In-situ interfacial passivation and self-adaptability synergistically stabilizing all-solid-state lithium metal batteries

The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.

Unraveling abnormal buried interface anion defect passivation mechanisms depending on cation-induced steric hindrance for efficient and stable perovskite solar cells

Although ionic liquids(ILs)have been widely employed to heal the defects in perovskite solar cells(PSCs),the corresponding defect passivation mechanisms are not thoroughly understood up to now.Herein,we first reveal an abnormal buried interface anion defect passivation mechanism depending on cationinduced steric hindrance.The IL molecules containing the same anion([BF4]^(-))and different sizes of imidazolium cations induced by substituent size are used to manipulate buried interface.It was revealed what passivated interfacial defects is mainly anions instead of cations.Theoretical and experimental results demonstrate that the large-sized cations can weaken the ionic bond strength between anions and cations,and facilitate the interaction between anions and SnO2as well as perovskites,which is conducive to interfacial defect passivation and ameliorating interfacial contact.It can be concluded that interfacial chemical interaction strength and defect passivation effect are positively correlated with the size of cations.The discovery breaks conventional thinking that large-sized modification molecules would weaken their chemical interaction with perovskite.Compared with the control device(21.54%),the device based on 1,3-Bis(1-adamantyl)-imidazolium tetrafluoroborate(BAIMBF4)with maximum size cations achieves a significantly enhanced efficiency of 23.61%along with much increased moisture,thermal and light stabilities.

High efficiency CZTSSe solar cells enabled by dual Ag-passivation approach via aqueous solution process

Ag substitution in Cu_(2)ZnSn(S,Se)_(4)(CZTSSe)is a promising way to mitigate Cu/Zn related defects,electrostatic fluctuations and Shockley-Read-Hall(SRH)recombination centers.However,high performance ACZTSSe solar cells are generally demonstrated with more Ag amounts and strenuous fabrication processes,which are not ideal when using cheap constituent materials CZTSSe.To reduce the Ag amount(2%-3%),local Ag substitutions into CZTSSe at front(F),back(B)and dual front/back(FB)were proposed.Experimental results revealed that F-passivation effectively reduced the Cu/Zn related defects and further limits the interface/bulk recombination whereas B-passivation improved the grain growth at the back interface and further allows enhanced transport of charge carriers.By employing the dual Agpassivation approach,the final ACZTSSe device parameters were significantly improved and remarkable power conversion efficiency(PCE)of 12.43%was achieved with eco-friendly aqueous solution process.

Mixed Cations Enabled Combined Bulk and Interfacial Passivation for Efficient and Stable Perovskite Solar Cells

Here,we report a mixed GAI and MAI(MGM)treatment method by forming a 2D alternating-cation-interlayer(ACI)phase(n=2)perovskite layer on the 3D perovskite,modulating the bulk and interfacial defects in the perovskite films simultaneously,leading to the suppressed nonradiative recombination,longer lifetime,higher mobility,and reduced trap density.Consequently,the devices’performance is enhanced to 24.5%and 18.7%for 0.12 and 64 cm^(2),respectively.In addition,the MGM treatment can be applied to a wide range of perovskite compositions,including MA-,FA-,MAFA-,and CsFAMA-based lead halide perovskites,making it a general method for preparing efficient perovskite solar cells.Without encapsulation,the treated devices show improved stabilities.

Surface Passivation Toward Efficient and Stable Perovskite Solar Cells

Although metal halide perovskites are increasingly popular for the next generation of efficient photovoltaic devices,the inevitable defects from the preparation process have become the notorious barrier to further improvement of performance,which increases non-radiative recombination and lowers the power conversion efficiency of solar cells.Surface passivation strategies have been affirmed as one of the most practical approaches to suppress these defects.Therefore,it is necessary to have a detailed review on the surface passivation to reveal the improvements of the devices.Herein,the mechanism and recent advances of surface passivation have been systematically summarized with respect to various passivation approaches,including the Lewis acid–base,the low-dimensional perovskite,inorganic molecules,and polymers.Finally,the review also offers the research trend and prospects of surface passivation.

