Polycrystalline Perovskite Films Research Articles

Defect Passivation Strategies in Two‐Dimensional Organic–Inorganic Hybrid Perovskites for Enhanced Photoelectric Performance

AbstractThe polycrystalline perovskite films treated with solutions inevitably are subjected to high‐density crystal defects, significantly affecting the performance and stability of perovskite‐based photodetectors. In this research, a reasonably designed organic small molecule using piperazine iodide (PI) as an additive is employed to modify the perovskite films. The results indicate that this designed molecule not only improves the crystallinity of the perovskite film but also effectively passivates defects by modifying the local electron density. Consequently, recombination of non‐radiation charges is inhibited, improving the optoelectronic performance and stability of the device. The modified flexible photoelectric device exhibits a responsivity of 3.07 mA W−1 under 405 nm laser illumination. Notably, it maintains a high responsivity even after 7000 bending cycles. Furthermore, generality of the strategy is verified by applying it to various types of two‐dimensional organic–inorganic hybrid perovskite. Additionally, another small molecular amine phthalimide (PTM) is selected as an additive to further verify the universality of this strategy, which reveals that it demonstrates the same passivation as PI. This strategy provides a novel idea for defect passivation of two‐dimensional organic–inorganic hybrid perovskite, signifying a practical application significance for developing flexible wearable devices with optimized performance, perovskite light‐emitting diodes, and solar cells.

Photophysical Properties of Submicrometer Ultrathin Perovskite Single-Crystal Films.

Organic-inorganic hybrid perovskite (OIHP) has attracted a great deal of interest with respect to diverse optoelectronic devices. However, the photophysical properties of the OIHP require further understanding because most of the investigations have been conducted with polycrystalline perovskites, which contain high-density structural defects. Here, diverse photophysical properties, including structural characterization, spectroscopic features, and photoexcited products, are studied in submicrometer CH3NH3PbBr3 ultrathin single-crystal (UTSC) films. Unlike polycrystalline films and large single crystals, the UTSC film provides a unique platform for studying spectroscopic characteristics of single-crystal perovskites. Compared with the polycrystalline film, the UTSC film presents an atomically flat morphology and near-perfect lattice with a lower defect density, leading to an isotropic system that can be applied in the construction of high-performance optoelectronic devices. Furthermore, a long lifetime emissive channel assigned to the trion is indicated, which is scarcely found in perovskite polycrystalline films. Our results profoundly improve our understanding of their photophysical properties and expand the horizons for perovskite materials in photonic applications.

Multiple Dynamic Hydrogen Bonding Networks Boost the Mechanical Stability of Flexible Perovskite Solar Cells

AbstractFlexible perovskite solar cells often experience constant or cyclic bending during their service life. Catastrophic failure of devices may occur due to the crack of polycrystalline perovskite films and delamination at the perovskite and the substrate interfaces, posing a significant stability concern. Here, a multiple dynamic hydrogen bonding polymer network is developed to enhance the mechanical strength of flexible perovskite solar cells in two ways. The main chain of poly(acrylic acid) decreases the mismatch of the coefficient of thermal expansion between the perovskite and the substrate by 16.7% through its flexibility and spatial occupation. The dopamine branch chains provide multiple dynamic hydrogen bonding sites, which contribute to increased energy dissipation upon stress deformation and reduce Young's modulus of perovskite by 54.3%. The inverted flexible perovskite solar cells achieve a champion power conversion efficiency of 23.02% and retain 81.3% of the initial PCE over 2000 h under continuous 1‐sun equivalent illumination. Moreover, devices show excellent mechanical stability by remaining 90.2% of the original value after 5000 bending cycles.

Unveiling the Effect of Cooling Rate on Grown-in Defects Concentration in Polycrystalline Perovskite Films for Solar Cells with Improved Stability.

