Methylammonium Lead Iodide Films Research Articles

Carbon monoxide induced self-doping in methylammonium lead iodide films and associated long-term degradation effects

Carbon monoxide interacts strongly with the MAPbI3film surface and can displace the adsorbed O2leading to loss of the organic moiety, accompanied by lowering of the work function and softening of the perovskite film due to formation of PbI2.

Efficient approach for optical and morphological characterization of hybrid perovskite films based on reflectance and transmittance measurements

Organo-inorganic perovskites (OIPs) have been intensively studied due to their potential application in low-cost, high-efficiency energy conversion in solar cells. Despite the great improvement in the quality of OIP films, wide dispersion in the same batch of perovskite-based devices remains an obstacle to obtaining highly reproducible results. For that reason, new and efficient strategies for testing deposition results is essential. Here we present a simple and efficient procedure for characterizing optical and morphological properties based on simultaneous reflectance and transmittance measurements under normal incidence over a methylammonium lead iodide film. The proposed method provides qualitative and quantitative morphological information associated with the film roughness as well as information about the position of the optical gap and possible contributions to optical dispersion in the structure that can be used as a simple diagnostic tool to optimize film deposition. Results are compared and validated with electronic and atomic force microscopy, as well as first-principles calculations.

Effect of Pristine Graphene on Methylammonium Lead Iodide Films and Implications on Solar Cell Performance

The relatively low stability of solar cells based on hybrid halide perovskites is the main issue to be solved for the implementation in real life of these extraordinary materials. Degradation is accelerated by temperature, moisture, oxygen, and light and mediated by halide easy hopping. The approach here is to incorporate pristine graphene, which is hydrophobic and impermeable to gases and likely limits ionic diffusion while maintaining adequate electronic conductivity. Low concentrations of few-layer graphene platelets (up to 24 × 10–3 wt %) were incorporated to MAPbI3 films for a detailed structural, optical, and transport study whose results are then used to fabricate solar cells with graphene-doped active layers. The lowest graphene content delays the degradation of films with time and light irradiation and leads to enhanced photovoltaic performance and stability of the solar cells, with relative improvement over devices without graphene of 15% in the power conversion efficiency, PCE. A higher graphene content further stabilizes the perovskite films but is detrimental for in-operation devices. A trade-off between the possible sealing effect of the perovskite grains by graphene, that limits ionic diffusion, and the reduction of the crystalline domain size that reduces electronic transport, and, especially, the detected increase of film porosity, that facilitates the access to atmospheric gases, is proposed to be at the origin of the observed trends. This work demonstrated how the synergy between these materials can help to develop cost-effective routes to overcome the stability barrier of metal halide perovskites, introducing active layer design strategies that allow commercialization to take off.

Surface electrical properties modulation by multimode polarizations inside hybrid perovskite films investigated through contact electrification effect

Surface electrical properties is of great significance for developing high-performance organic-inorganic hybrid perovskite based electronic devices. The photovoltage-induced ions transport and redistribution at the surface region have been well studied, but their contributions to the surface electrical properties are still lack of experimental evidences. In this article, a self-powered polymer-based contact electrification probe (PCE-probe) is proposed to investigate the photovoltage- or applied bias-induced ion transport polarization (PI) and ferroelectric polarization (PF) inside the methylammonium lead iodide films (MAPI). Results show that both the PI- and PF-induced ion transport and redistribution create a similar local ion-doping region near the surface. Positive or negative ion-doping produces a n-type or p-type layer, which enhances the interficial junction inside MAPI-based solar cells and benefits the seperation and transfer of photogenerated carriers or excitons. The PI and PF effects can be added up or subtracted from each other depending on the polarization configuration. A qualitative relationship between the PCE-probe output and CE-effect, PI- and PF-induced transferred surface charges is investigated. These results can help to understand the polarization nature inside and the high power conversion efficiency of MAPI-based photovoltaic devices, and provide a feasible analysis method of PCE-probe for detecting surface electrical properties.

Robust, High-Performing Maize-Perovskite-Based Solar Cells with Improved Stability.

Herein, we focus on improving the long-term chemical and thermomechanical stability of perovskite solar cells (PSCs), two major challenges currently limiting their commercial deployment. Our strategy incorporates a long-chain starch polymer into the perovskite precursor. The starch polymer confers multiple beneficial effects by forming hydrogen bonds with the methylammonium iodide precursor, templating perovskite growth that results in a compact and homogeneous film deposited in a simple one-step coating (antisolvent-free). The inclusion of starch in the methylammonium lead iodide films strongly improves their thermomechanical and environmental stability while maintaining a high photovoltaic performance. The fracture energy (Gc) of the film is increased to above 5 J/m2 by creating a nanocomposite that provides intrinsic reinforcement at grain boundaries. Additionally, improved optoelectronic properties achieved with the starch polymer enable good photostability of the active layer and enhanced resistance to thermal cycling.

