Heat-triggered Dynamic Self-healing Framework for Variable-temperature Stable Perovskite Solar Cells

Heat-triggered Dynamic Self-healing Framework for Variable-temperature Stable Perovskite Solar Cells | 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 Article Heat-triggered Dynamic Self-healing Framework for Variable-temperature Stable Perovskite Solar Cells Meng Li, Ying Tang, Zuhong Zhang, Guixiang Li, Chaochao Qin, Zhen-Huang Su, and 8 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4527071/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 Metal halide perovskite solar cells (PSCs) are promising as the next-generation photovoltaic technology. However, the inferior stability under various temperatures remains a significant obstacle to commercialization. Here, we implement a heat-triggered dynamic self-healing framework (HDSF) to repair defects at grain boundaries caused by thermal variability, enhancing PSCs' temperature stability. HDSF, distributed at the grain boundaries and surface of the perovskite film, stabilizes the perovskite lattice and releases the perovskite crystal stress through the dynamic exchange reaction and shape memory effect of sulfide bonds. The resultant PSCs achieved a power-conversion efficiency (PCE) of 26.32% (certified 25.84%) with elevated temperature stability, retaining 94.2% of the initial PCE after 500 h at 85℃. In a variable temperature cycling test (between −40℃ and 80℃), the HDSF-treated device retained 87.6% of its initial PCE at −40℃ and 92.6% at 80℃ after 160 thermal cycles. This heat-triggered dynamic self-healing strategy could significantly enhance the reliability of PSCs in application scenarios. Physical sciences/Materials science/Materials for devices/Information storage Physical sciences/Physics/Electronics, photonics and device physics/Photonic devices Figures Figure 1 Figure 2 Figure 3 Figure 4 Introduction Metal hybrid perovskite solar cells (PSCs) with an outstanding efficiency higher than 26% 1 can rival commercialized polycrystalline silicon (c-Si) solar cells. And they emerged as a disruptive photovoltaic (PV) technology due to the simple fabrication technologies and excellent photovoltaic performance 2-3 . Despite tremendous advances in power conversion efficiency (PCE), the operational stability of devices in complex practical environments remains a still a substantial hurdle to commercialization. Perovskite films usually suffer from lattice distortion and crystal phase transition under thermal stress due to the ionic nature and weak bonding of the crystal structures. This can lead to ion migration and crystal decomposition inside the perovskite crystal, ultimately damaging the photoelectric characteristics and stability of devices 4-8 . Research groups have developed significant approaches to improve the thermal stability of PSCs, such as additives engineering, interface modification, and grain boundary passivation 9-13 . However, these “static” measures only alleviate the internal stress of the device caused by high temperatures, and cannot repair defects from the expansion and contraction of the perovskite lattice in variable thermal environments. In practical application scenarios, PSCs experience wide temperature fluctuations due to seasonal changes and day-night cycles 14 . These fluctuations can cause phase transformations or irreversible thermal degradation in the perovskite film due to its low deposition energy 15 , primarily mediated by defects from thermal stress 6 . The irreversible nature of these defects and the low ion migration activation energy contribute to the decomposition of the perovskite structure, harming carrier transport characteristics. Moreover, the long-term defects accumulation will seriously impair the stability of devices. Therefore, mitigating residual thermal stress and dynamically inhibiting defect formation in perovskite films during temperature variations is crucial for achieving long-term operational stability of PSCs. Herein, we report a heat-triggered dynamic self-healing strategy to enhance the thermal stability of PSCs. A thermally triggered dynamic self-healing framework (HDSF) was introduced into the perovskite film to repair defects caused by thermal damage. The electron-donating atoms in the HDSF conjugated framework passivate the uncoordinated Pb 2+ atomson the surface of the perovskite film through coordinated covalent bonds, suppressing the formation of excess secondary phase PbI 2 . HDSF is mainly distributed on the surface and grain boundary of the perovskite film, stabilizing the crystal lattice and reducing the distortion caused by temperature changes. When the ambient temperature rises (60℃–80℃), the disulfide bond in HDSF adjusts the thermal stress of the perovskite crystals under variable temperature conditions through dynamic exchange reaction and shape memory effect 16 . This dynamic repair mechanism addresses defects at the grain boundaries caused by thermal strain, improving the variable temperature stability of PSCs. Thermal admittance spectrum (TAS) and femtosecond transient absorption spectrum (Fs-TA) show that HDSF-treated devices have lower defect state density and higher charge transport capability. Ultimately, the HDSF-treated device achieved a champion efficiency of 26.32% (certified 25.84%) with excellent temperature stability, maintaining 87.6% of its initial PCE at −40℃ and 92.6% at 80℃ after 160 cycles between −40℃ and 80℃. Formation of HDSF and interaction with perovskite crystals First, we explored the formation process of HDSF. Fig. 1a depicts the reaction process of dewatering and polycondensation of 4-aminophenyl disulfide (APD) and Tri (4-formylphenyl) amine (TPA) to form HDSF. It also shows the interaction between HDSF and the perovskite lattice, and the heat-triggered dynamic exchange process of the disulfide bond. We employed proton nuclear magnetic resonance ( 1 H-NMR) and fourier-transform infrared (FTIR) to verify the formation of HDSF. When APD deoxygenates and TPA dehydrogenates, the H on the generated C=N bond appears at 8.6 ppm 17 , indicated by the red arrow ( Fig. 1b ). At the same time, the typical tensile vibration peak C=N was observed at 1622 cm −1 in the FTIR spectra 18 ( Fig. 1c and Supplementary Fig. 1 ). The above results fully confirm the formation of HDSF. We investigated the incorporation of HDSF and its interaction with the perovskite lattice using X-ray photoelectron spectroscopy (XPS). Supplementary Fig. 2 shows two N 1s peaks for the control film, assigned to C-N and C=N, while HDSF-treated film exhibits a new peak of C=N-C belonging to HDSF, indicating the incorporation of HDSF into the perovskite film. Fig. 1d shows two characteristic peaks of I 3d 3/2 (630.4 eV) and I 3d 5/2 (618.9 eV) for the control perovskite film shifted to lower binding energy due to hydrogen bonding formation (N‐H…I, ‐N‐H…I‐Pb‐I). The coordination between HDSF and perovskite crystals, and hydrogen bond formation, constructs an orderly and stable interaction network between HDSF and the perovskite lattice, thus stabilizing the [PbI 6 ] 4- octahedral structure and transforming the crystal structure from metastable to stable 19-23 . Additionally, two characteristic peaks of Pb 4f 5/2 (143.2 eV) and Pb 4f 7/2 (138.3 eV) for the control film also shifted towards lower binding energy after introducing HDSF. This shift indicates the formation of a coordination bond between O, N, and S atoms in HDSF and the uncoordinated Pb 2+ in the perovskite lattice, thus increasing the electron cloud density around Pb 24-26 . To investigate the effect of HDSF on the morphology and crystallization dynamics of the prepared perovskite films, we utilized a scanning electron microscope (SEM), grazing-incidence wide-angle X-ray scattering (GIWAXS), and X-ray diffraction (XRD) to compare the film quality. Supplementary Fig. 3a,b show the SEM top-view images of both control and HDSF-treated films. A significant amount of secondary phase PbI 2 (white species) 27-28 is observed on the surface of the control perovskite film, which forms as the decomposition product after heating 12 . Excessive PbI 2 tends to be decomposed into gaseous I 2 and metallic lead Pb 0 under light and heat, acting as the catalytic site for the decay of perovskite films. This is one of the main reasons for the poor thermal stability of perovskite devices 29-30 . In contrast, the perovskite film with HDSF shows almost no excess PbI 2 . This is attributed to the coordination between the electron donor atoms (O, N, S) in HDSF and the uncoordinated Pb 2+ on the surface of perovskite, which inhibits the generation of excessive secondary PbI 2 . By comparing the statistical distribution diagram of perovskite grains ( Supplementary Fig. 3c,d ), we found that the average grain size of perovskite films increased from 303.42 nm for the control film to 439.10 nm of the HDSF-treated films, indicating the beneficial effect of HDSF in regulating the growth of perovskite films. The effect of HDSF on the crystal structure of the perovskite film was further explored using GIWAXS at different incidence angles 27,31 (0.4° and 0.15°). Fig. 1e,f and Supplementary Fig. 4 show that the HDSF-treated films did not exhibit any new Debye-Scherrer-like ring (D-S ring) compared to the control films. Additionally, the secondary phase PbI 2 is almost absent in the HDSF-treated films. The azimuthal integrated 1D GIWAX spectra are shown in Supplementary Fig. 5 . These results confirm that HDSF can effectively inhibit the production of excess PbI 2 and promote the formation of pure perovskite phase. As illustrated in Supplementary Fig. 6 , the XRD patterns of the HDSF-treated films present the same diffraction peak positions as the control film, indicating that HDSF does not induce structural changes within the perovskite lattice. The above results suggest that HDSF is primarily distributed on the surface and at the grain boundaries of the perovskite film, rather than entering the crystal lattice 18,32 . Defects and charge transfer characteristics To investigate the density of trap states (t-DOS) within the perovskite thin films, we used thermal admittance spectroscopy (TAS). As depicted in N t -E w curves ( Fig. 2a ), the HDSF-treated device shows a lower trap state density over the entire trap depth region. The shallow traps, in the range of 0.35–0.40 eV, are associated with grain