Stability of Perovskite Thin Films under Working Condition: Bias-Dependent Degradation and Grain Boundary Effects

Witnessed by the rapid increase of power conversion efficiency to 25.5%, organic–inorganic hybrid perovskite solar cells (PSCs) are becoming promising candidates of next-generation photovoltaics. However, PSCs can be unstable under the influence of light and bias. Especially, grain boundaries (GBs) are vulnerable to attack by light and bias in perovskite films, leading to degradation of photovoltaic properties of PSCs. Herein, photocurrent atomic force microscopy and Kelvin probe force microscopy are employed to systematically investigate the bias-dependent charge transport behaviors and stability of (FAPbI₃)_0.85(MAPbBr₃)_0.15 perovskite under working condition. Bias-dependent morphology and photocurrent images show irreversible decomposition of the perovskite at a bias of 0.1 V or below, which is accelerated by light illumination, leading to formation of an interfacial layer that restricts carrier transport. Meanwhile, GBs appear to enhance carrier transport at larger bias, but serve as breakthrough sites for perovskite decomposition at smaller bias. Introducing excess methylammonium iodide promotes decomposition, while potassium iodide passivation greatly relieves the decomposition. These results support the ion migration mechanism of decomposition through interfaces and GBs. This work provides a deeper understanding of bias-induced degradation of PSCs as well as bias-dependent double-edged roles of GBs, and forms valuable guidance for appropriate operation of PSCs.     

In Situ Growth of 2D Perovskite Capping Layer for Stable and Efficient Perovskite Solar Cells

2D halide perovskites have recently been recognized as a promising avenue in perovskite solar cells (PSCs) in terms of encouraging stability and defect passivation effect. However, the efficiency (less than 15%) of ultrastable 2D Ruddlesden–Popper PSCs still lag far behind their traditional 3D perovskite counterparts. Here, a rationally designed 2D‐3D perovskite stacking‐layered architecture by in situ growing 2D PEA₂PbI₄ capping layers on top of 3D perovskite film, which drastically improves the stability of PSCs without compromising their high performance, is reported. Such a 2D perovskite capping layer induces larger Fermi‐level splitting in the 2D‐3D perovskite film under light illumination, resulting in an enhanced open‐circuit voltage (V_oc) and thus a higher efficiency of 18.51% in the 2D‐3D PSCs. Time‐resolved photoluminescence decay measurements indicate the facilitated hole extraction in the 2D‐3D stacking‐layered perovskite films, which is ascribed to the optimized energy band alignment and reduced nonradiative recombination at the subgap states. Benefiting from the high moisture resistivity as well as suppressed ion migration of the 2D perovskite, the 2D‐3D PSCs show significantly improved long‐term stability, retaining nearly 90% of the initial power conversion efficiency after 1000 h exposure in the ambient conditions with a high relative humidity level of 60 ± 10%.     

Functionalization of Graphene Oxide Films with Au and MoOx Nanoparticles as Efficient p‐Contact Electrodes for Inverted Planar Perovskite Solar Cells

A graphene oxide (GO) film is functionalized with metal (Au) and metal‐oxide (MoO_x) nanoparticles (NPs) as a hole‐extraction layer for high‐performance inverted planar‐heterojunction perovskite solar cells (PSCs). These NPs can increase the work function of GO, which is confirmed with X‐ray photoelectron spectra, Kelvin probe force microscopy, and ultraviolet photoelectron spectra measurements. The down‐shifts of work functions lead to a decreased level of potential energy and hence increased V_oc of the PSC devices. Although the GO‐AuNP film shows rapid hole extraction and increased V_oc, a J_sc improvement is not observed because of localization of the extracted holes inside the AuNP that leads to rapid charge recombination, which is confirmed with transient photoelectric measurements. The power conversion efficiency (PCE) of the GO‐AuNP device attains 14.6%, which is comparable with that of the GO‐based device (14.4%). In contrast, the rapid hole extraction from perovskite to the GO‐MoO_x layer does not cause trapping of holes and delocalization of holes in the GO film accelerates rapid charge transfer to the indium tin oxide substrate; charge recombination in the perovskite/GO‐MoO_x interface is hence significantly retarded. The GO‐MoO_x device consequently shows significantly enhanced V_oc and J_sc, for which its device performance attains PCE of 16.7% with great reproducibility and enduring stability.     