Highly crystalline methylammonium lead iodide films: Phase transition from tetragonal to cubic structure by thermal annealing

Herein, a very simple, solvent free, scalable, and single-step approach to prepare organometal halide perovskite powders via mechanochemical synthesis followed by the deposition of perovskite films by spin coating is reported. This work particularly deals with various parameters that influence the crystallization process and morphology (hyperbranched) of methylammonium lead iodide films. Moreover, the influence of growth temperature on the morphology and the transition from tetragonal to cubic structure are investigated. The mechanosynthesized perovskite provides hyperbranched morphology and crystalline films in a hexagonal shape and serves as a better precursor for the absorber layer in perovskite solar cells.

Amorphous AlO6–SnO2 nanocomposite electron-selective layers yielding over 21% efficiency in ambient-air-processed MAPbI3-based planar solar cells

Despite intensive efforts to increase the power conversion efficiency (PCE) of perovskite solar cells (PSCs), the inevitable stress/strain that is occurred in devices and diverse defects generated during the solution process make achieving the theoretical limit of PSCs difficult. Herein, a novel AlO6–SnO2 nanocomposite electron-selective layer (ESL) is reported, where amorphous AlO6 is distributed uniformly in an amorphous SnO2 network film. Compared with a pristine-SnO2 ESL, an amorphous AlO6–SnO2 ESL increases the size of the perovskite grains achieving a low grain-boundary density, reduces the stress acting as an internal and interfacial nonradiative recombination pathway, exhibits high conductivity and fast charge extraction, and achieves an ideal band offset by upshifting the Fermi level. Through the synergistic multiple-passivation of the AlO6–SnO2 ESL, a PCE of 21.04% with a conventional ambient-air-processed methylammonium lead iodide film. In addition, the AlO6–SnO2-based PSCs exhibit improved stability and reduced hysteresis, making them promising materials for planar PSC applications.

Solution-Phase Halide Exchange and Targeted Annealing Kinetics in Lead Chloride Derived Hybrid Perovskites.

Hybrid perovskites are a promising class of materials for a range of optoelectronic applications. Many material properties are dictated by the details of the synthetic process, yet a mechanistic understanding is lacking for the majority of these materials. We have studied the formation of methylammonium lead iodide films derived from a lead chloride precursor to understand both the casting solution chemistry and its influence on the final, largely chlorine-free, film. Using solution-phase extended X-ray absorption spectroscopy, we observe a halide exchange with the primary solution plumbate species identified as PbI2.5Cl0.33. The mixed halide plumbate solution species leads to formation of the crystalline intermediate phase of (CH3NH3)2PbI3Cl. Using in situ synchrotron X-ray diffraction, we show that compositional control of the casting solution can control the annealing kinetics of film formation. Our study demonstrates the importance of solution-phase chemistry and its impact on lead halide perovskite synthesis.

Large-grain and smooth cesium doped CH3NH3PbI3 perovskite films by cesium iodide post-treatment for improved solar cells

Organic-inorganic hybrid perovskite solar cells have shown great prospect as a low-cost and high efficiency photovoltaic technology. The large grain and excellent surface morphology is most critical to obtain high performance perovskite solar cell. Here, a post-treatment method using Cesium iodide (CsI) solution is developed to improve the crystallization and morphology of the perovskite films. The solvent dissolves the small perovskite grains and the Cesium promote the large grain growth, which results in the increase in grain size from 270 nm to 650 nm and decrease in root-mean-square roughness from 15.8 nm to 8.6 nm. The decrease of defect states in the CsI treated methyl-ammonium lead iodide film is confirmed by the photoluminescence. Finally, the efficiency of the perovskite solar cells treated by 6 mg/ml CsI reached to 15.3%, which is 45.7% higher than that of the untreated device (10.5%).

