Synergistic Crystal and Interface Engineering for Efficient and Stable Perovskite Photovoltaics

The presence of bulk and surface defects in perovskite light harvesting materials limits the overall efficiency of perovskite solar cells (PSCs). The formation of such defects is suppressed by adding methylammonium chloride (MACl) as a crystallization aid to the precursor solution to realize high‐quality, large‐grain triple A‐cation perovskite films and that are combined with judicious engineering of the perovskite interface with the electron and hole selective contact materials. A planar SnO₂/TiO₂ double layer oxide is introduced to ascertain fast electron extraction and the surface of the perovskite facing the hole conductor is treated with iodine dissolved in isopropanol to passivate surface trap states resulting in a retardation of radiationless carrier recombination. A maximum solar to electric power conversion efficiency (PCE) of 21.65% and open circuit photovoltage (V_oc) of ≈1.24 V with only ≈370 mV loss in potential with respect to the band gap are achieved, by applying these modifications. Additionally, the defect healing enhances the operational stability of the devices that retain 96%, 90%, and 85% of their initial PCE values after 500 h under continuously light illumination at 20, 50, and 65 °C, respectively, demonstrating one of the most stable planar PSCs reported so far.     

Scalable Fabrication of Efficient Perovskite Solar Modules on Flexible Glass Substrates

Perovskite materials are good candidates for flexible photovoltaic applications due to their strong absorption and low‐temperature processing, but efficient flexible perovskite modules have not yet been realized. Here, a record efficiency flexible perovskite solar module is demonstrated by blade coating high‐quality perovskite films on flexible Corning Willow Glass using additive engineering. Ammonium chloride (NH₄Cl) is added into the perovskite precursor solution to retard the nucleation which prevents voids formation at the interface of perovskite and glass. The addition of NH₄Cl also suppresses the formation of PbI₂ and reduces the trap density in the perovskite films. The implementation of NH₄Cl enables the fabrication of single junction flexible perovskite solar devices with an efficiency of 19.72% on small‐area cells and a record aperture efficiency of 15.86% on modules with an area of 42.9 cm². This work provides a simple way to scale up high‐efficiency flexible perovskite modules for various applications.     

Simultaneous Contact and Grain‐Boundary Passivation in Planar Perovskite Solar Cells Using SnO2‐KCl Composite Electron Transport Layer

The performance of perovskite solar cells is sensitive to detrimental defects, which are prone to accumulate at the interfaces and grain boundaries of bulk perovskite films. Defect passivation at each region will lead to reduced trap density and thus less nonradiative recombination loss. However, it is challenging to passivate defects at both the grain boundaries and the bottom charge transport layer/perovskite interface, mainly due to the solvent incompatibility and complexity in perovskite formation. Here SnO₂‐KCl composite electron transport layer (ETL) is utilized in planar perovskite solar cells to simultaneously passivate the defects at the ETL/perovskite interface and the grain boundaries of perovskite film. The K and Cl ions at the ETL/perovskite interface passivate the ETL/perovskite contact. Meanwhile, K ions from the ETL can diffuse through the perovskite film and passivate the grain boundaries. An enhancement of open‐circuit voltage from 1.077 to 1.137 V and a corresponding power conversion efficiency increasing from 20.2% to 22.2% are achieved for the devices using SnO₂‐KCl composite ETL. The composite ETL strategy reported herein provides an avenue for defect passivation to further increase the efficiency of perovskite solar cells.     

Surface Engineering of TiO2 ETL for Highly Efficient and Hysteresis‐Less Planar Perovskite Solar Cell (21.4%) with Enhanced Open‐Circuit Voltage and Stability

