Residual PbI2 Research Articles

Understanding perovskite formation through the intramolecular exchange method in ambient conditions

Among the methods to prepare hybrid organic–inorganic perovskite films, the intramolecular exchange method was the first one that made possible to prepare perovskite solar cells with efficiencies higher than 20%. However, perovskite formation by this method is not completely understood, especially in ambient conditions. In this work, perovskite films were prepared by the intramolecular exchange method in ambient conditions. The spin coating speed and the frequency of the MAI solution dripping onto PbI2(DMSO) were varied during the deposition steps. With the combination of these two parameters, a rigid control of the solvent drying was possible. Thus, depending on the chosen conditions, the intermediate (MA)2Pb3I8·2DMSO was formed with residual PbI2. Otherwise, direct formation of perovskite film was attained. A mechanism for the direct formation of bulk perovskite was proposed. We also investigated how the posterior thermal annealing affects the crystallinity and defects in perovskite films. With prolonged thermal annealing, the excess of MAI can be avoided, increasing the efficiency and decreasing the hysteresis of the solar cells. The best perovskite solar cell achieved a stabilized power output of 12.9%. The findings of this work pave the way for realizing the fabrication of efficient perovskite solar cells in ambient atmosphere, a very desirable condition for cost-efficient large scale manufacturing of this technology.

Solvent vapor annealing of oriented PbI2 films for improved crystallization of perovskite films in the air

The photovoltaic performance of perovskite solar cells is extremely dependent on the crystallization and morphology of the perovskite film, which are affected by the deposition method. Here, we demonstrate a simple approach to form a microporous PbI2 film, with subsequent conversion to a compact, highly crystalline perovskite film. The PbI2 and corresponding perovskite films were further probed by two-dimensional X-ray diffraction. The resultant perovskite exhibited improved photovoltaic performance under ambient conditions with about 50% humidity. The PbI2 microporous structure was formed by exchanging residual DMSO with DMF vapor in the PbI2 film, which facilitated contact with the methylammonium iodide (MAI) solution. The process resulted in the formation of compact, smooth, pinhole-free perovskite films having no residual PbI2. Solar cells fabricated using this methodology exhibited power conversion efficiencies over 16% with negligible photocurrent hysteresis.

Adverse Effects of Excess Residual PbI2 on Photovoltaic Performance, Charge Separation, and Trap-State Properties in Mesoporous Structured Perovskite Solar Cells.

Organic-inorganic halide perovskite solar cells have rapidly come to prominence in the photovoltaic field. In this context, CH3 NH3 PbI3 , as the most widely adopted active layer, has been attracting great attention. Generally, in a CH3 NH3 PbI3 layer, unreacted PbI2 inevitably coexists with the perovskite crystals, especially following a two-step fabrication process. There appears to be a consensus that an appropriate amount of unreacted PbI2 is beneficial to the overall photovoltaic performance of a device, the only disadvantageous aspect of excess residual PbI2 being viewed as its insulating nature. However, the further development of such perovskite-based devices requires a deeper understanding of the role of residual PbI2 . In this work, PbI2 -enriched and PbI2 -controlled perovskite films, as two extreme cases, have been prepared by modulating the crystallinity of a pre-deposited PbI2 film. The effects of excess residual PbI2 have been elucidated on the basis of spectroscopic and optoelectronic studies. The initial charge separation, the trap-state density, and the trap-state distribution have all been found to be adversely affected in PbI2 -enriched devices, to the detriment of photovoltaic performance. This leads to a biphasic recombination process and accelerates the charge carrier recombination dynamics.

Improved Reproducibility for Perovskite Solar Cells with 1 cm2 Active Area by a Modified Two-Step Process.

With rapid progress in recent years, organohalide perovskite solar cells (PSC) are promising candidates for a new generation of highly efficient thin-film photovoltaic technologies, for which up-scaling is an essential step toward commercialization. In this work, we propose a modified two-step method to deposit the CH3NH3PbI3 (MAPbI3) perovskite film that improves the uniformity, photovoltaic performance, and repeatability of large-area perovskite solar cells. This method is based on the commonly used two-step method, with one additional process involving treating the perovskite film with concentrated methylammonium iodide (MAI) solution. This additional treatment is proved to be helpful for tailoring the residual PbI2 level to an optimal range that is favorable for both optical absorption and inhibition of recombination. Scanning electron microscopy and photoluminescence image analysis further reveal that, compared to the standard two-step and one-step methods, this method is very robust for achieving uniform and pinhole-free large-area films. This is validated by the photovoltaic performance of the prototype devices with an active area of 1 cm2, where we achieved the champion efficiency of ∼14.5% and an average efficiency of ∼13.5%, with excellent reproducibility.

High-efficiency perovskite solar cells prepared by using a sandwich structure MAI-PbI2-MAI precursor film.

