High Efficiency Planar p‐i‐n Perovskite Solar Cells Using Low‐Cost Fluorene‐Based Hole Transporting Material

For commercial applications, it is a challenge to find suitable and low‐cost hole‐transporting material (HTM) in perovskite solar cells (PSCs), where high efficiency spiro‐OMeTAD and PTAA are expensive. A HTM based on 9,9‐dihexyl‐9H‐fluorene and N,N‐di‐p‐methylthiophenylamine (denoted as FMT) is designed and synthesized. High‐yield FMT with a linear structure is synthesized in two steps. The dopant‐free FMT‐based planar p‐i‐n perovskite solar cells (pp‐PSCs) exhibit a high power conversion efficiency (PCE) of 19.06%, which is among the highest PCEs reported for the pp‐PSCs based on organic HTM. For comparison, a PEDOT:PSS HTM‐based pp‐PSC is fabricated under the same conditions, and its PCE is found to be 13.9%.     

Dithieno[3,2‐b:2′,3′‐d]pyrrol‐Cored Hole Transport Material Enabling Over 21% Efficiency Dopant‐Free Perovskite Solar Cells

Dopant‐free hole transport materials (HTMs) are essential for commercialization of perovskite solar cells (PSCs). However, power conversion efficiencies (PCEs) of the state‐of‐the‐art PSCs with small molecule dopant‐free HTMs are below 20%. Herein, a simple dithieno[3,2‐b:2′,3′‐d]pyrrol‐cored small molecule, DTP‐C6Th, is reported as a promising dopant‐free HTM. Compared with commonly used spiro‐OMeTAD, DTP‐C6Th exhibits a similar energy level, a better hole mobility of 4.18 × 10^?4 cm² V^?1 s^?1, and more efficient hole extraction, enabling efficient and stable PSCs with a dopant‐free HTM. With the addition of an ultrathin poly(methyl methacrylate) passivation layer and properly tuning the composition of the perovskite absorber layer, a champion PCE of 21.04% is achieved, which is the highest value for small molecule dopant‐free HTM based PSCs to date. Additionally, PSCs using the DTP‐C6Th HTM exhibit significantly improved long‐term stability compared with the conventional cells with the metal additive doped spiro‐OMeTAD HTM. Therefore, this work provides a new candidate and effective device engineering strategy for achieving high PCEs with dopant‐free HTMs.     

Double-layered hole transport material of CuInS2/Spiro for highly efficient and stable perovskite solar cells

In this paper, double-layered hole transport material (HTM) was designed and fabricated by adding a thin CuInS₂ film between perovskite and Spiro-OMeTAD (Spiro) layers. The power conversion efficiency (PCE) of the perovskite solar cells (PSCs) with double-layered HTM of CuInS₂/Spiro was improved to 19.63% from 17.97% for the devices with pure Spiro. Moreover, the operational stability of the PSCs with double-layered HTM of CuInS₂/Spiro was enhanced. The PCE of the PSCs with CuInS₂/Spiro retains 91% of the initial value after 30 days storage in ambient atmosphere. The experimental results indicate that the improved performance could be come from the energy band match between CuInS₂ and Spiro, fast hole extraction and transport, and decreased charge recombination in the PSCs with double-layered HTM of CuInS₂/Spiro. This work provides a promising prospect to design a low-cost and high stability HTM for commercial PSCs.     

Self‐Crystallized Multifunctional 2D Perovskite for Efficient and Stable Perovskite Solar Cells

Recently, perovskite solar cells (PSC) with high power‐conversion efficiency (PCE) and long‐term stability have been achieved by employing 2D perovskite layers on 3D perovskite light absorbers. However, in‐depth studies on the material and the interface between the two perovskite layers are still required to understand the role of the 2D perovskite in PSCs. Self‐crystallization of 2D perovskite is successfully induced by deposition of benzyl ammonium iodide (BnAI) on top of a 3D perovskite light absorber. The self‐crystallized 2D perovskite can perform a multifunctional role in facilitating hole transfer, owing to its random crystalline orientation and passivating traps in the 3D perovskite. The use of the multifunctional 2D perovskite (M2P) leads to improvement in PCE and long‐term stability of PSCs both with and without organic hole transporting material (HTM), 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenyl‐amine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) compared to the devices without the M2P.     

