High-quality Perovskite Thin Films Research Articles

Grain size control in quasi-two-dimensional perovskite thin film via intermediate phase engineering for efficient bound exciton generation

AbstractQuasi-two dimensional (2D) perovskites have emerged as a promising class of materials due to their remarkable photoluminescence efficiency, which stems from their exceptionally high exciton binding energies. The spatial confinement of excitons within smaller grain sizes could enhance the formation of biexcitons leading to higher radiative recombination efficiency. However, the synthesis of high-quality quasi-2D perovskite thin films with controllable grain sizes remains a challenging task. In this study, we present a facile method for achieving quasi-2D perovskite thin films with controllable grain sizes ranging from 500 to 900 nm. This is accomplished by intermediate phase engineering during the film fabrication process. Our results demonstrate that quasi-2D perovskite films with smaller grain sizes exhibit more efficient bound exciton generation and a reduced stimulated emission threshold down to 15.89 µJ cm−2. Furthermore, femtosecond transient absorption measurements reveal that the decay time of bound excitons is shorter in quasi-2D perovskites with smaller grain sizes compared to that of those with larger grains at the same pump density, which is 230.5 ps. This observation suggests a more efficient exciton recombination process in the smaller grain size regime. Our findings would offer a promising approach for the development of efficient bound exciton lasers.

Studying the effect of ambient temperature variations on perovskite precursor film formation using different antisolvents

This study investigates the sensitivity of two antisolvents to ambient temperature fluctuations during the fabrication of triple-cation perovskite thin films. Chlorobenzene (CB) and ethyl acetate (EA) were employed as antisolvents in the preparation of perovskite solar cells (PSCs) under identical ambient temperature variation conditions. The experimental results reveal that the quality of the perovskite films does not exhibit a consistent trend in response to ambient temperature changes depending on the antisolvent used. When CB was used as the antisolvent, the highest-performing device, produced at an ambient temperature of 18 °C, achieved a power conversion efficiency (PCE) of 19.9 %. In contrast, when EA was employed as the antisolvent, the highest-performing device was fabricated at 25 °C, reaching a PCE of 20.5 %. Furthermore, when the ambient temperature exceeded 30 °C, all films prepared with either antisolvent exhibited significant cracking, indicating that elevated temperatures adversely affect perovskite film formation. To further investigate the mechanism through which ambient temperature affects the film-forming process, antisolvents at varying temperatures were used during perovskite film preparation to simulate transient temperature increases during formation. This study reveals that the impact of ambient temperature variations on perovskite film formation does not exhibit a uniform trend but is significantly influenced by the choice of antisolvent. Moreover, this work offers valuable insights for optimizing the fabrication of high-quality perovskite thin films.

Controllable Crystallization of Perovskite Films during the Blade-Coating Fabrication Process for Efficient and Stable Solar Cells

The scalable production of high-quality perovskite thin films is pivotal for the industrialization of perovskite thin film solar cells. Consequently, the solvent system employed for the fabrication of large-area perovskite films via coating processes has attracted significant attention. In this study, a solvent system utilizing a volatile solvent as the primary reagent has been developed to facilitate the rapid nucleation of volatile compounds. While adding the liquid Lewis base dimethylformamide (DMF) can help to improve the microstructure of perovskite films, its slow volatilization renders the crystal growth process uncontrollable. Based on the solvent system containing DMF and ethanol (EtOH), introducing a small amount of NH4Cl increases the proportion of the intermediate phase in the precursor films. This not only results in a controllable growth process for the perovskite crystals but also contributes to the improvement of the film microstructure. Under the simulated illumination (AM1.5, 1000 W/m2), the photoelectric conversion efficiency (PCE) of the inverted solar cells has been improved to 20.12%. Furthermore, after 500 hours of continuous illumination, the photovoltaic device can retain 95.6 % of the initial, indicating that the solvent system is suitable for the scalable fabrication of high-quality FAPbI3 thin films.