Interfacial studies and band alignment engineering on the electron transport layer (ETL) play a key role for fabrication of high‐performance perovskite solar cells (PSCs). Here, an amorphous layer of SnO₂ (a‐SnO₂) between the TiO₂ ETL and the perovskite absorber is inserted and the charge transport properties of the device are studied. The double‐layer structure of TiO₂ compact layer (c‐TiO₂) and a‐SnO₂ ETL leads to modification of interface energetics, resulting in improved charge collection and decreased carrier recombination in PSCs. The optimized device based on a‐SnO₂/c‐TiO₂ ETL shows a maximum power conversion efficiency (PCE) of 21.4% as compared to 19.33% for c‐TiO₂ based device. Moreover, the modified device demonstrates a maximum open‐circuit voltage (V_oc) of 1.223 V with 387 mV loss in potential, which is among the highest reported value for PSCs with negligible hysteresis. The stability results show that the device on c‐TiO₂/a‐SnO₂ retains about 91% of its initial PCE value after 500 h light illumination, which is higher than pure c‐TiO₂ (67%) based devices. Interestingly, using a‐SnO₂/c‐TiO₂ ETL the PCE loss was only 10% of initial value under continuous UV light illumination after 30 h, which is higher than that of c‐TiO₂ based device (28% PCE loss).     

High Open-Circuit Voltage (1.197 V) in Large-Area (1 cm2) Inverted Perovskite Solar Cell via Interface Planarization and Highly Polar Self-Assembled Monolayer

The efficiency loss caused by area scaling is one of the key factors hindering the industrial development of perovskite solar cells. The energy loss and contact issues in the buried interface are the main reasons. Here, a new self-assembled monolayer (SAM), Ph-4PACz, with a large dipole moment (2.32 D) is obtained . It is found that Ph-4PACz with high polarity can improve the band alignment and minimize the energy loss , resulting in an open-circuit voltage (V_oc) as high as 1.2 V for 1.55 eV perovskite. However, when applied to large-area devices, the fill factor (FF) still suffered from significant attenuation. Therefore, alumina nanoparticles (Al₂O₃-NPs) are introduced to the interface between Ph-4PACz and rough FTO substrate to further improve the flatness , resulting in a conformal perovskite film with almost no voids in the buried interface, thus promoting low exciton binding energy, fast hot-carrier extraction and low non-radiative recombination. The final devices achieved a small-area power conversion efficiency (PCE) of 25.60% and a large-area (1 cm²) PCE of 24.61% (certified at 24.48%), which represents one of the highest PCE for single device ≥ 1 cm² area. Additionally, mini-modules and stability testing are also carried out to demonstrate the feasibility of commercialization.     

High‐Performance Flexible Perovskite Solar Cells via Precise Control of Electron Transport Layer

Flexible perovskite solar cells (f‐PSCs) have attracted great attention due to their promising commercial prospects. However, the performance of f‐PSCs is generally worse than that of their rigid counterparts. Herein, it is found that the unsatisfactory performance of planar heterojunction (PHJ) f‐PSCs can be attributed to the undesirable morphology of electron transport layer (ETL), which results from the rough surface of the flexible substrate. Precise control over the thickness and morphology of ETL tin dioxide (SnO₂) not only reduces the reflectance of the indium tin oxide (ITO) on polyethylene 2,6‐naphthalate (PEN) substrate and enhances photon collection, but also decreases the trap‐state densities of perovskite films and the charge transfer resistance, leading to a great enhancement of device performance. Consequently, the f‐PSCs, with a structure of PEN/ITO/SnO₂/perovskite/Spiro‐OMeTAD/Ag, exhibit a power conversion efficiency (PCE) up to 19.51% and a steady output of 19.01%. Furthermore, the f‐PSCs show a robust bending resistance and maintain about 95% of initial PCE after 6000 bending cycles at a bending radius of 8 mm, and they present an outstanding long‐term stability and retain about 90% of the initial performance after >1000 h storage in air (10% relative humidity) without encapsulation.     

Chlorinated Fullerene Dimers for Interfacial Engineering Toward Stable Planar Perovskite Solar Cells with 22.3% Efficiency

A major limit for planar perovskite solar cells is the trap‐mediated hysteresis and instability, due to the defective metal oxide interface with the perovskite layer. Passivation engineering with fullerenes has been identified as an effective approach to modify this interface. The rational design of fullerene molecules with exceptional electrical properties and versatile chemical moieties for targeted defect passivation is therefore highly demanded. In this work, novel fulleropyrrolidine (NMBF‐X, X?H or Cl) monomers and dimers are synthesized and incorporated between metal oxides (i.e. TiO₂, SnO₂) and perovskites (i.e. MAPbI₃ and (FAPbI₃)_x(MAPbBr₃)_1‐x). The fullerene dimers provide superior stability and efficiency improvements compared to the corresponding monomers, with chlorinated fullerene dimers being most effective at coordinating with both metal oxides and perovskite via the chlorine terminals. The non‐encapsulated planar device delivers a maximum power conversion efficiency of 22.3% without any hysteresis, while maintaining over 98% of initial efficiency after ambient storage for 1000 h, and exhibiting an order of magnitude improvement of the T₈₀ lifetime.     

