, the interfacial dipole formed at the cathode interface reduces the workfunction of SnO₂, while PDCBT with deeper‐lying highest occupied molecular orbital (HOMO) level provides a better energy‐level matching at the anode, leading to a significant enhancement in open‐circuit voltage (V_oc) of the PVSCs. Second, the PN4N layer can also tune the surface wetting property to promote the growth of high‐quality all‐inorganic perovskite films with larger grain size and higher crystallinity. Most importantly, both theoretical and experimental results reveal that PN4N and PDCBT can interact strongly with the perovskite crystal, which effectively passivates the electronic surface trap states and suppresses the photoinduced halide segregation of CsPbI₂Br films. Therefore, the optimized CsPbI₂Br PVSCs exhibit reduced interfacial recombination with efficiency over 16%, which is one of the highest efficiencies reported for all‐inorganic PVSCs. A high photostability with a less than 10% efficiency drop is demonstrated for the CsPbI₂Br PVSCs with dual interfacial modifications under continuous 1 sun equivalent illumination for 400 h.     

Highly Efficient Perovskite–Perovskite Tandem Solar Cells Reaching 80% of the Theoretical Limit in Photovoltage

Organic–inorganic hybrid perovskite multijunction solar cells have immense potential to realize power conversion efficiencies (PCEs) beyond the Shockley–Queisser limit of single‐junction solar cells; however, they are limited by large nonideal photovoltage loss (V _oc,loss) in small‐ and large‐bandgap subcells. Here, an integrated approach is utilized to improve the V _oc of subcells with optimized bandgaps and fabricate perovskite–perovskite tandem solar cells with small V _oc,loss. A fullerene variant, Indene‐C₆₀ bis‐adduct, is used to achieve optimized interfacial contact in a small‐bandgap (≈1.2 eV) subcell, which facilitates higher quasi‐Fermi level splitting, reduces nonradiative recombination, alleviates hysteresis instabilities, and improves V _oc to 0.84 V. Compositional engineering of large‐bandgap (≈1.8 eV) perovskite is employed to realize a subcell with a transparent top electrode and photostabilized V _oc of 1.22 V. The resultant monolithic perovskite–perovskite tandem solar cell shows a high V _oc of 1.98 V (approaching 80% of the theoretical limit) and a stabilized PCE of 18.5%. The significantly minimized nonideal V _oc,loss is better than state‐of‐the‐art silicon–perovskite tandem solar cells, which highlights the prospects of using perovskite–perovskite tandems for solar‐energy generation. It also unlocks opportunities for solar water splitting using hybrid perovskites with solar‐to‐hydrogen efficiencies beyond 15%.     

Highly Efficient Porphyrin‐Based OPV/Perovskite Hybrid Solar Cells with Extended Photoresponse and High Fill Factor

Employing a layer of bulk‐heterojunction (BHJ) organic semiconductors on top of perovskite to further extend its photoresponse is considered as a simple and promising way to enhance the efficiency of perovskite‐based solar cells, instead of using tandem devices or near infrared (NIR)‐absorbing Sn‐containing perovskites. However, the progress made from this approach is quite limited because very few such hybrid solar cells can simultaneously show high short‐circuit current (J_SC) and fill factor (FF). To find an appropriate NIR‐absorbing BHJ is essential for highly efficient, organic, photovoltaics (OPV)/perovskite hybrid solar cells. The materials involved in the BHJ layer not only need to have broad photoresponse to increase J_SC, but also possess suitable energy levels and high mobility to afford high V_OC and FF. In this work, a new porphyrin is synthesized and blended with [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) to function as an efficient BHJ for OPV/perovskite hybrid solar cells. The extended photoresponse, well‐matched energy levels, and high hole mobility from optimized BHJ morphology afford a very high power conversion efficiency (PCE) (19.02%) with high V_oc, J_SC, and FF achieved simultaneously. This is the highest value reported so far for such hybrid devices, which demonstrates the feasibility of further improving the efficiency of perovskite devices.     