PbTiO3 as Electron‐Selective Layer for High‐Efficiency Perovskite Solar Cells: Enhanced Electron Extraction via Tunable Ferroelectric Polarization

PbTiO₃ (PTO) is explored as a versatile and tunable electron‐selective layer (ESL) for perovskite solar cells. To demonstrate effectiveness of PTO for electron–hole separation and charge transfer, perovskite solar cells are designed and fabricated in the laboratory with the PTO as the ESL. The cells achieve a power conversion efficiency (PCE) of ≈12.28% upon preliminary optimization. It is found that the PTO ferroelectric layer can not only increase the PCE, but also tune the photocurrent via tuning PTO's ferroelectric polarization. Moreover, to understand the physical mechanism underlying the carrier transport by the ferroelectric polarization, the electronic structure of PTO/CH₃NH₃PbI₃ heterostructure is computed using the first‐principles methods, for which the triplet state is used to simulate charge transfer in the heterostructure. It is shown that the synergistic effect of type II band alignment and the specific ferroelectric polarization direction provide the effective extraction of electrons from the light absorber, while minimize recombination of photogenerated electron–hole pairs. Overall, the ferroelectric PTO is a promising and tunable ESL for optimizing electron transport in the perovskite solar cells. The design offers a different strategy for altering direction of carrier transport in solar cells.     

Rubidium Fluoride Modified SnO2 for Planar n-i-p Perovskite Solar Cells

Regulating the electron transport layer (ETL) has been an effective way to promote the power conversion efficiency (PCE) of perovskite solar cells (PSCs) as well as suppress their hysteresis. Herein, the SnO₂ ETL using a cost-effective modification material rubidium fluoride (RbF) is modified in two methods: 1) adding RbF into SnO₂ colloidal dispersion, F and Sn have a strong interaction, confirmed via X-ray photoelectron spectra and density functional theory results, contributing to the improved electron mobility of SnO₂; 2) depositing RbF at the SnO₂/perovskite interface, Rb⁺ cations actively escape into the interstitial sites of the perovskite lattice to inhibit ions migration and reduce non-radiative recombination, which dedicates to the improved open-circuit voltage (V_oc) for the PSCs with suppressed hysteresis. In addition, double-sided passivated PSCs, RbF on the SnO₂ surface, and p-methoxyphenethylammonium iodide on the perovskite surface, produces an outstanding PCE of 23.38% with a V_oc of 1.213 V, corresponding to an extremely small V_oc deficit of 0.347 V.     

Fully Printed High-Performance Quasi-Two-Dimensional Perovskite Solar Cells via Multifunctional Interfacial Engineering

Planar n–i–p carbon perovskite solar cells (PSCs) with a hole transport layer that can be fabricated at low temperatures at low-cost exhibit great potential for large-scale manufacturing. Moreover, 2D perovskites have attracted considerable attention owing to their higher stability. In this work, scalable and highly efficient fully printed large-area carbon electrode-based 2D perovskite modules are reported through the insertion of a thin naphthaleneimide derivative (CATNI)-based interfacial layer between tin (IV) oxide and the perovskite layer. The results show that this facilitates the formation of the interfacial contact, suppresses energy losses, and substantially improves the performance parameters of the PSCs, especially their V_OC value. A significantly enhanced V_OC of 1.13 V is achieved resulting in the device PCE value reaching over 18%, which is one of the highest reported for fully printed PSCs so far. It is found that with the deployment of this CATNI-based interfacial layer, a more efficient carrier extraction is achieved. This ultimately contributed to enhanced spectral response as well as improved V_OC for these carbon electrodes based on fully printed devices. Finally, the carbon-perovskite solar modules (carbon-PSMs) are fabricated on ITO glass substrates with dimensions of 5.0 × 5.0 cm. These prepared modules exhibited outstanding photovoltaic performance with the highest PCE value of over 14.6%.     

Pyrite‐Based Bi‐Functional Layer for Long‐Term Stability and High‐Performance of Organo‐Lead Halide Perovskite Solar Cells

Organo‐lead halide perovskite solar cells (PSCs) have received great attention because of their optimized optical and electrical properties for solar cell applications. Recently, a dramatic increase in the photovoltaic performance of PSCs with organic hole transport materials (HTMs) has been reported. However, as of now, future commercialization can be hampered because the stability of PSCs with organic HTM has not been guaranteed for long periods under conventional working conditions, including moist conditions. Furthermore, conventional organic HTMs are normally expensive because material synthesis and purification are complicated. It is herein reported, for the first time, octadecylamine‐capped pyrite nanoparticles (ODA‐FeS₂ NPs) as a bi‐functional layer (charge extraction layer and moisture‐proof layer) for organo‐lead halide PSCs. FeS₂ is a promising candidate for the HTM of PSCs because of its high conductivity and suitable energy levels for hole extraction. A bi‐functional layer based on ODA‐FeS₂ NPs shows excellent hole transport ability and moisture‐proof performance. Through this approach, the best‐performing device with ODA‐FeS₂ NPs‐based bi‐functional layer shows a power conversion efficiency of 12.6% and maintains stable photovoltaic performance in 50% relative humidity for 1000 h. As a result, this study has the potential to break through the barriers for the commercialization of PSCs.     