boundary defects 33-34 , while the deep traps, in the range of 0.40–0.52 eV, correspond to traps at the perovskite surface 35-36 . This reduction in both shallow and deep trap states is attributed to the coordination between HDSF and uncoordinated Pb 2+ at the grain boundaries and surface of perovskite thin films 37 . To further quantify the trap densities in the perovskite thin films, we performed the space charge limited current (SCLC) measurement based on electron-only devices (FTO/SnO 2 /Cs 0.05 FA 0.85 MA 0.1 PbI 3 /PCBM/Ag) and hole-only devices (FTO/PEDOT:PSS/Cs 0.05 FA 0.85 MA 0.1 PbI 3 /Spiro-OMeTAD/Ag). As shown in Supplementary Fig. 7 , for the electron-only devices, the V TFL of the HDSF-treated device is 0.15 V, compared to 0.20 V for the control device. The corresponding trap densities are 2.82 × 10 15 cm -3 , and 3.76 × 10 15 cm -3 , respectively. A similar trend was observed in the hole-only devices, with the HDSF-treated device showing a hole trap density of 3.01 × 10 15 cm -3 , while the control device exhibited a higher trap density of 5.07 × 10 15 cm -3 . These results further confirm that HDSF effectively passivates surface and grain boundary defects in the perovskite films. Electrochemical impedance spectroscopy (EIS) was utilized to explore the charge transfer and recombination behavior of devices. In the Nyquist plot, the low-frequency region represents the recombination resistance (R rec ), and the high-frequency region represents the transfer resistance (R tra ) 38-39 . The inner illustrations in Supplementary Fig. 8 show the corresponding equivalent circuit diagrams and an enlargement of the R tra region. We observed that HDSF-treated devices exhibit a lower R tra and a higher R rec compared to the control devices. This indicates that HDSF effectively inhibits charge recombination and promotes charge transfer between the perovskite films and the transport layers 40-42 . We performed light-dependent V OC and J SC measurements to understand the carrier recombination mechanism in perovskite films. As shown in Fig. 2b , the ideality factor extracted from the fitting curves for the HDSF-treated devices is 1.61, while that for the control device is 1.84. This implies that trap-assisted recombination is effectively suppressed in the HDSF-treated devices 43-44 . Additionally, the index (α) values extracted from the plots of J sc ∝I α are 0.975 and 0.987 for the control device and HDSF-treated device, respectively ( Supplementary Fig. 9 ). This indicates that the HDSF-treated device has lower bimolecular recombination, allowing photogenerated carriers to be extracted and transferred smoothly 45-47 . This finding is further confirmed by the steady-state photoluminescence (PL) and time-resolved photoluminescence (TRPL) spectra of perovskite films deposited on quartz glass. Supplementary Fig. 10 shows that the PL intensity of the HDSF-treated perovskite film is higher than that of the control film. Moreover, a double exponential decay model was used to fit TRPL curves ( Supplementary Fig. 11 ). The fitting results ( Supplementary Table 1 ) show that the average lifetime (τ ave ) of the HDSF-treated perovskite film is significantly longer than that of the control film (147.74 ns vs. 68.98 ns). This extended lifetime is attributed to the effective defect passivation and suppression of non-radiative recombination by HDSF 44,48-50 . To further explore the carrier transport dynamics of the devices, femtosecond transient absorption (Fs-TA) spectra were measured. The structure of the tested semi-device (FTO/SAM/Cs 0.05 FA 0.85 MA 0.1 PbI 3 /PCBM) is shown in Supplementary Fig. 12 . A 400 nm pumped laser was implemented to prob absorption signals, inducing an absorption change (ΔA) associated with ground-state bleaching (GSB), which reflects the photoinduced carrier dynamics in the valance and conduction bands of the perovskite film 51-52 . The pseudocolor TAS plots ( Supplementary Fig. 13 ) elucidate that both the control perovskite film and the HDSF-treated perovskite film displayed significant GSB peaks at about 760 nm. The quenching rate of the GSB peak signal indicates the efficiency of carrier transport from perovskite to adjacent carrier transport layers 53 . Compared to the delay-time-dependent TA spectra of the control device ( Fig. 2c ), the TA spectra of the HDSF-treated device ( Fig. 2d ) show a more rapidly faded signal, indicating enhanced charge extraction from the perovskite to transport layers 54 . A bi-exponential decay model was used to fit the decay kinetics of the GSB peaks. Supplementary Fig. 14 shows that the HDSF-treated samples decay faster, further illustrating that HDSF promotes charge transfer from perovskite to adjacent layers. Transient photovoltage (TPV) and transient photocurrent (TPC) were conducted to analyze the charge recombination and extraction behavior. As shown in TPV curves ( Fig. 2e ), the HDSF-treated device exhibits a longer decay lifetime (2.06 μs) compared to the control counterpart (1.58 μs). Conversely, the photocurrent decay response of the HDSF-treated device (0.56 μs) is faster than that of the control device (0.73 μs) ( Supplementary Fig. 15 ). These results confirm that HDSF effectively inhibits defect recombination and accelerate the extraction of photogenerated carrier 36,44,55-57 . Additionally, the J-V curves under dark conditions ( Supplementary Fig. 16 ), show that the HDSF treatment enables a significantly lower leakage current, indicating that the photogenerated carriers are more efficiently transmitted to the corresponding electrode rather than being captured by defect centers 18,28 . The charge collection probability ( P c )-internal voltage ( V int ) curve ( Fig. 2f ) further demonstrates that the HDSF-treated device presents a superior charge collection capability than the control device 58-61 . Properties and temperature stability of perovskite films and devices Fig. 3a provides a schematic illustration of heat-triggered self-healing properties via dynamic exchange of disulfide bonds in HDSF 16,19 . To investigate the effect of HDSF on the stability of perovskite films under variable temperatures, we employed XRD and SEM to characterize the perovskite films subjected to variable temperature cycles (from room temperature heating to 80℃, then cooling to −40℃, and finally returning to room temperature for a variable temperature cycle, with a ramp rate of 20°C per minute). As illustrated in Fig. 3b , c , the quantity of PbI 2 in the control perovskite film incrementally rises with an increasing number of thermal cycles. Notably, the control sample exhibited excessive PbI 2 after 160 variable temperature cycles, leading to internal instability of the device and accelerating perovskite decomposition under light and thermal stress 29 . Excessive PbI 2 also increases non-radiative recombination and impairs charge transfer behavior 62-63 . In contrast, the HDSF-treated perovskite film exhibits significantly lower PbI 2 content compared to the control film. The top-view SEM images ( Fig. 3d-g ) align with XRD results, further supporting that HDSF effectively inhibits the thermal decomposition of perovskite films. The residual tensile thermal stress in perovskite films was also investigated by the grazing incident X-ray diffraction (GIXRD) with the classical 2θ-sin 2 (ψ) method, where θ and ψ represent the diffraction and tilt angles 27,46,51,64 . The (012) plane oriented at ~31.6° was selected for the strain analysis due to its larger diffraction angle and multiplication factor, providing more reliable structure symmetry information 52,65-68 . As shown in Fig. 3h , i , by varying ψ angles from 0° to 50°, the scattering peak of control perovskite gradually shifts to the lower 2θ direction. This shift indicates an increase in crystal plane distance (d(012)) and the presence of tensile stress in perovskite films 69 . The linear fitting curves for 2θ and sin 2 ψ ( Fig. 3j) reveal that the control perovskite film exhibits a large negative slope, indicating severe tensile stress. This stress arises from the mismatch between the thermal expansion coefficient of the perovskite layer and the substrate, resulting in the biaxial residual tensile thermal stress of the perovskite film after annealing 32,63 . These thermal tensile strains reduce the defect formation energy and ion migration activation energy 70 , leading to device instability during temperature variations 71 . In contrast, the HDSF-treated film presents a much smaller slope, indicating that HDSF is conducive to stress release. This stress relief can be attributed to the distribution of HDSF at the grain boundaries of perovskite grains, which stabilizes the crystal lattice and reduces the strain field 72 . Along with the thermally triggered self-healing characteristics of disulfide bonds, the stress compensation reduces the tensile strain in the perovskite, thereby improving the stability of the perovskite structure during temperature change. To evaluate the effect of HDSF on the photovoltaic performance of perovskite devices, we prepared p-i-n devices with the structure of glass/fluorine-doped tin oxide (FTO)/self-assembled monolayers (mixtures of [2-(9H-Carbazol-9-yl)ethyl]phosphonic Acid (2PACz) and [4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid (Me-4PACz))/perovskite/2D passivation layer/[6,6] -Phenyl -C 61 -butyric acid methylester (PC 61 BM)/bathocuproine (BCP)/silver (Ag). The 2D passivation layer is Phenethylammonium bromide (PEABr). As shown in the J-V curves ( Fig. 4a , b ), the control device (0.0982 cm 2 ) exhibits a PCE of 24.48%, with a V OC of 1.15 V, a J SC of 25.98 mA/cm 2 and an FF of 81.95%. In comparison, the PCE of the HDSF-treated champion device is 26.32%, with a V OC of 1.19 V, a J SC of 26.10 mA /cm 2 , and an FF of 84.73%. One of the HDSF-treated devices was sent to an independent laboratory (Fujian Metrology Institute, National PV Measurement and Testing Center of Microsystem and Information Technology, Fujian, China) for certification, where a PCE of 25.84% (with V OC of 1.185 V, J SC of 26.11 mA/cm 2 , and FF of 83.52%) was confirmed ( Supplementary Fig. 17 ). Additionally, 1 cm 2 -sized devices were prepared to further verify the improvement of HDSF on the photovoltaic performance of larger area devices ( Fig. 4c ). Compared with the control device (22.49%), the HDSF-treated device achieved a