Enhanced Carrier Dynamics Resulted from Non-Volatile Chloride Additive for Improved Average Efficiency of PSCs

Enhanced Carrier Dynamics Resulted from Non-Volatile Chloride Additive for Improved Average Efficiency of PSCs | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Enhanced Carrier Dynamics Resulted from Non-Volatile Chloride Additive for Improved Average Efficiency of PSCs Zheng Zhang, Haimin Li, Haohui Li, Bo An, Yuhao Wei, Jia Liao, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7604240/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Chlorine additives are commonly used to optimize perovskite solar cells (PSCs). However, due to strong volatility, organic chlorine additives often result in poor stability and residual lead iodide (PbI 2 ). Here, we report a method to improve perovskite film crystallization via the formation of lead chloride (PbCl 2 )-induced intermediate phase in a two-step process. Results show that non-volatile PbCl 2 not only creates a porous structure favorable for solid-liquid reactions during the second step deposition but also forms a MAPbCl 3 intermediate phase with methylammonium chloride (MACl), which greatly promotes the crystallization quality of perovskite (PVK) films. Additionally, transient absorption (TA) spectroscopy indicates that an appropriate amount of PbCl 2 can improve the carrier dynamics, while excess additives would deteriorate the charge activity. As a result, the average power conversion efficiency (PCE) of the optimal modified devices is promoted from 18.79% to 21.34% with a champion efficiency of 23.15%. And the hysteresis index (HI) reduced from 17.48% to 6.09%. PbCl 2 added PSCs can retain 78% of its initial PCE after 1000 hours under 50% relative humidity (RH) in ambient air. Our work provides a novel approach to precisely control the carrier dynamics and clarifies the mechanism of PbCl 2 in the growth process of perovskite films. perovskite solar cells crystallization band alignment carrier dynamic hysteresis Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 1. Introduction Over the past few decades, perovskite solar cells (PSCs) have attracted significant research interest due to their exceptional optoelectronic properties 1 , 2 . The power conversion efficiency (PCE) of PSCs has witnessed a remarkable progression from the initial 3.8% to over 26% in recent years 3 . However, the commercialization of PSCs is hindered by challenges inherent in fabrication techniques, including incomplete precursor reaction, inhomogeneous film morphology, and batch-to-batch variability 4 – 7 . These issues lead to suboptimal device performance and reliability, thereby impeding large-scale industrial adoption 8 . A substantial body of research has concentrated on interface modification, process optimization, and charge transport layer engineering, primarily aimed at mitigating defects arising from fabrication processes 9 – 12 . At the macroscopic level, defects within the absorb layer are primarily attributed to inhomogeneous surface morphology and attenuated optical absorption 13 . At the microscopic scale, these defects originate from three key mechanisms: (1) ionic migration of A-site cations, B-site metal ions, and X-site halides within the perovskite lattice 14 , 15 ; (2) stoichiometric deviations from the ideal ABX 3 composition 16 , 17 ; and (3) intrinsic material properties 18 . Collectively, the trap states introduced by these factors would inevitably impede carrier generation and deteriorate charge extraction efficiency between the perovskite and transport layers. So far, improving the quality of perovskite layer is the most direct way to enhance the properties of PSCs. Among diverse strategies, additive engineering has emerged as a facile yet highly effective approach to restrain defects and promote efficiency of the devices. Volatile chlorine additives, such as methylammonium chloride (MACl) and formamidine chloride (FACl), can significantly increase the grain size of perovskites by forming an intermediate phase 19 – 24 . Non-volatile chlorine additives, such as phenethylammonium chloride (PEACl), rubidium chloride (RbCl), and cesium chloride (CsCl), can enter into perovskite lattice to promote energy level alignment and adjust the structural tolerance factor, release lattice stress and passivate defects 25 – 31 . In addition, the study also shows that in the two-step method, RbCl can convert PbI 2 into (PbI 2 ) 2 RbCl intermediate phase 32 . The introduction of inorganic additives can efficiently impede the swift evaporation of volatile chloride and enhance the crystallization quality of perovskite films 33 – 35 . In this work, a sequential deposition process based on PbCl 2 was developed for the preparation of perovskite solar cells. Compared with PbI 2 , the crystallization process of PbCl 2 with organic precursors are validly improved, thus provide crystal seeds for the growth of perovskites. In addition, chloride intermediates are more stable than that of iodide ones in the reaction. The results show that PbCl 2 participates introduce porous morphology for lead iodide films, which is conducive for the penetration and reaction of organic precursors in the next step, thus can greatly improve the crystallization of PVKs. At the same time, it is found that the intervention of PbCl 2 improves the carrier dynamics and the energy level arrangement of the devices, thereby promotes the open-circuit voltage ( V OC ). Consequently, the devices modified with optimal PbCl 2 exhibit a significant improvement in average PCE from 18.5% to 21%, and the highest efficiency is boosted from 20.88% to 23.15% with obviously enhanced moisture stability. Meanwhile, the hysteresis index (HI) greatly decreased from 17.48% to 6.09%. 2. Experimental section 2.1. Materials ITO glass substrates (7 Ω sq − 1 ) were purchased from Advanced Electronic Technology Co., Ltd. Tin (IV) oxide, 15% in H 2 O colloidal dispersion liquid, was purchased from Alfa Aesar. Formamidinium iodide (FAI), methylamine hydrogen chloride (MACl), lead (II) iodide (PbI 2 ), lead (II) chloride (PbCl 2 ), 2,2′,7,7′-tetrakis (N,N-di-pmethoxyphenylamine)-9,9′-spirobifluorene (Spiro-OMeTAD, 99.5%), 4-tert-butylpyridine (TBP, AR), and Lithium bis(trifluoromethanesulphonyl)imide (Li-TFSI, AR) were purchased from Xi’an Polymer Light Technology Corp. N,N-dimethylformamide (DMF, 99.8%), dimethyl sulfoxide (DMSO, 99.9%), chlorobenzene (CB, 99.9%), acetonitrile (ACN, 99.9%), and isopropanol (IPA, 99.99%) was purchased from Aladdin. 2.2. Preparation of precursor solution SnO 2 colloid was diluted with deionised water in a ratio of 1:5 by volume to obtain the ETL precursor solution. To formulate the perovskite precursor, PbI 2 were mixed with PbCl 2 in different mass ratio (0%, 5%, 10%) followed by the addition of DMF with DMSO in a volume ratio of 9:1 to form the inorganic precursor solution. (More details can be found in the supplementary information Table S1 .) FAI and MACl were then added to 1 mL of IPA in a mass ratio of 9:1 to obtain the inorganic precursor solution. Finally, 72.3 mg of Spiro-OMeTAD, 29 µL of TBP and 17.5 µL of Li-TFSI solution (520 mg of lithium imide melted in 1 ml of ACN) were added to 1 ml of CB to obtain the HTL precursor solution. 2.3. Device fabrication ITO glass substrates were sequentially cleaned with ethanol, isopropanol, deionized water, and ethanol in an ultrasonic bath for 15 minutes, followed by drying with a nitrogen stream. The pre-cleaned ITO substrates underwent ultraviolet ozone treatment for 20 minutes to enhance their wettability. Subsequently, a 50 µL ETL precursor solution was spin-coated onto each ITO substrate at 3000 rpm for 30 seconds, followed by annealing on a hot plate at 150°C for 30 minutes. The ITO substrates were then subjected to an additional 20 minutes of ultraviolet ozone treatment before being immediately transferred to a glove box for further use. The perovskite layer was deposited using a two-step process. First, 70 µL of the PbI 2 precursor solution was spin-coated onto the substrate at 1500 rpm for 30 seconds, then annealed at 70°C for 10 seconds. Next, 120 µL of the organic cation precursor was spin-coated onto the PbI 2 film at 1600 rpm for 30 seconds. The wet film was annealed at 150°C for 15 minutes to form the perovskite layer. Following this, 50 µL of the HTL precursor solution was spin-coated at 4000 rpm on the perovskite layer for 30 seconds. Finally, the prepared device was placed in a dry, ambient environment for 12 hours for oxidation to enhance the conductivity of the HTL. Approximately 80 nm of silver electrode was deposited onto the HTL using magnetron sputtering, and the effective area of the device was delineated as 0.08 cm² using a shadow mask. 2.4. Characterizations The morphologies of the surface and cross-sectional images of the perovskite films were obtained by a field emission scanning electron microscope (FEI Quanta 650 FEG) with 10 kV. Femtosecond transient absorption (TA) measurements are made using a pump detection system (Helios, ultrafast system). Steady and time-resolved photoluminescence spectroscopies (PL and TRPL) were carried out by a fluorescence spectrometer (FLS 1000, Edinburgh Instruments). X-ray photoelectron spectroscopy (XPS) was performed using an X-ray photoelectron spectrometer (AXIS Ultra DLD) with a monochro-matic Al Kα X-ray source. The UV-visible absorption spectrum is measured by the UV-visible photometer (SHIMADZU UV-3600PLUS). AFM and KPFM were carried out by a scanning microwave impedance microscopy (Keysight 7500 AFM/STM). The J-V curve of photovoltaic cells were obtained using a Keithley 2400 source meter under an AM 1.5G illumination solar simulator (Newport, Oriel Sol3A). Electrochemical impedance spectroscopy (EIS), Space-Charge-Limited Current (SCLC), Mott-schottky curve were obtained using an electrochemical workstation (CHI660D). EQE was tested using the Photoelectric Electron Conversion Efficiency (IPCE) system (PVE300, Bentham, Inc.). The contact Angle of perovskite film was obtained by automatic contact angle measuring instrument (OCA25, TBU95, THX-05). 