UV‐Inert ZnTiO3 Electron Selective Layer for Photostable Perovskite Solar Cells

Although planar‐structured perovskite solar cells (PSCs) have power conversion efficiencies exceeding 24%, the poor photostability, especially with ultraviolet irradiance (UV) severely limits commercial application. The most commonly‐used TiO₂ electron selective layer has a strong photocatalytic effect on perovskite/TiO₂ interface when TiO₂ is excited by UV light. Here a UV‐inert ZnTiO₃ is reported as the electron selective layer in planar PSCs. ZnTiO₃ is a perovskite‐structured semiconductor with excellent chemical stability and poor photocatalysis. Solar cells are fabricated with a structure of indium doped tin oxide (ITO)/ZnTiO₃/Cs_0.05FA_0.81MA_0.14PbI_2.55Br_0.45/Sprio‐MeOTAD/Au. The champion device exhibits a stabilized power conversion efficiency of 19.8% with improved photostability. The device holds 90% of its initial efficiency after 100 h of UV soaking (365 nm, 8 mW cm^?2), compared with 55% for TiO₂‐based devices. This work provides a new class of electron selective materials with excellent UV stability in perovskite solar cell applications.     

A Low-Temperature Additive-Involved Leaching Method for Highly Efficient Inorganic Perovskite Solar Cells

Inorganic CsPbI₃ perovskite with an optical bandgap ranging from 1.67 to 1.75 eV is a promising light-harvesting material as a top cell in tandem solar cells, but its high fabrication temperature can damage the middle layers or the bottom subcells. Here, an additive-involved leaching method to fabricate CsPbI₃ perovskite films is demonstrated, which can decrease the preparation temperature to 100 °C. The CsPbI₃ perovskite films with high crystallinity are achieved by a solution assisted reaction between DMAPbI₃ and Cs₄PbI₆ with the leaching of DMA⁺, Cs⁺, and I⁻. The as-prepared CsPbI₃ perovskite films exhibit much superior stability compared to their high-temperature counterparts. As a result, a power conversion efficiency of over 16% is obtained, and the unencapsulated device maintains over 93% of the initial efficiency after aging for 30 days in air with a relative humidity of 10%.     

Dimensional Engineering of a Graded 3D–2D Halide Perovskite Interface Enables Ultrahigh Voc Enhanced Stability in the p‐i‐n Photovoltaics

2D halide perovskite materials have shown great advantages in terms of stability when applied in a photovoltaic device. However, the impediment of charge transport within the layered structure drags down the device performance. Here for the first time, a 3D–2D (MAPbI₃‐PEA₂Pb₂I₄) graded perovskite interface is demonstrated with synergistic advantages. In addition to the significantly improved ambient stability, this graded combination modifies the interface energy level in such a way that reduces interface charge recombination, leading to an ultrahigh V _oc at 1.17 V, a record for NiO‐based p‐i‐n photovoltaic devices. Moreover, benefiting from the graded structure induced continuously upshifts energy level, the photovoltaic device attains a high J _sc of 21.80 mA cm^?2 and a high fill factor of 0.78, resulting in an overall power conversion efficiency (PCE) of 19.89%. More importantly, it is showed that such a graded interface structure also suppresses ion migration in the device, accounting for its significantly enhanced thermal stability.     