Efficient Semi‑Transparent Wide‑Bandgap Perovskite Solar Cells Enabled by Pure‑Chloride 2D‑Perovskite Passivation

Wide-bandgap(WBG)perovskite solar cells suffer from severe non-radiative recombination and exhibit relatively large opencircuit voltage(V_(OC))deficits,limiting their photovoltaic performance.Here,we address these issues by in-situ forming a well-defined 2D perovskite(PMA)_(2)PbCl_(4)(phenmethylammonium is referred to as PMA)passivation layer on top of the WBG active layer.The 2D layer with highly pure dimensionality and halide components is realized by intentionally tailoring the side-chain substituent at the aryl ring of the post-treatment reagent.First-principle calculation and single-crystal X-ray diffraction results reveal that weak intermolecular interactions between bulky PMA cations and relatively low cation-halide hydrogen bonding strength are crucial in forming the well-defined 2D phase.The(PMA)_(2)PbCl_(4)forms improved type-I energy level alignment with the WBG perovskite,reducing the electron recombination at the perovskite/hole-transport-layer interface.Applying this strategy in fabricating semi-transparent WBG perovskite solar cells(indium tin oxide as the back electrode),the V_(OC)deficits can be reduced to 0.49 V,comparable with the reported state-of-the-art WBG perovskite solar cells using metal electrodes.Consequently,we obtain hysteresis-free 18.60%-efficient WBG perovskite solar cells with a high V_(OC)of 1.23 V.

Defect passivation by nontoxic biomaterial yields 21% efficiency perovskite solar cells

Defect passivation is one of the most important strategies to boost both the efficiency and stability of perovskite solar cells(PSCs).Here,nontoxic and sustainable forest-based biomaterial,betulin,is first introduced into perovskites.The experiments and calculations reveal that betulin can effectively passivate the uncoordinated lead ions in perovskites via sharing the lone pair electrons of hydroxyl group,promoting charge transport.As a result,the power conversion efficiencies of the p-i-n planar PSCs remarkably increase from 19.14%to 21.15%,with the improvement of other parameters.The hydrogen bonds of betulin lock methylamine and halogen ions along the grain boundaries and on the film surface and thus suppress ion migration,further stabilizing perovskite crystal structures.These positive effects enable the PSCs to maintain 90%of the initial efficiency after 30 days in ambient air with 60%±5%relative humidity,75%after 300 h aging at 85℃,and 55%after 250 h light soaking,respectively.This work opens a new pathway for using nontoxic and low-cost biomaterials from forest to make highly efficient and stable PSCs.

Recent Progress of Surface Passivation Molecules for Perovskite Solar Cell Applications

Due to the solution processable nature,the prepared perovskite films are polycrystalline with considerable number of defects.These defects,especially defects at interface accelerate the carrier recombination and reduce the carrier collection.Besides,the surface defects also affect the long-term stability of the perovskite solar cells(PVSCs).To solve this problem,surface passivation molecules are introduced at selective interface(the interface between perovskite and carrier selective layer).This review summarizes recent progress of small molecules used in PVSCs.Firstly,different types of defect states in perovskite films are introduced and their effects on device performance are discussed.Subsequently,surface passivation molecules are divided into four categories,and the interaction between the functional groups of the surface passivation molecules and selective defect states in perovskite films are highlighted.Finally,we look into the prospects and challenges in design noble small molecules for PVSCs applications.

Simultaneously enhanced moisture tolerance and defect passivation of perovskite solar cells with cross-linked grain encapsulation

The grain surfaces(film surface and grain boundary)of polycrystalline perovskite films are vulnerable sites in solar cells since they pose a high defect density and initiate the degradation of perovskite absorber.Achieving simultaneously defect passivation and grain protection from moisture is crucial for the viability of perovskite solar cells.Here,an in situ cross-linked grain encapsulation(CLGE)strategy that improves both device stability and defect passivation is reported.Cross-linkable semiconducting small molecules are mixed into the antisolvent to uniformly form a compact and conducting cross-linked layer over the grain surfaces.This cross-linked coating layer not only passivates trap states and facilitates hole extraction,but also enhances the device stability by preventing moisture diffusion.Using the CLGE strategy,a high power conversion efficiency(PCE)of 22.7%is obtained in 1.55-eV bandgap planar perovskite solar cells.The unencapsulated devices with CLGE exhibit significantly enhanced device stability again moisture and maintain>90%of their initial PCE after shelf storage under ambient condition for over10,000 h.