Numerous efforts are devoted to reducing the defects at perovskite surface and/or grain boundary; however, the grown-in defects inside grain is rarely studied. Here, the influence of cooling rate on the point defects concentration in polycrystalline perovskite film during heat treatment processing is investigated. With the combination of theoretical and experimental studies, this work reveals that the supersaturated point defects in perovskite films generate during the cooling process and its concentration improves as the cooling rate increases. The supersaturated point defects can be minimized through slowing the cooling rate. As a result, the optimized FAPbI3 polycrystalline films achieve a superior carrier lifetime of up to 12.6 µs and improved stability. The champion device delivers a 25.47% PCE (certified 24.7%) and retain 90% of their initial value after >1100 h of operation at the maximum power point. These results provide a fundamental understanding of the mechanisms of grown-in defects formation in polycrystalline perovskite film.

Dense Perovskite Thick Film Enabled by Saturated Solution Filling for Sensitive X-ray Detection and Imaging.

Thick polycrystalline perovskite films synthesized by using solution processes show great potential in X-ray detection applications. However, due to the evaporation of the solvent, many pinholes and defects appear in the thick films, which deteriorate their optoelectronic properties and diminish their X-ray detection performance. Therefore, the preparation of large area and dense perovskite thick films is desired. Herein, we propose an effective strategy of filling the pores with a saturated precursor solution. By adding the saturated perovskite solution to the polycrystalline perovskite thick film, the original perovskite film will not be destroyed because of the solution-solute equilibrium relationship. Instead, it promotes in situ crystal growth within the thick film during the annealing process. The loosely packed grains in the original thick perovskite film are connected, and the pores and defects are partially filled and fixed. Finally, a much denser perovskite thick film with improved optoelectronic properties has been obtained. The optimized thick film exhibits an X-ray sensitivity of 1616.01 μC Gyair-1 cm-2 under an electric field of 44.44 V mm-1 and a low detection limit of 28.64 nGyair s-1 under an electric field of 22.22 V mm-1. These values exceed the 323.86 μC Gyair-1 cm-2 and 40.52 nGyair s-1 of the pristine perovskite thick film measured under the same conditions. The optimized thick film also shows promising working stability and X-ray imaging capability.

4-Methoxy phenethylammonium halide salts for surface passivation of perovskite films towards efficient and stable solar cells

Surface defects-mediated non-radiative charge recombination in polycrystalline perovskite films has been widely acknowledged to be responsible for the undesired open-circuit voltage (VOC) deficit, which is still a great challenge for perovskite solar cells (PSCs) to achieve the Shockley-Queisser efficiency limit. Herein, we report the use of 4-methoxy phenethylammonium halide salts (4-MeO-PEAX, X = I, Br, Cl) on the surface of formamidinium-cesium (FACs) perovskite films for surface passivation. The impact of halogen species in 4-MeO-PEAX on the quality of FACs perovskite films and device performance are comparatively investigated. We find that the prepared FACs perovskite films demonstrate dramatically reduced defect density and surface roughness, improved crystallinity, preferred (001) orientation and prolonged carrier lifetime after the post-treatment by 4-MeO-PEACl. Consequently, the 4-MeO-PEACl post-processed p-i-n PSCs have achieved a significantly improved power conversion efficiency of 22.63 % and VOC of 1.13 V. The unencapsulated devices post-treated with 4-MeO-PEACl maintained 90 %, 88 % and 84 % of their initial efficiencies, after being thermally stressed at 65 ℃ under dark for 312 h, stored in ambient air for 720 h and operated under continuous 1 sun equivalent illumination with maximum power point tracking at 50 ℃ for 1000 h, respectively.

Interface Passivation of a Pyridine-Based Bifunctional Molecule for Inverted Perovskite Solar Cells.