Phosphate-based ionic liquids for advanced interface modification in perovskite photovoltaics: Novel insights for ionic liquid molecule design

Interface modification stands out as a crucial method to enhance the performance of perovskite solar cells. This study explores the utilization of the ionic liquid 1-Methyl-3-propylimidazolium phosphate (MPIMPH), containing phosphate (PO43−) groups, as a modifier for SnO2/perovskite interfaces. Detailed investigations delve into the specific impact of IL MPIMPH on defects in tin dioxide, perovskite defects, perovskite crystallization, morphology, and overall device performance. Initially, Density Functional Theory (DFT) is employed to evaluate the defect passivation potential of different anions on tin vacancies within the SnO2 matrix, revealing the exceptional defect passivation ability of the PO43− group. Chemical interactions between ILs MPIMPH and SnO2, as well as perovskite, are confirmed, establishing a fundamental basis for interface defect passivation. ILs-based interface modification enhances interface contact, influencing the lead iodide conversion into perovskite and perovskite crystallization, ultimately leading to the formation of high-quality perovskite thin films. ILs also effectively suppress interfacial charge recombination and optimize the energy alignment of the SnO2/perovskite interface to enhance carrier extraction. Benefiting from the interface modification with ILs, the optimized device achieved an impressive device efficiency of 24.24 % with remarkable durability. This work provides an novel aspect for designing ionic liquids to enhance interface modification, contributing to upscaling and application of perovskite photovoltaics.

Monolithically grown CSPbBr3 by chemical vapor deposition for Self-Powered photodetector

The high-quality monolithic growth of perovskite films with larger grains on any substrate is a challenging task due to the instability of morphology, carrier mobility and chemical stability. In this work, we demonstrated the strategy to grow CsPbBr3 films with micron-sized grains along the (002) surface by chemical vapor deposition. The structural and optical characterizations have shown that the as-grown CsPbBr3 thin films are compact and packed without pin holes and have excellent optical quality for use in high-performance optoelectronic devices. The planar photodetector with the device configuration Ag/CsPbBr3/Ag shows a high photoresponsivity of 506.32 A/W and a specific detectivity of 8.29 × 1012 Jones at an incident light illumination of 22.3 µW/cm2. On the other hand, the vertically stacked device with ITO/SnO2/CsPbBr3/CuSCN/Ag configuration exhibits a photoresponsivity of 10.13 A/W at 0.05 V bias and 96 mA/W under 0 V bias. Specifically, the response time of the device in planar geometry is 241/205 ms, while the vertically stacked device has a response time of 20.51/21 ms at 0.05 V bias and 20.51/30 ms at 0 V bias. The results provide a new strategy for the growth of high-quality perovskite thin films and their effective application for high-performance optoelectronic devices.

Thermally Evaporated Metal Halide Perovskites and Their Analogues: Film Fabrication, Applications and Beyond.

Metal halide perovskites emerge as promising semiconductors for optoelectronic devices due to ease of fabrication, attractive photophysical properties, their low cost, highly tunable material properties, and high performance. High-quality thin films of metal halide perovskites are the basis of most of these applications including solar cells, light-emitting diodes, photodetectors, and electronic memristors. A typical fabrication method for perovskite thin films is the solution method, which has several limitations in device reproducibility, adverse environmental impact, and utilization of raw materials. Thermal evaporation holds great promise in addressing these bottlenecks in fabricating high-quality halide perovskite thin films. It also has high compatibility with mass-production platforms that are well-established in industries. This review first introduces the basics of the thermal evaporation method with a particular focus on the critical parameters influencing the thin film deposition. The research progress of the fabrication of metal halide perovskite thin films is further summarized by different thermal evaporation approaches and their applications in solar cells and other optoelectronic devices. Finally, research challenges and future opportunities for both fundamental research and commercialization are discussed.