Correction to “Surface Ligands for Methylammonium Lead Iodide Films: Surface Coverage, Energetics, and Photovoltaic Performance”

Correction to “Surface Ligands for Methylammonium Lead Iodide Films: Surface Coverage, Energetics, and Photovoltaic Performance”

Thermal assisted blade coating methylammonium lead iodide films with non-toxic solvent precursors for efficient perovskite solar cells and sub-module

Atmospheric thermal assisted blade coating (TABC) method, which is quick film crystallization and easier fabrication than the commonly used spin-coating process, to prepare a high quality CH3NH3PbI3 perovskite film is investigated in this work. Selection of the perovskite precursor solvents and controlling the ratio of the mixed solvent as well as substrate temperature for perovskite film formation are important factors in this TABC process. Based on the results obtained in this work, substrate temperature is the key factor for managing the perovskite film phase transition which influences the film roughness and crystallinity. Furthermore, the high-quality perovskite films are prepared by perovskite precursors with mixture of solvents containing GBL/DMSO at the ratio from 1/9 to 5/5. By using the optimum substrate temperature of 130 °C and the GBL/DMSO solvent ratio of 1/9 (G01D09) for the preparation of small area n-i-p and p-i-n PSCs as well as the p-i-n type perovskite sub-module, the power conversion efficiencies of 17.55%, 16.90% and 13.03%, respectively, are acquired under the illumination of 100 mW/cm2 (AM 1.5G).

Surface Ligands for Methylammonium Lead Iodide Films: Surface Coverage, Energetics, and Photovoltaic Performance

Surface ligand treatment provides a promising approach for passivating defect states, improving material and device stability, manipulating interfacial energetics, and improving the performance of ...

Interface limited hole extraction from methylammonium lead iodide films

A new method is proposed to determine charge diffusion coefficient and transfer velocity to extraction layers. Hole diffusion coefficient in MAPbI3 is constant between 1016 – 1017 cm−3, a hallmark of band transport but overall extraction is interface limited.

Influence of Grain Size on Phase Transitions in Halide Perovskite Films

AbstractGrain size in polycrystalline halide perovskite films is known to have an impact on the optoelectronic properties of the films, but its influence on their soft structural properties and phase transitions is unclear. Here, temperature‐dependent X‐ray diffraction, absorption, and macro‐ and micro‐photoluminescence measurements are used to investigate the tetragonal to orthorhombic phase transition in thin methylammonium lead iodide films with grain sizes ranging from the micrometer scale down to the tens of nanometer scale. It is shown that the phase transition nominally at ≈150 K is increasingly suppressed with decreasing grain size and, in the smallest grains, the first evidence of a phase transition is only seen at temperatures as low as ≈80 K. With decreasing grain size, an increasing magnitude of the hysteresis is also seen in the structural and optoelectronic properties when cooling to, and then upon heating from, 100 K. This work reveals the remarkable sensitivity of the optoelectronic, physical, and phase properties to the local environment of the perovskite structure, which will have large ramifications for phase and defect engineering in operating devices.

Ultrafast Carrier Dynamics of Dual Emissions from the Orthorhombic Phase in Methylammonium Lead Iodide Perovskites Revealed by Two-Dimensional Coherent Spectroscopy.

The fundamental understanding of photoexcitation landscape and dynamics in hybrid organic-inorganic perovskites is essential for improving their performance in solar cells and other applications. The dual emission features from the orthorhombic phase in perovskites have been the focus of numerous recent studies, and yet their underlying molecular origin remains elusive. We use optical two-dimensional coherent spectroscopy to study the carrier dynamics and coupling of the dual emissions in a methylammonium lead iodide film at 115 K. The two-dimensional spectra reveal an ultrafast redistribution of the photoexcited carriers into the two emission resonances within 250 fs. The high-energy resonance is a short-lived transient state, and the low-energy emission state interacts with coherent phonons. The observed carrier dynamics provide important experimental evidence that can be compared with potential theoretical models and contribute to the understanding of the dual emissions as well as the overall energy level structure in hybrid organic-inorganic perovskites.

Hydrophobic polythiophene hole-transport layers to address the moisture-induced decomposition problem of perovskite solar cells

Perovskite solar cells have emerged as one of the most promising next-generation photovoltaic technologies and have achieved a record power conversion efficiency of 22.7%. The technology meets industrial demands for cost effectiveness and scalability; however, the instability of lead halide perovskites toward moisture is a major barrier to their commercial development. Previous studies have revealed that the use of hydrophobic hole-transport layers (e.g., poly(3-hexylthiophene), P3HT) can slow the ingress of water vapor and improve the lifetime of the underlying perovskite, suggesting a route to longer lived devices. In this work, we report the synthesis of a variety of poly(3-alkoxythiophenes) with different side chains. The side chains range from hydrophilic (triethylene glycol methyl ether) to extremely hydrophobic (highly fluorinated hexyloxy). We evaluated the polymers, alongside commercially available P3HT, for their ability to stabilize methylammonium lead iodide films at high relative humidities. The fluorinated polythiophenes were able to substantially improve the perovskite lifetime, suggesting that more hydrophobic hole-transport layers may be a route to more stable perovskite solar cells.