Improvement and Regeneration of Perovskite Solar Cells via Methylamine Gas Post‐Treatment

The control of film morphology is crucial in achieving high‐performance perovskite solar cells (PSCs). Herein, the crystals of the perovskite films are reconstructed by post‐treating the MAPbI₃ devices with methylamine gas, yielding a homogeneous nucleation and crystallization of the perovskite in the triple mesoscopic inorganic layers structured PSCs. As a result, a uniform, compact, and crystalline perovskite layer is obtained after the methylamine gas post‐treatment, yielding high power conversion efficiency (PCE) of 15.26%, 128.8% higher than that of the device before processing. More importantly, this post‐treatment process allows the regeneration of the photodegraded PSCs via the crystal reconstruction and the PCE can recover to 91% of the initial value after two cycles of the photodegradation‐recovery process. This simple method allows for the regeneration of perovskite solar cells on site without reconstruction or replacing any components, thus prolonging the service life of the perovskite solar cells and distinguishing from any other photovoltaic devices in practice.     

Dopant‐Free,Amorphous–Crystalline Heterophase SnO2 Electron Transport Bilayer Enables >20% Efficiency in Triple‐Cation Perovskite Solar Cells

Improving the ohmic contact and interfacial morphology between an electron transport layer (ETL) and perovskite film is the key to boost the efficiency of planar perovskite solar cells (PSCs). In the current work, an amorphous–crystalline heterophase tin oxide bilayer (Bi‐SnO₂) ETL is prepared via a low‐temperature solution process. Compared with the amorphous SnO₂ sol–gel film (SG‐SnO₂) or the crystalline SnO₂ nanoparticle (NP‐SnO₂) counterparts, the heterophase Bi‐SnO₂ ETL exhibits improved surface morphology, considerably fewer oxygen defects, and better energy band alignment with the perovskite without sacrificing the optical transmittance. The best PSC device (active area ≈ 0.09 cm²) based on a Bi‐SnO₂ ETL is hysteresis‐less and achieves an outstanding power conversion efficiency of ≈20.39%, which is one of the highest efficiencies reported for SnO₂‐triple cation perovskite system based on green antisolvent. More fascinatingly, large‐area PSCs (active areas of ≈3.55 cm²) based on the Bi‐SnO₂ ETL also achieves an extraordinarily high efficiency of ≈14.93% with negligible hysteresis. The improved device performance of the Bi‐SnO₂‐based PSC arises predominantly from the improved ohmic contact and suppressed bimolecular recombination at the ETL/perovskite interface. The tailored morphology and energy band structure of the Bi‐SnO₂ has enabled the scalable fabrication of highly efficient, hysteresis‐less PSCs.     

Enhanced Performance of Planar Perovskite Solar Cells Induced by Van Der Waals Epitaxial Growth of Mixed Perovskite Films on WS2 Flakes

Organic–inorganic metal halide perovskite solar cells (PSCs) have attracted much research interest owing to their high power conversion efficiency (PCE), solution processability, and the great potential for commercialization. However, the device performance is closely related to the quality of the perovskite film and the interface properties, which cannot be easily controlled by solution processes. Here, 2D WS₂ flakes with defect‐free surfaces are introduced as a template for van der Waals epitaxial growth of mixed perovskite films by solution process for the first time. The mixed perovskite films demonstrate a preferable growth along (001) direction on WS₂ surfaces. In addition, the WS₂/perovskite heterojunction forms a cascade energy alignment for efficient charge extraction and reduced interfacial recombination. The inverted PSCs with WS₂ interlayers show high PCEs up to 21.1%, which is among the highest efficiency of inverted planar PSCs. This work demonstrates that high‐mobility 2D materials can find important applications in PSCs as well as other perovskite‐based optoelectronic devices.     