Origin of Open‐Circuit Voltage Enhancements in Planar Perovskite Solar Cells Induced by Addition of Bulky Organic Cations

The origin of performance enhancements in p‐i‐n perovskite solar cells (PSCs) when incorporating low concentrations of the bulky cation 1‐naphthylmethylamine (NMA) are discussed. A 0.25 vol % addition of NMA increases the open circuit voltage (V_oc) of methylammonium lead iodide (MAPbI₃) PSCs from 1.06 to 1.16 V and their power conversion efficiency (PCE) from 18.7% to 20.1%. X‐ray photoelectron spectroscopy and low energy ion scattering data show NMA is located at grain surfaces, not the bulk. Scanning electron microscopy shows combining NMA addition with solvent assisted annealing creates large grains that span the active layer. Steady state and transient photoluminescence data show NMA suppresses non‐radiative recombination resulting from charge trapping, consistent with passivation of grain surfaces. Increasing the NMA concentration reduces device short‐circuit current density and PCE, also suppressing photoluminescence quenching at charge transport layers. Both V_oc and PCE enhancements are observed when bulky cations (phenyl(ethyl/methyl)ammonium) are incorporated, but not smaller cations (Cs/MA)—indicating size is a key parameter. Finally, it demonstrates that NMA also enhances mixed iodide/bromide wide bandgap PSCs (V_oc of 1.22 V with a 1.68 eV bandgap). The results demonstrate a facile approach to maximizing V_oc and provide insights into morphological control and charge carrier dynamics induced by bulky cations in PSCs.     

Hydrothermally Treated SnO2 as the Electron Transport Layer in High‐Efficiency Flexible Perovskite Solar Cells with a Certificated Efficiency of 17.3%

Perovskite solar cells (PSCs) are one of the most promising solar energy conversion technologies owing to their rapidly developing power conversion efficiency (PCE). Low‐temperature solution processing of the perovskite layer enables the fabrication of flexible devices. However, their application has been greatly hindered due to the lack of strategies to fabricate high‐quality electron transport layers (ETLs) at the low temperatures (≈100 °C) that most flexible plastic substrates can withstand, leading to poor performances for flexible PSCs. In this work, through combining the spin‐coating process with a hydrothermal treatment method, ligand‐free and highly crystalline SnO₂ ETLs are successfully fabricated at low temperature. The flexible PSCs based on this SnO₂ ETL exhibit an excellent PCE of 18.1% (certified 17.3%). The flexible PSCs maintained 85% of the initial PCE after 1000 bending cycles and over 90% of the initial PCE after being stored in ambient air for 30 days without encapsulation. The investigation reveals that hydrothermal treatment not only promotes the complete removal of organic surfactants coated onto the surface of the SnO₂ nanoparticles by hot water vapor but also enhances crystallization through the high vapor pressure of water, leading to the formation of high‐quality SnO₂ ETLs.     

Multiple Function Synchronous Optimization by PbS Quantum Dots for Highly Stable Planar Perovskite Solar Cells with Efficiency Exceeding 23%

Colloidal lead sulfide (PbS) quantum dots (QDs), which possess quantum confinement effect and processing compatibility with perovskite, are regarded as an excellent material for optimizing perovskite solar cells (PSCs). However, the existing PSCs optimized by PbS QDs are still facing the challenges of poor performance of the charge transport layers, low utilization in the near-infrared (NIR) region, and unsuitable energy level alignment, which limit the improvement of power conversion efficiency (PCE). Herein, a synchronous optimization strategy is realized via simultaneously introducing PbS QDs into SnO₂ electron transport layer and employing rare-earth-doped PbS QDs (Eu:PbS QDs) film with hydrophobic chain ligands as the NIR light-absorping layer and hole transport layer (HTL) of devices. PbS QDs effectively decrease the density of trap states by passivating defects. Eu:PbS QDs film with adjustable bandgap is employed as an absorption layer to broaden the NIR spectral absorption. The well-matched energy level between Eu:PbS QDs layer and perovskite layer implies efficient hole transfer at the interface. The successful synchronous optimization greatly elevates all photovoltaic parameters, reaching a maximum PCE of 23.27%. This PCE is the highest for PSCs utilizing PbS QDs material in recent years. The optimized PSCs retain long-term moisture and light stability.     