Defect passivation through electrostatic interaction for high performance flexible perovskite solar cells

The light weight,good bending resistance and low production cost make flexible perovskite solar cells(PSCs)good candidates in wearable electronics,portable charger,remote power,and flying objects.High power conversion efficiency(PCE)plays a crucial role on obtaining the high mass specific power of flexible devices.However,the performance for flexible PSCs is still having a large room to be improved.Here,we added the 2-amino-5-cyanopyridine(ACP)molecule with a polar electron density distribution in the perovskite precursor solution to improve the performance of flexible PSCs.The cyano groups with electron-withdrawing ability are expected to passivate positively charged point defects,while amines with electron donating ability are expected to passivate negatively charged point defects in perovskite films.Thanks to the effective passivation of defects at the grain boundary and surface of perovskite films,the PCE of flexible PSCs is obviously increased from 16.9%to 18.0%.These results provide a universal approach to improve performance of flexible PSCs by healing the defects in perovskite films through electrostatic interactions.

Boosting efficiency and stability of 2D alternating cation perovskite solar cells via rational surface-modification: Marked passivation efficacy of anion

Two-dimensional(2D) alternating cation(ACI) perovskite surface defects,especially dominant iodine vacancies(V_Ⅰ) and undercoordinated Pb^(2+),limit the performance of perovskite solar cells(PVSCs).To address the issue,1-butyl-3-methylimidazolium trifluoro-methane-sulfonate(BMIMOTF) and its iodide counterpart(BMIMI) are utilized to modify the perovskite surface respectively.We find that BMIMI can change the perovskite surface,whereas BMIMOTF shows a nondestructive and more effective defect passivation,giving significantly reduced defect density and suppressed charge-carrier nonradiative recombination.This mainly attributes to the marked passivation efficacy of OTF-anion on V_Ⅰ and undercoordinated Pb^(2+),rather than BMIMI^(+) cation.Benefiting from the rational surface-modification of BMMIMOTF,the films exhibit an optimized energy level alignment,enhanced hydrophobicity and suppressed ion migration.Consequently,the BMIMOTF-modified devices achieve an impressive efficiency of 21.38% with a record open-circuit voltage of 1.195 V,which is among the best efficiencies reported for 2D PVSCs,and display greatly enhanced humidity and thermal stability.

Simultaneous passivation of bulk and interface defects through synergistic effect of anion and cation toward efficient and stable planar perovskite solar cells

Bulk and interface carrier nonradiative recombination losses impede the further improvement of power conversion efficiency(PCE)and stability of perovskite solar cells(PSCs).It is highly necessary to develop multifunctional strategy to minimize surface and interface nonradiative recombination losses.Herein,we report a bulk and interface defect passivation strategy via the synergistic effect of anions and cations,where multifunctional potassium sulphate(K_(2)SO_(4))is incorporated at SnO_(2)/perovskite interface.We find that K^(+)ions in K_(2)SO_(4)diffuse into perovskite layer and suppress the formation of bulk defects in perovskite films,and the SO_(4)^(2-)ions remain located at interface via the strong chemical interaction with SnO_(2)layer and perovskite layer,respectively.Through this synergistic modification strategy,effective defect passivation and improved energy band alignment are achieved simultaneously.These beneficial effects are translated into an efficiency increase from 19.45%to 21.18%with a low voltage deficit of0.53 V mainly as a result of boosted open-circuit voltage(V_(oc))after K_(2)SO_(4)modification.In addition,the K_(2)SO_(4)modification contributes to ameliorated stability.The present work provides a route to minimize bulk and interface nonradiative recombination losses for the simultaneous realization of PCE and stability enhancement by rational anion and cation synergistic engineering.

