Advanced Raman Spectroscopy of Methylammonium Lead Iodide: Development of a Non-destructive Characterisation Methodology.
ABSTRACT: In recent years, there has been an impressively fast technological progress in the development of highly efficient lead halide perovskite solar cells. However, the stability of perovskite films and respective solar cells is still an open point of concern and calls for advanced characterization methods. In this work, we identify appropriate measurement conditions for a meaningful analysis of spin-coated absorber-grade perovskite thin films based on methylammonium (MA) lead iodide (MAPbI3) by Raman spectroscopy. The material under investigation and its derivates is the most commonly used for high efficiency devices in the literatures and has yielded working solar cell devices with efficiencies around 10% in our laboratory. We report highly detailed Raman spectra obtained with excitation at 532?nm and 633?nm and their deconvolution taking advantage of the simultaneous fitting of spectra obtained with varying excitation wavelengths. Finally, we propose a fast and contactless methodology based on Raman to probe composition variations and/or degradation of these perovskite thin films and discuss the potential of the presented technique as quality control and degradation monitoring tool in other organic-inorganic perovskite materials and complete solar cell devices.
Project description:The most studied perovskite-based solar cells reported up to date contain the toxic lead in its composition. Photovoltaic research and development towards non-toxic, lead-free perovskite solar cells are critical to finding alternatives to reduce human health concerns associated with them. Bismuth-based perovskite variants, especially in the form of methylammonium bismuth iodide (MBI), is a good candidate for the non-toxic light absorber. However, the reported perovskite variant MBI thin films prepared by the solution process so far suffers from poor morphology and surface coverage. In this work, we investigate for the first time the optoelectronic, crystallographic and morphological properties of MBI thin films prepared via thermal co-evaporation of MAI and BiI3. We find by modifying the precursor ratio that the layer with pure MBI composition lead to uniform, compact and homogeneous layers, broadening the options of deposition techniques for lead-free based perovskite solar cells.
Project description:We present a Raman study on the phase transitions of organic/inorganic hybrid perovskite materials, CH₃NH₃PbX₃ (X = I, Br), which are used as solar cells with high power conversion efficiency. The temperature dependence of the Raman bands of CH₃NH₃PbX₃ (X = I, Br) was measured in the temperature ranges of 290 to 100 K for CH₃NH₃PbBr₃ and 340 to 110 K for CH₃NH₃PbI₃. Broad ν₁ bands at ~326 cm-1 for MAPbBr₃ and at ~240 cm-1 for MAPbI₃ were assigned to the MA⁻PbX₃ cage vibrations. These bands exhibited anomalous temperature dependence, which was attributable to motional narrowing originating from fast changes between the orientational states of CH₃NH₃⁺ in the cage. Phase transitions were characterized by changes in the bandwidths and peak positions of the MA⁻cage vibration and some bands associated with the NH₃⁺ group.
Project description:Four solvents (isopropanol (IPA), n-butyl alcohol (NBA), n-amyl alcohol (NAA), and n-hexyl alcohol (NHA)) were investigated to prepare CH?NH?I (methylammonium iodide, MAI) solutions to transform PbI? film into CH?NH?PbI? (MAPbI?) film. It was found that the morphology of the perovskite MAPbI? film was not only affected by the chain of the solvent molecule, but also by the concentration of MAI. The use of solvents with a long alkyl chain (NAA and NHA) allowed the MAPbI? to grow via an in situ transformation step, which easily made the perovskite films compact, but with a high surface roughness due to the growth of unexpected nanorods/nanoplates. The solvent with a short alkyl chain (IPA) led to the dissolution-crystallization growth mechanism, resulting in rapid generation of perovskite films with a number of pinholes. A high-quality (compact, smooth, pinhole-free) perovskite film was obtained with NBA and an optimized MAI concentration of 8 mg/mL. The corresponding perovskite solar cells achieved a maximum power conversion efficiency (PCE) of 16.66% and average PCE of 14.76% (for 40 cells).
Project description:In recent years, hybrid organic-inorganic halide perovskites have been widely studied for the low-cost fabrication of a wide range of optoelectronic devices, including impressive perovskite-based solar cells. Amongst the key factors influencing the performance of these devices, recent efforts have focused on tailoring the granularity and microstructure of the perovskite films. Albeit, a cost-effective technique allowing to carefully control their microstructure in ambient environmental conditions has not been realized. We report on a solvent-antisolvent ambient processed CH3NH3PbI3-xClx based thin films using a simple and robust solvent engineering technique to achieve large grains (>5 µm) having excellent crystalline quality and surface coverage with very low pinhole density. Using optimized treatment (75% chlorobenzene and 25% ethanol), we achieve highly-compact perovskite films with 99.97% surface coverage to produce solar cells with power conversion efficiencies (PCEs) up-to 14.0%. In these planar solar cells, we find that the density and size of the pinholes are the dominant factors that affect their overall performances. This work provides a promising solvent treatment technique in ambient conditions and paves the way for further optimization of large area thin films and high performance perovskite solar cells.
Project description:Organic semiconductors are commonly used as charge-extraction layers in metal-halide perovskite solar cells. However, parasitic light absorption in the sun-facing front molecular layer, through which sun light must propagate before reaching the perovskite layer, may lower the power conversion efficiency of such devices. Here, we show that such losses may be eliminated through efficient excitation energy transfer from a photoexcited polymer layer to the underlying perovskite. Experimentally observed energy transfer between a range of different polymer films and a methylammonium lead iodide perovskite layer was used as basis for modelling the efficacy of the mechanism as a function of layer thickness, photoluminescence quantum efficiency and absorption coefficient of the organic polymer film. Our findings reveal that efficient energy transfer can be achieved for thin (?10 nm) organic charge-extraction layers exhibiting high photoluminescence quantum efficiency. We further explore how the morphology of such thin polymer layers may be affected by interface formation with the perovskite.