Multifunctional Cross-Linked Polyurethane Polymer as Interface Layer for Efficient and Stable Perovskite Solar Cells

In the past decade, perovskite solar cells (PSCs) have made remarkable progress in improving power conversion efficiency (PCE). In order to further improve the photovoltaic performance and long-term stability of PSCs, the interface layer is essential. A multifunctional cross-linked polyurethane (CLPU) is designed and synthesized via the spontaneous quaternization of polyurethane and 1, 6-diiodohexane on the surface of the perovskite layer. CLPU layer cannot only effectively induce secondary crystallization and passivate the surface defects of perovskite, reduce the non-radiative recombination, but also effectively block the moisture invasion. By this strategy, Cs_0.05FA_0.95PbI₃ PSCs with excellent reproducibility, is realized, achieving a PCE of 23.14% with an open-circuit voltage of 1.11 V, a short-circuit current density of 25.69 mA cm⁻², and a fill factor of 0.81. In addition, the unencapsulated devices show enhanced stability in 35 ± 5% relative humidity (RH) near 3000 h and in 65 ± 5% RH over 700 h. This study provides valuable insights into the role of CLPU interface layer in PSCs, which are essential for the design of high-performance devices.     

Synergetic Excess PbI2 and Reduced Pb Leakage Management Strategy for 24.28% Efficient,Stable and Eco-Friendly Perovskite Solar Cells

Introducing excess PbI₂ has proven to be an effective in situ passivation strategy for enhancing efficiency of perovskite solar cells (PSCs). Nevertheless, the photoinstability and hysteresis are still tough issues owing to the photolysis nature of PbI₂. Moreover, the humidity-related degradation of perovskite films is also a difficult territory to cover in such an in situ passivation strategy. Herein, a synergistic strategy is reported via initiatively inducing vertical graded PbI₂ distribution (GPD) in the whole perovskite film and capping a cis-Ru(H₂dcbpy)(dnbpy)(NCS)₂ (Z907) internal encapsulation (IE) layer on the surface to ameliorate the above issues. The GPD design can enhance luminescence, prolong carrier lifetimes, ascertaining the improvement of efficiency and elimination of photoinstability in the PSCs. Besides, the introduced IE layer not only can promote the moisture and thermal resistance, but also inhibit Pb leakage and ion migration in the PSCs. Through the synergetic regulations, the resultant PSCs exhibit an impressive open circuit voltage (V_OC) of 1.253 V, fill factor of 81.25%, and power conversion efficiency (PCE) of 24.28%. Moreover, the PSCs maintain 91% of its initial PCE at relative humidity of 85% after 500 h aging and 94% under continuous heating at 85 °C after 750 h aging.     

In Situ Growth of 2D Perovskite Capping Layer for Stable and Efficient Perovskite Solar Cells

2D halide perovskites have recently been recognized as a promising avenue in perovskite solar cells (PSCs) in terms of encouraging stability and defect passivation effect. However, the efficiency (less than 15%) of ultrastable 2D Ruddlesden–Popper PSCs still lag far behind their traditional 3D perovskite counterparts. Here, a rationally designed 2D‐3D perovskite stacking‐layered architecture by in situ growing 2D PEA₂PbI₄ capping layers on top of 3D perovskite film, which drastically improves the stability of PSCs without compromising their high performance, is reported. Such a 2D perovskite capping layer induces larger Fermi‐level splitting in the 2D‐3D perovskite film under light illumination, resulting in an enhanced open‐circuit voltage (V_oc) and thus a higher efficiency of 18.51% in the 2D‐3D PSCs. Time‐resolved photoluminescence decay measurements indicate the facilitated hole extraction in the 2D‐3D stacking‐layered perovskite films, which is ascribed to the optimized energy band alignment and reduced nonradiative recombination at the subgap states. Benefiting from the high moisture resistivity as well as suppressed ion migration of the 2D perovskite, the 2D‐3D PSCs show significantly improved long‐term stability, retaining nearly 90% of the initial power conversion efficiency after 1000 h exposure in the ambient conditions with a high relative humidity level of 60 ± 10%.     