Surface Regulation through Dipolar Molecule Boosting the Efficiency of Mixed 2D/3D Perovskite Solar Cell to 24%

Mixed 2D/3D perovskite solar cells (PSCs) show promising performances in efficiency and long-term stability. The functional groups terminated on a large organic molecule used to construct 2D capping layer play a key role in the chemical interaction mechanism and thus influence the device performance. In this study, 4-(trifluoromethyl) benzamidine hydrochloride (TFPhFACl) is adopted to construct 2D capping layer atop 3D perovskite. It is found that there are two mechanisms synergistically contributing to the increase of efficiency: 1) The TFPhFA⁺ cations form a dipole layer promoting the interfacial charge transport. 2) The suppressed nonradiative recombination of perovskite through the coordination of TFPhFA⁺ cations with Pb–I octahedron, as well as the recrystallization of 3D perovskite induced by Cl^- ions. As a result, the PSC delivers an efficiency of 24.0% with improved open-circuit voltage (V_OC) of 1.16 V, short-circuit current density (J_SC) of 25.42 mA cm^-2, and fill factor of 81.26%. The device shows no decrease in efficiency after 1500 h stored in the air indicating the good stability. The utilization of TFPhFACl not only provides a facile way to optimize the interfacial problems, but also gives a new perspective for rational design of large spacer molecule for constructing efficient 2D/3D PSCs.     

Unraveling the Reasons for Efficiency Loss in Perovskite Solar Cells

The effect of the presence of unreacted PbI₂ on the perovskite solar cells efficiency is reported. N,N‐Dimethylformamide vapor treatment is introduced to study the influence of complete conversion to a power conversion efficiency of the device. It is discovered that the optimized morphology of the PbI₂ under layer is essential to form a dense perovskite layer preventing recombination by direct contact between TiO₂ and a hole transporting layer, and to increase the charge collection efficiency. The present findings provide an insight into the morphology and growth mechanism of perovskite layer, the correlation between the device performance, and the film deposition process.     

Origin of Hysteresis in CH3NH3PbI3 Perovskite Thin Films

Organic–inorganic hybrid perovskite solar cells are attracting the attention of researchers owing to the high level of performance they exhibit in photovoltaic device applications. However, the attainment of an even higher level of performance is hindered by their anomalous current–voltage (I–V) hysteresis behavior. Even though experimental and theoretical studies have suggested that the perovskite materials may have a ferroelectric nature, it is still far from being fully understood. In this study, the origin of the hysteresis behavior in CH₃NH₃PbI₃ perovskite thin films is investigated. The behavior of ferroelectricity using piezoresponse force microscopy is first examined. Then, by comparing the scan‐rate‐dependent nano/macroscopic I–V curves, it is found that ion migration assisted by the grain boundaries is a dominant origin of I–V hysteresis from a macroscopic viewpoint. Consequently, the observations suggest that, even though ferroelectricity exists in the CH₃NH₃PbI₃ perovskite materials, ion migration primarily contributes to the macroscopic I–V hysteresis. The presented results can provide fundamental guidelines to the resolution of hysteresis issues in organic–inorganic hybrid perovskite materials.     

Synergetic Excess PbI2 and Reduced Pb Leakage Management Strategy for 24.28% Efficient,Stable and Eco-Friendly Perovskite Solar Cells

Introducing excess PbI₂ has proven to be an effective in situ passivation strategy for enhancing efficiency of perovskite solar cells (PSCs). Nevertheless, the photoinstability and hysteresis are still tough issues owing to the photolysis nature of PbI₂. Moreover, the humidity-related degradation of perovskite films is also a difficult territory to cover in such an in situ passivation strategy. Herein, a synergistic strategy is reported via initiatively inducing vertical graded PbI₂ distribution (GPD) in the whole perovskite film and capping a cis-Ru(H₂dcbpy)(dnbpy)(NCS)₂ (Z907) internal encapsulation (IE) layer on the surface to ameliorate the above issues. The GPD design can enhance luminescence, prolong carrier lifetimes, ascertaining the improvement of efficiency and elimination of photoinstability in the PSCs. Besides, the introduced IE layer not only can promote the moisture and thermal resistance, but also inhibit Pb leakage and ion migration in the PSCs. Through the synergetic regulations, the resultant PSCs exhibit an impressive open circuit voltage (V_OC) of 1.253 V, fill factor of 81.25%, and power conversion efficiency (PCE) of 24.28%. Moreover, the PSCs maintain 91% of its initial PCE at relative humidity of 85% after 500 h aging and 94% under continuous heating at 85 °C after 750 h aging.     