Organic-inorganic hybrid perovskite solar cells (PSCs) have recently been demonstrated to be promising renewable harvesters because of their prominent photovoltaic power conversion efficiency (PCE), although their stability and efficiency still have not reached commercial criteria. Trouble-oriented analyses showcase that defect reduction among the grain boundaries and interfaces in the prepared perovskite polycrystalline films is a practical strategy, which has prompted researchers to develop functional molecules for interface passivation. Herein, the pyridine-based bifunctional molecule dimethylpyridine-3,5-dicarboxylate (DPDC) was employed as the interface between the electron-transport layer and perovskite layer, which achieved a champion PCE of 21.37% for an inverted MAPbI3-based PSC, which was greater than 18.64% for the control device. The mechanistic studies indicated that the significantly improved performance was mainly attributed to the remarkably enhanced fill factor with a value greater than 83%, which was primarily due to the nonradiative recombination suppression offered by the passivation effect of DPDC. Moreover, the promoted carrier mobility together with the enlarged crystal size contributed to a higher short-circuit current density. In addition, an increase in the open-circuit voltage was also observed in the DPDC-treated PSC, which benefited from the improved work function for reducing the energy loss during carrier transport. Furthermore, the DPDC-treated PSC showed substantially enhanced stability, with an over 80% retention rate of its initial PCE value over 300 h even at a 60% relative humidity level, which was attributed to the hydrophobic nature of the DPDC molecule and effective defect passivation. This work is expected not only to serve as an effective strategy for using a pyridine-based bifunctional molecule to passivate perovskite interfaces to enhance photovoltaic performance but also to shed light on the interface passivation mechanism.

Constructing Multi‐Functional Polymeric‐Termination Surface Enables High‐Performance Flexible Perovskite LEDs

AbstractFlexible perovskite light‐emitting diodes (f‐PeLEDs) have attracted increasing interest to realize true‐color, low‐cost, and light‐weight wearable optoelectronic and flexible display applications. However, their external quantum efficiency (EQE) and mechanical stability lag far behind because of the inherent surface and brittle issues of polycrystalline perovskite films. In this work, a multi‐functional polymeric‐termination surface of perovskite film is constructed for achieving efficient and mechanically stable f‐PeLEDs. It takes the roles to not only reduce defects through equipping coordination groups to improve emission properties, but also optimize film morphology and eliminate pinholes to solve the long‐standing issue of leakage current. Meanwhile, the polymeric‐termination surface with anchoring points and polymeric soft chains on perovskites demonstrates synergetic effects beyond the corresponding functional group‐only or polymer‐only strategies in reducing the Young's modulus and improving the mechanical flexibility. Ultimately, the record EQE of 22.1% and significantly enhanced mechanical stability of maintaining 82% of the initial performance after 2000 bending cycles with radius of 5 mm are achieved in pure‐green f‐PeLEDs. The work paves the way for the development of high‐performance flexible optoelectronic devices.

Anion Binding Interaction Enhances the Robustness of Iodide for High-Performance Perovskite Solar Cells.

Owing to the ionic bond nature of the Pb-I bond, the iodide at the interface of perovskite polycrystalline films was easily lost during the preparation process, resulting in the formation of a large number of iodine vacancy defects. The presence of iodine vacancy defects can cause nonradiative recombination, provide a pathway for iodide migration, and be harmful to the power conversion efficiency (PCE) and stability of organic-inorganic hybrid perovskite solar cells (HPSCs). Here, in order to increase the robustness of iodides at the interface, a strategy to introduce anion binding effects was developed to stabilize the perovskite films. It was demonstrated that the N,N'-diphenylurea (DPU), characterized by high anionic binding constants and a Y-shaped structure, provides a relatively strong hydrogen bond donor site to effectively reduce the iodine loss during film preparation and inhibits iodide migration in the device working condition. As expected, the reduced iodine loss considerably improves the quality of the perovskite films and suppresses nonradiative recombination. The performance of the device after DPU modification was significantly increased, with the PCE rising from 23.65 to 25.01% with huge stability enhancement as well.