Defect passivation with potassium trifluoroborate for efficient spray-coated perovskite solar cells in air

Defects as non-radiative recombination centers hinder the further efficiency improvements of perovskite solar cells(PSCs).Additive engineering has been demonstrated to be an effective method for defect passivation in perovskite films.Here,we employed(4-methoxyphenyl)potassium trifluoroborate(C_(7)H_(7)BF_(3)KO)with and K+functional groups to passivate spray-coated(FAPbI_(3))_(x)(MAPbBr_(3))_(1-x) perovskite and eliminate hysteresis.It is shown that the F of can form hydrogen bonds with the H atom in the amino group of MA+/FA+ions of perovskite,thus reducing the generation of MA+/FA+vacancies and improving device efficiency.Meanwhile,K+and reduced MA+/FA+vacancies can inhibit ion migration,thereby eliminating hysteresis.With the aid of C_(7)H_(7)BF_(3)KO,we obtained hysteresis-free PSCs with the maximum efficiency of 19.5%by spray-coating in air.Our work demonstrates that additive engineering is promising to improve the performance of spray-coated PSCs.

Dramatic reduction in dark current ofβ-Ga_(2)O_(3) ultraviolet photodectors viaβ-(Al_(0.25)Ga_(0.75))_(2)O_(3) surface passivation

Solar-blind ultraviolet photodetectors with metal-semiconductor-metal structure were fabricated based onβ-(Al_(0.25)Ga_(0.75))_(2)O_(3)/β-Ga_(2)O_(3) film grown by metal-organic chemical vapor deposition.It was known that various surface states increase dark current and a large number of defects can hinder the transport of carriers,resulting in low switching ratio and low responsivity of the device.In this work,β-(Al_(0.25)Ga_(0.75))_(2)O_(3) films are used as surface passivation materials.Owning to its wide band gap,we obtain excellent light transmission and high lattice matching withβ-Ga_(2)O_(3).We explore the change and mechanism of the detection performance of theβ-Ga_(2)O_(3) detector afterβ-(Al_(0.25)Ga_(0.75))_(2)O_(3) surface passivation.It is found that under the illumination with 254 nm light at bias 5 V,theβ-(Al_(0.25)Ga_(0.75))_(2)O_(3)/β-Ga_(2)O_(3)photodetectors show dark current of just 18 pA and high current on/off ratio of 2.16×10^(5).The dark current is sharply reduced about 50 times after passivation of theβ-Ga_(2)O_(3) surface,and current on/off ratio increases by approximately 2 times.It is obvious thatβ-Ga_(2)O_(3) detectors withβ-(Al_(0.25)Ga_(0.75))_(2)O_(3) surface passivation can offer superior detector performance.

Surface Passivation of Perovskite Solar Cells Toward Improved Efficiency and Stability

The advancement of perovskite solar cells(PVSCs)technology toward commercialized promotion needs high efficiency and optimum stability.By introducing a small molecular material such as tetratetracontane(TTC,CH3(CH2)42CH3)at the fullerene(C60)/perovskite interface of planar p-i-n PVSCs,we significantly reduced the interfacial traps,thereby suppressing electron recombination and facilitating electron extraction.Consequently,an improved efficiency of 20.05% was achieved with a high fill factor of 79.4%,which is one of the best performances for small molecular-modified PVSCs.Moreover,the hydrophobic TTC successfully protects the perovskite film from water damage.As a result,we realized a better long-term stability that maintains 87% of the initial efficiency after continuous exposure for 200 h in air.

H^+ Passivation of Poly-Si Solar CellsProcessed by Different Annealing Processes

The effects of different annealing processes on the photovoltaic (PV) properties and the spectral response as well as minority carrier lifetime in the bulk of unanalyzed PF5 ion implantation poly-Si solar cells were investigated. The different hydrogen passivation effects of defects in poly-Si induced by three heat treatment processes are reported. We used RTA-rapid thermal annealing, YAG pulse laser annealing and CTSA-classical three-step annealing for this study. The results show that cells processed by RTA (800°C, 4 sec) achieved the best PV properties and spectral response among all annealed samples. Under this precess condition, no or few defects were induced in bulk. While RTA (>-850°C for 4 sec), CTSA as well as YAG laser processes induced defects of different nature and concentration in the bulk of cells. It is further shown that hydrogen ion implantation significantly improved, the performances of poly-Si cells. It is able to efficiently remove the YAG laser induced defects in bulk. However, it cannot completely passivate the defects induced by CTSA and RTA processes.