Precursor Engineering for All‐Inorganic CsPbI2Br Perovskite Solar Cells with 14.78% Efficiency

The optoelectronic properties of perovskite films are closely related to the film quality, so depositing dense, uniform, and stable perovskite films is crucial for fabricating high‐performance perovskite solar cells (PSCs). CsPbI₂Br perovskite, prized for its superb stability toward light soaking and thermal aging, has received a great deal of attention recently. However, the air instability and poor performance of CsPbI₂Br PSCs are hindering its further progress. Here, an approach is reported for depositing high‐quality CsPbI₂Br films via the Lewis base adducts PbI₂(DMSO) and PbBr₂(DMSO) as precursors to slow the crystallization of the perovskite film. This process produces CsPbI₂Br films with large‐scale crystalline grains, flat surfaces, low defects, and long carrier lifetimes. More interestingly, PbI₂(DMSO) and PbBr₂(DMSO) adducts could significantly improve the stability of CsPbI₂Br films in air. Using films prepared by this technique, a power conversion efficiency (PCE) of 14.78% is obtained in CsPbI₂Br PSCs, which is the highest PCE value reported for CsPbI₂Br‐based PSCs to date. In addition, the PSCs based on DMSO adducts show an extended operational lifetime in air. These excellent performances indicate that preparing high‐quality inorganic perovskite films by using DMSO adducts will be a potential method for improving the performance of other inorganic PSCs.     

A Universal Strategy to Utilize Polymeric Semiconductors for Perovskite Solar Cells with Enhanced Efficiency and Longevity

In this contribution, a facile and universal method is successfully reported to fabricate perovskite solar cells (PSCs) with enhanced efficiency and stability. Through dissolving functional conjugated polymers in antisolvent chlorobenzene to treat the spinning CH₃NH₃PbI₃ perovskite film, the resultant devices exhibit significantly enhanced efficiency and longevity simultaneously. In‐depth characterizations demonstrate that thin polymer layer well covers the top surface of perovskite film, resulting in certain surface passivation and morphology modification. More importantly, it is shown that through rational chemical modification, namely molecular fluorination, the air stability and photostability of the perovskite solar cells are remarkably enhanced. Considering the vast selection of conjugated polymer materials and easy functional design, promising new results are expected in further enhancement of device performance. It is believed that the findings provide exciting insights into the role of conjugated polymer in improving the current perovskite‐based solar cells.     

Performance Optimization of Polymer Solar Cells Using Electrostatically Sprayed Photoactive Layers

Polymer solar cells (PSCs) are fabricated using a novel film deposition method, the electrostatic spray (e‐spray) technique. Stable atomization and uniform deposition of the polymer blend by e‐spray are achieved by manipulating the solution concentration, the solvent composition, and the electric field. The performance of PSCs is primarily influenced by the inherent film morphology of the e‐sprayed polymer‐blend active layers, which is significantly different from that of the conventional films that are formed using the spin‐coating (SC) method. The intrinsically formed interfacial boundaries between the e‐sprayed blend pancakes resist charge transport, which unfavorably influences device efficiency. The internal series resistance (R_S) of the PSCs that are formed using the e‐spray method (e‐spray‐PSC) is significantly reduced by a solvent vapor soaking (SVS) treatment in addition to the conventional thermodynamic nanomorphology controls. The detailed relationship between the morphologies (film morphology and internal nanomorphology) and the R_S is revealed using impedance spectroscopy. The performance of the e‐spray‐PSCs is comparable to those of the PSCs that are fabricated using the SC method under identical conditions. Therefore, the e‐spray method can be used to fabricate ultralow‐cost PSCs, because of the performance results combined with the intrinsic advantages that the e‐spray method is simple and has a low materials loss.     