Crystallization Kinetics of Perovskite Films by a Green Mixture Antisolvent for Efficient NiOx-Based Inverted Solar Cells.

Environment-friendly antisolvents are critical for obtaining highly efficient, reproducible, and sustainable perovskite solar cells (PSCs). Here, we introduced a green mixture antisolvent of ethyl acetate-isopropanol (EA/IPA) to finely regulate the crystal grain growth and related film properties, including the morphology, crystal structure, and chemical composition of the perovskite thin film. The IPA with suitable content in EA plays a key role in achieving a smooth and compact high-quality perovskite thin film, leading to the suppression of film defect-induced nonradiative recombination. As a result, the PSCs based on the EA/IPA (5:1) antisolvent showed a power conversion efficiency of 22.9% with an open-circuit voltage of 1.17 V.

Fabricating Planar Perovskite Solar Cells through a Greener Approach.

High-quality perovskite thin films are typically produced via solvent engineering, which results in efficient perovskite solar cells (PSCs). Nevertheless, the use of hazardous solvents like precursor solvents (N-Methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), gamma-butyrolactone (GBL)) and antisolvents (chlorobenzene (CB), dibutyl ether (DEE), diethyl ether (Et2O), etc.) is crucial to the preparation of perovskite solutions and the control of perovskite thin film crystallization. The consumption of hazardous solvents poses an imminent threat to both the health of manufacturers and the environment. Consequently, before PSCs are commercialized, the current concerns about the toxicity of solvents must be addressed. In this study, we fabricated highly efficient planar PSCs using a novel, environmentally friendly method. Initially, we employed a greener solvent engineering approach that substituted the hazardous precursor solvents with an environmentally friendly solvent called triethyl phosphate (TEP). In the following stage, we fabricated perovskite thin films without the use of an antisolvent by employing a two-step procedure. Of all the greener techniques used to fabricate PSCs, the FTO/SnO2/MAFAPbI3/spiro-OMeTAD planar device configuration yielded the highest PCE of 20.98%. Therefore, this work addresses the toxicity of the solvents used in the perovskite film fabrication procedure and provides a promising universal method for producing PSCs with high efficiency. The aforementioned environmentally friendly approach might allow for PSC fabrication on an industrial scale in the future under sustainable conditions.

Strain-induced modulation of electronic structure in correlated Dirac semimetal Pv-CaIrO3 epitaxial thin films

Perovskite CaIrO3 is theoretically predicted to be a Dirac node semimetal near the Mott transition, which possesses a considerable interplay between electron correlations and spin–orbit coupling. Electron correlations can significantly tune the behavior of relativistic Dirac fermions. Here, we have grown high-quality perovskite CaIrO3 thin films on different substrates using oxide molecular beam epitaxy to modulate both electron correlations and Dirac electron states. Through in situ angle-resolved photoemission spectroscopy, we demonstrate a systematic evolution of the bandwidth and effective mass of Jeff=1/2 band in perovskite CaIrO3 induced by strain. The bandwidth of the Jeff=1/2 band undergoes an evident increase under in-plane compressive strain, which could be attributed to the weakening of electron correlations. The compressive strain can potentially shift the position of the Dirac node relative to the Fermi level and play a vital role in the transition from hole-type to electron-type transport characteristics. Our work provides a feasible approach for manipulating the topological Dirac electron states by engineering the strength of electron correlations.