3. Results and discussion Figure 1 a-c show the top-view scanning electron microscopy (SEM) images of perovskite films with different PbCl 2 content. The surface without PbCl 2 contained abundant grayish-white morphology, likely PbI 2 or δ-phase 36 . These non-photovoltaic active phases could cause severe interfacial charge carrier recombination and compromise the overall flatness of the devices. Meanwhile, Figure S1 a-c show the average grain size increased from 500 nm to 900 nm with increased PbCl 2 concentration, when PbCl 2 at 10%, it decreased to 800 nm, indicating that PbCl 2 promotes grain growth up to a critical concentration, beyond which the effect reaches diminishing returns. Additionally, Fig. 1 d-f, Figure S2 , and Figure S3 reveal that, compared to the pristine one, the 5% PbCl 2 -doped lead iodide film forms a porous structure that facilitates formamidinium (FA) diffusion and solid-liquid reactions, and the surface roughness (RMS) increases from 27.8 nm to 34.1 nm. Meanwhile, for the 10% PbCl 2 -doped lead iodide film, due to the poor solubility of PbCl 2 in DMF, abundant plate-like PbCl 2 precipitate on the surface of PbI 2 37 , thus results into dense morphology, which is detrimental to subsequent organic precursor reactions (shown in Figure S4 ) 38 . Figure 1 g demonstrates the mechanism of the preparation process. Thickness analysis was performed for different PbCl 2 -doped samples, as shown in Figure S4 , it can be seen that as PbCl 2 concentration increased, the thickness of the PVK film is increased from 450 nm to 840 nm. However, pores can be clearly found in the 10% PbCl 2 added film, indicating that 5% is an optimal value. The thickness of the 5% PbCl 2 modified films with different perovskite content was analyzed by probe profilometer, as shown in Figure S5 . It can be seen that the average thickness of the optimal modified active layer are 442 nm, 532 nm, 640 nm, and 742 nm for PVK concentration of 1.2 mmol,1.3 mmol, 1.4 mmol, and 1.5 mmol, respectively. Further validation through photovoltaic characterization ( Figure S6 and S7 ) reveal that 1.4 mmol concentration achieves the highest PCE for both PbCl 2 -free and 5% doped devices. Specifically, the 0% control sample shows an average PCE of 18.79%, whereas the 5% sample demonstrates an improved value of 21.34%, accompanied by enhancements in V OC , short circuit current density ( J SC ), and fill factor (FF). Based on comprehensive morphological and electrical performance evaluations, the 5% PbCl 2 -doped 1.4 mmol PVK was selected as the target condition, with the 0% 1.4 mmol serving as the control one for subsequent analysis. Transient absorption (TA) spectroscopy is a powerful technique for probing carrier dynamics in perovskite films on nanosecond (ns) timescale. The samples investigated were perovskite films with an electron transport layer (ETL), required extremely high flatness, with the thickness of the solid samples not exceeding 1 mm, and were excited by a pump photon energy of 1.77 eV and fluence of 5 µJ cm − 2 . As shown in Fig. 2 a-c, distinct differences in photo-induced absorbance changes (ΔA) were observed among perovskite films with varying PbCl 2 contents, reflecting transitions from the ground state to excited states under pump excitation. Ground-state bleach signals (GSB, red and green area) were detected at 1.55 eV, 1.58 eV, and 1.60 eV for all samples. which is assigned to the band state filling effects of carriers into the band-edge of perovskite materials 39 . Figure 2 d-f reveal normalized transient absorption profiles of control and 5% PbCl 2 -doped perovskite films over a 0.4–10 ps time delay. Both samples exhibited a prominent high-energy tail (1.65–1.7 eV), indicative of thermal carrier cooling processes. Notably, the high-energy tail in the PbCl 2 -doped film contracted significantly faster than that in the control one, demonstrating that PbCl 2 modulates carrier cooling dynamics 40 . Additionally, a redshift in the bleach signal was observed with increased delay time, attributed to Auger recombination within the perovskite films 41 . The non-radiative energy transfer mechanism populates higher-energy states by exciting additional carriers, causing the bleach signal to shift toward longer wavelengths as electrons relax to lower-energy excited states. Figure 2 g presents the carrier dynamic curves of samples with different PbCl 2 contents at 790 nm. The fitting results and methodology are detailed in Table S2 . The average carrier lifetimes for 0%, 5%, and 10% PbCl 2 -doped PVKs were 840 ps, 828 ps, and 1190 ps, respectively. The shorter carrier lifetime observed in 5% PbCl 2 -doped sample indicates a lower density of defect states, which is more favorable for charge transport at the ETL interface. Steady-state and transient photoluminescence (PL) spectra were measured for 0%, 5%, and 10% PbCl 2 -doped perovskite films under test conditions of 20℃ and humidity below 30%. As shown in Fig. 2 h, the 5% PVK exhibited the strongest PL intensity, while the 10% one showed the weakest signal, indicating the lowest carrier recombination in the 5% film. Time-resolved photoluminescence (TRPL) (Fig. 2 i) and fitting data in Table S3 demonstrated that the 5% PbCl 2 -doped perovskite film showed the longest carrier lifetime (571.92 ns). suggesting reduced defect density in the photoactive layer, as fewer defects lead to suppressed non-radiative recombination and prolonged carrier lifetimes. Figure 3 a shows X-ray diffraction (XRD) patterns of unannealed wet perovskite films. The target film exhibits new peaks at 4.4°, 8.7° and 17.3°, which are attributed to MAPbCl 3 intermediate phases formed via rapid reactions between PbCl 2 and MACl 42 . In contrast, the control one displays a dominant PbI 2 peak at 12.6° with only a minor δ-phase peak at 9.7°. Figure 3 b further illustrates the crystallization disparity between the target and control films. The modified film exhibits well-defined α-phase peaks at 14.1° ((001) plane) and 28.3° ((002) plane), alongside a δ-phase peak at 11.95°. Conversely, the pristine one shows a strong PbI 2 peak at 12.6° and a weak α-phase peak at 14.6°, suggesting incomplete δ to α conversion. These results demonstrate that PbCl 2 enables more efficient crystallization through intermediate-phase engineering, which, combined with improved PbI 2 reactivity in porous films, ultimately enhances PCE. X - ray photoelectron spectroscopy (XPS) was employed to further investigate the interfacial interactions in perovskite films induced by PbCl 2 and the green line represents the result of background processing. The survey XPS spectra are presented in Figure S8 . Figure 3 c reveals a positive shift in the Pb 4f binding energy that attributed to the introduction of highly electronegative element chlorine into perovskite lattice, which reduces the electron cloud density around Pb 2+ ions and increases the binding energy. Similarly, the I 3d binding energy shift observed in Fig. 3 (d) arises from chlorine electron withdrawing effect on iodide ions since chlorine reveals stronger electronegativity compared to iodine. Figure 3 e demonstrates that although MACl was added into the control sample, no Cl-related characteristic peaks were detected in the film, which indicates that Cl evaporated during the annealing process, leaving negligible organic volatile Cl residues in the perovskite layer. In contrast, due to the strong Pb-Cl interaction driven by chlorine high electronegativity, the target sample prevents Cl from escaping the lattice during processing 