significant PCE of 24.43%. The improvement in PCE is mainly due to the significant increase in FF and V OC , which can be attributed to HDSF’s ability to stabilize the lattice, promote charge transfer, and inhibit defection-assisted non-radiative recombination 73 . The increase of the built-in potential ( V bi ) for the HDSF-treated device ( Supplementary Fig. 18 ) indicates that HDSF enhances the internal driving force for photogenerated carriers, thereby reducing recombination loss and improving V OC 74 . The integral J SC values obtained from the EQE spectra ( Supplementary Fig. 19 ) of the control device and the HDSF-treated device are 25.07 mA/cm 2 and 25.44 mA/cm 2 , respectively. These values are consistent with the corresponding J SC values derived from J-V curves. Moreover, Supplementary Fig. 20 shows the statistical diagram of device parameters, which further confirms the optimization of HDSF on device performance and reveals the good repeatability of HDSF-treated devices. In addition to high PCE, long-term and variable temperature stability of perovskite devices are critical for practical applications. The stabilized power output (SPO) can be observed at the maximum power point (MPP) under one-sun irradiation. Supplementary Fig. 21 shows that the SPO of the control and the HDSF-treated devices are 22.69% and 25.77%, respectively, consistent with the results from the J-V curves. We further investigated the operational stability of the devices by conducting MPP tracking under continuous illumination. As shown in Fig. 4d , the HDSF-treated device retains 96.9% of the initial PCE after 500 h of continuous operation, compared to 83.9% for the control device. The enhancement in light stability undoubtedly proves that HDSF can stabilize the lattice and effectively inhibit ion migration during operation 18 . To evaluate the stability of perovskite devices under variable temperatures, the photovoltaic parameters of the devices after temperature cycling between −40℃ and 80℃ are counted. The relevant statistical parameters in Fig. 4e,f and Supplementary Fig. 22 , show that the HDSF-treated devices exhibit good repeatability and thermal stability. When stored at 85℃ in a nitrogen atmosphere for 500 h, the HDSF-treated device maintained 94.2% of its original efficiency, whereas the control device retained only 81.1% ( Supplementary Fig. 23 ). The temperature stability of the devices is shown in Fig. 4g,h . The PCE of the control device suffered severe attenuation after 160 cycles, maintaining only 67.4% and 72.3% of the initial efficiency at −40℃ and 80℃, respectively. In contrast, the HDSF-treated device retained 87.6% of its initial PCE at −40℃ and 92.6% at 80℃. Compared with control devices, the HDSF-treated devices exhibit significantly improved thermal stability and variable temperature stability. This enhancement is primarily due to the thermally triggered self-healing property of HDSF, which reduces the tensile strain in perovskite during temperature changes through stress compensation. This self-healing capacity effectively stabilizes the devices, enhancing their performance and longevity during temperature fluctuations. Conclusions In summary, we innovatively demonstrated the heat-triggered dynamic self-healing strategy by incorporating HDSF as an additive to enhance the temperature stability of PSCs via healing the thermo-induced defects during temperature changes. The introduction of HDSF regulates the stress in devices under variable temperature conditions and dynamically repairs defects at the grain boundaries of perovskite caused by thermal strain through the dynamic exchange reaction and shape memory effect of disulfide bonds. As a result, the HDSF-treated device achieved a champion PCE of 26.32% (certified 25.84%) with a stabilized power output of 25.77%. Moreover, it exhibited remarkable temperature stability, retaining 94.2% of its initial efficiency after 500 h of dark storage at 85℃. Additionally, the HDSF-treated device maintained 87.6% of its initial efficiency at − 40℃ and 92.6% at 80℃ after 160 thermal cycles. This work paves the path to realize highly efficient and temperature-stable PSCs via a novel heat-triggered dynamic self-healing strategy for thermo-induced damage. Methods Materials The indium tin oxide (FTO) substrate was purchased from Libra Technologies (GD-H8). [2-(9H-Carbazol-9-yl)ethyl]phosphonic Acid (2PACz, >98.0%), [4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid (Me-4PACz, >99.0%) and bathocuproine (BCP, >99.0%) were purchased from TCI. [ 6 , 6 ]-phenyl-C61-butyric acid methyl ester (PC 61 BM, 99.9%) was gained from Advanced Choice Technology. Formamidinium iodide (FAI, > 99.99%), methylammonium iodide (MAI, > 99.99%), and phenethylammonium bromide (PEABr) were purchased from Greatcell Solar Materials. Cesium iodide (CsI, 99.999%), and lead iodide (PbI 2 , 99.999%) were obtained from p-OLED. All reagents were purchased from J&K Scientific including chlorobenzene (CB, 99%), N,N-dimethylformamide (DMF, 99.8%), dimethyl sulfoxide (DMSO, 99%), and isopropanol (IPA, ≥ 99.9%). 4-Aminophenyl disulfide (APD-NH 2 , 98%) and tri (4-formylphenyl) amine (TPA-CHO, 97%) were purchased from Aladdin Scientific company. All materials were used as received without any additional processing. Device Fabrication FTO glass substrates were cleaned sequentially with detergent, deionized water, acetone, and ethanol under sonication for 15 mins, respectively. Then they were dried in an oven at 60℃ and treated with oxygen plasma for 20 min before using. Subsequently, a uniform and dense SAM layer was deposited onto the FTO substrate by spin-coating 2PACz (0.17 mg mL − 1 ) and Me-4PACz (0.33 mg mL − 1 ) at 3000 rpm for 30 s with a ramp of 1000 rpm s − 1 and annealing at 100°C for 10 min. After SAM/FTO was cooled to room temperature, 100 uL 1.5 M Cs 0.05 FA 0.85 MA 0.1 PbI 3 perovskite precursor solution (including PbI 2 :FAI:MAI:CsI (760.7 mg:219.3 mg:23.8 mg:19.5 mg) with 10 mg MACl additive in a mixed solution of 800 uL DMF and 200 uL DMSO with or without 10 uL 0.04 mmol HDSF (9.93 mg APD-NH 2 :13.17 mg TPA-CHO in 1 mL DMSO)) was coated on SAM layer at 6000 rpm for 35 s, then 200 uL CB was added evenly and slowly at 25 s. After that, the perovskite films were annealed at 100°C for 30 min to complete the perovskite growth. Subsequently, 100 uL PEABr solution (1 mg PEABr was dissolved in 995 uL IPA and 5 uL DMSO mixed solution) was spun onto the perovskite film at 4000 rpm (with a ramping rate of 2000 rpm s − 1 ) for 30 s and then annealing at 100℃ for 5 min. Next, 100 uL PC 61 BM solution (20 mg PC 61 BM was dissolved in 1 mL CB) was coated on the PEABr layer without annealing. All the spin-coating processes were conducted in an N 2 -filled glovebox with O 2 and H 2 O contents less than 0.1 ppm. Finally, a 7 nm BCP layer and a 100 nm Ag layer were thermally evaporated under a pressure of 2×10 − 6 hPa, respectively. Characterizations Proton Nuclear Magnetic Resonance ( 1 H-NMR) spectra were measured using a Bruker AVANCE NEO-400 NMR spectrometer. Fourier-transform infrared (FTIR) spectra were measured with a Bruker ALPHA II spectrometer. The surface morphologies and microstructures of Cs 0.05 FA 0.85 MA 0.1 PbI 3 perovskite films for top-view images were researched by scanning electron microscopy (SEM, SUPRA40, Carl Zeiss) with electron beam accelerating at 5 kV. The charge transfer performance of Cs 0.05 FA 0.85 MA 0.1 PbI 3 perovskite films was characterized by Ultrafast Systems (Helios) under the conditions of pump light intensity of 30 µJ/cm 2 with a 400 nm pump laser. The diffraction patterns of perovskite films were implemented by X-ray diffraction (XRD, D8-Discover, Bruker). The grazing incidence X-ray diffraction (GIXRD) (Rigaku SmartLab 3kW) was utilized to characterize the residual tensile thermal stress of perovskite films. Grazing incidence wide angle X-ray scattering (GIWAX) spectra were obtained by BL14B1 beamline of the Shanghai Synchrotron Radiation Facility (SSRF). X-ray photoelectron spectroscopy (XPS) was carried out by Thermo Fisher ESCALAB250Xi. The external quantum efficiency (EQE) spectra were obtained by QER of EnliTech. The current-voltage characteristics of the devices were measured by a Keithley 2400 source meter unit under AM 1.5G (100 mW/cm 2 ) illumination from a solar simulator (EnliTech, SS-X50, with A + spectrum). The solar simulator was calibrated by a reference Silicon cell (EnliTech, certificated by NIST) with a KG2 filter. Device areas of 0.0982 cm 2 and 1 cm 2 were defined by a metal aperture mask. Dark I-V curves for hole-only and electron-only devices based on the SAM/Cs 0.05 FA 0.85 MA 0.1 PbI 3 films were characterized by Ivium Electrochemical Workstation (Netherlands). Trap density of states (t-DOS) was tested using a Precision Impedance Analyzer (Agilent 4294A, 40 HZ-1 MHZ). Photoluminescence (PL) and Time-Resolved Photoluminescence (TRPL) spectra were obtained by FLS980 (Edinburgh Instruments). Transient Photovoltage (TPV) and Transient Photocurrent (TPC) curves were measured by a transient photocurrent/voltage tester (Shanghai Jinzhu Technology Co., LTD, laser 570 nm). The temperature-dependent test system is mainly equipped with temperature and vacuum controllers, a vacuum pump, a sample chamber, a solar simulator, and liquid nitrogen. Temperature was controlled by Standalone Temperature Controller (mK2000B) coupled with a hot and cold plate (HCP421-PM), a temperature control sensor (100 Ω Platinum RTD), circulating water, a liquid nitrogen cooling system (INSTEC LN2-P), a vacuum pore (KF16), an LN2 dewar flask, a DC power supply, and temperature control software (Instec App). The temperature setting range is from − 190°C to 400°C with stability of ± 0.05°C. The minimum heating and cooling rate is about ± 0.1°C/h, the maximum heating rate is + 150°C/min at 37°C, and the maximum cooling rate is − 50°C/min at 37°C. Temperature control is accurate to 0.001℃. During temperature variation testing, the device was placed in a sample chamber with controllable temperature and vacuum conditions. The thermal cycling process was controlled between − 40°C and + 80°C, with the temperature regulated primarily by liquid nitrogen. The test temperature parameters were mainly determined by setting proportional, integral, and differential (PID) parameters. Reporting summary Further information on research