Project description:Solution-based methods represent the most widespread approach used to deposit hybrid organic-inorganic perovskite films for low-cost but efficient solar cells. However, solution-process techniques offer limited control over film morphology and crystallinity, and most importantly do not allow sequential film deposition to produce perovskite-perovskite heterostructures. Here the successful deposition of CH3NH3PbI3 (MAPI) thin films by RF-magnetron sputtering is reported, an industry-tested method to grow large area devices with precisely controlled stoichiometry. MAPI films are grown starting from a single-target made of CH3NH3I (MAI) and PbI2. Films are single-phase, with a barely detectable content of unreacted PbI2, full surface coverage and thickness ranging from less than 200?nm to more than 3 ?m. Light absorption and emission properties of the deposited films are comparable to as-grown solution-processed MAPI films. The development of vapor-phase deposition methods is of interest to advance perovskite photovoltaic devices with the possibility of fabricating perovskite multijunction solar cells or multicolor bright light-emitting devices in the whole visible spectrum.
Project description:Defects from grain interiors and boundaries of perovskite films cause significant nonradiative recombination energy loss, and thus perovskite films with controlled crystallinity and large grains is critical for improvement of both photovoltaic performance and stability for perovskite-based solar cells. Here, a methylamine (MA0) gas-assisted crystallization method is developed for fabrication of methylammonium lead iodide (MAPbI3) perovskite films. In the process, the perovskite film is formed via controlled release of MA0 gas molecules from a liquid intermediate phase MAPbI3·xMA0. The resulting perovskite film comprises millimeter-sized grains with (110)-uniaxial crystallographic orientation, exhibiting much low trap density, long carrier lifetime, and excellent environmental stability. The corresponding perovskite solar cell exhibits a power conversion efficiency (PCE) of ~ 21.36%, which is among the highest reported for MAPbI3-based devices. This method provides important progress towards the fabrication of high-quality perovskite thin films for low-cost, highly efficient and stable perovskite solar cells.
Project description:Reducing the spatial inhomogeneity of solution-processed, multicrystalline methylammonium lead iodide (MAPbI<sub>3</sub>) perovskite is of great importance for improving its power conversion efficiency, suppressing point-to-point deviations, and delaying degradation during operation. Various techniques, such as conducting-mode atomic force microscopy and photoluminescence mapping, have been applied for this intriguing class of materials, revealing nonuniform electronic properties on the nanometer-to-micrometer scale. Here, we designed a new space- and time-resolved microwave conductivity system that enables mapping of the transient photoconductivity with resolution greater than ?45 ?m. We examined the effects of the precursor concentration of MAPbI<sub>3</sub> and the mixing of halides (I<sup>-</sup> and Br<sup>-</sup>) on the charge carrier dynamics, crystal size, and inhomogeneity of the films. The optoelectronic inhomogeneity of MAPbI<sub>3</sub> and MAPb(I<sub>1-<i>x</i></sub> Br <i><sub>x</sub></i> )<sub>3</sub> on the sub-millimeter and millimeter scales shows a general correlation with their crystallite sizes, whereas the precursor concentration and halide mixing affect the inhomogeneity in a different way, providing a basis for uniform processing of a multicrystalline perovskite film.
Project description:Halide perovskites of the form ABX3 have shown outstanding properties for solar cells. The highest reported compositions consist of mixtures of A-site cations methylammonium (MA), formamidinium (FA) and cesium, and X-site iodide and bromide ions, and are produced by solution processing. However, it is unclear whether solution processing will yield sufficient spatial performance uniformity for large-scale photovoltaic modules or compatibility with deposition of multilayered tandem solar cell stacks. In addition, the volatile MA cation presents long-term stability issues. Here, we report the multisource vacuum deposition of FA0.7Cs0.3Pb(I0.9Br0.1)3 perovskite thin films with high-quality morphological, structural, and optoelectronic properties. We find that the controlled addition of excess PbI2 during the deposition is critical for achieving high performance and stability of the absorber material, and we fabricate p-i-n solar cells with stabilized power output of 18.2%. We also reveal the sensitivity of the deposition process to a range of parameters, including substrate, annealing temperature, evaporation rates, and source purity, providing a guide for further evaporation efforts. Our results demonstrate the enormous promise for MA-free perovskite solar cells employing industry-scalable multisource evaporation processes.
Project description:In this work, we report a physical deposition based, compact (cp) layer synthesis for planar heterojunction perovskite solar cells. Typical solution-based synthesis of cp layer for perovskite solar cells involves low-quality of thin films, high-temperature annealing, non-flexible devices, limitation of large-scale production and that the effects of the cp layer on carrier transport have not been fully understood. In this research, using radio frequency magnetron sputtering (RFMS), TiO2 cp layers were fabricated and the thickness could be controlled by deposition time; CH3NH3PbI3 films were prepared by evaporation &immersion (E &I) method, in which PbI2 films made by thermal evaporation technique were immersed in CH3NH3I solution. The devices exhibit power conversion efficiency (PCE) of 12.1% and the photovoltaic performance can maintain 77% of its initial PCE after 1440 h. The method developed in this study has the capability of fabricating large active area devices (40 × 40 mm(2)) showing a promising PCE of 4.8%. Low temperature and flexible devices were realized and a PCE of 8.9% was obtained on the PET/ITO substrates. These approaches could be used in thin film based solar cells which require high-quality films leading to reduced fabrication cost and improved device performance.