Over 24% Efficient Poly(vinylidene fluoride) (PVDF)-Coordinated Perovskite Solar Cells with a Photovoltage up to 1.22 V

Recently, organic–inorganic metal halide perovskite solar cells (PSCs) have achieved rapid improvement, however, the efficiencies are still behind the Shockley–Queisser theory mainly due to their high energy loss (E_LOSS) in open-circuit voltage (V_OC). Due to the polycrystalline nature of the solution-prepared perovskite films, defects at the grain boundaries as the non-radiative recombination centers greatly affect the V_OC and limit the device efficiency. Herein, poly(vinylidene fluoride) (PVDF) is introduced as polymer-templates in the perovskite film, where the fluorine atoms in the PVDF network can form strong hydrogen-bonds with organic cations and coordinate bonds with Pb²⁺. The strong interaction between PVDF and perovksite enables slow crystal growth and efficient defect passivation, which effectively reduce non-radiation recombination and minimize E_LOSS of V_OC. PVDF-based PSCs achieve a champion efficiency of 24.21% with a excellent voltage of 1.22 V, which is one of the highest V_OC values reported for FAMAPb(I/Br)₃-based PSCs. Furthermore, the strong hydrophobic fluorine atoms in PVDF endow the device with excellent humidity stability, the unencapsulated solar cell maintain the initial efficiency of >90% for 2500 h under air ambient of ≈50% humid and a consistently high V_OC of 1.20 V.     

Synergistic Crystallization Modulation and Defects passivation via Additive Engineering Stabilize Perovskite Films for Efficient Solar Cells

Organic-inorganic lead halide perovskite are promising photovoltaic materials, but their intrinsic defects and crystalline quality severely deteriorate the solar cells efficiency and stability. Herein, potassium 1,1,2,2,3,3-hexafluoroprop-ane-1,3-disulfonimide (KHFDF) is introduced into PbI₂ precursor solution to passivate various defects and improve the crystalline quality of perovskite films. It is found that KHFDF can inhibit PbI₂ crystallization, thus tuning the crystal orientation and growth of perovskite films. Furthermore, KHFDF with dual-functional sulfonyl group cannot only passivate grain boundaries (GBs), but also passivate the defects at GBs via strong interaction with undercoordinated Pb²⁺ and/or hydrogen bonding with FA⁺, while the K⁺ counter cations allow ionic interaction with undercoordinated I⁻. As a result, the KHFDF-modified films exhibit high quality with a larger grain size and a reduced trap-state density, thereby suppressing the trap-state nonradiative recombination. And the devices show a champion efficiency up to 24.15%, benefiting from a sharp enhancement of open-circuit voltage (V_oc) of 1.183 V and fill factor of 81.78%. In addition, due to the enhanced humidity tolerance and chemical structure stability, the devices exhibit excellent long-term humidity and thermal stability without encapsulation.     

3D Polydentate Complexing Agents for Passivating Defects and Modulating Crystallinity for High-Performance Perovskite Solar Cells

The grain boundaries (GBs)/surface defects within perovskite film directly impede the further improvement of photoelectric conversion efficiency (PCE) and stability of planar perovskite solar cells (PSCs). Herein, 3D phytic acid (PA) and phytic acid dipotassium (PAD) with polydentate are explored to synchronously passivate the defects of perovskite absorber directly in multiple spatial directions. The strong electron-donating groups ( H₂PO₄) in the PA molecule afford six anchor sites to bind firmly with uncoordinated Pb²⁺ at the GBs/surface and modulate perovskite crystallization, thus enhancing the quality of perovskite film. Particularly, PAD containing an additional (K→PO) push–pull structure promotes the dominant coordination of phosphate group (PO) with Pb²⁺ and passivates halide anion defects due to the complexation of potassium ions (K⁺) with iodide ions (I^-). Consequently, the PAD-complexed PSCs deliver a champion PCE of 23.18%, which is remarkably higher than that of the control device (19.94%). Meanwhile, PAD-complexed PSCs exhibit superior moisture and thermal stability, remaining 79% of their initial PCE after 1000 h under continuous illumination, while the control device remain only 48% of their PCE after 1000 h. This work provides important insights into designing multifunctional 3D passivators for the purpose of simultaneously enhancing the efficiency and stability of devices.     