Unlocking the potential of antisolvent-free perovskite solar cells: Modulating crystallization and intermediates through a binary volatile additive strategy

High-quality perovskite polycrystalline thin films are generally achieved through antisolvent-assisted crystallization, a crucial process that facilitates desolvation. However, antisolvent method is limited by issues of toxicity and fabrication complexity. Here, we introduce a “binary volatile additive” strategy using methylammonium chloride (MACl) and trifluoroacetamide (TFAA) in dimethylformamide/N-methyl-2-pyrrolidone co-solvent system, enabling end-to-end management of antisolvent-free crystallization process. Combining in-situ characterizations and DFT calculations, we prove that TFAA adjusts coordination with perovskite intermediates, facilitating solvent removal and promoting the formation of nuclei, while MACl reduces the formation energy of α-phase formamidinium-based perovskite. Moreover, TFAA not only releases the residual strain caused by MACl, but also in combination with MACl, synergistically widens crystallization window and regulates ripening process, allowing for precise fabrication of homogeneous perovskite films with suppressed defects. By employing the “binary volatile additive” approach, we achieve perovskite solar cells with a power conversion efficiency up to 22.4% and elongated storage life (93% PCE retention over 1000 hours). Our study offers a simple and sustainable approach to produce high-quality perovskite films without the acquisition of antisolvent, streamlining the fabrication process.

Enhancing grain growth of caesium-formamidinium-based lead halide perovskite thin films through PbI2 precursor engineering in vapor-solid reaction

Vapor-solid reaction methods are highly regarded as potential solutions for large-scale production of perovskite thin films due to their scalability, compatibility with silicon tandem technology, and lack of solvents. However, the limited penetration of organic vapor through the solid inorganic film results in a slow growth rate of perovskite, leading to poor crystallinity and small grain size. This high defect density in the grain boundaries hinders the enhancement of device performance. In this study, we used 1,3-diaminoguanidine monohydrochloride as an additive in the PbI2 precursor films, which effectively improved perovskite grain growth in the vapor-solid reaction process. After optimization, we achieved high-quality perovskite thin films with a large grain size exceeding 5 μm. Notably, solar devices based on these large-grain perovskite thin films achieved a high power conversion efficiency up to 21.13%.

Fabrication of high quality lead-free double perovskite Cs2AgBiBr6 thin film and its application in memristor with ultralow operation voltage

Recently, the lead-free double perovskite Cs2AgBiBr6 has been considered as a promising candidate for next-generation nonvolatile memory and artificial synapse devices due to its high stability and low toxicity compared to its lead-based counterparts. In this work, we developed a simple and effective method to produce high-quality lead-free double perovskite Cs2AgBiBr6 thin films without pinholes and particles by applying a low-pressure assisted method under ambient condition with a relative humidity (RH) of about 45%. The formation of pinholes and Ag precipitation in the perovskite Cs2AgBiBr6 films is effectively suppressed by the proper ratio of N,N-dimenthylformamide (DMF) mixed in dimethyl sulfoxide (DMSO) solvents. Furthermore, the grain size of the Cs2AgBiBr6 films can be significantly increased by increasing the post-annealing temperature. Finally, a sandwiched structure memristor with an ITO/Cs2AgBiBr6/Ta configuration was successfully demonstrated, featuring ultralow operation voltage (V Set ∼ 57 ± 23 mV, V Reset ∼ −692 ± 68 mV) and satisfactory memory window (the ratio of R HRS/R LRS ∼ 10 times), which makes it suitable for low-power consumption information storage devices.

Comprehensive interface engineering based on target anchoring agents for efficient and stable inverted perovskite solar cells

We propose a strategy that m-MTDATA into the PTAA/perovskite interface to enhance the wettability of PTAA and align energy levels of HTMs. PhABr is deposited onto perovskite surface to remove excessive residual PbI2 and compensates iodine vacancies.

Triple-junction perovskite-perovskite-silicon solar cells with power conversion efficiency of 24.4.