Solar Cells: Performance Optimization of Polymer Solar Cells Using Electrostatically Sprayed Photoactive Layers (Adv. Funct. Mater. 20/2010)

Polymer solar cells (PSCs) are fabricated using a novel film deposition method, the electrostatic spray (e‐spray) technique. Stable atomization and uniform deposition of the polymer blend by e‐spray are achieved by manipulating the solution concentration, the solvent composition, and the electric field. The performance of PSCs is primarily influenced by the inherent film morphology of the e‐sprayed polymer‐blend active layers, which is significantly different from that of the conventional films that are formed using the spin‐coating (SC) method. The intrinsically formed interfacial boundaries between the e‐sprayed blend pancakes resist charge transport, which unfavorably influences device efficiency. The internal series resistance (R_S) of the PSCs that are formed using the e‐spray method (e‐spray‐PSC) is significantly reduced by a solvent vapor soaking (SVS) treatment in addition to the conventional thermodynamic nanomorphology controls. The detailed relationship between the morphologies (film morphology and internal nanomorphology) and the R_S is revealed using impedance spectroscopy. The performance of the e‐spray‐PSCs is comparable to those of the PSCs that are fabricated using the SC method under identical conditions. Therefore, the e‐spray method can be used to fabricate ultralow‐cost PSCs, because of the performance results combined with the intrinsic advantages that the e‐spray method is simple and has a low materials loss.     

Mapping Morphological and Structural Properties of Lead Halide Perovskites by Scanning Nanofocus XRD

Scanning nanofocus X‐ray diffraction (nXRD) performed at a synchrotron is used to simultaneously probe the morphology and the structural properties of spin‐coated CH₃NH₃PbI₃ (MAPI) perovskite films for photovoltaic devices. MAPI films are spin‐coated on a Si/SiO₂/poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) substrate held at different temperatures during the deposition in order to tune the perovskite film coverage. The films are then investigated using nXRD and scanning electron microscopy (SEM). The advantages of nXRD over SEM and other techniques are discussed. A method to visualize, selectively isolate, and structurally characterize single perovskite grains buried within a complex, polycrystalline film is developed. The results of nXRD measurements are correlated with solar cell device measurements, and it is shown that spin‐coating the perovskite precursor solution at elevated temperatures leads to improved surface coverage and enhanced solar cell performance.     

Enhanced Hole-Carrier Selectivity in Wide Bandgap Halide Perovskite Photovoltaic Devices for Indoor Internet of Things Applications

Halide perovskite-based photovoltaic (PV) devices have recently emerged for low energy consumption electronic devices such as Internet of Things (IoT). In this work, an effective strategy to form a hole-selective layer using phenethylammonium iodide (PEAI) salt is presented that demonstrates unprecedently high open-circuit voltage of 0.9 V with 18 µW cm⁻² under 200 lux (cool white light-emitting diodes). An appropriate post-deposited amount of PEAI (2 mg) strongly interacts with the perovskite surface forming a conformal coating of PEAI on the perovskite film surface, which improves the crystallinity and absorption of the film. Here, Kelvin probe force microscopy results indicate the diminished potential difference across the grain boundaries and grain interiors after the PEAI deposition, constructing an electrically and chemically homogeneous surface. Also, the surface becomes more p-type with a downshift of a valence band maximum, confirmed by ultraviolet photoelectron spectroscopy measurement, facilitating the transport of holes to the hole transport layer (HTL). The hole-selective layer-deposited devices exhibit reduced hysteresis in light current density–voltage curves and maintain steadily high fill factor across the different light intensities (200–1000 lux). This work highlights the importance of the HTL/perovskite interface that prepares the indoor halide perovskite PV devices for powering IoT device.     