Construction of Polyoxometalate-Based Material for Eliminating Multiple Pb-Based Defects and Enhancing Thermal Stability of Perovskite Solar Cells

The high-quality perovskite film with few defects plays an important role in the power conversion efficiency (PCE) and long-term stability of perovskite solar cells. Here, an efficient strategy is proposed to eliminate Pb⁰ and passivate Pb²⁺ simultaneously by employing a stable polyoxometalate-based material CoW₁₂@MIL-101(Cr) in the precursor solution of perovskite. The controllable oxidation ability of CoW₁₂ is optimized through the interaction with metal–organic frameworks, resulting in a doped perovskite film with regular morphology, large grain size, and low defects density. The solvent effects and formation of intermediate materials in the precursor solution are further investigated by an in situ thermogravimetry-Fourier transform infrared spectroscopy analysis. In addition, the champion doped-device showed enhanced PCE to 21.39% and excellent stability, maintaining 85% and 89% of the original PCE after heating at 85 °C in N₂ atmosphere and stored in ambient conditions (25 °C, 40% humidity) for 1000 h, respectively.     

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.     

Host-Guest Complexation Strategy for Passivating Pb-Dimer Related Defects in Perovskite Photovoltaics

Although there is extensive attention to the eminent perovskite solar cells, the deep-level defects such as Pb-Pb dimers in the solution-processed polycrystalline perovskites inevitably result in photovoltaic output losses and subsequent degradation. Recently, it is reported that an electron-donating group can passivate Pb dimer defects efficiently. However, the mechanism for the causation of metallic lead (Pb⁰) from the iodide vacancy (V_I) is unclear. Herein, a chain reaction mechanism is proposed for the possible transformation process from V_I to Pb⁰ with the Pb dimer intermediates. In this regard, a host-guest strategy is adopted by using 4-tert-Butyl-1-(ethoxycarbonyl- methoxy) thiacalix[4]arene (tBuTCA) to complex with the cations and out-of-cage (Lead(II) iodide) PbI₂. Moreover, a host-guest complexation can be formed due to the Pb²⁺-π interactions. Continuously, the negative charge compensation for iodine vacancy can hinder the formation of Pb-Pb dimer, thus significantly suppressing non-radiative recombination. Consequently, the resulting solar cells show more than 24% power conversion efficiencies and maintain over 96% of their initial performance without encapsulation for 486 h under an ambient environment. This work highlights the significance of supramolecular engineering in constructing a high-quality perovskite for efficient and stable perovskite solar cells.     

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.     

Modifying Surface Termination of CsPbI3 Grain Boundaries by 2D Perovskite Layer for Efficient and Stable Photovoltaics

It is highly desirable for all-inorganic perovskite solar cells (PVSCs) to have reduced nonideal interfacial charge recombination in order to improve the performance. Although the construction of a 2D capping layer on 3D perovskite is an effective way to suppress interfacial nonradiative recombination, it is difficult to apply it to all-inorganic perovskites because of the resistance of Cs⁺ cesium ions in cation exchange reactions. To alleviate this problem, a simple approach using an ultra-thin 2D perovskite to terminate CsPbI₃ grain boundaries (GBs) without damaging the original 3D perovskite is developed. The 2D perovskite at the GBs not only enhances the charge-carrier extraction and transport but also effectively suppresses nonradiative recombination. In addition, because the 2D perovskite can prevent the moisture and oxygen from penetrating into the GBs and at the same time suppress the ion migration, the 2D terminated CsPbI₃ films exhibit significantly improved stability against humidity. Moreover, the devices without encapsulation can retain ≈81% of its initial power conversion efficiency (PCE) after being stored at 40 ± 5% relative humidity for 84 h. The 2D-based champion device exhibits a high PCE of 18.82% with a high open-circuit voltage of 1.16 V.     