Improved Amplified Spontaneous Emission in Polycrystalline Perovskite Films by the Dual‐Site Synergistic Passivation Effects of ZnS

AbstractHalide perovskite materials are considered a promising optical gain medium for stimulated emission and have aroused tremendous interest in the field of laser research. The development of low‐threshold optically pumped amplified spontaneous emission (ASE) is critical for the advancement of continuous wave (CW) and electrically pumped micro‐nano lasers. In this work, an efficient ZnS additive is incorporated into the FA0.85MA0.15PbI2.55Br0.45 perovskite films to diminish the ASE threshold and extend the photostability by the dual‐site synergistic passivation. The experimental measurements and first‐principles calculations based on the density functional theory (DFT) are employed to elucidate the doping mechanism. The designed ZnS‐based perovskite films yield a mitigated ASE threshold of 8.5 µJ cm−2 with an elevated optical gain coefficient of 109.06 cm−1, which outperform those of the control films (12.7 µJ cm−2 and 74.10 cm−1). The in‐depth experimental characterizations and theoretical calculations have corroborated that the improvement of ASE performance can be ascribed to the dual‐site synergistic passivation effects of Zn2+ and S2−, which reduces the surface defects of perovskite films, suppresses the nonradiative charge recombination and improves the optical stability. This work provides a resultful strategy to construct the solution‐processed perovskite lasers with low thresholds and superior stability.

Enhancing the photovoltaic responses of MAPbI3 poly-crystalline perovskite films via adjusting the properties of PEDOT:PSS hole transport material with a low-polarity solvent treatment process

The surface and electrical characteristics of the poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) materials are manipulated using a low-polarity solvent treatment process, which influences the formation and nucleation/crystal growth process of the CH3NH3PbI3 (MAPbI3) perovskite films and thereby determining the crystal orientation and grain size. The hydrophilicity of the PEDOT:PSS composite material fabricated on the ITO/glass sample is reduced with the xylenes solvent treatment or a hexamethyldisilazane:xylenes solvent mixture treatment, which can be used to form the photo-active perovskite crystals and thereby reducing the photocurrent hysteresis of the fabricated perovskite based photovoltaic devices. It is worthwhile to mention that the non-perfectness of closed-loop in the photocurrent density-voltage curves under the forward and backward scans can be used as an indicator to assess the properties of the MAPbI3 films. Our findings can facilitate the development of perovskite based optoelectronic devices.

One-Dimensional orthorhombic CsPbI3 polycrystalline thick film for efficient and highly stable direct X-ray detection and imaging

An ideal direct X-ray detector should convert a low dose of X-ray photons into large quantity of electrical signals, coupled with sustained long-term stability. Nevertheless, a notable conflict arises between X-ray absorption efficiency and carrier transport in thick polycrystalline perovskite films. Moreover, conventional perovskite materials exhibit inherent challenges regarding the stability of their crystal phase and the consistency of the photocurrent. To circumvent these limitations, a polycrystalline perovskite thick film is proposed using orthorhombic CsPbI3 (δ-CsPbI3) as a highly stable active material. Combined with the liquid epitaxy process, δ-CsPbI3 prefers one-dimensional growth along the carrier transportation direction, which suppresses the formation of grain boundaries, enabling high carrier mobility while maintaining X-ray absorption for a thick polycrystalline film. Consequently, the polycrystalline δ-CsPbI3 based detector exhibits a highest sensitivity of 1768.46 μC Gyair-1 cm−2 at an electric field of 432 V mm−1 which is 88.42-fold higher than α-Se based detectors and 190-fold higher than the single crystalline δ-CsPbI3 based detector, respectively. The sensitivity maintains 91.34 % of its initial state after 7 days exposure in the air. Combing with a thin-film transistor array, the detector achieves 8-bit imaging within a 64 × 64 matrix. This work provides a feasible method for commercialized production of high-performance direct X-ray detectors.

Coherent Carrier Spin Dynamics in FAPbBr3 Perovskite Crystals.