The recent tremendous progress in monolithic perovskite-based double-junction solar cells is just the start of a new era of ultra-high-efficiency multi-junction photovoltaics. We report on triple-junction perovskite-perovskite-silicon solar cells with a record power conversion efficiency of 24.4%. Optimizing the light management of each perovskite sub-cell (∼1.84 and ∼1.52 eV for top and middle cells, respectively), we maximize the current generation up to 11.6 mA cm-2. Key to this achievement was our development of a high-performance middle perovskite sub-cell, employing a stable pure-α-phase high-quality formamidinium lead iodide perovskite thin film (free of wrinkles, cracks, and pinholes). This enables a high open-circuit voltage of 2.84 V in a triple junction. Non-encapsulated triple-junction devices retain up to 96.6% of their initial efficiency if stored in the dark at 85 °C for 1081 h.

Epitaxial Growth of α-FAPbI3 at a Well-Matched Heterointerface for Efficient Perovskite Solar Cells and Solar Modules.

Although the FAPbI3 perovskite system exhibits an impressive optoelectronic characteristic and thermal stability because of its energetically unstable black phase at room temperature, it is considerably challenging to attain a controllable and oriented nucleation of α-FAPbI3 . To overcome this challenge, a 2D perovskite with a released inorganic octahedral distortion designed by weakening the hydrogen interactions between the organic interlayer and [PbI6 ]4- octahedron is presented in this study. A highly matched heterointerface can be formed between the (002) facet of the 2D structure and the (100) crystal plane of the cubic α-FAPbI3 , thereby lowering the crystallization energy and inducing a heterogeneous nucleation of α-FAPbI3 . This "epitaxial growth" mechanism results form the highly preferred crystallographic orientation of the (100) facets, improved crystal quality and film uniformity, substantially increased charge transporting characteristics, and suppressed nonradiative recombination losses. An impressive power conversion efficiency (PCE) of 25.4% (certified 25.2%) is achieved using target PSCs, which demonstrates outstanding ambient and operational stability. The feasibility of this strategy is proved for the scalable deposition of homogeneous and high-quality perovskite thin films by demonstrating the remarkably increased PCE of the large-area perovskite solar module, from 18.2% to 20.1%.

High-Quality Hybrid Perovskite Thin Films by Post-Treatment Technologies in Photovoltaic Applications.

Incredible progress in photovoltaic devices based on hybrid perovskite materials has been made in the past few decades, and a record-certified power conversion efficiency (PCE) of over 26% has been achieved in single-junction perovskite solar cells (PSCs). In the fabrication of high-efficiency PSCs, the postprocessing procedures toward perovskites are essential for designing high-quality perovskite thin films; developing efficient and reliable post-treatment techniques is very important to promote the progress of PSCs. Here, recent post-treatment technological reforms toward perovskite thin films are summarized, and the principal functions of the post-treatment strategies on the design of high-quality perovskite films have been thoroughly analyzed by dividing into two categories in this review: thermal annealing (TA)-related technique and TA-free technique. The latest research progress of the above two types of post-treatment techniques is summarized and discussed, focusing on the optimization of postprocessing conditions, the regulation of perovskite qualities, and the enhancement of device performance. Finally, an outlook of the prospect trends and future challenges for the fabrication of the perovskite layer and the production of highly efficient PSCs is given.

Self-sacrifice PbI2 seed layer-assisted crystal growth for improved perovskite thin films for efficient and stable transportation layer-free photodetectors

Recently, the growth of improved perovskite thin films with high crystallinity and low defects has been an important research subject owing to their critical roles in achieving efficient and stable optoelectronic devices. In this work, we introduced a self-sacrifice PbI2 seed layer to prepare improved CH3NH3PbI3 thin films with high crystallinity and reduced defects. It showed that the PbI2 seed layer at the buried interface acted as nuclei and modulated the crystal growth of CH3NH3PbI3, which induced the vertically upward growth of CH3NH3PbI3, resulting in increased sizes of grains and reduced grain boundaries. Further observations verified the suppression of defect and trap states in the obtained CH3NH3PbI3 thin films. On this basis, efficient and stable transportation layer-free Au/CH3NH3PbI3/indium tin oxide photodetectors have been demonstrated, where the responsivity and detectivity are as high as 0.54 A/W and 7.5 × 1012 Jones, respectively, at the bias of 0 V. It is supposed that the self-sacrifice PbI2 seed layer-assisted crystal growth method will find applications in fabricating high-quality and stable perovskite thin film devices in the future.

