Fabio Matteocci

Solid-state solar modules based on mesoscopic organometal halide perovskite: a route towards the up-scaling process

We fabricated the first solid state modules based on organometal halide perovskite CH3NH3PbI3-xClx using Spiro-OMeTAD and poly(3-hexylthiophene) as hole transport materials. Device up-scaling was performed using innovative procedures to realize large-area cells and the integrated series-interconnections. The perovskite-based modules show a maximum conversion efficiency of 5.1% using both poly(3-hexylthiophene) and Spiro-OMeTAD. A long-term stability test was performed (in air, under AM1.5G, 1 Sun illumination conditions) using both materials showing different behaviour under continuous light stress. Whilst the poly(3-hexylthiophene)-based module efficiency drops by about 80% with respect to the initial value after 170 hours, the Spiro-based module shows a promising long-term stability maintaining more than 60% of its initial efficiency after 335 hours.

Vertical TiO2 Nanorods as a Medium for Stable and High-Efficiency Perovskite Solar Modules

Perovskite solar cells employing CH3NH3PbI3-xClx active layers show power conversion efficiency (PCE) as high as 20% in single cells and 13% in large area modules. However, their operational stability has often been limited due to degradation of the CH3NH3PbI3-xClx active layer. Here, we report a perovskite solar module (PSM, best and av. PCE 10.5 and 8.1%), employing solution-grown TiO2 nanorods (NRs) as the electron transport layer, which showed an increase in performance (∼5%) even after shelf-life investigation for 2500 h. A crucial issue on the module fabrication was the patterning of the TiO2 NRs, which was solved by interfacial engineering during the growth process and using an optimized laser pulse for patterning. A shelf-life comparison with PSMs built on TiO2 nanoparticles (NPs, best and av. PCE 7.9 and 5.5%) of similar thickness and on a compact TiO2 layer (CL, best and av. PCE 5.8 and 4.9%) shows, in contrast to that observed for NR PSMs, that PCE in NPs and CL PSMs dropped by ∼50 and ∼90%, respectively. This is due to the fact that the CH3NH3PbI3-xClx active layer shows superior phase stability when incorporated in devices with TiO2 NR scaffolds.

Interface and Composition Analysis on Perovskite Solar Cells

Organometal halide (hybrid) perovskite solar cells have been fabricated following four different deposition procedures and investigated in order to find correlations between the solar cell characteristics/performance and their structure and composition as determined by combining depth-resolved imaging with time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and analytical scanning transmission electron microscopy (STEM). The interface quality is found to be strongly affected by the perovskite deposition procedure, and in particular from the environment where the conversion of the starting precursors into the final perovskite is performed (air, nitrogen, or vacuum). The conversion efficiency of the precursors into the hybrid perovskite layer is compared between the different solar cells by looking at the ToF-SIMS intensities of the characteristic molecular fragments from the perovskite and the precursor materials. Energy dispersive X-ray spectroscopy in the STEM confirms the macroscopic ToF-SIMS findings and allows elemental mapping with nanometer resolution. Clear evidence for iodine diffusion has been observed and related to the fabrication procedure.

High-Efficiency Perovskite Solar Cell Based on Poly(3-Hexylthiophene): Influence of Molecular Weight and Mesoscopic Scaffold Layer

Here, we investigated the effect of the molecular weight (MW) of poly 3-hexylthiophene (P3HT) hole-transport material on the performance of perovskite solar cells (PSCs). We found that by increasing the MW the photovoltaic performances of the cells are enhanced leading to an improvement of the overall efficiency. P3HT-based PSCs with a MW of 124 kDa can achieve an overall average efficiency of 16.2 %, double with respect to the ones with a MW of 44 kDa. Opposite to spiro-OMeTAD-based PSCs, the photovoltaic parameters of the P3HT-based devices are enhanced by increasing the mesoporous TiO2 layer thickness from 250 to 500 nm. Moreover, for a titania scaffold layer thickness of 500 nm, the efficiency of P3HT-based PSCs with high MW is larger than the spiro-OMeTAD based PSCs with the same scaffold layer thickness. Recombination reactions of the devices were also investigated by voltage decay and electrochemical impedance spectroscopy. We found that the relationship between P3HT MW and cell performance is related to the reduction of charge recombination and to the increase of the P3HT light absorption by increasing the MW.

Elemental Mapping of Perovskite Solar Cells by Using Multivariate Analysis: An Insight into Degradation Processes

The technology of perovskite-based solar cells is evolving rapidly, reaching certified power conversion efficiency values now exceeding 20 %. One of the main drawbacks hindering progress in the field is the long-term stability of the cells: the mixed halide perovskites used in most devices are sensitive to humidity and degrade on a timescale varying from hours to weeks. The degradation mechanisms are poorly understood, but likely arise from combined physical and chemical modifications at the nanometer scale. The characterization of pristine and degraded materials is difficult owing to their complex chemical and physical structure and their relatively poor stability. In this work, we investigated the changes in local composition and morphology of a standard device after 2 months of air exposure in the dark, using scanning transmission electron microscopy (STEM) with nanometer resolution for imaging and analysis. Because of a state-of-the-art technique that combines STEM and energy dispersive X-ray spectroscopy (EDX), and the use of different decomposition algorithms for multivariate analysis, we highlighted the migration of elements across the interfaces between the layers comprising the device. We also noticed a morphological degradation of the hole-transporting layer (HTL), representing one of the main factors enabling the infiltration of moisture in the device, which results in reduced performance.