Two-step deposition has been widely used in the perovskite layer preparation for perovskite solar cells due to its attractive morphology controllability. However, the limited diffusivity of CH3NH3I (MAI) might cause some PbI2 to remain in the perovskite film. The residual PbI2 in the perovskite film would lead to inferior performance of devices, such as, low power conversion efficiency (PCE), poor reproducibility and weak air stability. In this work, we developed a sandwich structure MAI-PbI2-MAI precursor film to prepare a PbI2-free CH3NH3PbI3 perovskite film. In comparison to the two-step approach, the MAI-PbI2-MAI precursor film with a typical sandwich structure formed a uniform and pinhole-free perovskite film without any PbI2 residue, which could significantly improve the performance of the devices. Moreover, the bottom MAI layer of the MAI-PbI2-MAI precursor film could improve the interfacial contact of the porous TiO2 layer, leading to the promotion of the charge transfer and reduction of the recombination rate. Therefore, the devices fabricated from the sandwich structure MAI-PbI2-MAI precursor films showed dramatic improvements of open-circuit voltage (Voc), short-circuit current density (Jsc), fill factor (FF) and PCE. As a result, a promising PCE of 17.8% with good long-term air stability was achieved for the MAI-PbI2-MAI precursor film based PSC, which is better than that prepared by a two-step approach.

Investigation into the Advantages of Pure Perovskite Film without PbI2 for High Performance Solar Cell.

In CH3NH3PbI3-based high efficiency perovskite solar cells (PSCs), tiny amount of PbI2 impurity was often found with the perovskite crystal. However, for two-step solution process-based perovskite films, most of findings have been based on the films having different morphologies between with and without PbI2. This was mainly due to the inferior morphology of pure perovskite film without PbI2, inevitably produced when the remaining PbI2 forced to be converted to perovskite, so advantages of pure perovskite photoactive layer without PbI2 impurity have been overlooked. In this work, we designed a printing-based two-step process, which could not only generate pure perovskite crystal without PbI2, but also provide uniform and full surface coverage perovskite film, of which nanoscale morphology was comparable to that prepared by conventional two-step solution process having residual PbI2. Our results showed that, in two-step solution process-based PSC, pure perovskite had better photon absorption and longer carrier lifetime, leading to superior photocurrent generation with higher power conversion efficiency. Furthermore, this process was further applicable to prepare mixed phase pure perovskite crystal without PbI2 impurity, and we showed that the additional merits such as extended absorption to longer wavelength, increased carrier lifetime and reduced carrier recombination could be secured.

Perspective: Understanding of ripening growth model for minimum residual PbI2 and its limitation in the planar perovskite solar cells

The power conversion efficiency of lead halide perovskite solar cells recently surpassed 22.1%. In this study, we suggest the perovskite absorber growth mechanism of the two-step process could be explained by an Ostwald ripening growth model for planar-structure perovskite solar cells. We attempt to find out the source of two main problems such as unreacted PbI2 and non-uniformed morphology by the proposed ripening growth mechanism and experimental results. This growth mechanism opens the way toward understanding a key aspect of the photovoltaic operation of high-efficiency, two-step perovskite solar cells.

Effect of PbI2 deposition rate on two-step PVD/CVD all-vacuum prepared perovskite

In this work we fabricate all-vacuum processed methyl ammonium lead halide perovskite by a sequence of physical vapour deposition of PbI2 and chemical vapour deposition (CVD) of CH3NH3I under a static atmosphere. We demonstrate that for higher deposition rate the (001) planes of PbI2 film show a higher degree of alignment parallel to the sample's surface. From X-ray diffraction data of the resulted perovskite film we derive that the intercalation rate of CH3NH3I is fostered for PbI2 films with higher degree of (001) planes alignment. The stoichiometry of the produced perovskite film is also studied by Hard X-ray photoelectron spectroscopy measurements. Complete all-vacuum perovskite solar cells were fabricated on glass/ITO substrates coated by an ultra-thin (5nm) Zn-phthalocyanine film as hole selective layer. A dependence of residual PbI2 on the solar cells performance is displayed, while photovoltaic devices with efficiency up to η=11.6% were achieved.

Efficiency enhancement of perovskite solar cells by fabricating as-prepared film before sequential spin-coating procedure

Sequential spin-coating procedure is a widely adopted strategy to prepare CH3NH3PbI3 on mesostructured TiO2 electrode for organolead halide perovskite-based solar cells. However, this method suffers from the rough surface and excessively residual PbI2 in the resulting perovskite film, deteriorating the device performance seriously. Herein, a facial modified sequential solution deposition method, by introducing an as-prepared CH3NH3PbI3 and PbI2 film before the traditional two-step process, was proposed to fabricate the perovskite-based solar cell with smooth morphology and trace amount of remaining PbI2. The optimal as-prepared film introduced improves the efficiency of CH3NH3PbI3 solar cells from 9.11% to 11.16%. The enhancement of device performance can be attributed to the increased light absorption ability and decreased recombination rate of carriers in CH3NH3PbI3 absorber.

High quality perovskite films fabricated from Lewis acid–base adduct through molecular exchange

High quality CH3NH3PbI3 perovskite films without residual PbI2 are fabricated from the Lewis adduct of PbI2·xDMF through molecular exchange. The photovoltaic performances of the perovskite solar cells are thus improved significantly.