A Practical Approach Toward Highly Reproducible and High-Quality Perovskite Films Based on an Aging Treatment.

Solution processing of hybrid perovskite semiconductors is a highly promising approach for the fabrication of cost-effective electronic and optoelectronic devices. However, challenges with this approach lie in overcoming the controllability of the perovskite film morphology and the reproducibility of device efficiencies. Here, a facile and practical aging treatment (AT) strategy is reported to modulate the perovskite crystal growth to produce sufficiently high-quality perovskite thin films with improved homogeneity and full-coverage morphology. The resulting AT-films exhibit fewer defects, faster charge carrier transfer/extraction, and suppressed non-radiative recombination compared with reference. The AT-devices achieve a noticeable improvement in the reproducibility, operational stability, and photovoltaic performance of devices, with the average efficiency increased by 16%. It also demonstrates the feasibility and scalability of AT strategy in optimizing the film morphology and device performance for other perovskite components including MAPbI3 , (MAPbBr3 )15 (FAPbI3 )85 , and Cs0.05 (MAPbBr3 )0.17 (FAPbI3 )0.83 . This method opens an effective avenue to improve the quality of perovskite films and photovoltaic devices in a scalable and reproducible manner.

Synergistic Surface Defect Passivation of Ionic Liquids for Efficient and Stable MAPbI3-Based Inverted Perovskite Solar Cells.

Organic-inorganic hybrid perovskite solar cells are fabricated using polycrystalline perovskite thin films, which possess high densities of point and surface defects. The surface defects of perovskite thin films are the key factors that affect the device performance. Therefore, the reduction of harmful defects is the primary task for improving device performance. Therefore, in this study, high-quality perovskite thin films are prepared using an ionic liquid, dithiocarbamate diethylamine (DADA), to passivate the interface. The electron-rich sulfur atom in the DADA molecule chelates with the uncoordinated lead ion in the perovskite films, and the diethylammonium cation forms a hydrogen bond with the free iodine ion, which further improves the passivation. The synergistic passivation and improved morphology of the perovskite thin films substantially reduce the number of charged defects on the film surface and prolong the carrier lifetime. In addition, the DADA surface treatment increases the work function of the perovskite film, which is beneficial for carrier transport. Under standard solar-lighting conditions, the power conversion efficiency (PCE) of the device increases from 19.13 to 21.36%, and the fill factor is as high as 83.17%. Owing to both the hydrophobicity of DADA molecules and the passivation of ion defects, the PCE of the device remains above 80%, even for the device stored for 500 h in air at a relative humidity of 65%, and the device stability is substantially improved.

Investigations on the stability of the ambient processed bismuth based lead-free A3Bi2I9 (A = MA; Cs) perovskite thin-films for optoelectronic applications

Lead (Pb)-free bismuth (Bi) halide-based hybrid perovskites exhibit promising optoelectronic properties with low toxicity and air-stability. Fully ambient processed and high-quality perovskite thin-films are much desired for the industrialization of perovskite solar cells. So far, most of the lead-free perovskite halide thin films are processed and fabricated inside the glove box with ppm level atmosphere-controlled environment due to their poor stability. In this work, we report a one-step solution process employing solvent engineering to obtain highly crystalline and uniform (CH3NH3)3Bi2I9 (MBI) and Cs3Bi2I9 (CBI) perovskite thin-films prepared completely under ambient atmosphere. We further verified the stability of these MBI and CBI perovskite thin-films by exposing them to the ambient air with relative humidity and at room temperature for 180 days. The comparative structural, surface morphology and optical analysis of the samples show that bismuth halide perovskite can be an ideal candidate for fabrication in ambient atmosphere.