Visualizing Nonradiative Mobile Defects in Organic–Inorganic Perovskite Materials

AbstractOrganic–inorganic perovskite materials have mobile charged point defects that migrate in response to voltage biasing and illumination, causing device performance variation over time. Improvements in device stability and reliability require methods to visualize point defect migration, estimate ionic mobilities, and identify factors influencing their migration. In this work, a versatile method is demonstrated to track nonradiative point defect migration in situ. Photoluminescence mapping of laterally biased perovskite films is used to track continuous changes in nonradiative recombination as charge‐trapping defects migrate between the device electrodes. A Monte Carlo framework of defect drift and diffusion is developed that is consistent with experimental photoluminescence observations, which combined enables point defect mobility estimation in methylammonium lead iodide films. Furthermore, measurements performed on materials with varied grain sizes demonstrate that point defect mobility is 1500× faster at grain boundaries compared to bulk. These findings imply that grain morphology can be used to tune point defect mobility such that large‐grained or single‐crystal materials inhibit point defect migration. The methods used in this work can be applied to visualize and quantify the migration of charge‐trapping point defects in a wide range of state‐of‐the‐art perovskite materials targeted toward reduced ionic mobilities and superior device stability.

Dimethylammonium Incorporation in Lead Acetate Based MAPbI3 Perovskite Solar Cells.

Over the last years, several different pathways have been suggested for producing perovskite thin films for solar cell applications. While the merit of these methods with respect to the solar cell efficiency have been shown, the actual composition of the resulting thin films is often not investigated. Here, we show that methylammonium lead iodide films produced using lead acetate as a lead source can have up to 15 % dimethylammonium incorporated into their crystal structure, even though this ion is often consider to be too large for incorporation. The origin of this ion lies in the precursor solution, where it is formed in a reaction that is facilitated by the basic character of the acetate ions. We further show that these dimethylammonium ions are incorporated in a random fashion throughout the crystal structure, owing to the lack of observable ordered domains.

Modulating Surface Morphology Related to Crystallization Speed of Perovskite Grain and Optical Semiconductor and Crystallization Properties of the Absorber Layer Under Controlled Doping of Potassium Ions for Solar Cells.

Perovskite thin films with excellent optical semiconductor and crystallization properties and superior surface morphology are normally considered to be vital to perovskite solar cells (PSCs). In this paper, we systematically survey the process of modulating surface morphology and optical semiconductor and crystallization properties of methylammonium lead iodide film by controlling doping of K+ for PSC prepared in air and propose the mechanism of large K+-doped perovskite grain formation related to crystallization speed. The increase in the crystallization speed leads to the production of large grains without localized-solvent-vapor (LSV) pores via moderate doping of K+, and the exorbitant crystallization speed induces super large grains with LSV pores via excessive doping of K+. Furthermore, the semiconductor properties (absorption band edge wavelength, PL emission peak wavelength, energy band gap) of perovskite film can be significantly tuned by controlled doping of K+. The investigation of the detailed process of modulating surface morphology and semiconductor properties of perovskite thin film by controlled doping of K+ may provide guidance and pave the way for superior component design of absorption materials for cost-efficient PSCs.

Breakdown of water super-permeation in electrically insulating graphene oxide films: role of dual interlayer spacing

Conventional graphene oxide (GO) is characterized by low sp2 content in a sp3 rich matrix, which is responsible both for electrical insulation and water super-permeation. Upon reduction, electrical conduction is achieved at the expense of water permeation ability. Here, we demonstrate that charge conduction and water permeation can be simultaneously restricted in a functionalized form of GO. Gravimetric studies reveal that diffusion of water vapor through a glassy polymer membrane is arrested by loading a hydrophobic form of GO (H-GO) in the polymer matrix, even as such, water inhibition cannot be realized by substantially increasing the thickness of the bare polymer. As an application, the ability of the coating to impede the degradation of methyl ammonium lead iodide films under high humidity conditions is demonstrated. At the same time the H-GO film has a resistance over 107 times higher when compared to thermally reduced GO of similar sp2 fraction. We attribute this unique behavior to the presence of a sub-micron matrix of GO with simultaneous presence of large (∼9.5 Å) and small (∼4.7 Å) interlayer spacing. This leads to disruption of the spatially distributed percolation pathways for electrical charge, and it also serves to block the nanocapillary networks for water molecules.