In Situ Polymerization of Cross-Linked Perovskite–Polymer Composites for Highly Stable and Efficient Perovskite Solar Cells

Mixed-halide perovskites have emerged as outstanding light absorbers that enable the fabrication of efficient solar cells; however, their instability hinders the commercialization of such systems. Grain-boundary (GB) defects and lattice tensile strain are critical intrinsic-instability factors in polycrystalline perovskite films. In this study, the light-induced cross-linking of acrylamide (Am) monomers with non-crystalline perovskite films is used to fabricate highly efficient and stable perovskite solar cells (PSCs). The Am monomers induce the preferred crystal orientation in the polycrystalline perovskite films, enlarge the perovskite grain size, and cross-link the perovskite grains. Additionally, the liquid properties of Am effectively releases lattice strain during perovskite-film crystallization. The cross-linked interfacial layer functions as an airtight wall that protects the perovskite film from water corrosion. Devices fabricated using the proposed strategy show an excellent power conversion efficiency (PCE) of 24.45% with an open-circuit voltage (V_OC) of 1.199 V, which, to date, is the highest V_OC reported for hybrid PSCs with electron transport layers (ETLs) comprised of TiO₂. Large-area PSC modules fabricated using the proposed strategy show a power conversion efficiency of 20.31% (with a high fill factor of 77.1%) over an active area of 33 cm², with excellent storage stability.     

Interface‐Modification‐Induced Gradient Energy Band for Highly Efficient CsPbIBr2 Perovskite Solar Cells

Inorganic cesium lead halide perovskite solar cells (PSCs) have received enormous attention due to their excellent stability compared with that of their organic–inorganic counterparts. However, the lack of optimization strategies leads the inorganic PSCs to suffer from low efficiency arising from significant recombination. To overcome this dilemma, a surface modification of the electron transport layer (ETL)/perovskite interface is undertaken by using SmBr₃ to improve the crystallization and morphology of the perovskite layer for enhanced ETL/perovskite interface interaction. Encouragingly, a gradient energy band is created at the interface with an outstanding hole blocking effect. As a result, both the charge recombination occurring at the interface and the nonradiative recombination inside the perovskite are suppressed, and, simultaneously, the charge extraction is improved successfully. Therefore, the power conversion efficiency of the CsPbIBr₂ PSCs is increased to as high as 10.88% under one sun illumination, which is 30% higher than its counterparts without the modification. It is logically inferred that this valuable optimization strategy can be extended to other analogous structures and materials.     

Simultaneous Improved Performance and Thermal Stability of Planar Metal Ion Incorporated CsPbI2Br All‐Inorganic Perovskite Solar Cells Based on MgZnO Nanocrystalline Electron Transporting Layer

The high thermal stability and facile synthesis of CsPbI₂Br all‐inorganic perovskite solar cells (AI‐PSCs) have attracted tremendous attention. As far as electron‐transporting layers (ETLs) are concerned, low temperature processing and reduced interfacial recombination centers through tunable energy levels determine the feasibility of the perovskite devices. Although the TiO₂ is the most popular ETL used in PSCs, its processing temperature and moderate electron mobility hamper the performance and feasibility. Herein, the highly stable, low‐temperature processed MgZnO nanocrystal‐based ETLs for dynamic hot‐air processed Mn²⁺ incorporated CsPbI2Br AI‐PSCs are reported. By holding its regular planar “n–i–p” type device architecture, the MgZnO ETL and poly(3‐hexylthiophene‐2,5‐diyl) hole transporting layer, 15.52% power conversion efficiency (PCE) is demonstrated. The thermal‐stability analysis reveals that the conventional ZnO ETL‐based AI‐PSCs show a serious instability and poor efficiency than the Mg²⁺ modified MgZnO ETLs. The photovoltaic and stability analysis of this improved photovoltaic performance is attributed to the suitable wide‐bandgap, low ETL/perovskite interface recombination, and interface stability by Mg²⁺ doping. Interestingly, the thermal stability analysis of the unencapsulated AI‐PSCs maintains >95% of initial PCE more than 400 h at 85 °C for MgZnO ETL, revealing the suitability against thermal degradation than conventional ZnO ETL.     

Exploring Inorganic Binary Alkaline Halide to Passivate Defects in Low‐Temperature‐Processed Planar‐Structure Hybrid Perovskite Solar Cells