43 , 44 . As shown in Fig. 3 f, the N 1s peak of the target sample shifted to higher binding energy compared to the control one, indicating that the chemical environment around FA was altered due to Cl incorporation. Kelvin probe force microscopy (KPFM) was employed to characterize the surface contact potential difference (CPD) of perovskite films, using a gold (Au) tip. As shown in Fig. 4 a-b, the control sample exhibited CPD fluctuations exceeding 150 mV, significantly larger than the target of 100 mV, indicating a more homogeneous phase distribution in the PbCl 2 -doped films. After calculation using Eq. (1) 45 , Fig. 4 c-d reveal a 0.1 eV upward shift of work function in the target sample relative to the control one, which results into decreased Fermi level, favorable for electron transportation and thereby facilitates FF. According to Figure S9a , the addition of 5% lead chloride significantly enhances the absorbance in visible light region. However, excessive PbCl 2 addition leads to a reduction in film absorbance. Meanwhile, as presented in Figure S9b , Tauc-plot analysis reveals that the bandgaps ( E g ) of the 0% and 5% PbCl 2 perovskites are both 1.55 eV, while the 10% sample exhibits a slightly increased E g of 1.56 eV, indicating that PbCl 2 addition does not induce significant bandgap variation in the perovskite layer. The promoted work function and slightly changes of E g are schematically illustrated in Fig. 4 e. $$\:{W}_{F}=5.1-q（{CPD}_{Au}-{CPD}_{sample}）$$ 1 Where W F is the work function, q represents the elementary charge, and CPD AU refers to the CPD of gold (Au, with a work function of 5.1 eV), which is typically measured as -60 mV. To quantify the defect state density and carrier dynamics of the films, the space charge limited currents (SCLC), Mott-Schottky test, and alternating current (AC) impedance spectroscopy were employed to characterize the electrochemical properties of different devices. As shown in Fig. 5 a,b, the trap-filled limit voltages ( V TFL ) of the target and control device in single-electron devices were 0.32 V and 1.18 V, respectively, while those in single-hole devices were 0.55 V and 1.40 V. According to Eq. (2) 46 , the electron trap state density decreased from 3.02×10 16 cm − 3 in the control device to 8.20×10 15 cm − 3 in the target one, and the hole defect density decreased from 3.59×10 16 cm − 3 to 1.41×10 16 cm − 3 , which demonstrates that optimal PbCl 2 effectively reduces the defects in the perovskite layer 47 . $$\:{N}_{trap}=\frac{2{\epsilon\:}_{0}{\epsilon\:}{V}_{TFL}}{q{L}^{2}}$$ 2 In Eq. 2 , ε₀ and ε represent the vacuum permittivity (8.8542×10 − 14 F*cm − 1 ) and the relative permittivity of the perovskite material, respectively. The symbol q denotes the elementary charge, while L corresponds to the thickness of the perovskite layer which can be obtained from Figure S4 . Figure 5 c reveals that the built-in electric field are 0.84 V and 0.89 V for the control and target devices, respectively. Figure 5 d demonstrates the electrochemical impedance spectroscopy (EIS) of the perovskite solar cells. As shown in Table S4 , the simulation values obtained from EIS results indicate that both the charge transfer resistance ( R tr ) and recombination resistance ( R rec ) of the target device are higher than those of the control one, confirming that PbCl 2 effectively enhances carrier transport and reduces recombinations. Moreover, the series resistance ( R S ) of the modified cell is lower than that of the pristine one, which is closely related to the enhanced morphology of the PVK with 5% PbCl 2 . As shown in Fig. 5 e, the linear relationships between V OC and input light intensity are described by Eq. ( 3 ). The ideality factors (n) of the target and control devices are 1.22 and 1.3, respectively. In Fig. 5 f, the linear relationships between J SC and input light intensity are represented by Eq. ( 4 ), with the current-dependent factors (α) of the target and control device being 0.96 and 0.94, respectively, indicating superior performance after PbCl 2 modification 48 . As demonstrated in Fig. 5 g and Figure S10 , the target PSC exhibits significant improvements in V oc , J sc , FF, and PCE compared to the control one. Specifically, J sc increased from 23.78 mA·cm − 2 to 24.79 mA·cm − 2 , V oc rose from 1.12 V to 1.15 V, FF improved from 78.08% to 80.59%, and the PCE was boosted from 20.88% to 23.15%. Additionally, as presented in Figure S11 , forward-reverse hysteresis tests were conducted on both device (results shown in Table S5 ). Using Eq. (5), the hysteresis index (HI) of the target and control device were calculated as 6.09% and 17.48%, respectively, confirming reduced hysteresis in the modified cell. The external quantum efficiency (EQE) curves in Fig. 5 h show integrated current densities increasing from 23.12 mA·cm − 2 to 24.04 mA·cm − 2 after fitting. Steady-state PCE measurements at maximum power point (Fig. 5 i) yielded values of 22.51% for the target PCS and 20.29% for the control one. $$\:{V}_{OC}\propto\:n（{k}_{B}T/q）\text{l}\text{n}（{P}_{light}）$$ 3 $$\:{J}_{SC}\propto\:{（{P}_{light}）}^{\alpha\:}$$ 4 In Eqs. ( 3 ) and ( 4 ), P light refers to the incident light power on the active area of the cell (W·cm⁻²). k B denotes the Boltzmann constant (8.617×10 − 5 eV·K − 1 ), T is the test temperature (K), and the n value represents the ideality factor of the solar cell, n = 1 indicates diffusion current dominance and n = 2 means recombination current dominance. Practical PN junction devices typically exhibit 1 < n < 2 due to recombination centers in the space charge region. A smaller n value approaching 1 signifies reduced non-radiative recombination and lower defect density. Specifically, the α value represents the correlation factor between J SC and light intensity, where values closer to 1 indicate weaker bimolecular recombination in the device 49 , 50 . Moreover, environmental stability tests (Fig. 6 a,b) revealed that the target devices retained 87% efficiency after 2000 h in a nitrogen atmosphere and 78% efficiency after 1000 h at 50% relative humidity. The larger contact angles observed in Fig. 6 c,d further indicate enhanced moisture resistance of the target device. 4. Conclusion In summary, we have devised a strategy to fabricate stable, and dense perovskite films via the PbCl 2 -mediated formation of an intermediate phase. During the two-step deposition procedure, the inorganic PbCl 2 additive assumes multiple pivotal functions. It engages in an interaction with PbI 2 to generate a porous architecture, which promotes the solid-liquid reaction with the organic precursors. Meanwhile, it reacts with volatile MACl to yield the MAPbCl 3 intermediate phase, which not only diminishes the perovskite nucleation energy barrier but also incorporates Cl into the PVK lattice, thus enhances the energy level alignment between the perovskite and the ETL, and improves the carrier dynamics. Ultimately, in comparison with the control devices, through the optimization of the device thickness and the quantity of added PbCl 2 , we attained an enhanced average efficiency from 18.79% to 21.34%, with a champion PCE of 23.15%. Additionally, the HI was reduced from 17.48% to 6.09%, and promoted environmental stability was achieved. Our work not only furnishes a highly reproducible preparation approach for high quality PSCs but also clarifies the mechanism of the non-volatile chlorine additive PbCl 2 in the growth process of perovskite films. Declarations Declaration of Competing Interest The authors declare no conflict of interest. Author Contribution Zheng Zhang and Haimin Li (corresponding author) took the lead in writing the main manuscript text, including formulating the core framework of the study and organizing the key research content. Haohui Li and Bo An were mainly responsible for collecting and analyzing the research data, ensuring the accuracy and reliability of the data used in the manuscript. Yuhao Wei and Jia Liao prepared all the figures in the manuscript, including designing the figure layout, processing the image data and adding the necessary annotations. Xiangxue Lv and Xingchong Liu conducted an in-depth review of the relevant literature, sorted out the research background and current research status, and provided important support for the literature review part of the manuscript. Hanyu Wang participated in the discussion of the research results, put forward constructive opinions on the interpretation of the results and the improvement of the manuscript. All authors (Zheng Zhang, Haimin Li, Haohui Li, Bo An, Yuhao Wei, Jia Liao, Xiangxue Lv, Xingchong Liu, Hanyu Wang) carefully reviewed the entire manuscript, checked the logical consistency of the content, corrected the language errors and put forward suggestions for revision, and finally approved the submission version of the manuscript. Acknowledgements This work was supported by Sichuan Science and Technology Program (2024ZDZX0030), Chengdu Science and Technology Program (2024-JB00-00010-GX). References Jiang, Q.; Zhu, K., Rapid advances enabling high-performance inverted perovskite solar cells. Nature Reviews Materials 2024, 9 (6), 399-419.http://doi.org/10.1038/s41578-024-00678-x Zhang, X.; Wu, S.; Zhang, H.; Jen, A. K.; Zhan, Y.; Chu, J., Advances in inverted perovskite solar cells. Nature Photonics 2024, 18 , 1243–1253.http://doi.org/10.1038/s41566-024-01541-9 Han, J. Y.; Park, K.; Tan, S.; Vaynzof, Y.; Xue, J. J.; Diau, E. W. G.; Bawendi, M. G.; Lee, J. 