Multifunctional Enhancement for Highly Stable and Efficient Perovskite Solar Cells

With a certified efficiency as high as 25.2%, perovskite has taken the crown as the highest efficiency thin film solar cell material. Unfortunately, serious instability issues must be resolved before perovskite solar cells (PSCs) are commercialized. Aided by theoretical calculation, an appropriate multifunctional molecule, 2,2-difluoropropanediamide (DFPDA), is selected to ameliorate all the instability issues. Specifically, the carbonyl groups in DFPDA form chemical bonds with Pb²⁺ and passivate under-coordinated Pb²⁺ defects. Consequently, the perovskite crystallization rate is reduced and high-quality films are produced with fewer defects. The amino groups not only bind with iodide to suppress ion migration but also increase the electron density on the carbonyl groups to further enhance their passivation effect. Furthermore, the fluorine groups in DFPDA form both an effective barrier on the perovskite to improve its moisture stability and a bridge between the perovskite and HTL for effective charge transport. In addition, they show an effective doping effect in the HTL to improve its carrier mobility. With the help of the combined effects of these groups in DFPDA, the PSCs with DFPDA additive achieve a champion efficiency of 22.21% and a substantially improved stability against moisture, heat, and light.     

The Synergistic Effect of Pemirolast Potassium on Carrier Management and Strain Release for High-Performance Inverted Perovskite Solar Cells

The quality of the perovskite absorption layer is critical for the high efficiency and long-term stability of perovskite solar cells (PSCs). The inhomogeneity due to local lattice mismatch causes severe residual strain in low-quality perovskite films, which greatly limits the availability of high-performance PSCs. In this study, a multi-active-site potassium salt, pemirolast potassium (PP), is added to perovskite films to improve carrier dynamics and release residual stress. X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) measurements suggest that the proposed multifunctional additive bonds with uncoordinated Pb²⁺ through the carbonyl group/tetrazole N and passivated I atom defects. Moreover, the residual stress release is effective from the surface to the entire perovskite layer, and carrier extraction/transport is promoted in PP-modified perovskite films. As a result, a champion power conversion efficiency (PCE) of 23.06% with an ultra-high fill factor (FF) of 84.36% is achieved in the PP-modified device, which ranks among the best in formamidinium-cesium (FACs) PSCs. In addition, the PP-modified device exhibits excellent thermal stability due to the inhibited phase separation. This work provides a reliable way to improve the efficiency and stability of PSCs by releasing residual stress in perovskite films through additive engineering.     

A Polymer Defect Passivator for Efficient Hole-Conductor-Free Printable Mesoscopic Perovskite Solar Cells

Due to the low cost and excellent potential for mass production, printable mesoscopic perovskite solar cells (p-MPSCs) have drawn a lot of attention among other device structures. However, the low open-circuit voltage (V_OC) of such devices restricts their power conversion efficiency (PCE). This limitation is brought by the high defect density at perovskite grain boundaries in the mesoporous scaffold, which results in severe nonradiative recombination and is detrimental to the V_OC. To improve the perovskite crystallization process, passivate the perovskite defects, and enhance the PCE, additive engineering is an effective way. Herein, a polymeric Lewis base polysuccinimide (PSI) is added to the perovskite precursor solution as an additive. It improves the perovskite crystallinity and its carbonyl groups strongly coordinate with Pb²⁺, which can effectively passivate defects. Additionally, compared with its monomer, succinimide (SI), PSI serves as a better defect passivator because the long-chained macromolecule can be firmly anchored on those defect sites and form a stronger interaction with perovskite grains. As a result, the champion device has a PCE of 18.84%, and the V_OC rises from 973 to 1030 mV. This study offers a new strategy for fabricating efficient p-MPSCs.     