Planar perovskite solar cells obtained by low‐temperature solution processing are of great promise, given a high compatibility with flexible substrates and perovskite‐based tandem devices, whilst benefitting from relatively simple manufacturing methods. However, ionic defects at surfaces usually cause detrimental carrier recombination, which links to one of dominant losses in device performance, slow transient responses, and notorious hysteresis. Here, it is shown that several different types of ionic defects can be simultaneously passivated by simple inorganic binary alkaline halide salts with their cations and anions. Compared to previous literature reports, this work demonstrates a promising passivation technology for perovskite solar cells. The efficient defect passivation significantly suppresses the recombination at the SnO₂/perovskite interface, contributing to an increase in the open‐circuit voltage, the fast response of steady‐state efficiency, and the elimination of hysteresis. By this strong leveraging of multiple‐element passivation, low‐temperature‐processed, planar‐structured perovskite solar cells of 20.5% efficiencies, having negligible hysteresis, are obtained. Moreover, this defect‐passivation enhances the stability of solar cells with efficiency beyond 20%, retaining 90% of their initial performance after 30 d. This approach aims at developing the concept of defect engineering, which can be expanded to multiple‐element passivation from monoelement counterparts using simple and low‐cost inorganic materials.     

3D–2D–0D Interface Profiling for Record Efficiency All‐Inorganic CsPbBrI2 Perovskite Solar Cells with Superior Stability

All‐inorganic CsPbBrI₂ perovskite has great advantages in terms of ambient phase stability and suitable band gap (1.91 eV) for photovoltaic applications. However, the typically used structure causes reduced device performance, primarily due to the large recombination at the interface between the perovskite, and the hole‐extraction layer (HEL). In this paper, an efficient CsPbBrI₂ perovskite solar cell (PSC) with a dimensionally graded heterojunction is reported, in which the CsPbBrI₂ material is distributed within bulk–nanosheet–quantum dots or 3D–2D–0D dimension‐profiled interface structure so that the energy alignment is optimized in between the valence and conduction bands of both CsPbBrI₂ and the HEL layers. Specifically, the valence‐/conduction‐band edge is leveraged to bend with synergistic advantages: the graded combination enhances the hole extraction and conduction efficiency with effectively decreased recombination loss during the hole‐transfer process, leading to an enhanced built‐in electric field, hence a high V_OC of as much as 1.19 V. The profiled structure induces continuously upshifted energy levels, resulting in a higher J_SC of as much as 12.93 mA cm^?2 and fill factor as high as 80.5%, and therefore record power conversion efficiency (PCE) of 12.39%. As far as it is known, this is the highest PCE for CsPbBrI₂ perovskite‐based PSC.     

Understanding and Eliminating Hysteresis for Highly Efficient Planar Perovskite Solar Cells

Through detailed device characterization using cross‐sectional Kelvin probe force microscopy (KPFM) and trap density of states measurements, we identify that the J–V hysteresis seen in planar organic–inorganic hybrid perovskite solar cells (PVSCs) using SnO₂ electron selective layers (ESLs) synthesized by low‐temperature plasma‐enhanced atomic‐layer deposition (PEALD) method is mainly caused by the imbalanced charge transportation between the ESL/perovskite and the hole selective layer/perovskite interfaces. We find that this charge transportation imbalance is originated from the poor electrical conductivity of the low‐temperature PEALD SnO₂ ESL. We further discover that a facile low‐temperature thermal annealing of SnO₂ ESLs can effectively improve the electrical mobility of low‐temperature PEALD SnO₂ ESLs and consequently significantly reduce or even eliminate the J–V hysteresis. With the reduction of J–V hysteresis and optimization of deposition process, planar PVSCs with stabilized output powers up to 20.3% are achieved. The results of this study provide insights for further enhancing the efficiency of planar PVSCs.     

Spontaneous Interface Ion Exchange: Passivating Surface Defects of Perovskite Solar Cells with Enhanced Photovoltage

Interface engineering is of great concern in photovoltaic devices. For the solution‐processed perovskite solar cells, the modification of the bottom surface of the perovskite layer is a challenge due to solvent incompatibility. Herein, a Cl‐containing tin‐based electron transport layer; SnO_x‐Cl, is designed to realize an in situ, spontaneous ion‐exchange reaction at the interface of SnO_x‐Cl/MAPbI₃. The interfacial ion rearrangement not only effectively passivates the physical contact defects, but, at the same time, the diffusion of Cl ions in the perovskite film also causes longitudinal grain growth and further reduces the grain boundary density. As a result, an efficiency of 20.32% is achieved with an extremely high open‐circuit voltage of 1.19 V. This versatile design of the underlying carrier transport layer provides a new way to improve the performance of perovskite solar cells and other optoelectronic devices.     