A Thermodynamically Favored Crystal Orientation in Mixed Formamidinium/Methylammonium Perovskite for Efficient Solar Cells

Crystal orientation has a great impact on the properties of perovskite films and the resultant device performance. Up to now, the exquisite control of crystal orientation (the preferred crystallographic planes and the crystal stacking mode with respect to the particular planes) in mixed‐cation perovskites has received limited success, and the underlying mechanism that governs device performance is still not clear. Here, a thermodynamically favored crystal orientation in formamidinium/methylammonium (FA/MA) mixed‐cation perovskites is finely tuned by composition engineering. Density functional theory calculations reveal that the FA/MA ratio affects the surface energy of the mixed perovskites, leading to the variation of preferential orientation consequently. The preferable growth along the (001) crystal plane, when lying parallel to the substrates, affects their charge transportation and collection properties. Under the optimized condition, the mixed‐cation perovskite (FA_1–x MA_x PbI_2.87Br_0.13 (Cl)) solar cells deliver a champion power conversion efficiency over 21%, with a certified efficiency of 20.50 ± 0.50%. The present work not only provides a vital step in understanding the intrinsic properties of mixed‐cation perovskites but also lays the foundation for further investigation and application in perovskite optoelectronics.     

Ligand-Assisted Self-Assembly of 3D Perovskite Nanocrystals into Chiral Inorganic Quasi-2D Perovskites (n = 3) with Ligand-Ratio-Dependent Chirality Inversion

Chiral inorganic quasi-2D perovskites are prepared by self-assembling 3D perovskites in solution for the first time. The quasi-2D perovskite synthesized is a pure-phase perovskite with <n> = 3 and is periodically arranged, which is a big breakthrough in quasi-2D inorganic perovskites.  With the individual chiral CsPbBr₃ nanocrystals (NCs) assemble into quasi-2D perovskite, the g-factor significantly improved (≈5 × 10⁻³). In addition, the chiroptical activity of quasi-2D perovskites is explored to be improved with the lateral size increasing. In the first stage of assembly, chiral optical activity is increased due to the lateral size-dependent optical activity, while the changes in the later stages are attributable to the chiral morphology. Interestingly, chirality inversion is found to be correlated to the number of ligands. It is believed that different conformers of chiral ligands caused by steric hindrance of the original ligand oleylamine result in opposite circular dichroism (CD) polarities. The chirality inversion phenomenon is universal, regardless of the choice of ligands. This work opens up a new path for the synthesis of quasi-2D perovskites and provides more opportunities for the modulation of chiral optical activity.     

Highly Efficient and Stable Solar Cells Based on Crystalline Oriented 2D/3D Hybrid Perovskite

Highly efficient and stable 2D/3D hybrid perovskite solar cells using 2‐thiophenemethylammonium (ThMA) as the spacer cation are successfully demonstrated. It is found that the incorporation of ThMA spacer cation into 3D perovskite, which forms a 2D/3D hybrid structure, can effectively induce the crystalline growth and orientation, passivate the trap states, and hinder the ion motion, resulting in improved carrier lifetime and reduced recombination losses. The optimized device exhibits a power conversion efficiency (PCE) of 21.49%, combined with a high V_OC of 1.16 V and a notable fill factor (FF) of 81%. More importantly, an encapsulated 2D/3D hybrid perovskite device sustains ≈99% of its initial PCE after 1680 h in the ambient atmosphere, whereas the control 3D perovskite device drops to ≈80% of the original performance. Importantly, the device stability under continuous light soaking (100 mW cm^?2) is enhanced significantly for 2D/3D perovskite device in comparison with that of the control device. These results reveal excellent photovoltaic properties and intrinsic stabilities of the 2D/3D hybrid perovskites using ThMA as the spacer cation.     

Metal Cations in Efficient Perovskite Solar Cells: Progress and Perspective

Metal halide perovskite solar cells (PVSCs) have revolutionized photovoltaics since the first prototype in 2009, and up to now the highest efficiency has soared to 24.2%, which is on par with commercial thin film cells and not far from monocrystalline silicon solar cells. Optimizing device performance and improving stability have always been the research highlight of PVSCs. Metal cations are introduced into perovskites to further optimize the quality, and this strategy is showing a vigorous development trend. Here, the progress of research into metal cations for PVSCs is discussed by focusing on the position of the cations in perovskites, the modulation of the film quality, and the influence on the photovoltaic performance. Metal cations are considered in the order of alkali cations, alkaline earth cations, then metal cations in the ds and d regions, and ultimately trivalent cations (p‐ and f‐block metal cations) according to the periodic table of elements. Finally, this work is summarized and some relevant issues are discussed.