design is available in the Nature Portfolio Reporting Summary linked to this article. Declarations Data availability The data that support the findings of this study are available from the corresponding authors on reasonable request. Source data are provided with this paper. Acknowledgments The authors acknowledge the support of all the technicians at Henan Normal University and Henan University. The authors thank the beamline BL14B1 at the Shanghai Synchrotron Radiation Facility (SSRF) for providing the beam time. Y. Liu thanks the financial support from Zhongyuan Scholar of Henan Province (No.224000510007). Y. Yang acknowledges funding from the National Natural Science Foundation of China (Grant No.11974103). M. Li thanks the support from the China Postdoctoral Science Foundation (No.2022M721026), the Joint Fund of Provincial Science and Technology Research, Development Plan of Henan Province (No. 232301420004), and the Outstanding Youth Fund of the Natural Science Foundation of Henan Province (No.242300421069). Author contributions M.L., Y.L., A.A. and Y.T. conceived the idea and designed the experiments. Y.T. conducted most of the experiments and wrote the manuscript. Z.Z. performed EQE and device stability measurements. C.Q. carried out the TAS measurements and analyzed the data. G.L., H.L., F.Y., Y.Y. M.H.A., L.D., L.W., and M.L. participated in editing the manuscript. Z.S. performed GIWAX measurements and analyzed the data. All authors read and commented on the manuscript. Competing interests The authors declare no competing interests. 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\u003cstrong\u003ed\u003c/strong\u003e, XPS spectra of I 3d and Pb 4f for PVK and PVK: HDSF films. For simplicity, perovskite is abbreviated as PVK. GIWAXS patterns of perovskite films at incident angles of 0.4° for (\u003cstrong\u003ee\u003c/strong\u003e) control PVK, and (\u003cstrong\u003ef\u003c/strong\u003e) PVK: HDSF films.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4527071/v1/ccf351fda7faebd3bdb83fd0.png"},{"id":58547809,"identity":"07f4b2ec-b3cb-48a5-8538-49f85bf08b9e","added_by":"auto","created_at":"2024-06-18 06:03:09","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":347889,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eCarrier transport mechanism\u003c/strong\u003e. \u003cstrong\u003ea\u003c/strong\u003e, t-DOS curves. \u003cstrong\u003eb\u003c/strong\u003e, \u003cem\u003eV\u003c/em\u003e\u003csub\u003eoc\u003c/sub\u003e versus light intensity plots for devices with and without HDSF. TA spectra at different delay times of (\u003cstrong\u003ec\u003c/strong\u003e) FTO/SAM/PVK/PCBM, (\u003cstrong\u003ed\u003c/strong\u003e) FTO/SAM/PVK: HDSF/PCBM semi-devices. \u003cstrong\u003ee\u003c/strong\u003e, TPV measurements of the control and HDSF-treated devices. \u003cstrong\u003ef\u003c/strong\u003e, Charge collection probability of devices with and without HDSF.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4527071/v1/a71b6fe4f51da9946f6424ce.png"},{"id":58546979,"identity":"ffe014d8-dc2b-4c1b-aa7e-d735d3fdd879","added_by":"auto","created_at":"2024-06-18 05:55:09","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":1012990,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eTemperature stability analysis of perovskite films. a\u003c/strong\u003e, Schematic illustration of heat-triggered self-healing properties via dynamic exchange of disulfide bonds in HDSF. The XRD evolution of (\u003cstrong\u003eb\u003c/strong\u003e) control and (\u003cstrong\u003ec\u003c/strong\u003e) HDSF-treated perovskite films during thermal cycle tests. Top-view SEM images of control PVK films (\u003cstrong\u003ed\u003c/strong\u003e) before and (\u003cstrong\u003ee\u003c/strong\u003e) after 160 thermal cycles, PVK: HDSF films (\u003cstrong\u003ef\u003c/strong\u003e) before and (\u003cstrong\u003eg\u003c/strong\u003e) after 160 thermal cycles. GIXRD patterns of (012) plane at different tilt angles of (\u003cstrong\u003eh\u003c/strong\u003e) PVK, and (\u003cstrong\u003ei\u003c/strong\u003e) PVK: HDSF films. \u003cstrong\u003ej\u003c/strong\u003e, Macroscope residual strain distribution analysis by linear fitting of 2θ-sin\u003csup\u003e2\u003c/sup\u003eψ for control PVK and PVK: HDSF films.\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4527071/v1/c3278220bd5e33185f804dcf.png"},{"id":58546981,"identity":"eb890132-a1d4-4afb-8ac5-87a8b77004d9","added_by":"auto","created_at":"2024-06-18 05:55:09","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":651736,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ePerformance and temperature stability of PSCs\u003c/strong\u003e. \u003cem\u003eJ-V\u003c/em\u003e curves of (\u003cstrong\u003ea\u003c/strong\u003e) control device, and (\u003cstrong\u003eb\u003c/strong\u003e) HDSF-treated device (0.0982 cm\u003csup\u003e2\u003c/sup\u003e). \u003cstrong\u003ec\u003c/strong\u003e, \u003cem\u003eJ-V\u003c/em\u003e curves of large area devices (1 cm\u003csup\u003e2\u003c/sup\u003e) with and without HDSF. \u003cstrong\u003ed\u003c/strong\u003e, Stability measurement of devices with and without HDSF at the maximum power point (MPP) under 100 mW cm\u003csup\u003e−2\u003c/sup\u003e white light-emitting diode stored in an N\u003csub\u003e2\u003c/sub\u003e atmosphere. Temperature-dependent PCE for (\u003cstrong\u003ee\u003c/strong\u003e) control devices and (\u003cstrong\u003ef\u003c/strong\u003e) HDSF-treated devices (10 devices per type). \u003cstrong\u003eg\u003c/strong\u003e, −40°C and (\u003cstrong\u003eh\u003c/strong\u003e) 80°C of control and HDSF-treated devices against thermal cycles between −40°C and +80°C. Rapid thermal cycling was implemented with a ramp rate of 20°C per minute. During cycling to −40°C and +80°C, the device had an additional 2-minute waiting window to reach thermal equilibrium. The process started at room temperature, heated to +80°C, then cooled to −40°C, ending back at room temperature. The duration of a full cycle is approximately 16 minutes.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4527071/v1/426be423a017aa323b971973.png"},{"id":62046264,"identity":"84f7affe-63d2-459e-9b92-93bd622d814b","added_by":"auto","created_at":"2024-08-08 15:59:01","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4026286,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4527071/v1/5008c7d0-4605-4415-ae12-6c5c9b166645.pdf"},{"id":58546980,"identity":"ca47e8e8-414c-4a29-9955-b777a4e6aaf5","added_by":"auto","created_at":"2024-06-18 05:55:09","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":14076761,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cbr\u003e\u003c/p\u003e","description":"","filename":"SupplementaryInformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-4527071/v1/554df1997e17e4b5003607b9.docx"}],"financialInterests":"There is \u003cb\u003eNO\u003c/b\u003e Competing Interest.","formattedTitle":"Heat-triggered Dynamic Self-healing Framework for Variable-temperature Stable Perovskite Solar Cells","fulltext":[{"header":"Introduction","content":"\u003cp\u003eMetal hybrid perovskite solar cells (PSCs) with an outstanding efficiency higher than 26%\u003csup\u003e1\u003c/sup\u003e can rival commercialized polycrystalline silicon (c-Si) solar cells. And they emerged as a disruptive photovoltaic (PV) technology due to the simple fabrication technologies and excellent photovoltaic performance\u003csup\u003e2-3\u003c/sup\u003e.\u0026nbsp;Despite tremendous advances in\u0026nbsp;power conversion efficiency (PCE),\u0026nbsp;the operational stability of devices in complex practical environments remains a still a substantial hurdle to commercialization.\u003c/p\u003e\n\u003cp\u003ePerovskite films usually suffer from lattice distortion and crystal phase transition under thermal stress due to the ionic nature and weak bonding of the crystal structures. This can lead to ion migration and crystal decomposition inside the perovskite crystal, ultimately damaging the photoelectric characteristics and stability of devices\u003csup\u003e4-8\u003c/sup\u003e. Research groups have developed significant approaches to improve the thermal stability of PSCs, such as additives engineering, interface modification, and grain boundary passivation\u003csup\u003e9-13\u003c/sup\u003e. However,\u0026nbsp;these \u0026ldquo;static\u0026rdquo; measures only alleviate the internal stress of the device caused by high temperatures, and cannot repair defects from the expansion and contraction of the perovskite lattice in variable thermal environments. In practical application scenarios, PSCs experience wide temperature fluctuations due to seasonal changes and day-night cycles\u003csup\u003e14\u003c/sup\u003e. These fluctuations can cause phase transformations or irreversible thermal degradation in the perovskite film due to its low deposition energy\u003csup\u003e15\u003c/sup\u003e, primarily mediated by defects from thermal stress\u003csup\u003e6\u003c/sup\u003e. The irreversible nature of these defects and the low ion migration activation energy contribute to the decomposition of the perovskite structure, harming carrier transport characteristics. Moreover, the long-term defects accumulation will seriously impair the stability of devices. Therefore, mitigating residual thermal stress and dynamically inhibiting defect formation in perovskite films during temperature variations is crucial for achieving long-term operational stability of PSCs.\u003c/p\u003e\n\u003cp\u003eHerein, we report a heat-triggered dynamic self-healing strategy to enhance the thermal stability of PSCs. A thermally triggered dynamic self-healing framework (HDSF) was introduced into the\u0026nbsp;perovskite film to repair defects caused by thermal damage. The electron-donating atoms in the HDSF conjugated framework passivate the uncoordinated Pb\u003csup\u003e2+\u003c/sup\u003eatomson the surface of the perovskite film through coordinated covalent bonds, suppressing the formation of excess secondary phase PbI\u003csub\u003e2\u003c/sub\u003e.