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SEM images of PbI\u003csub\u003e2\u003c/sub\u003e films of (d) 0% PbCl\u003csub\u003e2\u003c/sub\u003e, (e) 5% PbCl\u003csub\u003e2\u003c/sub\u003e and (f) 10% PbCl\u003csub\u003e2\u003c/sub\u003e. (g) Schematic diagram of the preparation process of perovskite films with and without PbCl\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-7604240/v1/5573ae8388b7d0d1b99da068.png"},{"id":92889365,"identity":"00406da1-48c3-4faf-b049-0eb6a631f341","added_by":"auto","created_at":"2025-10-06 17:27:00","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":376174,"visible":true,"origin":"","legend":"\u003cp\u003e(a-c) Two-dimensional false-color images of TA spectra of perovskite films with different PbCl\u003csub\u003e2\u003c/sub\u003e contents. (d-f) TA curves of different PbCl\u003csub\u003e2\u003c/sub\u003e contents perovskite films at 0.4 ps to 10 ps delay time. (g) Normalized carrier dynamic plots of samples with different lead chloride contents at 790 nm. (h) PL spectrum of perovskite films with different PbCl\u003csub\u003e2\u003c/sub\u003e content on glass. (i) TRPL spectrum f perovskite films with different PbCl\u003csub\u003e2\u003c/sub\u003e content on glass.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-7604240/v1/9acd49f4613e40c038c997dc.png"},{"id":92889367,"identity":"20a23bec-b679-469c-87f1-b22e1808e3d2","added_by":"auto","created_at":"2025-10-06 17:27:00","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":167673,"visible":true,"origin":"","legend":"\u003cp\u003eXRD patterns of target and control perovskite films (a) without annealing and (b) after annealing. XPS spectra of (c) Pb 4f, (d) I 3d, (e) Cl 2p, and (e) N 1s for the target and control perovskite films.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-7604240/v1/cd387cb937b6bcb42cccf34e.png"},{"id":92890219,"identity":"11f6104d-021b-4c3f-b60c-92c6d145d83f","added_by":"auto","created_at":"2025-10-06 17:43:00","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":393328,"visible":true,"origin":"","legend":"\u003cp\u003eTwo-dimensional KPFM distribution images and line scan curves of perovskite films in the (a) control and the (b) target (along the black arrow). (c) CPD and (d) W\u003csub\u003eF\u003c/sub\u003e histogram of target and control perovskite films. (e) Diagram of energy level arrangement of target and control perovskite films.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-7604240/v1/ffd3b4d54236c24641d93a49.png"},{"id":92889369,"identity":"ef1de7c9-fa40-4e75-ab19-163a252ba782","added_by":"auto","created_at":"2025-10-06 17:27:00","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":272046,"visible":true,"origin":"","legend":"\u003cp\u003eSCLC diagram of target and control, (a) electron-only device, (b) hole-only device. (c) Mott-Schottky curves of target and control device. (d) EIS diagram of target and control device. (e-f) Light intensity dependence diagram of target and control device. (g) \u003cem\u003eJ-V\u003c/em\u003ecurves for target and control optimal device. (h) EQE and integrated current curves of target and control optimal devices. (i) Steady-state output curves of target and control optimal device (under AM 1.5G condition).\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-7604240/v1/db097e088ad8fbbbbb59e9ad.png"},{"id":92889375,"identity":"a95f3901-7511-40b2-9047-a2fd38efada2","added_by":"auto","created_at":"2025-10-06 17:27:00","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":199029,"visible":true,"origin":"","legend":"\u003cp\u003e(a)\u003cstrong\u003e \u003c/strong\u003eStability diagram of target and control sample in a nitrogen glove box environment. (b) Stability diagram of target and control sample in atmospheric environment at RH=50%, 25℃. (c-d) Contact Angle diagram of target and control perovskite film with water\u003csup\u003e51\u003c/sup\u003e.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-7604240/v1/008171d76ff67b5d75a435a5.png"},{"id":92891117,"identity":"26d952fa-a00c-484e-a24b-dd13e37b88a0","added_by":"auto","created_at":"2025-10-06 17:59:02","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2570558,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7604240/v1/59ccd56e-e288-4915-b623-d40e163dee3d.pdf"},{"id":92889372,"identity":"167edd33-4531-48d9-9470-74cccfbb0824","added_by":"auto","created_at":"2025-10-06 17:27:00","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":4742614,"visible":true,"origin":"","legend":"","description":"","filename":"Supportinginformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-7604240/v1/dc2cd5b8b17b961c95b5290d.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Enhanced Carrier Dynamics Resulted from Non-Volatile Chloride Additive for Improved Average Efficiency of PSCs","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eOver the past few decades, perovskite solar cells (PSCs) have attracted significant research interest due to their exceptional optoelectronic properties\u003csup\u003e\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u003c/sup\u003e. The power conversion efficiency (PCE) of PSCs has witnessed a remarkable progression from the initial 3.8% to over 26% in recent years\u003csup\u003e\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u003c/sup\u003e. However, the commercialization of PSCs is hindered by challenges inherent in fabrication techniques, including incomplete precursor reaction, inhomogeneous film morphology, and batch-to-batch variability\u003csup\u003e\u003cspan additionalcitationids=\"CR5 CR6\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e\u003c/sup\u003e. These issues lead to suboptimal device performance and reliability, thereby impeding large-scale industrial adoption\u003csup\u003e\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e\u003cp\u003eA substantial body of research has concentrated on interface modification, process optimization, and charge transport layer engineering, primarily aimed at mitigating defects arising from fabrication processes\u003csup\u003e\u003cspan additionalcitationids=\"CR10 CR11\" citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u003c/sup\u003e. At the macroscopic level, defects within the absorb layer are primarily attributed to inhomogeneous surface morphology and attenuated optical absorption\u003csup\u003e\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e\u003c/sup\u003e. At the microscopic scale, these defects originate from three key mechanisms: (1) ionic migration of A-site cations, B-site metal ions, and X-site halides within the perovskite lattice\u003csup\u003e\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u003c/sup\u003e; (2) stoichiometric deviations from the ideal ABX\u003csub\u003e3\u003c/sub\u003e composition\u003csup\u003e\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e\u003c/sup\u003e; and (3) intrinsic material properties\u003csup\u003e\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e\u003c/sup\u003e. Collectively, the trap states introduced by these factors would inevitably impede carrier generation and deteriorate charge extraction efficiency between the perovskite and transport layers.