Side-Chain Functionalized Polymer Hole-Transporting Materials with Defect Passivation Effect for Highly Efficient Inverted Quasi-2D Perovskite Solar Cells

Compared with inverted 3D perovskite solar cell (PSCs), inverted quasi-2D PSCs have advantages in device stability, but the device efficiency is still lagging behind. Constructing polymer hole-transporting materials (HTMs) with passivation functions to improve the buried interface and crystallization properties of perovskite films is one of the effective strategies to improve the performance of inverted quasi-2D PSCs. Herein, two novel side-chain functionalized polymer HTMs containing methylthio-based passivation groups are designed, named PVCz-SMeTPA and PVCz-SMeDAD, for inverted quasi-2D PSCs. Benefited from the non-conjugated flexible backbone bearing functionalized side-chain groups, the polymer HTMs exhibit excellent film-forming properties, well-matched energy levels and improved charge mobility, which facilitates the charge extraction and transport between HTM and quasi-2D perovskite layer. More importantly, by introducing methylthio units, the polymer HTMs can enhance the contact and interactions with quasi-2D perovskite, and further passivating the buried interface defects and assisting the deposition of high-quality perovskite. Due to the suppressed interfacial non-radiative recombination, the inverted quasi-2D PSCs using PVCz-SMeTPA and PVCz-SMeDAD achieve impressive power conversion efficiency (PCE) of 21.41% and 20.63% with open-circuit voltage of 1.23 and 1.22 V, respectively. Furthermore, the PVCz-SMeTPA based inverted quasi-2D PSCs also exhibits negligible hysteresis and considerably improved thermal and long-term stability.     

Highly-Stable CsPbI3 Perovskite Solar Cells with an Efficiency of 21.11% via Fluorinated 4-Amino-Benzoate Cesium Bifacial Passivation

The poor interface quality between cesium lead triiodide (CsPbI₃) perovskite and the electron transport layer limits the stability and efficiency of CsPbI₃ perovskite solar cells (PSCs). Herein, a 4-amino-2,3,5,6-tetrafluorobenzoate cesium (ATFC) is designed as a bifacial defect passivator to tailor the perovskite/TiO₂ interface. The comprehensive experiments demonstrate that ATFC can not only optimize the conductivity, electron mobility, and energy band structure of the TiO₂ layer by passivation of the undercoordinated Ti⁴⁺, oxygen vacancy (V_O), and free  OH defects but also promote the yield of high-quality CsPbI₃ film by synergistic passivation of undercoordinated Pb²⁺ defects with the  CO group and F atom, and limiting I⁻ migration via F···I interaction. Benefiting from the above interactions, the ATFC-modified CsPbI₃ device yields a champion power conversion efficiency (PCE) of 21.11% and an excellent open-circuit voltage (V_OC) of 1.24 V. Meanwhile, the optimized CsPbI₃ PSC maintains 92.74% of its initial efficiency after aging 800 h in air atmosphere, and has almost no efficiency attenuation after tracking at maximum power point for 350 h.     

Porphyrinic Metal–Organic Framework Quantum Dots for Stable n–i–p Perovskite Solar Cells

As the power-conversion efficiency (PCE) of organic–inorganic lead halide perovskite solar cells (PSCs) is approaching the theoretical maximum, the most crucial issue concerns long-term ambient stability. Here, the application of PCN-224 quantum dots (QDs) is reported, a typical Zr-based porphyrinic metal–organic framework (MOF), to enhance the ambient stability of PSCs. PCN-224 QDs with abundant Lewis-base groups (e.g., CO, C−N, CN) contribute to high-quality perovskite films with enlarged grain size and reduced defect density by interaction with under-coordinated Pb²⁺. Meanwhile, PCN-224 QDs enable the well-matched energy level at the perovskite/hole transport layer (HTL) interface, thereby facilitating hole extraction and transport. More importantly, PCN-224 QDs-treated HTL can capture Li⁺ from bis(trifluoromethanesulfonyl)imide additive, leading to the reduced aggregation and less direct contact with moisture for hygroscopic Li-TFSI. Moreover, PCN-224 QDs mitigated Li⁺ ion migration into the perovskite layer, thus avoiding the formation of deleterious defects. The resultant devices yield a champion PCE of 22.51%, along with substantially improved durability, including humidity, thermal and light soaking stabilities. The findings provide a new approach toward efficient and stable PSCs by applying MOF QDs.     