\u0026nbsp;HDSF is mainly distributed on the surface and grain boundary of the perovskite film, stabilizing the crystal lattice and reducing the distortion caused by temperature changes. When the ambient temperature rises (60℃\u0026ndash;80℃), the disulfide bond in HDSF adjusts the thermal stress of the perovskite crystals under variable temperature conditions through dynamic exchange reaction and shape memory effect\u003csup\u003e16\u003c/sup\u003e. This dynamic repair mechanism addresses defects at the grain boundaries caused by thermal strain, improving the variable temperature stability of PSCs. Thermal admittance spectrum (TAS) and femtosecond transient absorption spectrum (Fs-TA) show that HDSF-treated devices have lower defect state density and higher charge transport capability. Ultimately, the HDSF-treated device achieved a champion efficiency of 26.32% (certified 25.84%) with excellent temperature stability, maintaining 87.6% of its initial PCE at \u0026minus;40℃ and 92.6% at 80℃ after 160 cycles between \u0026minus;40℃ and 80℃.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e\u003cem\u003eFormation of HDSF and interaction with perovskite crystals\u003c/em\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eFirst, we explored the formation process of HDSF. \u003cstrong\u003eFig. 1a\u003c/strong\u003e depicts the reaction process of dewatering and polycondensation of 4-aminophenyl disulfide (APD) and Tri (4-formylphenyl) amine (TPA) to form HDSF. It also shows the interaction between HDSF and the perovskite lattice, and the heat-triggered dynamic exchange process of the disulfide bond. We employed proton nuclear magnetic resonance (\u003csup\u003e1\u003c/sup\u003eH-NMR) and fourier-transform infrared (FTIR) to verify the formation of HDSF. When APD deoxygenates and TPA dehydrogenates, the H on the generated C=N bond appears at 8.6 ppm\u003csup\u003e17\u003c/sup\u003e, indicated by the red arrow (\u003cstrong\u003eFig. 1b\u003c/strong\u003e). At the same time, the typical tensile vibration peak C=N was observed at 1622 cm\u003csup\u003e\u0026minus;1\u003c/sup\u003e in the FTIR spectra\u003csup\u003e18\u003c/sup\u003e (\u003cstrong\u003eFig. 1c and Supplementary Fig. 1\u003c/strong\u003e). The above results fully confirm the formation of HDSF. We investigated the incorporation of HDSF and its interaction with the perovskite lattice using X-ray photoelectron spectroscopy (XPS). \u003cstrong\u003eSupplementary Fig. 2\u0026nbsp;\u003c/strong\u003eshows two\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eN 1s peaks for the control film, assigned to C-N and C=N, while HDSF-treated film exhibits a new peak of C=N-C belonging to HDSF, indicating the incorporation of HDSF into the perovskite film. \u003cstrong\u003eFig. 1d\u003c/strong\u003e shows two characteristic peaks of I 3d\u003csub\u003e3/2\u0026nbsp;\u003c/sub\u003e(630.4 eV)\u003csub\u003e\u0026nbsp;\u003c/sub\u003eand I 3d\u003csub\u003e\u0026nbsp;5/2\u0026nbsp;\u003c/sub\u003e(618.9 eV) for the control perovskite film shifted to lower binding energy due to hydrogen bonding formation\u0026nbsp;(N‐H\u0026hellip;I, ‐N‐H\u0026hellip;I‐Pb‐I). The coordination between HDSF and perovskite crystals, and hydrogen bond formation, constructs\u0026nbsp;an orderly and stable interaction network between HDSF and the perovskite lattice, thus stabilizing the [PbI\u003csub\u003e6\u003c/sub\u003e]\u003csup\u003e4-\u003c/sup\u003e octahedral structure and transforming the crystal structure from metastable to stable\u003csup\u003e19-23\u003c/sup\u003e. Additionally, two characteristic peaks of Pb 4f\u003csub\u003e5/2\u0026nbsp;\u003c/sub\u003e(143.2 eV)\u003csub\u003e\u0026nbsp;\u003c/sub\u003eand\u003csub\u003e\u0026nbsp;\u003c/sub\u003ePb 4f\u003csub\u003e7/2\u0026nbsp;\u003c/sub\u003e(138.3 eV) for the control film also shifted towards lower binding energy after introducing HDSF. This shift indicates the formation of a coordination bond between O, N, and S atoms in HDSF and the uncoordinated Pb\u003csup\u003e2+\u003c/sup\u003e in the perovskite lattice, thus increasing the electron cloud density around Pb\u003csup\u003e24-26\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eTo investigate the effect of HDSF on the morphology and crystallization dynamics of the prepared perovskite films, we utilized a scanning electron microscope (SEM), grazing-incidence wide-angle X-ray scattering (GIWAXS), and X-ray diffraction (XRD) to compare the film quality.\u0026nbsp;\u003cstrong\u003eSupplementary\u003c/strong\u003e\u003cstrong\u003e\u0026nbsp;Fig. 3a,b\u003c/strong\u003e show the SEM top-view images of both control and HDSF-treated films. A significant amount of secondary phase PbI\u003csub\u003e2\u003c/sub\u003e (white species)\u003csup\u003e27-28\u003c/sup\u003e is observed on the surface of the control perovskite film, which forms as the decomposition product after heating\u003csup\u003e12\u003c/sup\u003e. Excessive PbI\u003csub\u003e2\u003c/sub\u003e tends to be decomposed into gaseous I\u003csub\u003e2\u003c/sub\u003e and metallic lead Pb\u003csub\u003e0\u003c/sub\u003e under light and heat, acting as the catalytic site for the decay of perovskite films. This is one of the main reasons for the poor thermal stability of perovskite devices\u003csup\u003e29-30\u003c/sup\u003e. In contrast, the perovskite film with HDSF shows almost no excess PbI\u003csub\u003e2\u003c/sub\u003e.\u0026nbsp;This is attributed to the coordination between the electron donor atoms (O, N, S) in HDSF and the uncoordinated Pb\u003csup\u003e2+\u003c/sup\u003e on the surface of perovskite, which inhibits the generation of excessive secondary PbI\u003csub\u003e2\u003c/sub\u003e. By comparing the statistical distribution diagram of perovskite grains (\u003cstrong\u003eSupplementary Fig. 3c,d\u003c/strong\u003e), we found that the average grain size of perovskite films increased from 303.42 nm for the control film to 439.10 nm of the HDSF-treated films, indicating the beneficial effect of HDSF in regulating the growth of perovskite films.\u003c/p\u003e\n\u003cp\u003eThe effect of HDSF on the crystal structure\u003csup\u003e\u0026nbsp;\u003c/sup\u003eof the perovskite film was further explored using GIWAXS at different incidence angles\u003csup\u003e27,31\u003c/sup\u003e (0.4\u0026deg; and 0.15\u0026deg;). \u003cstrong\u003eFig. 1e,f\u0026nbsp;\u003c/strong\u003eand\u003cstrong\u003e\u0026nbsp;Supplementary Fig. 4\u0026nbsp;\u003c/strong\u003eshow that the HDSF-treated films did not exhibit any new Debye-Scherrer-like ring (D-S ring) compared to the control films. Additionally, the secondary phase PbI\u003csub\u003e2\u003c/sub\u003e is almost absent in the HDSF-treated films. The azimuthal integrated 1D GIWAX spectra are shown in\u0026nbsp;\u003cstrong\u003eSupplementary\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eFig. 5\u003c/strong\u003e. These results confirm that HDSF can effectively inhibit the production of excess PbI\u003csub\u003e2\u003c/sub\u003e and promote the formation of pure perovskite phase. As illustrated in\u0026nbsp;\u003cstrong\u003eSupplementary\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eFig. 6\u003c/strong\u003e, the XRD patterns of the HDSF-treated films present the same diffraction peak positions as the control film, indicating that HDSF does not induce structural changes within the perovskite lattice. The above results suggest that HDSF is primarily distributed on the surface and at the grain boundaries of the perovskite film, rather than entering the crystal lattice\u0026nbsp;\u003csup\u003e18,32\u003c/sup\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e\u003cem\u003eDefects and charge transfer characteristics\u003c/em\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eTo investigate the density of trap states (t-DOS) within the perovskite thin films, we used thermal admittance spectroscopy (TAS). As depicted in N\u003csub\u003et\u003c/sub\u003e-E\u003csub\u003ew\u003c/sub\u003e curves (\u003cstrong\u003eFig. 2a\u003c/strong\u003e), the HDSF-treated device shows a lower trap state density over the entire trap depth region. The shallow traps, in the range of 0.35\u0026ndash;0.40 eV, are associated with grain boundary defects\u003csup\u003e33-34\u003c/sup\u003e,\u0026nbsp;while the deep traps, in the range of 0.40\u0026ndash;0.52 eV, correspond to traps at the perovskite surface\u003csup\u003e35-36\u003c/sup\u003e.\u0026nbsp;This reduction in both shallow and deep trap states is attributed to the coordination between HDSF and uncoordinated Pb\u003csup\u003e2+\u003c/sup\u003e at the grain boundaries and surface of perovskite thin films\u003csup\u003e37\u003c/sup\u003e. To further quantify the trap densities in the perovskite thin films, we performed the space charge limited current (SCLC) measurement based on electron-only devices (FTO/SnO\u003csub\u003e2\u003c/sub\u003e/Cs\u003csub\u003e0.05\u003c/sub\u003eFA\u003csub\u003e0.85\u003c/sub\u003eMA\u003csub\u003e0.1\u003c/sub\u003ePbI\u003csub\u003e3\u003c/sub\u003e/PCBM/Ag) and hole-only devices (FTO/PEDOT:PSS/Cs\u003csub\u003e0.05\u003c/sub\u003eFA\u003csub\u003e0.85\u003c/sub\u003eMA\u003csub\u003e0.1\u003c/sub\u003ePbI\u003csub\u003e3\u003c/sub\u003e/Spiro-OMeTAD/Ag). As shown in \u003cstrong\u003eSupplementary Fig. 7\u003c/strong\u003e, for the electron-only devices, the V\u003csub\u003eTFL\u003c/sub\u003e of the HDSF-treated device is 0.15 V, \u0026nbsp;compared to 0.20 V for the control device. The corresponding trap densities are 2.82 \u0026times; 10\u003csup\u003e15\u003c/sup\u003e cm\u003csup\u003e-3\u003c/sup\u003e, and 3.76 \u0026times; 10\u003csup\u003e15\u003c/sup\u003e cm\u003csup\u003e-3\u003c/sup\u003e, respectively.\u0026nbsp;A similar trend was\u0026nbsp;observed in the hole-only devices, with the HDSF-treated device showing a hole trap density of 3.01 \u0026times; 10\u003csup\u003e15\u003c/sup\u003e cm\u003csup\u003e-3\u003c/sup\u003e, while the control device exhibited a higher trap density of 5.07 \u0026times; 10\u003csup\u003e15\u003c/sup\u003e cm\u003csup\u003e-3\u003c/sup\u003e. These results further confirm that HDSF effectively passivates surface and grain boundary defects in the perovskite films.