Absence of Structural Impact of Noble Nanoparticles on P3HT: PCBM Blends for Plasmon Enhanced Bulk-Heterojunction Organic Solar Cells Probed by Synchrotron Grazing Incidence X-Ray Diffraction

The incorporation of noble metal nanoparticles, displaying localized surface plasmon resonance, in the active area of donor-acceptor bulk-heterojunction organic photovoltaic devices is an industrially compatible light trapping strategy, able to guarantee better absorption of the incident photons and give an efficiency improvement between 12% and 38%. In the present work, we investigate the effect of Au and Ag nanoparticles blended with P3HT: PCBM on the P3HT crystallization dynamics by synchrotron grazing incidence X-ray diffraction. We conclude that the presence of (1) 80nm Au, (2) mix of 5nm, 50nm, 80nm Au, (3) 40nm Ag, and (4) 10nm, 40nm, 60nm Ag colloidal nanoparticles, at different concentrations below 0.3 wt% in P3HT: PCBM blends, does not affect the behaviour of the blends themselves

Grain rotation and lattice deformation during perovskite spray coating and annealing probed in situ by GI-WAXS

We report for the first time on grain rotation in CH3NH3PbI3 perovskite films for ∼12% efficient planar solar cells and present a new method for investigating their texture evolution during thermal annealing. Our technique is based on in situ 2D grazing incidence wide-angle X-ray scattering (GI-WAXS) and employs a 10 keV wide-focussed X-ray beam to simultaneously probe a large number of grains. The ability to track the texture dynamics from a statistically relevant number of spots diffracting from single grains during thermal annealing and in grazing incidence geometry can have applications understanding the processing dynamics of a range of new materials

Monitoring the Formation of a CH<inf>3</inf>NH<inf>3</inf>PbI<inf>3-</inf><inf>x</inf>Cl<inf>x</inf> Perovskite during Thermal Annealing Using X-Ray Scattering

Grazing incidence wide and small angle X-ray scattering (GIWAXS and GISAXS) measurements have been used to study the crystallization kinetics of the organolead halide perovskite CH3NH3PbI3-xClx during thermal annealing. In situ GIWAXS measurements recorded during annealing are used to characterize and quantify the transition from a crystalline precursor to the perovskite structure. In situ GISAXS measurements indicate an evolution of crystallite sizes during annealing, with the number of crystallites having sizes between 30 and 400 nm increasing through the annealing process. Using ex situ scanning electron microscopy, this evolution in length scales is confirmed and a concurrent increase in film surface coverage is observed, a parameter crucial for efficient solar cell performance. A series of photovoltaic devices are then fabricated in which perovskite films have been annealed for different times, and variations in device performance are explained on the basis of X-ray scattering measurements

Impact of A-Site Cation Modification on Charge Transport Properties of Lead Halide Perovskite for Photovoltaics Applications

Perovskite solar cells (PSCs) have reached a formidable power conversion efficiency of 25.7% over the years of development. One of the strategies that has been responsible for the development of stable and highly efficient PSCs is modifications of the monovalent A-site cations (methylammonium, MA; formamidinium, FA; cesium, Cs, etc.) in lead halide perovskites. Herein, the impact of modifying the monovalent cation (MA, FAMA, CsFAMA, potassium-passivated CsFAMA, rubidium-passivated CsFAMA) in lead halide perovskite on their optoelectronic, charge transport, and photovoltaic behavior is systematically studied. Reduced trap density and improved charge carrier mobility after introduction of FA and Cs in the MAPb(I0.85Br0.15)3 system are confirmed. Further passivation of the triple-cation perovskite with K and Rb enhances the optoelectronic characteristics, charge transport, and charge extraction efficiency in halide perovskite solar cells

Degradation Kinetics of Inverted Perovskite Solar Cells

We explore the degradation behaviour under continuous illumination and direct oxygen exposure of inverted unencapsulated formamidinium(FA)0.83Cs0.17Pb(I0.8Br0.2)3, CH3NH3PbI3, and CH3NH3PbI3-xClx perovskite solar cells. We continuously test the devices in-situ and in-operando with current-voltage sweeps, transient photocurrent, and transient photovoltage measurements, and find that degradation in the CH3NH3PbI3-xClx solar cells due to oxygen exposure occurs over shorter timescales than FA0.83Cs0.17Pb(I0.8Br0.2)3 mixed-cation devices. We attribute these oxygen-induced losses in the power conversion efficiencies to the formation of electron traps within the perovskite photoactive layer. Our results highlight that the formamidinium-caesium mixed-cation perovskites are much less sensitive to oxygen-induced degradation than the methylammonium-based perovskite cells, and that further improvements in perovskite solar cell stability should focus on the mitigation of trap generation during ageing

Localized effect of PbI2 excess in perovskite solar cells probed by high-resolution chemical–optoelectronic mapping

We report the laser irradiation of CH3NH3PbI3 solar cells to generate and control localized PbI2 degradation product. We show that by tuning the laser power and illumination time, we can controllably form a local excess of PbI2. High-resolution advanced multi-mapping techniques are used to highlight the effect of PbI2 on the photophysical and photoelectrical properties in a complete perovskite device. Whereas a thick PbI2 film at the perovskite/hole transport layer interface has a detrimental effect on the photocurrent and photoluminescence, a thin PbI2 film (<20 nm) leads to a significant photocurrent increase, which is ascribed to the passivation of non-radiative defects and reduced charge recombination at the interface. Our findings reveal that laser irradiation is a new approach to understand the effect of PbI2 surface layers and potentially offers a means to passivate trap states and improve PV properties of perovskite devices

EFM data mapped into 2D images of tip-sample contact potential difference and capacitance second derivative

We report a simple technique for mapping Electrostatic Force Microscopy (EFM) bias sweep data into 2D images. The method allows simultaneous probing, in the same scanning area, of the contact potential difference and the second derivative of the capacitance between tip and sample, along with the height information. The only required equipment consists of a microscope with lift-mode EFM capable of phase shift detection. We designate this approach as Scanning Probe Potential Electrostatic Force Microscopy (SPP-EFM). An open-source MATLAB Graphical User Interface (GUI) for images acquisition, processing and analysis has been developed. The technique is tested with Indium Tin Oxide (ITO) and with poly(3-hexylthiophene) (P3HT) nanowires for organic transistor applications

Lattice strain causes non-radiative losses in halide perovskites

Halide perovskites are found to exhibit strain patterns over large areas, which influences the lifetimes of charge carriers.EPSR

Local Strain Heterogeneity Influences the Optoelectronic Properties of Halide Perovskites

Halide perovskites are promising semiconductors for optoelectronics, yet thin films show substantial microscale heterogeneity. Understanding the origins of these variations is essential for mitigating parasitic losses such as non-radiative decay. Here, we probe the structural and chemical origins of the heterogeneity by utilizing scanning X-ray diffraction beamlines at two different synchrotrons combined with high-resolution transmission electron microscopy to spatially characterize the crystallographic properties of individual micrometer-sized perovskite grains in high-quality films. We reveal new levels of heterogeneity on the ten-micrometer scale (super-grains) and even ten-nanometer scale (sub-grain domains). By directly correlating these properties with their corresponding local time-resolved photoluminescence properties, we find that regions showing the greatest luminescence losses correspond to strained regions, which arise from enhanced defect concentrations. Our work reveals remarkably complex heterogeneity across multiple length scales, shedding new light on the defect tolerance of perovskites