\u003c/p\u003e\u003cp\u003eSo far, improving the quality of perovskite layer is the most direct way to enhance the properties of PSCs. Among diverse strategies, additive engineering has emerged as a facile yet highly effective approach to restrain defects and promote efficiency of the devices. Volatile chlorine additives, such as methylammonium chloride (MACl) and formamidine chloride (FACl), can significantly increase the grain size of perovskites by forming an intermediate phase\u003csup\u003e\u003cspan additionalcitationids=\"CR20 CR21 CR22 CR23\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e\u003c/sup\u003e. Non-volatile chlorine additives, such as phenethylammonium chloride (PEACl), rubidium chloride (RbCl), and cesium chloride (CsCl), can enter into perovskite lattice to promote energy level alignment and adjust the structural tolerance factor, release lattice stress and passivate defects\u003csup\u003e\u003cspan additionalcitationids=\"CR26 CR27 CR28 CR29 CR30\" citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u003c/sup\u003e. In addition, the study also shows that in the two-step method, RbCl can convert PbI\u003csub\u003e2\u003c/sub\u003e into (PbI\u003csub\u003e2\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003eRbCl intermediate phase\u003csup\u003e\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e\u003c/sup\u003e. The introduction of inorganic additives can efficiently impede the swift evaporation of volatile chloride and enhance the crystallization quality of perovskite films \u003csup\u003e\u003cspan additionalcitationids=\"CR34\" citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e\u003cp\u003eIn this work, a sequential deposition process based on PbCl\u003csub\u003e2\u003c/sub\u003e was developed for the preparation of perovskite solar cells. Compared with PbI\u003csub\u003e2\u003c/sub\u003e, the crystallization process of PbCl\u003csub\u003e2\u003c/sub\u003e with organic precursors are validly improved, thus provide crystal seeds for the growth of perovskites. In addition, chloride intermediates are more stable than that of iodide ones in the reaction. The results show that PbCl\u003csub\u003e2\u003c/sub\u003e participates introduce porous morphology for lead iodide films, which is conducive for the penetration and reaction of organic precursors in the next step, thus can greatly improve the crystallization of PVKs. At the same time, it is found that the intervention of PbCl\u003csub\u003e2\u003c/sub\u003e improves the carrier dynamics and the energy level arrangement of the devices, thereby promotes the open-circuit voltage (\u003cem\u003eV\u003c/em\u003e\u003csub\u003eOC\u003c/sub\u003e). Consequently, the devices modified with optimal PbCl\u003csub\u003e2\u003c/sub\u003e exhibit a significant improvement in average PCE from 18.5% to 21%, and the highest efficiency is boosted from 20.88% to 23.15% with obviously enhanced moisture stability. Meanwhile, the hysteresis index (HI) greatly decreased from 17.48% to 6.09%.\u003c/p\u003e"},{"header":"2. Experimental section","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\u003ch2\u003e2.1. Materials\u003c/h2\u003e\u003cp\u003eITO glass substrates (7 Ω sq\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) were purchased from Advanced Electronic Technology Co., Ltd. Tin (IV) oxide, 15% in H\u003csub\u003e2\u003c/sub\u003eO colloidal dispersion liquid, was purchased from Alfa Aesar. Formamidinium iodide (FAI), methylamine hydrogen chloride (MACl), lead (II) iodide (PbI\u003csub\u003e2\u003c/sub\u003e), lead (II) chloride (PbCl\u003csub\u003e2\u003c/sub\u003e), 2,2\u0026prime;,7,7\u0026prime;-tetrakis (N,N-di-pmethoxyphenylamine)-9,9\u0026prime;-spirobifluorene (Spiro-OMeTAD, 99.5%), 4-tert-butylpyridine (TBP, AR), and Lithium bis(trifluoromethanesulphonyl)imide (Li-TFSI, AR) were purchased from Xi\u0026rsquo;an Polymer Light Technology Corp. N,N-dimethylformamide (DMF, 99.8%), dimethyl sulfoxide (DMSO, 99.9%), chlorobenzene (CB, 99.9%), acetonitrile (ACN, 99.9%), and isopropanol (IPA, 99.99%) was purchased from Aladdin.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\u003ch2\u003e2.2. Preparation of precursor solution\u003c/h2\u003e\u003cp\u003eSnO\u003csub\u003e2\u003c/sub\u003e colloid was diluted with deionised water in a ratio of 1:5 by volume to obtain the ETL precursor solution. To formulate the perovskite precursor, PbI\u003csub\u003e2\u003c/sub\u003e were mixed with PbCl\u003csub\u003e2\u003c/sub\u003e in different mass ratio (0%, 5%, 10%) followed by the addition of DMF with DMSO in a volume ratio of 9:1 to form the inorganic precursor solution. (More details can be found in the supplementary information \u003cb\u003eTable \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e\u003c/b\u003e.) FAI and MACl were then added to 1 mL of IPA in a mass ratio of 9:1 to obtain the inorganic precursor solution. Finally, 72.3 mg of Spiro-OMeTAD, 29 \u0026micro;L of TBP and 17.5 \u0026micro;L of Li-TFSI solution (520 mg of lithium imide melted in 1 ml of ACN) were added to 1 ml of CB to obtain the HTL precursor solution.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\u003ch2\u003e2.3. Device fabrication\u003c/h2\u003e\u003cp\u003eITO glass substrates were sequentially cleaned with ethanol, isopropanol, deionized water, and ethanol in an ultrasonic bath for 15 minutes, followed by drying with a nitrogen stream. The pre-cleaned ITO substrates underwent ultraviolet ozone treatment for 20 minutes to enhance their wettability. Subsequently, a 50 \u0026micro;L ETL precursor solution was spin-coated onto each ITO substrate at 3000 rpm for 30 seconds, followed by annealing on a hot plate at 150\u0026deg;C for 30 minutes. The ITO substrates were then subjected to an additional 20 minutes of ultraviolet ozone treatment before being immediately transferred to a glove box for further use. The perovskite layer was deposited using a two-step process. First, 70 \u0026micro;L of the PbI\u003csub\u003e2\u003c/sub\u003e precursor solution was spin-coated onto the substrate at 1500 rpm for 30 seconds, then annealed at 70\u0026deg;C for 10 seconds. Next, 120 \u0026micro;L of the organic cation precursor was spin-coated onto the PbI\u003csub\u003e2\u003c/sub\u003e film at 1600 rpm for 30 seconds. The wet film was annealed at 150\u0026deg;C for 15 minutes to form the perovskite layer. Following this, 50 \u0026micro;L of the HTL precursor solution was spin-coated at 4000 rpm on the perovskite layer for 30 seconds. Finally, the prepared device was placed in a dry, ambient environment for 12 hours for oxidation to enhance the conductivity of the HTL. Approximately 80 nm of silver electrode was deposited onto the HTL using magnetron sputtering, and the effective area of the device was delineated as 0.08 cm\u0026sup2; using a shadow mask.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e\u003ch2\u003e2.4. Characterizations\u003c/h2\u003e\u003cp\u003eThe morphologies of the surface and cross-sectional images of the perovskite films were obtained by a field emission scanning electron microscope (FEI Quanta 650 FEG) with 10 kV. Femtosecond transient absorption (TA) measurements are made using a pump detection system (Helios, ultrafast system). Steady and time-resolved photoluminescence spectroscopies (PL and TRPL) were carried out by a fluorescence spectrometer (FLS 1000, Edinburgh Instruments). X-ray photoelectron spectroscopy (XPS) was performed using an X-ray photoelectron spectrometer (AXIS Ultra DLD) with a monochro-matic Al Kα X-ray source. The UV-visible absorption spectrum is measured by the UV-visible photometer (SHIMADZU UV-3600PLUS). AFM and KPFM were carried out by a scanning microwave impedance microscopy (Keysight 7500 AFM/STM). The J-V curve of photovoltaic cells were obtained using a Keithley 2400 source meter under an AM 1.5G illumination solar simulator (Newport, Oriel Sol3A). Electrochemical impedance spectroscopy (EIS), Space-Charge-Limited Current (SCLC), Mott-schottky curve were obtained using an electrochemical workstation (CHI660D). EQE was tested using the Photoelectric Electron Conversion Efficiency (IPCE) system (PVE300, Bentham, Inc.). The contact Angle of perovskite film was obtained by automatic contact angle measuring instrument (OCA25, TBU95, THX-05).\u003c/p\u003e\u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cp\u003eFigure \u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea-c show the top-view scanning electron microscopy (SEM) images of perovskite films with different PbCl\u003csub\u003e2\u003c/sub\u003e content. The surface without PbCl\u003csub\u003e2\u003c/sub\u003e contained abundant grayish-white morphology, likely PbI\u003csub\u003e2\u003c/sub\u003e or δ-phase\u003csup\u003e\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u003c/sup\u003e. These non-photovoltaic active phases could cause severe interfacial charge carrier recombination and compromise the overall flatness of the devices. Meanwhile, \u003cb\u003eFigure \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003ea-c\u003c/b\u003e show the average grain size increased from 500 nm to 900 nm with increased PbCl\u003csub\u003e2\u003c/sub\u003e concentration, when PbCl\u003csub\u003e2\u003c/sub\u003e at 10%, it decreased to 800 nm, indicating that PbCl\u003csub\u003e2\u003c/sub\u003e promotes grain growth up to a critical concentration, beyond which the effect reaches diminishing returns. Additionally, Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ed-f, \u003cb\u003eFigure S2\u003c/b\u003e, and \u003cb\u003eFigure S3\u003c/b\u003e reveal that, compared to the pristine one, the 5% PbCl\u003csub\u003e2\u003c/sub\u003e-doped lead iodide film forms a porous structure that facilitates formamidinium (FA) diffusion and solid-liquid reactions, and the surface roughness (RMS) increases from 27.8 nm to 34.1 nm. Meanwhile, for the 10% PbCl\u003csub\u003e2\u003c/sub\u003e-doped lead iodide film, due to the poor solubility of PbCl\u003csub\u003e2\u003c/sub\u003e in DMF, abundant plate-like PbCl\u003csub\u003e2\u003c/sub\u003e precipitate on the surface of PbI\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e37\u003c/sup\u003e, thus results into dense morphology, which is detrimental to subsequent organic precursor reactions (shown in \u003cb\u003eFigure S4\u003c/b\u003e)\u003csup\u003e\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u003c/sup\u003e. Figure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eg demonstrates the mechanism of the preparation process.