\u003c/p\u003e\n\u003cp\u003eElectrochemical impedance spectroscopy (EIS) was utilized to explore the charge transfer and recombination behavior of devices. In the Nyquist plot, the low-frequency region represents the recombination resistance (R\u003csub\u003erec\u003c/sub\u003e), and the high-frequency region represents the transfer resistance (R\u003csub\u003etra\u003c/sub\u003e)\u003csup\u003e38-39\u003c/sup\u003e. The inner illustrations in \u003cstrong\u003eSupplementary Fig. 8\u003c/strong\u003e show the corresponding equivalent circuit diagrams and an enlargement of the R\u003csub\u003etra\u003c/sub\u003e region. We observed that HDSF-treated devices exhibit a lower R\u003csub\u003etra\u003c/sub\u003e and a higher R\u003csub\u003erec\u003c/sub\u003e compared to the control devices. This indicates that HDSF effectively inhibits charge recombination and promotes charge transfer between the perovskite films and the transport layers\u003csup\u003e40-42\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eWe performed\u0026nbsp;light-dependent \u003cem\u003eV\u003c/em\u003e\u003csub\u003eOC\u003c/sub\u003e and \u003cem\u003eJ\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e measurements to understand the carrier recombination mechanism in perovskite films.\u0026nbsp;As shown in \u003cstrong\u003eFig. 2b\u003c/strong\u003e, the ideality factor extracted from the fitting curves for the HDSF-treated devices is 1.61, while that for the control device is 1.84. This implies that trap-assisted recombination is effectively suppressed in the HDSF-treated devices\u003csup\u003e43-44\u003c/sup\u003e.\u0026nbsp;Additionally, the index (\u0026alpha;) values extracted from the plots of \u003cem\u003eJ\u003c/em\u003e\u003csub\u003esc\u003c/sub\u003e\u0026prop;I\u003csup\u003e\u0026alpha;\u003c/sup\u003e are\u0026nbsp;0.975\u0026nbsp;and 0.987\u0026nbsp;for\u0026nbsp;the control device and HDSF-treated device, respectively (\u003cstrong\u003eSupplementary Fig. 9\u003c/strong\u003e). This indicates that the HDSF-treated device has lower bimolecular recombination, allowing photogenerated carriers to be extracted and transferred smoothly\u003csup\u003e45-47\u003c/sup\u003e. This finding is further confirmed by the steady-state photoluminescence (PL) and time-resolved photoluminescence (TRPL) spectra of perovskite films deposited on quartz glass. \u003cstrong\u003eSupplementary Fig. 10\u003c/strong\u003e shows that the PL intensity of the HDSF-treated perovskite film is higher than that of the control film. Moreover, a double exponential decay model was used to fit TRPL curves (\u003cstrong\u003eSupplementary Fig. 11\u003c/strong\u003e). The fitting results (\u003cstrong\u003eSupplementary\u003c/strong\u003e \u003cstrong\u003eTable 1\u003c/strong\u003e) show that the average lifetime (\u0026tau;\u003csub\u003eave\u003c/sub\u003e) of the HDSF-treated perovskite film is significantly longer than that of the control film (147.74 ns vs. 68.98 ns). This extended lifetime is attributed to the effective defect passivation and suppression of non-radiative recombination by HDSF\u003csup\u003e44,48-50\u003c/sup\u003e.\u003c/p\u003e\n\u003cp\u003eTo further explore the carrier transport dynamics of the devices, femtosecond transient absorption (Fs-TA) spectra were measured. The structure of the tested semi-device (FTO/SAM/Cs\u003csub\u003e0.05\u003c/sub\u003eFA\u003csub\u003e0.85\u003c/sub\u003eMA\u003csub\u003e0.1\u003c/sub\u003ePbI\u003csub\u003e3\u003c/sub\u003e/PCBM) is shown in \u003cstrong\u003eSupplementary Fig. 12\u003c/strong\u003e. A 400 nm pumped laser was\u0026nbsp;implemented to prob absorption signals, inducing an absorption change (\u0026Delta;A)\u0026nbsp;associated with\u0026nbsp;ground-state bleaching (GSB), which reflects the photoinduced carrier dynamics in the valance and conduction bands of the perovskite film\u003csup\u003e51-52\u003c/sup\u003e.\u0026nbsp;The pseudocolor TAS plots (\u003cstrong\u003eSupplementary Fig. 13\u003c/strong\u003e) elucidate that both the control perovskite film and the HDSF-treated perovskite film displayed\u0026nbsp;significant\u0026nbsp;GSB peaks at about 760 nm.\u0026nbsp;The quenching rate of the GSB peak signal indicates the efficiency of carrier transport from perovskite to adjacent carrier transport layers\u003csup\u003e53\u003c/sup\u003e.\u0026nbsp;Compared to the delay-time-dependent TA spectra of the control device (\u003cstrong\u003eFig. 2c\u003c/strong\u003e), the TA spectra of the HDSF-treated device (\u003cstrong\u003eFig. 2d\u003c/strong\u003e)\u0026nbsp;show a more rapidly faded signal, indicating enhanced charge extraction from the perovskite to transport layers\u003csup\u003e54\u003c/sup\u003e. A bi-exponential decay model was used to fit the decay kinetics of the GSB peaks. \u003cstrong\u003eSupplementary Fig. 14\u003c/strong\u003e shows that the HDSF-treated samples decay faster, further illustrating that HDSF promotes charge transfer from perovskite to adjacent layers.\u003c/p\u003e\n\u003cp\u003eTransient photovoltage (TPV) and transient photocurrent (TPC) were conducted to analyze the charge recombination and extraction behavior. As shown in TPV curves (\u003cstrong\u003eFig. 2e\u003c/strong\u003e), the HDSF-treated device exhibits a longer decay lifetime (2.06 \u0026mu;s) compared to the control counterpart (1.58 \u0026mu;s). Conversely, the photocurrent decay response of the HDSF-treated device (0.56 \u0026mu;s) is faster than that of the control device (0.73 \u0026mu;s) (\u003cstrong\u003eSupplementary Fig. 15\u003c/strong\u003e). These results confirm that HDSF effectively inhibits defect recombination and accelerate the extraction of photogenerated carrier \u003csup\u003e36,44,55-57\u003c/sup\u003e. Additionally, the \u003cem\u003eJ-V\u003c/em\u003e curves under dark conditions (\u003cstrong\u003eSupplementary Fig. 16\u003c/strong\u003e), show that the HDSF treatment enables a significantly lower leakage current, indicating that the photogenerated carriers are more efficiently transmitted to the corresponding electrode rather than being captured by defect centers\u003csup\u003e18,28\u003c/sup\u003e. The charge collection probability (\u003cem\u003eP\u003c/em\u003e\u003csub\u003ec\u003c/sub\u003e)-internal voltage (\u003cem\u003eV\u003c/em\u003e\u003csub\u003eint\u003c/sub\u003e) curve (\u003cstrong\u003eFig. 2f\u003c/strong\u003e) further demonstrates that the HDSF-treated device presents a superior charge collection capability than the control device\u003csup\u003e58-61\u003c/sup\u003e.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e\u003cem\u003eProperties and temperature stability of perovskite films and devices\u003c/em\u003e\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFig. 3a\u003c/strong\u003e provides\u0026nbsp;a schematic illustration of heat-triggered self-healing properties via dynamic exchange of disulfide bonds in HDSF\u003csup\u003e16,19\u003c/sup\u003e.\u0026nbsp;To investigate the effect of HDSF on the stability of perovskite films under variable temperatures, we employed XRD and SEM to characterize the perovskite films subjected to variable temperature cycles (from room temperature heating to 80℃, then cooling to \u0026minus;40℃, and finally returning to room temperature for a variable temperature cycle,\u0026nbsp;with a ramp rate of 20\u0026deg;C per minute). As illustrated in \u003cstrong\u003eFig. 3b\u003c/strong\u003e,\u003cstrong\u003ec\u003c/strong\u003e, the quantity of PbI\u003csub\u003e2\u003c/sub\u003e in the control perovskite film incrementally rises with an increasing number of\u0026nbsp;thermal cycles.\u0026nbsp;Notably, the control sample\u0026nbsp;exhibited excessive\u0026nbsp;PbI\u003csub\u003e2\u003c/sub\u003e after 160\u0026nbsp;variable temperature cycles, leading to internal instability of the device and accelerating perovskite decomposition under light and thermal stress\u003csup\u003e29\u003c/sup\u003e.\u0026nbsp;Excessive PbI\u003csub\u003e2\u003c/sub\u003e also increases non-radiative recombination and impairs charge transfer behavior\u003csup\u003e62-63\u003c/sup\u003e.\u0026nbsp;In contrast, the HDSF-treated perovskite film exhibits significantly lower PbI\u003csub\u003e2\u003c/sub\u003e content compared to the control film.\u0026nbsp;The top-view SEM images (\u003cstrong\u003eFig. 3d-g\u003c/strong\u003e) align with XRD results, further supporting that HDSF effectively inhibits the thermal decomposition of perovskite films.\u003c/p\u003e\n\u003cp\u003eThe residual tensile thermal stress in perovskite films was also investigated by the grazing incident X-ray diffraction (GIXRD) with the classical 2\u0026theta;-sin\u003csup\u003e2\u003c/sup\u003e(\u0026psi;) method, where \u0026theta; and \u0026psi; represent the diffraction and tilt angles\u003csup\u003e27,46,51,64\u003c/sup\u003e. The (012) plane oriented at ~31.6\u0026deg; was selected for the strain analysis due to its larger diffraction angle and multiplication factor, providing more reliable structure symmetry information\u003csup\u003e52,65-68\u003c/sup\u003e. As shown in \u003cstrong\u003eFig. 3h\u003c/strong\u003e,\u003cstrong\u003ei\u003c/strong\u003e, by varying \u0026psi; angles from 0\u0026deg; to 50\u0026deg;, the scattering peak of control perovskite gradually shifts to the lower 2\u0026theta; direction. This shift indicates an increase in crystal plane distance (d(012)) and the presence of tensile stress in perovskite films\u003csup\u003e69\u003c/sup\u003e. The linear fitting curves for 2\u0026theta; and sin\u003csup\u003e2\u003c/sup\u003e\u0026psi; (\u003cstrong\u003eFig. 3j)\u003c/strong\u003e reveal that the control perovskite film exhibits a large negative slope, indicating severe tensile stress. This stress arises from the mismatch between the thermal expansion coefficient of the perovskite layer and the substrate, resulting in the biaxial residual tensile thermal stress of the perovskite film after annealing\u003csup\u003e32,63\u003c/sup\u003e.\u0026nbsp;These thermal tensile strains reduce the defect formation energy and ion migration activation energy\u003csup\u003e70\u003c/sup\u003e, leading to device instability during temperature variations\u003csup\u003e71\u003c/sup\u003e.\u0026nbsp;In contrast,\u0026nbsp;the HDSF-treated film presents a much smaller slope, indicating that HDSF is conducive to stress release. This stress relief can be attributed to the distribution of HDSF at the grain boundaries of perovskite grains, which stabilizes the crystal lattice and reduces the strain field\u003csup\u003e72\u003c/sup\u003e. Along with the thermally triggered self-healing characteristics of disulfide bonds, the stress compensation reduces the tensile strain in the perovskite, thereby improving the stability of the perovskite structure during temperature change.