Laser-Patterning Engineering for Perovskite Solar Modules With 95% Aperture Ratio

Small area hybrid organometal halide perovskite based solar cells reached performances comparable to the multicrystalline silicon wafer cells. However, industrial applications require the scaling-up of devices to module-size. Here, we report the first fully laser-processed large area (14.5 cm2) perovskite solar module with an aperture ratio of 95% and a power conversion efficiency of 9.3%. To obtain this result, we carried out thorough analyses and optimization of three laser processing steps required to realize the serial interconnection of various cells. By analyzing the statistics of the fabricated modules, we show that the error committed over the projected interconnection dimensions is sufficiently low to permit even higher aperture ratios without additional efforts.

Fabrication and Characterization of Mesoscopic Perovskite Photodiodes

Mesoscopic photodiodes were fabricated with hybrid organic/inorganic perovskite as absorber layer and Spiro-OMeTAD as hole transport Layer. The perovskite layer was grown using a two-step deposition technique. Our photodiode in addition to a good rectification behavior (three orders of magnitude, range -1 to 1 V) shows a small noise current (<; 1 pA/(Hz)1/2), a high responsivity value (0.35 A/W) at 500 nanometers, and a good spectral response in the entire visible range. The Bode analysis shows a bandwidth of 108 KHz.

Efficient fully laser-patterned flexible perovskite modules and solar cells based on low-temperature solution-processed SnO 2 /mesoporous-TiO 2 electron transport layers

Efficient flexible perovskite solar cells and modules were developed using a combination of SnO2 and mesoporous-TiO2 as a fully solution-processed electron transport layer (ETL). Cells using such ETLs delivered a maximum power conversion efficiency (PCE) of 14.8%, which was 30% higher than the PCE of cells with only SnO2 as the ETL. The presence of a mesoporous TiO2 scaffold layer over SnO2 led to higher rectification ratios, lower series resistances, and higher shunt resistances. The cells were also evaluated under 200 and 400 lx artificial indoor illumination and found to deliver maximum power densities of 9.77 μW/cm2 (estimated PCE of 12.8%) and 19.2 μW/cm2 (estimated PCE of 13.3%), respectively, representing the highest values among flexible photovoltaic technologies reported so far. Furthermore, for the first time, a fully laser-patterned flexible perovskite module was fabricated using a complete three-step laser scribing procedure (P1, P2, P3) with a PCE of 8.8% over an active area of 12 cm2 under an illumination of 1 sun.

A crystal engineering approach for scalable perovskite solar cells and module fabrication: a full out of glove box procedure

In the present work we used some crystallization trends which could be classified as a Crystal Engineering (CE) approach, for deposition of a pure cubic-phase thin film of CH3NH3PbI3 (MAPbI3) on the surface of a mesoporous TiO2 layer. Accordingly, by using the CE approach, we fabricated high efficiency perovskite solar cells (PSCs) and perovskite solar modules (PSMs) utilizing several Hole Transport Layers (HTLs). We optimized the sequential deposition method, developing the entire realization procedure in air. The results show that the CE approach remarkably improved the device performance reaching a power conversion efficiency of 17%, 16.8% and 7% for spiro-OMeTAD, P3HT and HTL free (direct contact of the perovskite layer with the gold layer) PSCs, respectively. Furthermore, perovskite solar modules (active area of 10.1 cm2), which are fabricated by the CE approach, could reach an overall efficiency of 13% and 12.1% by using spiro-OMeTAD and P3HT as HTLs, respectively. The sealed modules showed promising results in terms of stability maintaining 70% of the initial efficiency after 350 hours of light soaking at the maximum power point.

Spray deposition of exfoliated MoS2 flakes as hole transport layer in perovskite-based photovoltaics

We propose the use of solution-processed molybdenum disulfide (MoS₂) flakes as hole transport layer (HTL) for metal-organic perovskite solar cells. MoS₂ bulk crystals are exfoliated in 2-propanol and deposited on perovskite layers by spray coating. We fabricated cells with glass/FTO/compact-TiO₂/mesoporous-TiO₂/CH₃NH₃PbI₃/spiro-OMeTAD/Au structure and cells with the same structure but with MoS₂ flakes as HTL instead of spiro-OMeTAD, the most widely used HTL. The electrical characterization of the cells with MoS₂ as HTL show promising power conversion efficiency -η- of 3.9% with respect to cells with pristine spiro-OMeTAD (η=3.1%). Endurance test on 800-hour shelf life has shown higher stability for the MoS₂-based cells (ΔPCE/PCE=-17%) with respect to the doped spiro-OMeTAD-based one (ΔPCE/PCE =-45%). Further improvements are expected with the optimization of the MoS₂ deposition process