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eThickness analysis was performed for different PbCl\u003csub\u003e2\u003c/sub\u003e-doped samples, as shown in \u003cb\u003eFigure S4\u003c/b\u003e, it can be seen that as PbCl\u003csub\u003e2\u003c/sub\u003e concentration increased, the thickness of the PVK film is increased from 450 nm to 840 nm. However, pores can be clearly found in the 10% PbCl\u003csub\u003e2\u003c/sub\u003e added film, indicating that 5% is an optimal value. The thickness of the 5% PbCl\u003csub\u003e2\u003c/sub\u003e modified films with different perovskite content was analyzed by probe profilometer, as shown in \u003cb\u003eFigure S5\u003c/b\u003e. It can be seen that the average thickness of the optimal modified active layer are 442 nm, 532 nm, 640 nm, and 742 nm for PVK concentration of 1.2 mmol,1.3 mmol, 1.4 mmol, and 1.5 mmol, respectively. Further validation through photovoltaic characterization (\u003cb\u003eFigure S6 and S7\u003c/b\u003e) reveal that 1.4 mmol concentration achieves the highest PCE for both PbCl\u003csub\u003e2\u003c/sub\u003e-free and 5% doped devices. Specifically, the 0% control sample shows an average PCE of 18.79%, whereas the 5% sample demonstrates an improved value of 21.34%, accompanied by enhancements in \u003cem\u003eV\u003c/em\u003e\u003csub\u003eOC\u003c/sub\u003e, short circuit current density (\u003cem\u003eJ\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e), and fill factor (FF). Based on comprehensive morphological and electrical performance evaluations, the 5% PbCl\u003csub\u003e2\u003c/sub\u003e-doped 1.4 mmol PVK was selected as the target condition, with the 0% 1.4 mmol serving as the control one for subsequent analysis.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eTransient absorption (TA) spectroscopy is a powerful technique for probing carrier dynamics in perovskite films on nanosecond (ns) timescale. The samples investigated were perovskite films with an electron transport layer (ETL), required extremely high flatness, with the thickness of the solid samples not exceeding 1 mm, and were excited by a pump photon energy of 1.77 eV and fluence of 5 \u0026micro;J cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e2\u003c/span\u003ea-c, distinct differences in photo-induced absorbance changes (ΔA) were observed among perovskite films with varying PbCl\u003csub\u003e2\u003c/sub\u003e contents, reflecting transitions from the ground state to excited states under pump excitation. Ground-state bleach signals (GSB, red and green area) were detected at 1.55 eV, 1.58 eV, and 1.60 eV for all samples. which is assigned to the band state filling effects of carriers into the band-edge of perovskite materials\u003csup\u003e\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e2\u003c/span\u003ed-f reveal normalized transient absorption profiles of control and 5% PbCl\u003csub\u003e2\u003c/sub\u003e-doped perovskite films over a 0.4\u0026ndash;10 ps time delay. Both samples exhibited a prominent high-energy tail (1.65\u0026ndash;1.7 eV), indicative of thermal carrier cooling processes. Notably, the high-energy tail in the PbCl\u003csub\u003e2\u003c/sub\u003e-doped film contracted significantly faster than that in the control one, demonstrating that PbCl\u003csub\u003e2\u003c/sub\u003e modulates carrier cooling dynamics\u003csup\u003e\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u003c/sup\u003e. Additionally, a redshift in the bleach signal was observed with increased delay time, attributed to Auger recombination within the perovskite films\u003csup\u003e\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e\u003c/sup\u003e. The non-radiative energy transfer mechanism populates higher-energy states by exciting additional carriers, causing the bleach signal to shift toward longer wavelengths as electrons relax to lower-energy excited states.\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e2\u003c/span\u003eg presents the carrier dynamic curves of samples with different PbCl\u003csub\u003e2\u003c/sub\u003e contents at 790 nm. The fitting results and methodology are detailed in \u003cb\u003eTable S2\u003c/b\u003e. The average carrier lifetimes for 0%, 5%, and 10% PbCl\u003csub\u003e2\u003c/sub\u003e-doped PVKs were 840 ps, 828 ps, and 1190 ps, respectively. The shorter carrier lifetime observed in 5% PbCl\u003csub\u003e2\u003c/sub\u003e-doped sample indicates a lower density of defect states, which is more favorable for charge transport at the ETL interface.\u003c/p\u003e\u003cp\u003eSteady-state and transient photoluminescence (PL) spectra were measured for 0%, 5%, and 10% PbCl\u003csub\u003e2\u003c/sub\u003e-doped perovskite films under test conditions of 20℃ and humidity below 30%. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e2\u003c/span\u003eh, the 5% PVK exhibited the strongest PL intensity, while the 10% one showed the weakest signal, indicating the lowest carrier recombination in the 5% film. Time-resolved photoluminescence (TRPL) (Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e2\u003c/span\u003ei) and fitting data in \u003cb\u003eTable S3\u003c/b\u003e demonstrated that the 5% PbCl\u003csub\u003e2\u003c/sub\u003e-doped perovskite film showed the longest carrier lifetime (571.92 ns). suggesting reduced defect density in the photoactive layer, as fewer defects lead to suppressed non-radiative recombination and prolonged carrier lifetimes.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e3\u003c/span\u003ea shows X-ray diffraction (XRD) patterns of unannealed wet perovskite films. The target film exhibits new peaks at 4.4\u0026deg;, 8.7\u0026deg; and 17.3\u0026deg;, which are attributed to MAPbCl\u003csub\u003e3\u003c/sub\u003e intermediate phases formed via rapid reactions between PbCl\u003csub\u003e2\u003c/sub\u003e and MACl\u003csup\u003e\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e\u003c/sup\u003e. In contrast, the control one displays a dominant PbI\u003csub\u003e2\u003c/sub\u003e peak at 12.6\u0026deg; with only a minor δ-phase peak at 9.7\u0026deg;. Figure\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e3\u003c/span\u003eb further illustrates the crystallization disparity between the target and control films. The modified film exhibits well-defined α-phase peaks at 14.1\u0026deg; ((001) plane) and 28.3\u0026deg; ((002) plane), alongside a δ-phase peak at 11.95\u0026deg;. Conversely, the pristine one shows a strong PbI\u003csub\u003e2\u003c/sub\u003e peak at 12.6\u0026deg; and a weak α-phase peak at 14.6\u0026deg;, suggesting incomplete δ to α conversion. These results demonstrate that PbCl\u003csub\u003e2\u003c/sub\u003e enables more efficient crystallization through intermediate-phase engineering, which, combined with improved PbI\u003csub\u003e2\u003c/sub\u003e reactivity in porous films, ultimately enhances PCE.\u003c/p\u003e\u003cp\u003eX - ray photoelectron spectroscopy (XPS) was employed to further investigate the interfacial interactions in perovskite films induced by PbCl\u003csub\u003e2\u003c/sub\u003e and the green line represents the result of background processing. The survey XPS spectra are presented in \u003cb\u003eFigure S8\u003c/b\u003e. Figure\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e3\u003c/span\u003ec reveals a positive shift in the Pb 4f binding energy that attributed to the introduction of highly electronegative element chlorine into perovskite lattice, which reduces the electron cloud density around Pb\u003csup\u003e2+\u003c/sup\u003e ions and increases the binding energy. Similarly, the I 3d binding energy shift observed in Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e3\u003c/span\u003e\u003cb\u003e(d)\u003c/b\u003e arises from chlorine electron withdrawing effect on iodide ions since chlorine reveals stronger electronegativity compared to iodine.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e3\u003c/span\u003ee demonstrates that although MACl was added into the control sample, no Cl-related characteristic peaks were detected in the film, which indicates that Cl evaporated during the annealing process, leaving negligible organic volatile Cl residues in the perovskite layer. In contrast, due to the strong Pb-Cl interaction driven by chlorine high electronegativity, the target sample prevents Cl from escaping the lattice during processing\u003csup\u003e\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e, \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e\u003c/sup\u003e. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e3\u003c/span\u003ef, the N 1s peak of the target sample shifted to higher binding energy compared to the control one, indicating that the chemical environment around FA was altered due to Cl incorporation.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eKelvin probe force microscopy (KPFM) was employed to characterize the surface contact potential difference (CPD) of perovskite films, using a gold (Au) tip. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e4\u003c/span\u003ea-b, the control sample exhibited CPD fluctuations exceeding 150 mV, significantly larger than the target of 100 mV, indicating a more homogeneous phase distribution in the PbCl\u003csub\u003e2\u003c/sub\u003e-doped films. After calculation using Eq.\u0026nbsp;(1)\u003csup\u003e45\u003c/sup\u003e, Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e4\u003c/span\u003ec-d reveal a 0.1 eV upward shift of work function in the target sample relative to the control one, which results into decreased Fermi level, favorable for electron transportation and thereby facilitates FF. According to \u003cb\u003eFigure S9a\u003c/b\u003e, the addition of 5% lead chloride significantly enhances the absorbance in visible light region. However, excessive PbCl\u003csub\u003e2\u003c/sub\u003e addition leads to a reduction in film absorbance. Meanwhile, as presented in \u003cb\u003eFigure S9b\u003c/b\u003e, Tauc-plot analysis reveals that the bandgaps (\u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003eg\u003c/em\u003e\u003c/sub\u003e) of the 0% and 5% PbCl\u003csub\u003e2\u003c/sub\u003e perovskites are both 1.55 eV, while the 10% sample exhibits a slightly increased \u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003eg\u003c/em\u003e\u003c/sub\u003e of 1.56 eV, indicating that PbCl\u003csub\u003e2\u003c/sub\u003e addition does not induce significant bandgap variation in the perovskite layer. The promoted work function and slightly changes of \u003cem\u003eE\u003c/em\u003eg are schematically illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e4\u003c/span\u003ee.\u003c/p\u003e\u003cp\u003e\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$$\\:{W}_{F}=5.1-q（{CPD}_{Au}-{CPD}_{sample}）$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eWhere \u003cem\u003eW\u003c/em\u003e\u003csub\u003e\u003cem\u003eF\u003c/em\u003e\u003c/sub\u003e is the work function, \u003cem\u003eq\u003c/em\u003e represents the elementary charge, and CPD\u003csub\u003eAU\u003c/sub\u003e refers to the CPD of gold (Au, with a work function of 5.1 eV), which is typically measured as -60 mV.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eTo quantify the defect state density and carrier dynamics of the films, the space charge limited currents (SCLC), Mott-Schottky test, and alternating current (AC) impedance spectroscopy were employed to characterize the electrochemical properties of different devices. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e5\u003c/span\u003ea,b, the trap-filled limit voltages (\u003cem\u003eV\u003c/em\u003e\u003csub\u003eTFL\u003c/sub\u003e) of the target and control device in single-electron devices were 0.32 V and 1.18 V, respectively, while those in single-hole devices were 0.55 V and 1.40 V. According to Eq.\u0026nbsp;(2)\u003csup\u003e46\u003c/sup\u003e, the electron trap state density decreased from 3.02\u0026times;10\u003csup\u003e16\u003c/sup\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e in the control device to 8.20\u0026times;10\u003csup\u003e15\u003c/sup\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e in the target one, and the hole defect density decreased from 3.59\u0026times;10\u003csup\u003e16\u003c/sup\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e to 1.41\u0026times;10\u003csup\u003e16\u003c/sup\u003e cm\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e, which demonstrates that optimal PbCl\u003csub\u003e2\u003c/sub\u003e effectively reduces the defects in the perovskite layer\u003csup\u003e\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e\u003c/sup\u003e.\u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e\n$$\\:{N}_{trap}=\\frac{2{\\epsilon\\:}_{0}{\\epsilon\\:}{V}_{TFL}}{q{L}^{2}}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eIn Eq.\u0026nbsp;\u003cspan refid=\"Equ2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, ε₀ and ε represent the vacuum permittivity (8.8542\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;14\u003c/sup\u003e F*cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and the relative permittivity of the perovskite material, respectively. The symbol \u003cem\u003eq\u003c/em\u003e denotes the elementary charge, while \u003cem\u003eL\u003c/em\u003e corresponds to the thickness of the perovskite layer which can be obtained from \u003cb\u003eFigure S4\u003c/b\u003e.\u003c/p\u003e\u003cp\u003eFigure \u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e5\u003c/span\u003ec reveals that the built-in electric field are 0.84 V and 0.89 V for the control and target devices, respectively. Figure\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e5\u003c/span\u003ed demonstrates the electrochemical impedance spectroscopy (EIS) of the perovskite solar cells. As shown in \u003cb\u003eTable S4\u003c/b\u003e, the simulation values obtained from EIS results indicate that both the charge transfer resistance (\u003cem\u003eR\u003c/em\u003e\u003csub\u003etr\u003c/sub\u003e) and recombination resistance (\u003cem\u003eR\u003c/em\u003e\u003csub\u003erec\u003c/sub\u003e) of the target device are higher than those of the control one, confirming that PbCl\u003csub\u003e2\u003c/sub\u003e effectively enhances carrier transport and reduces recombinations. Moreover, the series resistance (\u003cem\u003eR\u003c/em\u003e\u003csub\u003eS\u003c/sub\u003e) of the modified cell is lower than that of the pristine one, which is closely related to the enhanced morphology of the PVK with 5% PbCl\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e\u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e5\u003c/span\u003ee, the linear relationships between \u003cem\u003eV\u003c/em\u003e\u003csub\u003eOC\u003c/sub\u003e and input light intensity are described by Eq.\u0026nbsp;(\u003cspan refid=\"Equ3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The ideality factors (n) of the target and control devices are 1.22 and 1.3, respectively. In Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e5\u003c/span\u003ef, the linear relationships between \u003cem\u003eJ\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e and input light intensity are represented by Eq.\u0026nbsp;(\u003cspan refid=\"Equ4\" class=\"InternalRef\"\u003e4\u003c/span\u003e), with the current-dependent factors (α) of the target and control device being 0.96 and 0.94, respectively, indicating superior performance after PbCl\u003csub\u003e2\u003c/sub\u003e modification\u003csup\u003e\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e\u003c/sup\u003e. As demonstrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e5\u003c/span\u003eg and \u003cb\u003eFigure S10\u003c/b\u003e, the target PSC exhibits significant improvements in \u003cem\u003eV\u003c/em\u003e\u003csub\u003eoc\u003c/sub\u003e, \u003cem\u003eJ\u003c/em\u003e\u003csub\u003esc\u003c/sub\u003e, FF, and PCE compared to the control one. Specifically, \u003cem\u003eJ\u003c/em\u003e\u003csub\u003esc\u003c/sub\u003e increased from 23.78 mA\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e to 24.79 mA\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e, \u003cem\u003eV\u003c/em\u003e\u003csub\u003eoc\u003c/sub\u003e rose from 1.12 V to 1.15 V, FF improved from 78.08% to 80.59%, and the PCE was boosted from 20.88% to 23.15%. Additionally, as presented in \u003cb\u003eFigure S11\u003c/b\u003e, forward-reverse hysteresis tests were conducted on both device (results shown in \u003cb\u003eTable S5\u003c/b\u003e). Using Eq.\u0026nbsp;(5), the hysteresis index (HI) of the target and control device were calculated as 6.09% and 17.48%, respectively, confirming reduced hysteresis in the modified cell. The external quantum efficiency (EQE) curves in Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e5\u003c/span\u003eh show integrated current densities increasing from 23.12 mA\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e to 24.04 mA\u0026middot;cm\u003csup\u003e\u0026minus;\u0026thinsp;2\u003c/sup\u003e after fitting. Steady-state PCE measurements at maximum power point (Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e5\u003c/span\u003ei) yielded values of 22.51% for the target PCS and 20.29% for the control one.