Coherent spin dynamics of electrons and holes are studied in hybrid organic-inorganic lead halide perovskite FAPbBr3 bulk single crystals using the time-resolved Kerr ellipticity technique at cryogenic temperatures. The Larmor spin precession of the carrier spins in a magnetic field is monitored to measure the Landé g-factors of electrons (+2.44) and holes (+0.41). These g-factors are highly isotropic. The measured spin dephasing times amount to a few nanoseconds, and the longitudinal hole spin relaxation time is 470 ns. The important role of the strong hyperfine interaction between carrier spins and nuclear spins is demonstrated via dynamic nuclear polarization. At low temperatures, electron and hole spin relaxation predominantly occurs via the hyperfine interaction, whose importance significantly decreases at temperatures above 12 K. We overview the spin dynamics in various lead halide perovskite crystals and polycrystalline films and conclude on their common features provided by charge carrier localization at cryogenic temperatures.

Enhanced Amplified Spontaneous Emission from Perovskite Films by a Multifunctional 4′‐Aminoacetophenone Hydrochloride Additive Assistant Engineering

AbstractMetal halide perovskites are considered as a prospective candidate as optical gain media for stimulated emission, and the advancement of amplified spontaneous emission (ASE) of perovskite materials is gradually becoming the key to realize the commercialization of perovskite lasers. Nonetheless, the ASE of solution‐processed polycrystalline perovskite films still experiences a high threshold and poor optical stability due to their high defect density and poor crystalline quality. In this scenario, a noticeably ameliorated ASE performance with decreased threshold and greater photo‐stability is demonstrated in solution‐processed (FAPbI3)0.85(MAPbBr3)0.15 polycrystalline perovskite films by introducing a neoteric 4′‐Aminoacetophenone hydrochloride (APCl) additive with cost‐effective fabrication. The ASE threshold of the APCl‐embedded perovskite films is prominently curtailed from 12.8 to 5.3 µJ cm−2, with an augmented optical gain, ASE output intensity, and optical durability. The ameliorated ASE performance can be credited to multifunctional effects of the APCl additive in the perovskite films, presenting a low defect density, an unambiguously elevated photoluminescence, a prolonged decay lifetime and thus enabling the easily achieved population inversion caused by the attenuated nonradiative carrier recombination in the optical gain media. These findings provide a significant foundation and pave the way for realizing the electrically excited lasing based on the perovskite materials.

The Role of Grain Boundaries in Organic–Inorganic Hybrid Perovskite Solar Cells and its Current Enhancement Strategies: A Review

Grain boundaries (GBs) in perovskite polycrystalline films are the most sensitive place for the formation of the defect states and the accumulation of impurities. Thus, abundant works have been carried out to explore their properties and then try to solve the induced problems. Currently, two important issues remain. First, the role of GBs in charge carrier dynamics is unclear due to their component complexity/defect tolerance nature and the insufficiency in testing accuracy. Some works conclude that GBs are benign, while others consider GBs as carrier recombination centers. Things for sure are the deterioration in ion transport and perovskite decomposition. Second, to solve the known hazards of GBs, a lot of additives have been added to anchoring ions and passivate defects. But in most of those works, GBs and perovskite surfaces are treated in the same manner ignoring the fact that GB is essentially a homogeneous junction in a narrow and slender space, while surface is a heterogeneous junction with a stratified structure. In this review, we focus on works insight into GBs and additives for them. Additionally, we also discuss the prospects of the maturity of GB exploration toward upscaling the manufacture of perovskite photovoltaic and related optoelectronic devices.

Oriented Growth for Efficient and Scalable Perovskite Solar Cells by Vapor–Solid Reaction

AbstractThe precise control and understanding of crystal orientation in perovskite polycrystalline films are crucial for the development of efficient and stable devices. However, achieving this control remains a significant challenge. Herein, a PbI2 oriented growth strategy is developed, combined with in situ vapor–solid reaction transformations, to achieve oriented growth of full‐vacuum perovskite films. Grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) analysis revealed the general pattern of PbI2 oriented vapor growth and in situ vapor–solid reaction transformation in this two‐step process. The resulting preferred orientation has effectively reduced trap state density, optimizing the carrier dynamics. As a result, champion efficiencies of 22.11% (0.148 cm2), 20.60% (1 cm2), and 19.41% (5 × 5 cm2 mini‐modules) are achieved, which are the highest value for perovskite based on vapor–solid reaction. Additionally, the oriented growth method is applicable to a variety of guide layers and is extended to 30 × 30 cm2 film, demonstrating the universality and scalability of the method.