Investigating local (photo-)current and structure of ZnPc:C60 bulk-heterojunctions

The performance of organic solar cells strongly depends on the nanoscale structure of the used mixed absorber layer. Utilizing photoconductive and conductive atomic force microscopy (pcAFM and cAFM), as well as transmission X-ray microscopy (TXM), we investigate the influence of different substrate temperatures T_sub on the thin-film structure and local photocurrent in bulk-heterojunctions (BHJs) of vacuum deposited zinc phthalocyanine (ZnPc) and Buckminsterfullerene (C₆₀) mixed absorber layers. In this paper, we present topography maps, photocurrent maps under short-circuit current conditions, dark-current maps, and TXM images with high lateral resolution down to 25 nm. We observe a strong influence of the substrate temperatures during deposition T_sub on the nanoscopical segregation of the two components in the BHJ. This segregation leads to a spatial extension of the dark-current and a reduced short-circuit current at higher substrate deposition temperatures T_sub.     

Ultrathin perovskite based solar cells with the efficiency enhanced by charge transfer process

We report a new approach of improving the solar cells efficiency based on ultrathin perovskite films. We propose the addition of CuPc compound to perovskite active layer for enhanced charge generation and transfer process by charge transfer process between CuPc and perovskite. The performance of the devices with and without addition of CuPc was studied in respect to thickness of the active layer. The thickness was varied by the change of the spin coating speed in the range of 4000, 7000 and 10000 rpm, different concentration of CuPc also been studied. The process of charge carrier recombination, crystallinity and Raman characteristics of the obtained films was studied. The perovskite device with an active layer of MAPbI₃ mixed with CuPc spin coated with the speed of 10000 rpm with thickness of about 150 nm demonstrated the efficiency of 12.7%. The ultrathin mixed perovskite film (10000 rpm perovskite film of 15% CuPc) based device presents 33% thickness and 85% efficiency of common pure perovskite device (4000 rpm pure perovskite film).     

Tuning Hole Transport Layer Using Urea for High‐Performance Perovskite Solar Cells

Interface engineering is critical to the development of highly efficient perovskite solar cells. Here, urea treatment of hole transport layer (e.g., poly(3,4‐ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS)) is reported to effectively tune its morphology, conductivity, and work function for improving the efficiency and stability of inverted MAPbI₃ perovskite solar cells (PSCs). This treatment has significantly increased MAPbI₃ photovoltaic performance to 18.8% for the urea treated PEDOT:PSS PSCs from 14.4% for pristine PEDOT:PSS devices. The use of urea controls phase separation between PEDOT and PSS segments, leading to the formation of a unique fiber‐shaped PEDOT:PSS film morphology with well‐organized charge transport pathways for improved conductivity from 0.2 S cm^?1 for pristine PEDOT:PSS to 12.75 S cm^?1 for 5 wt% urea treated PEDOT:PSS. The urea‐treatment also addresses a general challenge associated with the acidic nature of PEDOT:PSS, leading to a much improved ambient stability of PSCs. In addition, the device hysteresis is significantly minimized by optimizing the urea content in the treatment.     

A Versatile Buffer Layer for Polymer Solar Cells: Rendering Surface Potential by Regulating Dipole

Spin‐coated film of poly(vinylidenefluoride‐hexafluoropropylene) (P(VDF‐HFP)) acts as a cathode/anode buffer layer in polymer solar cells (PSCs) with conventional/inverted device structures. Such devices show optimized performances comparable with the controlled device, making P(VDF‐HFP) a good substitute for LiF/MoO₃ as a cathode/anode buffer layer. Ultraviolet photoelectron spectroscopy (UPS) and Kelvin force microscope (KFM) measurements show that increased surface potential of active layers improves cathode contact. In piezoresponse force microscopy (PFM) measurement, P(VDF‐HFP) responds to applied bias in phase curve, showing tunable dipole. This tunable dipole renders surface potential under applied bias. As a result, open‐circuit voltage of devices alters instantly with poling voltage. Moreover, positive poling of P(VDF‐HFP) together with simultaneous oxidation of Ag gradually improves performance of inverted structure device. Integer charge transfer (ICT) model elucidates improved electrode contacts by dipole tuning, varying surface potential and vacuum level shift. Understanding the function of dipole makes P(VDF‐HFP) a promising and versatile buffer layer for PSCs.