\u003c/p\u003e\n\u003cp\u003eTo evaluate the effect of HDSF on the photovoltaic performance of perovskite devices, we prepared p-i-n devices with the structure of glass/fluorine-doped tin oxide (FTO)/self-assembled monolayers (mixtures of [2-(9H-Carbazol-9-yl)ethyl]phosphonic Acid (2PACz) and [4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid (Me-4PACz))/perovskite/2D passivation layer/[6,6] -Phenyl -C\u003csub\u003e61\u003c/sub\u003e-butyric acid methylester (PC\u003csub\u003e61\u003c/sub\u003eBM)/bathocuproine (BCP)/silver (Ag). The 2D passivation layer is Phenethylammonium bromide (PEABr). As shown in the \u003cem\u003eJ-V\u003c/em\u003e curves (\u003cstrong\u003eFig. 4a\u003c/strong\u003e,\u003cstrong\u003eb\u003c/strong\u003e), the control device (0.0982 cm\u003csup\u003e2\u003c/sup\u003e) exhibits a PCE of 24.48%, with a \u003cem\u003eV\u003c/em\u003e\u003csub\u003eOC\u003c/sub\u003e of 1.15 V, a \u003cem\u003eJ\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e of 25.98 mA/cm\u003csup\u003e2\u003c/sup\u003e and an FF of 81.95%. In comparison, the PCE of the HDSF-treated champion device is 26.32%, with a \u003cem\u003eV\u003c/em\u003e\u003csub\u003eOC\u003c/sub\u003e of 1.19 V, a \u003cem\u003eJ\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e of 26.10 mA /cm\u003csup\u003e2\u003c/sup\u003e, and an FF of 84.73%. One of the HDSF-treated devices was sent to an independent laboratory (Fujian Metrology Institute, National PV Measurement and Testing Center of Microsystem and Information Technology, Fujian, China) for certification, where a PCE of 25.84% (with \u003cem\u003eV\u003c/em\u003e\u003csub\u003eOC\u003c/sub\u003e of 1.185 V, \u003cem\u003eJ\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e of 26.11 mA/cm\u003csup\u003e2\u003c/sup\u003e, and FF of 83.52%) was confirmed (\u003cstrong\u003eSupplementary Fig. 17\u003c/strong\u003e). Additionally, 1 cm\u003csup\u003e2\u003c/sup\u003e-sized devices were prepared to further verify the improvement of HDSF on the photovoltaic performance of larger area devices (\u003cstrong\u003eFig. 4c\u003c/strong\u003e). Compared with the control device (22.49%), the HDSF-treated device achieved a significant PCE of 24.43%. The improvement in PCE is mainly due to the significant increase in FF and \u003cem\u003eV\u003c/em\u003e\u003csub\u003eOC\u003c/sub\u003e, which can be attributed to HDSF\u0026rsquo;s ability to stabilize the lattice, promote charge transfer, and inhibit defection-assisted non-radiative recombination\u003csup\u003e73\u003c/sup\u003e.\u0026nbsp;The increase of the built-in potential (\u003cem\u003eV\u003c/em\u003e\u003csub\u003ebi\u003c/sub\u003e) for the HDSF-treated device (\u003cstrong\u003eSupplementary Fig. 18\u003c/strong\u003e) indicates that HDSF enhances the internal driving force for photogenerated carriers, thereby reducing recombination loss and improving \u003cem\u003eV\u003c/em\u003e\u003csub\u003eOC\u003c/sub\u003e\u003csup\u003e74\u003c/sup\u003e.\u0026nbsp;The integral \u003cem\u003eJ\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e values obtained from the EQE spectra (\u003cstrong\u003eSupplementary Fig. 19\u003c/strong\u003e) of the control device and the HDSF-treated device are 25.07 mA/cm\u003csup\u003e2\u003c/sup\u003e and 25.44 mA/cm\u003csup\u003e2\u003c/sup\u003e, respectively. These values are consistent with the\u003cem\u003e\u0026nbsp;\u003c/em\u003ecorresponding \u003cem\u003eJ\u003c/em\u003e\u003csub\u003eSC\u003c/sub\u003e values derived from\u003cem\u003e\u0026nbsp;J-V\u003c/em\u003e curves. Moreover, \u003cstrong\u003eSupplementary Fig. 20\u003c/strong\u003e shows the statistical diagram of device parameters, which further confirms the optimization of HDSF on device performance and reveals the good repeatability of HDSF-treated devices.\u003c/p\u003e\n\u003cp\u003eIn addition to high PCE, long-term and variable temperature stability of perovskite devices are critical for practical applications. The stabilized power output (SPO) can be observed at the maximum power point (MPP) under one-sun irradiation. \u003cstrong\u003eSupplementary Fig. 21\u003c/strong\u003e shows that the SPO of the control and the HDSF-treated devices are 22.69% and 25.77%, respectively, consistent with the results from the\u003cem\u003e\u0026nbsp;J-V\u003c/em\u003e curves. We further investigated the operational stability of the devices by conducting MPP tracking under continuous illumination. As shown in \u003cstrong\u003eFig. 4d\u003c/strong\u003e, the HDSF-treated device retains 96.9% of the initial PCE after 500 h of continuous operation, compared to 83.9% for the control device. The enhancement in light stability undoubtedly proves that HDSF can stabilize the lattice and effectively inhibit ion migration during operation\u003csup\u003e18\u003c/sup\u003e. To evaluate the stability of perovskite devices under variable temperatures, the photovoltaic parameters of the devices after temperature cycling between\u0026nbsp;\u0026minus;40℃ and 80℃ are counted. The relevant statistical parameters in \u003cstrong\u003eFig. 4e,f\u003c/strong\u003e and \u003cstrong\u003eSupplementary Fig. 22\u003c/strong\u003e,\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eshow that the HDSF-treated devices exhibit good repeatability and thermal stability. When stored at 85℃ in a nitrogen atmosphere for 500 h, the HDSF-treated device maintained 94.2% of its original efficiency, whereas the control device retained only 81.1% (\u003cstrong\u003eSupplementary Fig. 23\u003c/strong\u003e). The temperature stability of the devices is shown in \u003cstrong\u003eFig. 4g,h\u003c/strong\u003e. The PCE of the control device suffered severe attenuation after 160 cycles, maintaining only 67.4% and 72.3% of the initial efficiency at \u0026minus;40℃ and 80℃, respectively. In contrast, the HDSF-treated device retained 87.6% of its initial PCE at \u0026minus;40℃ and 92.6% at 80℃. Compared with control devices, the HDSF-treated devices exhibit significantly improved thermal stability and variable temperature stability. This enhancement is primarily due to the thermally triggered self-healing property of HDSF, which reduces the tensile strain in perovskite during temperature changes through stress compensation. This self-healing capacity effectively stabilizes the devices, enhancing their performance and longevity during temperature fluctuations.\u003c/p\u003e"},{"header":"Conclusions","content":"\u003cp\u003eIn summary, we innovatively demonstrated the heat-triggered dynamic self-healing strategy by incorporating HDSF as an additive to enhance the temperature stability of PSCs via healing the thermo-induced defects during temperature changes. The introduction of HDSF regulates the stress in devices under variable temperature conditions and dynamically repairs defects at the grain boundaries of perovskite caused by thermal strain through the dynamic exchange reaction and shape memory effect of disulfide bonds. As a result, the HDSF-treated device achieved a champion PCE of 26.32% (certified 25.84%) with a stabilized power output of 25.77%. Moreover, it exhibited remarkable temperature stability, retaining 94.2% of its initial efficiency after 500 h of dark storage at 85℃. Additionally, the HDSF-treated device maintained 87.6% of its initial efficiency at \u0026minus;\u0026thinsp;40℃ and 92.6% at 80℃ after 160 thermal cycles. This work paves the path to realize highly efficient and temperature-stable PSCs via a novel heat-triggered dynamic self-healing strategy for thermo-induced damage.\u003c/p\u003e"},{"header":"Methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eMaterials\u003c/h2\u003e \u003cp\u003eThe indium tin oxide (FTO) substrate was purchased from Libra Technologies (GD-H8). [2-(9H-Carbazol-9-yl)ethyl]phosphonic Acid (2PACz, \u0026gt;98.0%), [4-(3,6-Dimethyl-9H-carbazol-9-yl)butyl]phosphonic Acid (Me-4PACz, \u0026gt;99.0%) and bathocuproine (BCP, \u0026gt;99.0%) were purchased from TCI. [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]-phenyl-C61-butyric acid methyl ester (PC\u003csub\u003e61\u003c/sub\u003eBM, 99.9%) was gained from Advanced Choice Technology. Formamidinium iodide (FAI, \u0026gt;\u0026thinsp;99.99%), methylammonium iodide (MAI, \u0026gt;\u0026thinsp;99.99%), and phenethylammonium bromide (PEABr) were purchased from Greatcell Solar Materials. Cesium iodide (CsI, 99.999%), and lead iodide (PbI\u003csub\u003e2\u003c/sub\u003e, 99.999%) were obtained from p-OLED. All reagents were purchased from J\u0026amp;K Scientific including chlorobenzene (CB, 99%), N,N-dimethylformamide (DMF, 99.8%), dimethyl sulfoxide (DMSO, 99%), and isopropanol (IPA, \u0026ge;\u0026thinsp;99.9%). 4-Aminophenyl disulfide (APD-NH\u003csub\u003e2\u003c/sub\u003e, 98%) and tri (4-formylphenyl) amine (TPA-CHO, 97%) were purchased from Aladdin Scientific company. All materials were used as received without any additional processing.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003eDevice Fabrication\u003c/h2\u003e \u003cp\u003eFTO glass substrates were cleaned sequentially with detergent, deionized water, acetone, and ethanol under sonication for 15 mins, respectively. Then they were dried in an oven at 60℃ and treated with oxygen plasma for 20 min before using. Subsequently, a uniform and dense SAM layer was deposited onto the FTO substrate by spin-coating 2PACz (0.17 mg mL\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) and Me-4PACz (0.33 mg mL\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) at 3000 rpm for 30 s with a ramp of 1000 rpm s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and annealing at 100\u0026deg;C for 10 min. After SAM/FTO was cooled to room temperature, 100 uL 1.5 M Cs\u003csub\u003e0.05\u003c/sub\u003eFA\u003csub\u003e0.85\u003c/sub\u003eMA\u003csub\u003e0.1\u003c/sub\u003ePbI\u003csub\u003e3\u003c/sub\u003e perovskite precursor solution (including PbI\u003csub\u003e2\u003c/sub\u003e:FAI:MAI:CsI (760.7 mg:219.3 mg:23.8 mg:19.5 mg) with 10 mg MACl additive in a mixed solution of 800 uL DMF and 200 uL DMSO with or without 10 uL 0.04 mmol HDSF (9.93 mg APD-NH\u003csub\u003e2\u003c/sub\u003e:13.17 mg TPA-CHO in 1 mL DMSO)) was coated on SAM layer at 6000 rpm for 35 s, then 200 uL CB was added evenly and slowly at 25 s. After that, the perovskite films were annealed at 100\u0026deg;C for 30 min to complete the perovskite growth. Subsequently, 100 uL PEABr solution (1 mg PEABr was dissolved in 995 uL IPA and 5 uL DMSO mixed solution) was spun onto the perovskite film at 4000 rpm (with a ramping rate of 2000 rpm s\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) for 30 s and then annealing at 100℃ for 5 min. Next, 100 uL PC\u003csub\u003e61\u003c/sub\u003eBM solution (20 mg PC\u003csub\u003e61\u003c/sub\u003eBM was dissolved in 1 mL CB) was coated on the PEABr layer without annealing. All the spin-coating processes were conducted in an N\u003csub\u003e2\u003c/sub\u003e-filled glovebox with O\u003csub\u003e2\u003c/sub\u003e and H\u003csub\u003e2\u003c/sub\u003eO contents less than 0.1 ppm. Finally, a 7 nm BCP layer and a 100 nm Ag layer were thermally evaporated under a pressure of 2\u0026times;10\u003csup\u003e\u0026minus;\u0026thinsp;6\u003c/sup\u003e hPa, respectively.