Evaporated potassium chloride for double-sided interfacial passivation in inverted planar perovskite solar cells

Defect-induced charge carrier recombination at the interfaces between perovskite and adjacent charge transport layers restricts further improvements in the device performance of perovskite solar cells(PSCs).Defect passivation at these interfaces can reduce trap states and inhibit the induced nonradiative recombination.Herein,we report a double-sided interfacial passivation via simply evaporating potassium chloride(DIP-KCl)at both the hole transport layer(HTL)/perovskite and perovskite/electron transport layer(ETL)interfaces in inverted planar PSCs.We demonstrate that the bottom KCl layer at the HTL/perovskite interface not only reduces the interfacial defects and improves the interfacial contact,but also leads to increased perovskite crystallinity,while the top KCl layer at the perovskite/ETL interface efficiently passivates the perovskite top surface defects and facilitates electron extraction at this interface.Thus,suppressed nonradiative recombination and faster charge extraction at both interfaces close to the perovskite layer can be achieved by using our DIP-KCl strategy.As a result,inverted PSCs based on DIP-KCl present an increased efficiency from 17.1% to 19.2% and enhanced stability,retaining over 90% of their initial efficiency after aging at maximum power point tracking for 1000 h.This work provides a simple and efficient way for defect passivation to further increase the efficiency and stability of PSCs.

Surface passivation using pyridinium iodide for highly efficient planar perovskite solar cells

Perovskite solar cells have developed rapidly in the past decades.However,there are large amounts of ionic defects at the surface and grain boundaries of perovskte films which are detrimental to both the efficiency and stability of perovskite solar cells.Here,an organic halide salt pyridinium iodide(PyI) is used in cation-anion-mixed perovskite for surface defect passivation.Different from the treatment with Lewis base pyridine(Py) which can only bind to the under-coordinated Pb ions,zwitterion molecule PyI can not only fill negative charged iodine vacancies,but also interact with positive charged defects.Compared with Py treatment,PyI treatment results in smoother surface,less defect densities and nonradiative recombination in perovskite,leading to an improved VOC, negligible J-V hysteresis and stable performance of devices.As a result,the champion PyI-treated planar perovskite solar cell with a high VOC of 1.187 V achieves an efficiency of 21.42%,which is higher than 20.37% of Py-treated device,while the pristine device without any treatment gets an efficiency of 18.83% at the same experiment conditions.

Advanced Strategies of Passivating Perovskite Defects for High-Performance Solar Cells

Organic–inorganic halide perovskite(OIHP)solar cells have garnered great attention in the last decade since they continuously approach the Shockley–Queisser Limit.Compared with conventional organic and inorganic semiconductors,OIHPs possess the high tolerance on defects due to the dominated intrinsically shallow-level carrier-trapping centers.However,the existence of defects still causes the ion migration,produces the hysteresis effect,and accelerates the film degradation,eventually suppressing the device efficiency and stability.In this Review Article,we summarize recent impressive advance on passivating OIHP defects and discuss the future horizon of exploiting high-efficiency and long-stability OIHP solar cells in terms of defect managements.

Surface passivation and hole extraction:Bifunctional interfacial engineering toward high-performance all-inorganic CsPbIBr2 perovskite solar cells with efficiency exceeding 12%

All-inorganic CsPbIBr2perovskite solar cells(PSCs)have attracted considerable research attention in recent years due to their excellent thermal stability.However,their power conversion efficiencies(PCEs)are relatively low and still far below the theoretical limit.Here,we report the use of an organic dye molecule(namely VG1-C8)as a bifunctional interlayer between perovskite and the hole-transport layer in CsPbIBr2PSCs.Combined experimental and theoretical calculation results disclose that the multiple Lewis base sites in VG1-C8 can effectively passivate the trap states on the perovskite films.Meanwhile,theπ-conjugated dye molecule significantly accelerates the hole extraction from the perovskite absorber as evidenced by the photoluminescence analysis.Consequently,the VG1-C8 treatment simultaneously boosts the photovoltage and photocurrent density values from 1.26 V and 10.80 mA cm^(-2) to 1.31 V and 12.44 m A cm^(-2),respectively.This leads to a significant enhancement of PCE from 9.20%to12.10%under one sun irradiation(AM 1.5G).To our knowledge,this is the record efficiency reported so far for CsPbIBr_(2) PSCs.Thus,the present work demonstrates an effective interfacial passivation strategy for the development of highly efficient PSCs.