Cuprous iodide dose dependent passivation of MAPbI3 perovskite solar cells

MAPbI₃ has been considered as a candidate for the active layer of perovskite solar cells in recent years. We proposed a device model to investigate the contribution of cuprous iodide (CuI) to MAPbI₃ perovskite thin films to power conversion efficiency (PCE) and demonstrated that the dosage of CuI affects the grain size of thin films and the PCE. Through the results of the SEM analysis, we found that the grain boundaries of MAPbI₃ perovskite films decreased with increases in the dosage of CuI and the grain size increased significantly from 164 nm ± 49 nm–299 nm ± 127 nm. In addition, the results of the PL measurement showed that the PL intensity decreased after addition of CuI to the MAPbI₃ perovskite thin films, suggesting a reduction in the charge recombination. The XRD patterns indicated that the addition of CuI did not influence the main structure of the MAPbI₃ perovskite. Interestingly, CuI plays a key role in the passivation of defects in MAPbI₃ perovskite thin films, which can reduce non-radiative recombination and increase the fill factor and open-circuit voltage of the device. In this study, we adjusted the grain size and passivated the MAPbI₃ thin film by controlling the dosage of CuI. We also increased the power conversion efficiency from 10% to 13%. This type of perovskite solar cell provided a simple, low cost preparation process for practical applications.     

Defect Passivation in Perovskite Solar Cells by Cyano‐Based π‐Conjugated Molecules for Improved Performance and Stability

Defects at the surface and grain boundaries of metal–halide perovskite films lead to performance losses of perovskite solar cells (PSCs). Here, organic cyano‐based π‐conjugated molecules composed of indacenodithieno[3,2‐b]thiophene (IDTT) are reported and it is found that their cyano group can effectively passivate such defects. To achieve a homogeneous distribution, these molecules are dissolved in the antisolvent, used to initiate the perovskite crystallization. It is found that these molecules are self‐anchored at the grain boundaries due to their strong binding to undercoordinated Pb²⁺. On a device level, this passivation scheme enhances the charge separation and transport at the grain boundaries due to the well‐matched energetic levels between the passivant and the perovskite. Consequently, these benefits contribute directly to the achievement of power conversion efficiencies as high as 21.2%, as well as the improved environmental and thermal stability of the PSCs. The surface treatment provides a new strategy to simultaneously passivate defects and enhance charge extraction/transport at the device interface by manipulating the anchoring groups of the molecules.     

Anti-solvent engineering via potassium bromide additive for highly efficient and stable perovskite solar cells

Anti-solvent assisted crystallization is commonly employed method to achieve high-quality perovskites attributed to its great operability. Herein, we report an anti-solvent engineering approach via simply using potassium bromide (KBr) additive with commonly used chlorobenzene (CB) in triple-cation perovskite solar cells (PSCs). We show that the KBr additive in the CB anti-solvent not only increases the crystallinity and passivates the perovskite top surface defects, but also leads to suppressed nonradiative recombination and facilitates charge extraction at interfaces. Interestingly, due to the halide vacancies filling with K⁺ ions, hysteresis behavior in the treated perovskite layer was suppressed. Consequently, a champion power conversion efficiency (PCE) of 18.29% was yielded for anti-solvent engineering employing KBr (an 20% improvement in PCE compared to the CB-only anti-solvent device). Furthermore, the optimized device based on KBr demonstrated improved stability, maintaining 80% of its original efficiency after aging in an environment with a relative humidity of 30–50% for 1080 h. Our study reports the significant role of anti-solvent engineering in improving perovskite's quality for efficient PSCs and develops the potential for PSC commercialization.     