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003eCharacterizations\u003c/h2\u003e \u003cp\u003eProton Nuclear Magnetic Resonance (\u003csup\u003e1\u003c/sup\u003eH-NMR) spectra were measured using a Bruker AVANCE NEO-400 NMR spectrometer. Fourier-transform infrared (FTIR) spectra were measured with a Bruker ALPHA II spectrometer. The surface morphologies and microstructures of Cs\u003csub\u003e0.05\u003c/sub\u003eFA\u003csub\u003e0.85\u003c/sub\u003eMA\u003csub\u003e0.1\u003c/sub\u003ePbI\u003csub\u003e3\u003c/sub\u003e perovskite films for top-view images were researched by scanning electron microscopy (SEM, SUPRA40, Carl Zeiss) with electron beam accelerating at 5 kV. The charge transfer performance of Cs\u003csub\u003e0.05\u003c/sub\u003eFA\u003csub\u003e0.85\u003c/sub\u003eMA\u003csub\u003e0.1\u003c/sub\u003ePbI\u003csub\u003e3\u003c/sub\u003e perovskite films was characterized by Ultrafast Systems (Helios) under the conditions of pump light intensity of 30 \u0026micro;J/cm\u003csup\u003e2\u003c/sup\u003e with a 400 nm pump laser. The diffraction patterns of perovskite films were implemented by X-ray diffraction (XRD, D8-Discover, Bruker). The grazing incidence X-ray diffraction (GIXRD) (Rigaku SmartLab 3kW) was utilized to characterize the residual tensile thermal stress of perovskite films. Grazing incidence wide angle X-ray scattering (GIWAX) spectra were obtained by BL14B1 beamline of the Shanghai Synchrotron Radiation Facility (SSRF). X-ray photoelectron spectroscopy (XPS) was carried out by Thermo Fisher ESCALAB250Xi. The external quantum efficiency (EQE) spectra were obtained by QER of EnliTech. The current-voltage characteristics of the devices were measured by a Keithley 2400 source meter unit under AM 1.5G (100 mW/cm\u003csup\u003e2\u003c/sup\u003e) illumination from a solar simulator (EnliTech, SS-X50, with A\u003csup\u003e+\u003c/sup\u003e spectrum). The solar simulator was calibrated by a reference Silicon cell (EnliTech, certificated by NIST) with a KG2 filter. Device areas of 0.0982 cm\u003csup\u003e2\u003c/sup\u003e and 1 cm\u003csup\u003e2\u003c/sup\u003e were defined by a metal aperture mask. Dark \u003cem\u003eI-V\u003c/em\u003e curves for hole-only and electron-only devices based on the SAM/Cs\u003csub\u003e0.05\u003c/sub\u003eFA\u003csub\u003e0.85\u003c/sub\u003eMA\u003csub\u003e0.1\u003c/sub\u003ePbI\u003csub\u003e3\u003c/sub\u003e films were characterized by Ivium Electrochemical Workstation (Netherlands). Trap density of states (t-DOS) was tested using a Precision Impedance Analyzer (Agilent 4294A, 40 HZ-1 MHZ). Photoluminescence (PL) and Time-Resolved Photoluminescence (TRPL) spectra were obtained by FLS980 (Edinburgh Instruments). Transient Photovoltage (TPV) and Transient Photocurrent (TPC) curves were measured by a transient photocurrent/voltage tester (Shanghai Jinzhu Technology Co., LTD, laser 570 nm). The temperature-dependent test system is mainly equipped with temperature and vacuum controllers, a vacuum pump, a sample chamber, a solar simulator, and liquid nitrogen. Temperature was controlled by Standalone Temperature Controller (mK2000B) coupled with a hot and cold plate (HCP421-PM), a temperature control sensor (100 Ω Platinum RTD), circulating water, a liquid nitrogen cooling system (INSTEC LN2-P), a vacuum pore (KF16), an LN2 dewar flask, a DC power supply, and temperature control software (Instec App). The temperature setting range is from \u0026minus;\u0026thinsp;190\u0026deg;C to 400\u0026deg;C with stability of \u0026plusmn;\u0026thinsp;0.05\u0026deg;C. The minimum heating and cooling rate is about\u0026thinsp;\u0026plusmn;\u0026thinsp;0.1\u0026deg;C/h, the maximum heating rate is +\u0026thinsp;150\u0026deg;C/min at 37\u0026deg;C, and the maximum cooling rate is \u0026minus;\u0026thinsp;50\u0026deg;C/min at 37\u0026deg;C. Temperature control is accurate to 0.001℃. During temperature variation testing, the device was placed in a sample chamber with controllable temperature and vacuum conditions. The thermal cycling process was controlled between \u0026minus;\u0026thinsp;40\u0026deg;C and +\u0026thinsp;80\u0026deg;C, with the temperature regulated primarily by liquid nitrogen. The test temperature parameters were mainly determined by setting proportional, integral, and differential (PID) parameters.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003eReporting summary\u003c/h2\u003e \u003cp\u003eFurther information on research design is available in the Nature Portfolio Reporting Summary linked to this article.\u003c/p\u003e \u003c/div\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eData availability\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe data that support the findings of this study are available from the corresponding authors on reasonable request. Source data are provided with this paper.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgments\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors acknowledge the support of all the technicians at Henan Normal University and Henan University. The authors thank the beamline BL14B1 at the Shanghai Synchrotron Radiation Facility (SSRF) for providing the beam time. Y. Liu thanks the financial support from Zhongyuan Scholar of Henan Province (No.224000510007). Y. Yang acknowledges funding from\u0026nbsp;the National Natural Science Foundation of China (Grant No.11974103). M. Li thanks the support from the China Postdoctoral Science Foundation (No.2022M721026), the Joint Fund of Provincial Science and Technology Research, Development Plan of Henan Province (No. 232301420004), and the Outstanding Youth Fund of the Natural Science Foundation of Henan Province (No.242300421069).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eM.L., Y.L., A.A. and Y.T. conceived the idea and designed the experiments. Y.T. conducted most of the experiments and wrote the manuscript. Z.Z. performed EQE and device stability measurements. C.Q. carried out the TAS measurements and analyzed the data. G.L., H.L., F.Y., Y.Y. M.H.A., L.D., L.W., and M.L. participated in editing the manuscript. Z.S. performed GIWAX measurements and analyzed the data. All authors read and commented on the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eCompeting interests\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAdditional information\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eSupplementary information\u003c/strong\u003e The online version contains supplementary material available at\u0026nbsp;\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003e\u003cem\u003eBest Research-Cell Efficiency Chart\u003c/em\u003e (NREL, 2024); www.nrel.gov/pv/cell-efficiency.html.\u003c/li\u003e\n \u003cli\u003eLiu, C. et al. 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Mater.\u003c/em\u003e \u003cstrong\u003e33\u003c/strong\u003e, 2213123 (2023).\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":false,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"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},"keywords":"","lastPublishedDoi":"10.21203/rs.3.rs-4527071/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4527071/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003e\u003cstrong\u003eMetal halide perovskite solar cells (PSCs) are promising as the next-generation photovoltaic technology. However, the inferior stability under various temperatures remains a significant obstacle to commercialization. Here, we implement a heat-triggered dynamic self-healing framework (HDSF) to repair defects at grain boundaries caused by thermal variability, enhancing PSCs' temperature stability. HDSF, distributed at the grain boundaries and surface of the perovskite film, stabilizes the perovskite lattice and releases the perovskite crystal stress through the dynamic exchange reaction and shape memory effect of sulfide bonds. The resultant PSCs achieved a power-conversion efficiency (PCE) of 26.32% (certified 25.84%) with elevated temperature stability, retaining 94.2% of the initial PCE after 500 h at 85℃. In a variable temperature cycling test (between −40℃ and 80℃), the HDSF-treated device retained 87.6% of its initial PCE at −40℃ and 92.6% at 80℃ after 160 thermal cycles. This heat-triggered dynamic self-healing strategy could significantly enhance the reliability of PSCs in application scenarios.\u003c/strong\u003e\u003c/p\u003e","manuscriptTitle":"Heat-triggered Dynamic Self-healing Framework for Variable-temperature Stable Perovskite Solar Cells","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-06-18 05:55:04","doi":"10.21203/rs.3.rs-4527071/v1","editorialEvents":[],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"nature-communications","isNatureJournal":true,"hasQc":false,"allowDirectSubmit":false,"externalIdentity":"NCOMMS","sideBox":"Learn more about [Nature Communications](http://www.nature.com/ncomms/)","snPcode":"","submissionUrl":"https://mts-ncomms.nature.com/","title":"Nature Communications","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"ejp","reportingPortfolio":"Nature Communications","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"46d348b6-63dc-443e-8608-81eff2cfccc8","owner":[],"postedDate":"June 18th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":33367852,"name":"Physical sciences/Materials science/Materials for devices/Information storage"},{"id":33367853,"name":"Physical sciences/Physics/Electronics, photonics and device physics/Photonic devices"}],"tags":[],"updatedAt":"2024-10-24T10:55:15+00:00","versionOfRecord":[],"versionCreatedAt":"2024-06-18 05:55:04","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-4527071","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4527071","identity":"rs-4527071","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}