Controlled SnO2 Crystallinity Effectively Dominating Sodium Storage Performance

The exploration of sodium ion batteries (SIBs) is a profound challenge due to the rich sodium abundance and limited supply of lithium on earth. Here, amorphous SnO₂/graphene aerogel (a‐SnO₂/GA) nanocomposites have been successfully synthesized via a hydrothermal method for use as anode materials in SIBs. The designed annealing process produces crystalline SnO₂/graphene aerogel (c‐SnO₂/GA) nanocomposites. For the first time, the significant effects of SnO₂ crystallinity on sodium storage performance are studied in detail. Notably, a‐SnO₂/GA is more effective than c‐SnO₂/GA in overcoming electrode degradation from large volume changes associated with charge–discharge processes. Surprisingly, the amorphous SnO₂ delivers a high specific capacity of 380.2 mAh g^?1 after 100 cycles at a current density of 50 mA g^?1, which is almost three times as much as for crystalline SnO₂ (138.6 mAh g^?1). The impressive electrochemical performance of amorphous SnO₂ can be attributed to the intrinsic isotropic nature, the enhanced Na⁺ diffusion coefficient, and the strong interaction between amorphous SnO₂ and GA. In addition, amorphous SnO₂ particles with the smaller size better function to relieve the volume expansion/shrinkage. This study provides a significant research direction aiming to increase the electrochemical performance of the anode materials used in SIBs.     

Improving Interfacial Charge Recombination in Planar Heterojunction Perovskite Photovoltaics with Small Molecule as Electron Transport Layer

Although perovskite solar cells (PSCs) have emerged as a promising alternative to widely used fossil fuels, the involved high‐temperature preparation of metal oxides as a charge transport layer in most state‐of‐the‐art PSCs has been becoming a big stumbling block for future low‐temperature and large‐scale R2R manufacturing process. Such an issue strongly encourages scientists to find new type of materials to replace metal oxides. Except for expensive PC₆₁BM with unmanageable morphology and electrical properties, the past investigation on the development of low‐temperature‐processed and highly efficient electron transport layers (ETLs) has met some mixed success. In order to further enhance the performance of all‐solution‐processed PSCs, we propose a novel n‐type sulfur‐containing small molecule hexaazatrinaphtho[2,3‐c][1,2,5]thiadiazole (HATNT) with high electron mobility up to 1.73 × 10^?2 cm² V^?1 s^?1 as an ETL in planar heterojunction PSCs. A high power conversion efficiency of 18.1% is achieved, which is fully comparable with the efficiency from the control device fabricated with PC₆₁BM as ETL. This superior performance mainly attributes from more effective suppression of charge recombination at the perovskite/HATNT interface than that between the perovskite and PC₆₁ BM. Moreover, high electron mobility and strong interfacial interaction via S? I or S? Pb bonding should be also positive factors. Significantly, our results undoubtedly enable new guidelines in exploring n‐type organic small molecules for high‐performance PSCs.     

Hydrothermal growth of Zn2SnO4:Eu,Ca for red emission

Zinc stannate (Zn₂SnO₄) and Zn₂SnO₄ codoped with Eu³⁺ and Ca²⁺ (ZTO:Eu,Ca) were synthesized by hydrothermal method and characterized with X‐ray diffraction (XRD), energy‐dispersive X‐ray analysis (EDAX), Raman spectrometer, field emission scanning electron microscopy (FESEM), ultraviolet‐visible (UV‐vis) and photoluminescence (PL) spectrophotometers. PL analysis of Zn₂SnO₄ gives broad defect induced emission in the region 500–750 nm. The crystal structure of Zn₂SnO₄ was retained even with a nominal doping of Eu, Ca and its combination in the Zn₂SnO₄. The Eu³⁺ ions were found to occupy the non‐centrosymmetric sites of the Zn₂SnO₄ and gave emissions at 592, 615 and 702 nm. Zn₂SnO₄:Eu,Ca showed red emission at 615 nm attributed to the electronic transition from the excited state ⁵D₀ → ⁷F₂ of the 4f⁶ configuration of Eu³⁺. Nominal codoping of Eu³⁺ and Ca²⁺ ions promoted the quenching of orange emission from Eu³⁺ in Zn₂SnO₄:Eu,Ca.