Multifunctional Organic Potassium Salt Additives as the Efficient Defect Passivator for High-Efficiency and Stable Perovskite Solar Cells

Despite the rapid developments are achieved for perovskite solar cells (PSCs), the existence of various defects in the devices still limits the further enhancement of the power conversion efficiency (PCE) and the long-term stability of devices. Herein, the efficient organic potassium salt (OPS) of para-halogenated phenyl trifluoroborates is presented as the precursor additives to improve the performance of PSCs. Studies have shown that the 4-chlorophenyltrifluoroborate potassium salt (4-ClPTFBK) exhibits the most effective interaction with the perovskite lattice. Strong coordination between  BF₃⁻/halogen in anion and uncoordinated Pb²⁺/halide vacancies, along with the hydrogen bond between F in  BF₃⁻ and H in FA⁺ are observed. Thus, due to the synergistic contribution of the potassium and anionic groups, the high-quality perovskite film with large grain size and low defect density is achieved. As a result, the optimal devices show an enhanced efficiency of 24.50%, much higher than that of the control device (22.63%). Furthermore, the unencapsulated devices present remarkable thermal and long-term stability, maintaining 86% of the initial PCE after thermal test at 80 °C for 1000 h and 95% after storage in the air for 2460 h.     

Crystal Growth Regulation of α-FAPbI3 Perovskite Films for High-Efficiency Solar Cells with Long-Term Stability

The two-step sequentially deposition strategy has been widely used to produce high-performance FAPbI₃-based solar cells. However, due to the rapid reaction between PbI₂ and FAI, a dense perovskite film forms on top of the PbI₂ layer immediately and blocks the FAI diffusion into the bottom of the PbI₂ film for a complete reaction, which results in a low-efficiency and limited reproducibility of perovskite solar cells (PSCs). Here, high-quality α-FAPbI₃ perovskite films by crystal growth regulation with 4-fluorobenzamide additives is fabricated. The additives can interact with FAI to suppress the fast reaction between the FAI and PbI₂ and effectively passivate the under-coordinated Pb²⁺ or I^- defects. As a result, α-FAPbI₃ perovskite films with low trap density and large grain size are prepared. The modified PSCs present a high-power conversion efficiency of 24.08%, maintaining 90% of their initial efficiency after 1400 h in high humidity. This study provides an efficient strategy of synergistic crystallization and passivation to form high-quality α-FAPbI₃ films for high-performance PSCs.     

Mitigating Surface Deficiencies of Perovskite Single Crystals Enables Efficient Solar Cells with Enhanced Moisture and Reverse-Bias Stability

Metal halide perovskite single crystals are promising for diverse optoelectronic applications due to their outstanding properties. In comparison to the bulk, the crystal surface suffers from high defect density and is moisture sensitive; however, surface modification strategies of perovskite single crystals are relatively deficient. Herein, solar cells based on methylammonium lead triiodide (MAPbI₃) thin single crystals are selected as a prototype to improve single-crystal perovskite devices by surface modification. The surface trap passivation and protection against moisture of MAPbI₃ thin single crystals are achieved by one bifunctional molecule 3-mercaptopropyl(dimethoxy)methylsilane (MDMS). The sulfur atom of MDMS can coordinate with bare Pb²⁺ of MAPbI₃ single crystals to reduce surface defect density and nonradiative recombination. As a result, the modified devices show a remarkable efficiency of 22.2%, which is the highest value for single-crystal MAPbI₃ solar cells. Moreover, MDMS modification mitigates surface ion migration, leading to enhanced reverse-bias stability. Finally, the cross-link of silane molecules forms a protective layer on the crystal surface, which results in enhanced moisture stability of both materials and devices. This work provides an effective way for surface modification of perovskite single crystals, which is important for improving the performance of single-crystal perovskite solar cells, photodetectors, X-ray detectors, etc.