Surface saturation current densities of perovskite thin films from Suns‐photoluminescence quantum yield measurements

AbstractWe present a simple yet powerful analysis of Suns‐photoluminescence quantum yield measurements that can be used to determine the surface saturation current densities of thin film semiconductors. We apply the method to state‐of‐the‐art polycrystalline perovskite thin films of varying absorber thickness. We show that the non‐radiative bimolecular recombination in these samples originates from the surfaces. To the best of our knowledge, this is the first study to demonstrate and quantify non‐linear (bimolecular) surface recombination in perovskite thin films.

Solvation‐Driven Grain Boundary Passivation Improving the Performance of Perovskite Solar Cells

AbstractThe efficiency of perovskite solar cells (PSCs) is hindered by substantial defects within the grain boundaries (GBs) of polycrystalline perovskite films. Conventional post‐treatment strategies struggle to precisely repair these defects at GBs. Here, a targeted grain boundary passivation strategy through solvent effects by incorporating symmetrical biphenyl molecules is proposed, 4,4′‐diaminodiphenyl sulfone (DDS) and 4,4′‐sulfodiphenol (SDP), aiming to mitigate defects at GBs and optimize energy level arrangements through their electric dipole effects. Compared to the pristine device, the SDP‐modified device exhibits significant improvements, including a champion efficiency of 24.39% and an impressive fill factor, along with excellent operation stability. This work provides an effective and straightforward solution for improving the performance of PSCs.

Gamma-ray dose threshold for MAPbI3 solar cells.

In this work, we report on the effects observed in MAPbI3 polycrystalline films and solar cells under moderate gamma-ray doses of 3-21 kGy. We applied several instrumental techniques such as photoluminescence spectroscopy, time-resolved photoluminescence, Suns-VOC measurement, and impedance spectroscopy to characterize exposed samples. We observed a nonlinear dependency of such characteristics as PL intensity, career lifetime, ideality factor, and recombination resistance on the exposure dose. Small doses of 3-5 kGy annihilate some of the defect centers in the material, which results in improved carrier extraction and prolonged carrier lifetime, while with larger doses of 10 kGy and above, nonradiative recombination becomes predominant. In this way, we revealed a gamma-ray threshold for MAPbI3 films of around 10 kGy, above which it is not recommended to exploit this material. In space environment, yearly doses rarely exhibit 0.1 kGy (10 krad), and the MAPbI3 material has a sufficient margin of safety for space applications. Moreover, this unusual behaviour opens up the opportunity to use gamma-ray sources as an effective method to improve the quality of defective polycrystalline perovskite films before actual exploitation in an ionizing radiation-free environment.

Grain Characteristics of Perovskite Thin Films Based on SEM Image Segmentation

AbstractPerovskite solar cells (PSCs) have become the forefront and hot pot of new photovoltaic technology due to their high efficiency, low cost, and easy preparation. Understanding the microstructure characteristics of the perovskite films is one of the key factors to further improve the efficiency and stability. The characteristics of grains based on the self‐developed perovskite film morphology analysis software GrainD are studied in this article. Important perovskite film information such as the average radius of grains, the distribution pattern of grain size, the area of grain contact, and the total number of grains are obtained. The results show that the grain size distribution of the polycrystalline perovskite film follows the lognormal distribution. According to statistical probability theory and grain growth theory, the multiplication effect of multiple random factors of film growth is proposed as the reason for the lognormal distribution. This study provides an important method for analyzing the perovskite films and gives clues about the crystallization kinetics.