Improvement of CH₃NH₃PbI₃ Formation for Efficient and Better Reproducible Mesoscopic Perovskite Solar Cells.

High-performance perovskite solar cells (PSCs) are obtained through optimization of the formation of CH3NH3PbI3 nanocrystals on mesoporous TiO2 film, using a two-step sequential deposition process by first spin-coating a PbI2 film and then submerging it into CH3NH3I solution for perovskite conversion (PbI2 + CH3NH3I → CH3NH3PbI3). It is found that the PbI2 morphology from different film formation process (thermal drying, solvent extraction, and as-deposited) has a profound effect on the CH3NH3PbI3 active layer formation and its nanocrystalline composition. The residual PbI2 in the active layer contributes to substantial photocurrent losses, thus resulting in low and inconsistent PSC performances. The PbI2 film dried by solvent extraction shows enhanced CH3NH3PbI3 conversion as the loosely packed disk-like PbI2 crystals allow better CH3NH3I penetration and reaction in comparison to the multicrystal aggregates that are commonly obtained in the thermally dried PbI2 film. The as-deposited PbI2 wet film, without any further drying, exhibits complete conversion to CH3NH3PbI3 in MAI solution. The resulting PSCs reveal high power conversion efficiency of 15.60% with a batch-to-batch consistency of 14.60 ± 0.55%, whereas a lower efficiency of 13.80% with a poorer consistency of 11.20 ± 3.10% are obtained from the PSCs using thermally dried PbI2 films.

Improving the efficiency of perovskite solar cells through optimization of the CH3NH3PbI3 film growth in solution process method

Perovskite-structured organic–inorganic materials such as CH3NH3PbI3 are attracting much interest in the scientific community because of their abilities to function as revolutionary light harvesters and charge transfer materials for solar cells. To achieve high power conversion efficiency (PCE), it is critical to optimize the perovskite film layer. This paper reports the temperature and concentration controls on the two-step solution process. A diffusion-controlled growth mechanism is proposed for this process in tuning the morphology and purity of the perovskite film, which are proven to be important factors contributing to the photovoltaic performance. The highest PCE of 11.92% is achieved with an optimized perovskite crystal size of ∼150nm and an appropriate amount of residual PbI2. This study sheds light on the design and fabrication of highly efficient, low-cost, solution-processed perovskite solar cells.

Controlled growth of PbI2 nanoplates for rapid preparation of CH3NH3PbI3 in planar perovskite solar cells

Absorbers for planar perovskite solar cells are often prepared by two‐step deposition methods, where a thick compact PbI2 layer is deposited followed by conversion to perovskite using CH3NH3I solution. The surface of the precursor layer quickly reacts with the CH3NH3I solution, which hinders further diffusion of CH3NH3I into the layer, consequently leading to significant amounts of residual PbI2 at room temperature. Here, we report a novel concept that employs a porous nanostructured PbI2 layer consisting of nanoplates to rapidly prepare single phase perovskite layer. The non‐compact nanoplate morphology is achieved in a controllable manner by thermal evaporation of PbI2 on TiO2‐coated FTO substrate and allows easy penetration of CH3NH3I solution into the whole PbI2 layer, thus facilitating fast and complete conversion. The amount of PbI2 residual can be controlled by varying the CH3NH3I concentration. The growth of the nanoplates is governed by the intrinsic crystallographic structure of the deposited material, crystal characteristics of the underlying substrate, and deposition method. The introduced process enables planar perovskite solar cells with efficiency of 8.6% measured at maximum power point. This work opens a new route for rapid preparation of other three‐dimensional organic–inorganic hybrid perovskites by rational tailoring the metal halide morphology.

Enhanced Performance of Perovskite CH3NH3PbI3Solar Cell by Using CH3NH3I as Additive in Sequential Deposition

Sequential deposition is a widely adopted method to prepare CH3NH3PbI3 on mesostructured TiO2 electrode for organic lead halide perovskite solar cells. However, this method often suffers from the uncontrollable crystal size, surface morphology, and residual PbI2 in the resulting CH3NH3PbI3, which are all detrimental to the device performance. We herein present an optimized sequential solution deposition method by introducing different amount of CH3NH3I in PbI2 precursor solution in the first step to prepare CH3NH3PbI3 absorber on mesoporous TiO2 substrates. The addition of CH3NH3I in PbI2 precursor solution can affect the crystallization and composition of PbI2 raw films, resulting in the variation of UV-vis absorption and surface morphology. Proper addition of CH3NH3I not only enhances the absorption but also improves the efficiency of CH3NH3PbI3 solar cells from 11.13% to 13.37%. Photoluminescence spectra suggest that the improvement of device performance is attributed to the decrease of recombination rate of carriers in CH3NH3PbI3 absorber. This current method provides a highly repeatable route for enhancing the efficiency of CH3NH3PbI3 solar cell in the sequential solution deposition method.