Understanding Temperature‐Dependent Charge Extraction and Trapping in Perovskite Solar Cells

Understanding the factors that limit the performance of perovskite solar cells (PSCs) can be enriched by detailed temperature (T)‐dependent studies. Based on p‐i‐n type PSCs with prototype methylammonium lead triiodide (MAPbI₃) perovskite absorbers, T‐dependent photovoltaic properties are explored and negative T‐coefficients for the three device parameters (V_OC, J_SC, and FF) are observed within a wide low T‐range, leading to a maximum power conversion efficiency (PCE) of 21.4% with an impressive fill factor (FF) approaching 82% at 220 K. These T‐behaviors are explained by the enhanced interfacial charge transfer, reduced charge trapping with suppressed nonradiative recombination and narrowed optical bandgap at lower T. By comparing the T‐dependent device behaviors based on MAPbI₃ devices containing a PASP passivation layer, enhanced PCE at room temperature is observed but different tendencies showing attenuating T‐dependencies of J_SC and FF, which eventually leads to nearly T‐invariable PCEs. These results indicate that charge extraction with the utilized all‐organic charge transporting layers is not a limiting factor for low‐T device operation, meanwhile the trap passivation layer of choice can play a role in the T‐dependent photovoltaic properties and thus needs to be considered for PSCs operating in a temperature‐variable environment.     

Boosting the Efficiency of SnO2‐Triple Cation Perovskite System Beyond 20% Using Nonhalogenated Antisolvent

Solution‐processed triple‐cation perovskite solar cells (PSCs) rely on complex compositional engineering or delicate interfacial passivation to balance the trade‐off between cell efficiency and long‐term stability. Herein, the facile fabrication of highly efficient, stable, and hysteresis‐free tin oxide (SnO₂)‐based PSCs is demonstrated with a champion cell efficiency of 20.06% using a green, halogen‐free antisolvent. The antisolvent, composed of ethyl acetate (EA) solvent and hexane (Hex) in different proportions, works exquisitely in regulating perovskite crystal growth and passivating grain boundaries, leading to the formation of a crack‐free perovskite film with enlarged grain size. The high quality perovskite film inhibits carrier recombination and substantially improves the cell efficiency, without requiring an additional enhancer/passivation layer. Furthermore, these PSCs also demonstrate remarkable long‐term stability, whereby unencapsulated cells exhibit a power conversion efficiency (PCE) retention of ≈71% after >1500 hours of storage under ambient condition. For encapsulated cells, an astounding PCE retention of >98% is recorded after >3000 hours of storage in air. Overall, this work realizes the fabrication of SnO₂‐based PSCs with a performance greater or comparable to the state‐of‐the‐art PSCs produced with halogenated antisolvents. Evidently, EA–Hex antisolvent can be an extraordinary halogen‐free alternative in maximizing the performance of PSCs.     

Fully High‐Temperature‐Processed SnO2 as Blocking Layer and Scaffold for Efficient,Stable, and Hysteresis‐Free Mesoporous Perovskite Solar Cells

Planar perovskite solar cells (PSCs) based on low‐temperature‐processed (LTP) SnO₂ have demonstrated excellent photovoltaic properties duo to the high electron mobility, wide bandgap, and suitable band energy alignment of LTP SnO₂. However, planar PSCs or mesoporous (mp) PSCs based on high‐temperature‐processed (HTP) SnO₂ show much degraded performance. Here, a new strategy with fully HTP Mg‐doped quantum dot SnO₂ as blocking layer (bl) and a quite thin SnO₂ nanoparticle as mp layer are developed. The performances of both planar and mp PSCs has been greatly improved. The use of Mg‐SnO₂ in planar PSCs yields a high‐stabilized power conversion efficiency (PCE) of close to 17%. The champion of mp cells exhibits hysteresis free and stable performance with a high‐stabilized PCE of 19.12%. The inclusion of thin mp SnO₂ in PSCs not only plays a role of an energy bridge, facilitating electrons transfer from perovskite to SnO₂ bl, but also enhances the contact area of SnO₂ with perovskite absorber. Impedance analysis suggests that the thin mp layer is an “active scaffold” selectively collecting electrons from perovskite and can eliminate hysteresis and effectively suppress recombination. This is an inspiring advance toward high‐performance PSCs with HTP mp SnO₂.     