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003cdiv id=\"Equ3\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ3\" name=\"EquationSource\"\u003e\n$$\\:{V}_{OC}\\propto\\:n（{k}_{B}T/q）\\text{l}\\text{n}（{P}_{light}）$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e3\u003c/div\u003e\u003c/div\u003e\u003cdiv id=\"Equ4\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ4\" name=\"EquationSource\"\u003e\n$$\\:{J}_{SC}\\propto\\:{（{P}_{light}）}^{\\alpha\\:}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e4\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e\u003cp\u003eIn Eqs.\u0026nbsp;(\u003cspan refid=\"Equ3\" class=\"InternalRef\"\u003e3\u003c/span\u003e) and (\u003cspan refid=\"Equ4\" class=\"InternalRef\"\u003e4\u003c/span\u003e), \u003cem\u003eP\u003c/em\u003e\u003csub\u003elight\u003c/sub\u003e refers to the incident light power on the active area of the cell (W\u0026middot;cm⁻\u0026sup2;). \u003cem\u003ek\u003c/em\u003e\u003csub\u003eB\u003c/sub\u003e denotes the Boltzmann constant (8.617\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;5\u003c/sup\u003e eV\u0026middot;K\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e), \u003cem\u003eT\u003c/em\u003e is the test temperature (K), and the \u003cem\u003en\u003c/em\u003e value represents the ideality factor of the solar cell, n\u0026thinsp;=\u0026thinsp;1 indicates diffusion current dominance and \u003cem\u003en\u003c/em\u003e\u0026thinsp;=\u0026thinsp;2 means recombination current dominance. Practical PN junction devices typically exhibit 1\u0026thinsp;\u0026lt;\u0026thinsp;\u003cem\u003en\u003c/em\u003e\u0026thinsp;\u0026lt;\u0026thinsp;2 due to recombination centers in the space charge region. A smaller \u003cem\u003en\u003c/em\u003e value approaching 1 signifies reduced non-radiative recombination and lower defect density. Specifically, the \u003cem\u003eα\u003c/em\u003e value represents the correlation factor between \u003cem\u003eJ\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e and light intensity, where values closer to 1 indicate weaker bimolecular recombination in the device\u003csup\u003e\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e, \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e\u003c/sup\u003e.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003eMoreover, environmental stability tests (Fig.\u0026nbsp;\u003cspan refid=\"Fig18\" class=\"InternalRef\"\u003e6\u003c/span\u003ea,b) revealed that the target devices retained 87% efficiency after 2000 h in a nitrogen atmosphere and 78% efficiency after 1000 h at 50% relative humidity. The larger contact angles observed in Fig.\u0026nbsp;\u003cspan refid=\"Fig18\" class=\"InternalRef\"\u003e6\u003c/span\u003ec,d further indicate enhanced moisture resistance of the target device.\u003c/p\u003e\u003cp\u003e\u003c/p\u003e\u003cp\u003e\u003c/p\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eIn summary, we have devised a strategy to fabricate stable, and dense perovskite films via the PbCl\u003csub\u003e2\u003c/sub\u003e-mediated formation of an intermediate phase. During the two-step deposition procedure, the inorganic PbCl\u003csub\u003e2\u003c/sub\u003e additive assumes multiple pivotal functions. It engages in an interaction with PbI\u003csub\u003e2\u003c/sub\u003e to generate a porous architecture, which promotes the solid-liquid reaction with the organic precursors. Meanwhile, it reacts with volatile MACl to yield the MAPbCl\u003csub\u003e3\u003c/sub\u003e intermediate phase, which not only diminishes the perovskite nucleation energy barrier but also incorporates Cl into the PVK lattice, thus enhances the energy level alignment between the perovskite and the ETL, and improves the carrier dynamics. Ultimately, in comparison with the control devices, through the optimization of the device thickness and the quantity of added PbCl\u003csub\u003e2\u003c/sub\u003e, we attained an enhanced average efficiency from 18.79% to 21.34%, with a champion PCE of 23.15%. Additionally, the HI was reduced from 17.48% to 6.09%, and promoted environmental stability was achieved. Our work not only furnishes a highly reproducible preparation approach for high quality PSCs but also clarifies the mechanism of the non-volatile chlorine additive PbCl\u003csub\u003e2\u003c/sub\u003e in the growth process of perovskite films.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003ch2\u003eDeclaration of Competing Interest\u003c/h2\u003e\u003cp\u003eThe authors declare no conflict of interest.\u003c/p\u003e\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eZheng Zhang and Haimin Li (corresponding author) took the lead in writing the main manuscript text, including formulating the core framework of the study and organizing the key research content. Haohui Li and Bo An were mainly responsible for collecting and analyzing the research data, ensuring the accuracy and reliability of the data used in the manuscript. Yuhao Wei and Jia Liao prepared all the figures in the manuscript, including designing the figure layout, processing the image data and adding the necessary annotations. Xiangxue Lv and Xingchong Liu conducted an in-depth review of the relevant literature, sorted out the research background and current research status, and provided important support for the literature review part of the manuscript. Hanyu Wang participated in the discussion of the research results, put forward constructive opinions on the interpretation of the results and the improvement of the manuscript. All authors (Zheng Zhang, Haimin Li, Haohui Li, Bo An, Yuhao Wei, Jia Liao, Xiangxue Lv, Xingchong Liu, Hanyu Wang) carefully reviewed the entire manuscript, checked the logical consistency of the content, corrected the language errors and put forward suggestions for revision, and finally approved the submission version of the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e\u003cp\u003eThis work was supported by Sichuan Science and Technology Program (2024ZDZX0030), Chengdu Science and Technology Program (2024-JB00-00010-GX).\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eJiang, Q.; Zhu, K., Rapid advances enabling high-performance inverted perovskite solar cells. \u003cem\u003eNature Reviews Materials \u003c/em\u003e\u003cstrong\u003e2024,\u003c/strong\u003e \u003cem\u003e9\u003c/em\u003e (6), 399-419.http://doi.org/10.1038/s41578-024-00678-x\u003c/li\u003e\n\u003cli\u003eZhang, X.; Wu, S.; Zhang, H.; Jen, A. 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However, due to strong volatility, organic chlorine additives often result in poor stability and residual lead iodide (PbI\u003csub\u003e2\u003c/sub\u003e). Here, we report a method to improve perovskite film crystallization via the formation of lead chloride (PbCl\u003csub\u003e2\u003c/sub\u003e)-induced intermediate phase in a two-step process. Results show that non-volatile PbCl\u003csub\u003e2\u003c/sub\u003e not only creates a porous structure favorable for solid-liquid reactions during the second step deposition but also forms a MAPbCl\u003csub\u003e3\u003c/sub\u003e intermediate phase with methylammonium chloride (MACl), which greatly promotes the crystallization quality of perovskite (PVK) films. Additionally, transient absorption (TA) spectroscopy indicates that an appropriate amount of PbCl\u003csub\u003e2\u003c/sub\u003e can improve the carrier dynamics, while excess additives would deteriorate the charge activity. As a result, the average power conversion efficiency (PCE) of the optimal modified devices is promoted from 18.79% to 21.34% with a champion efficiency of 23.15%. And the hysteresis index (HI) reduced from 17.48% to 6.09%. PbCl\u003csub\u003e2\u003c/sub\u003e added PSCs can retain 78% of its initial PCE after 1000 hours under 50% relative humidity (RH) in ambient air. Our work provides a novel approach to precisely control the carrier dynamics and clarifies the mechanism of PbCl\u003csub\u003e2\u003c/sub\u003e in the growth process of perovskite films.\u003c/p\u003e","manuscriptTitle":"Enhanced Carrier Dynamics Resulted from Non-Volatile Chloride Additive for Improved Average Efficiency of PSCs","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-10-06 17:26:55","doi":"10.21203/rs.3.rs-7604240/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"a3320909-301a-4448-bae1-9fc35074a749","owner":[],"postedDate":"October 6th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-10-22T07:08:18+00:00","versionOfRecord":[],"versionCreatedAt":"2025-10-06 17:26:55","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-7604240","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7604240","identity":"rs-7604240","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}