Dual Interfacial Modification Engineering with 2D MXene Quantum Dots and Copper Sulphide Nanocrystals Enabled High‐Performance Perovskite Solar Cells

The performance of perovskite solar cells (PSCs) strongly depends on the electron transport layer (ETL), perovskite absorber, hole transport layer (HTL), and their interfaces. Herein, the first approach to utilize ultrathin 2D titanium‐carbide MXenes (Ti₃C₂T_x quantum dots, TQD) by engineering the perovskite/TiO₂ ETL interface and perovskite absorber and introducing Cu_1.8S nanocrystals to perfect the Spiro‐OMeTAD HTL is represented. A significant hysteresis‐free power conversion efficiency improvement from 18.31% to 21.64% of PSCs is achieved after modifications with the enhanced short‐circuit current density, open‐circuit voltages, and fill factor. Various advanced characterizations, including femtosecond transient absorption spectroscopy, electrochemical impedance spectroscopy, and ultraviolet photoelectron spectroscopy, elucidate that the TQD/Cu_1.8S significantly contribute to the improved crystalline quality of the perovskite film with its large grain size and improved electron/holes extraction efficiencies at perovskite/ETL and perovskite/HTL interfaces. Furthermore, the long‐time ambient and light stability of PSCs are largely boosted through the TQD and/or Cu_1.8S nanocrystals doping, originating from the better crystallization of perovskite, suppressing the film aggregation and crystallization of HTL, and inhibiting the ultraviolet‐induced photocatalysis of the ETL. The findings highlight the TQD and Cu_1.8S can act as a superfast electrons and holes tunnel for the optoelectronic devices.     

Fluorinated Pentafulvalene-Fused Hole-Transporting Material Enhances the Performance of Perovskite Solar Cells with Efficiency Exceeding 23%

Organic small molecular materials with coplanar π-conjugated system as HTMs in perovskite solar cells (PSCs) have attracted considerable attention due to their high charge transport capability and thermal stability. Herein, three novel pentafulvalene-fused derivatives with or without fluorine atoms incorporated ( YSH-oF and YSH-mF and YSH-H , respectively) are designed, synthesized, and applied as hole-transporting materials (HTMs) in PSCs fabrication. The fluorinated HTMs, YSH-oF and YSH-mF , exhibited higher hole mobility and better charge extraction at the perovskite/HTM interface than non-fluorinated one do, presumably due to the closer intermolecular π–π packing interactions. As a result, small-area (0.09 cm²) PSCs made with YSH-oF and YSH-mF achieved an impressive power conversion efficiency (PCE) of 23.59% and 22.76% respectively, with negligible hysteresis, in contrast with the 20.57% for the YSH-H -based devices. Furthermore, for large-area (1.00 cm²) devices, the PSCs employing YSH-oF exhibited a PCE of 21.92%. Moreover, excellent long-term device stability is demonstrated for PSCs with F-substituted HTMs ( YSH-oF and YSH-mF ), presumably due to the higher hydrophobicity. This study shows the great potential of fluorinated pentafulvalene-fused materials as low-cost HTM for efficient and stable PSCs.     

Molecularly Tailored Surface Defect Modifier for Efficient and Stable Perovskite Solar Cells

Surface defects cause non-radiative charge recombination and reduce the photovoltaic performance of perovskite solar cells (PSCs), thus effective passivation of defects has become a crucial method for achieving efficient and stable devices. Organic ammonium halides have been widely used for perovskite surface passivation, due to their simple preparation, lattice matching with perovskite, and high defects passivation ability. Herein, a surface passivator 2,4,6-trimethylbenzenaminium iodide (TMBAI) is employed as the interfacial layer between the spiro-OMeTAD and perovskite layer to modify the surface defect states. It is found that TMBAI treatment suppresses the nonradiative charge carrier recombination, resulting in a 60 mV increase of the open-circuit voltage (V_oc) (from 1.11 to 1.17 V) and raises the fill factor from 76.3% to 80.3%. As a result, the TMBAI-based PSCs device demonstrates a power conversion efficiency (PCE) of 23.7%. Remarkably, PSCs with an aperture area of 1 square centimeter produce a PCE of 21.7% under standard AM1.5 G sunlight. The unencapsulated TMBAI-modified device retains 92.6% and 90.1% of the initial values after 1000 and 550 h under ambient conditions (humidity 55%–65%) and one-sun continuous illumination, respectively.