Open Access Article
Maurizio
Stefanelli
a,
Muhammed P. U.
Haris
b,
Luigi
Vesce
acd,
Luigi A.
Castriotta
a,
Hafez
Nikbakht
a,
Fabio
Matteocci
a,
Samrana
Kazim
bef,
Alessandro
Triolo
g,
Shahzada
Ahmad
*bf and
Aldo
Di Carlo
*ag
aCHOSE, Department of Electronic Engineering, University of Rome “Tor Vergata”, 00133 Rome, Italy. E-mail: aldo.dicarlo@uniroma2.it
bBCMaterials - Basque Center for Materials, Applications and Nanostructures, Martina Casiano, UPV/EHU Science Park, Leioa, 48940, Spain. E-mail: shahzada.ahmad@bcmaterials.net
cDepartment of Biomedicine and Prevention, University of Rome “Tor Vergata”, 00133 Rome, Italy
dDepartment of Physics, University of Rome “Tor Vergata”, 00133 Rome, Italy
eMaterials Physics Center, CSIC-UPV/EHU, Paseo Manuel de Lardizabal 5, 20018 Donostia-San Sebastian, Spain
fIKERBASQUE, Basque Foundation for Science, Bilbao, 48009, Spain
gISM-CNR, Consiglio Nazionale delle Ricerche, 00133 Rome, Italy
First published on 4th July 2025
Formamidinium lead iodide (FAPI) is the most prominent perovskite material utilized in the fabrication of single-junction perovskite solar cells. However, the cubic α-phase perovskite is difficult to retain in precursor solutions for extended periods due to thermodynamic instability, which promotes the formation of the yellow δ-phase. In this study, we demonstrate the fabrication of solar cells and modules from FAPI powders synthesised using a single-step method with a non-hazardous solvent and routine purity grade lead iodide. The pre-synthesised α-FAPI and CsFAPI powders demonstrated considerable potential for scalability and reproducibility. It was observed that similar efficiencies were achieved in small-area cells and mini-modules fabricated using an industrially adaptable blade coating process conducted in an open environment. The enhanced solution rheology and the meticulous control of stoichiometry result in an oriented and less strained crystal lattice, thereby demonstrating superior reproducibility and stability of the perovskite prepared from pre-synthesised powder in comparison to the one produced from high-purity precursor. The methodology developed offers a scalable and cost-effective approach to the production of high-performance and stable perovskite solar modules, with efficiencies reaching 18.5% on a 12.15 cm2 active area module and a T95 above 1200 h in shelf life stability at 30% RH in a UV-filtered environment.
Broader contextHalide Perovskite (PVSK) Photovoltaics (PV) are moving from laboratory to pilot/production lines. The success of this transition is based on the use of stable formulation of PVSK and scalable coating techniques preferably in ambient air. Despite big efforts in the scaling up of PVSK technology in the literature, few works faced module fabrication entirely in ambient air. Furthermore, high purity raw materials for PVSK precursor solution and manual handling of them are critical points for the fabrication costs and the reproducibility of the stock solutions. In this work, we show the scaling up of PSC technology by a double step meniscus coating process out of a glovebox with green antisolvent quenching. The entire stack till HTL (nip configuration) is made in ambient air and with scalable techniques. In addition, we make use of pre-synthesised cesium-containg FAPI powder obtained by a single step synthesis with green solvent at room temperature and with low-cost and purity lead iodide. According to our knowledge, this work presents the first FAPI powder made from low-cost lead iodide employed in a fully ambient air fabrication method. |
For these reasons, pre-synthesized pure α-FAPI or CsFAPI powders have demonstrated high potential in ensuring device stability and reproducibility as well as efficiency.15,16 The synthesis can be carried out in different solvent media, including 2-methoxyethanol, acetonitrile, or even in an aqueous solution with high yield (>90%).1,17–20 After the precipitation step, the powder is filtered, annealed at 150 °C, washed with orthogonal solvents (i.e. diethyl ether, chlorobenzene) and kept in a vacuum atmosphere to extract the solvent traces. The synthesised powder can be processed in a typical solvent mixture (DMF/DMSO, 2-ME/NMP) and employed as a perovskite precursor ink. It has been demonstrated that perovskite crystals/powders are superior for exact-stoichiometry perovskite films with lower defects, resulting in highly uniform and efficient perovskite solar cells exceeding 24% PCE.21 Furthermore, the precursor solution obtained from the powder exhibits a longer shelf-life than the standard one.15
The precise control of the stoichiometry of the powder methodology is reflected in higher reproducibility and performance compared to the raw precursor's counterpart, thereby demonstrating the benefits of obtaining FAPI powders from low-purity precursors (PbI2) without performance loss.22,23 This approach to FAPI synthesis, involving batch production from low-purity precursors without the need to weigh each one individually from batch to batch, is well suited to an industrial context thanks to its favourable balance of cost and efficiency. Furthermore, compositional engineering is paramount to push stability, and cesium incorporation can allow the formation of Cs-FAPI, which possesses higher stability according to the Goldschmidt tolerance factor.24 Enhanced operational and moisture stability are demonstrated as well as milder temperature to α-phase transition with respect to the cesium-free counterpart.18,19,21,24–27
In this context, pre-synthetized α-FAPI powder is emerging as a material for large area devices. Jiang et al. employed low-purity PbI2 precursor material to synthesize FAPbI3 in 2-methoxy ethanol solvent (2-ME) via inverse temperature crystallization and fabricated corresponding solar cells and mini-modules through spin-coating inside the glove box. The best-performing device measured an efficiency of 23.9% on small area devices and 19.5% on 13.44 cm2 mini-module active area.28 Moreover, the cells retained more than 95% of the initial power conversion efficiency (PCE) after 400 h of storage in shelf-life conditions. Further, Tong et al. proposed a method to avoid impurities from powder synthesis using hydroiodide acid, formamidiunium acetate, lead iodide, and γ-butyrolactone, and defect-less FAPI perovskite films were fabricated through solubility management. The best-performing spin-coated device displayed an efficiency of 23% and 16% for a small area and 22 cm2 active area module, respectively.17 Recently, Du et al. have emploied CsFAPI single crystals as perovskite precursors underlying the impact of colloids and volatile solvents for effective and homogeneous nucleation. The suppressed secondary nucleation and extended growth of crystals enable high throughput fabrication of full printed carbon-based devices in a controlled environment (RH < 5%) with an efficiency of 19.3% and 16.2% on a small area and 16.84 cm2 active area mini-module, respectively.29
FAPI powders are a promising material for module fabrication, but have only been used thus far in a controlled atmosphere within a glove box. There are currently no reports on the scaling up of this process to module size in ambient air. The objective of this work is to address this gap by demonstrating the fabrication of modules in ambient air using pre-synthesized powders. In order to achieve this objective, we have selected CsxFA1−xPbI3 perovskite powder (CsFAPI-pw), with a cesium content (x) of less than 10%, which has been synthesised with one-pot synthesis in a non-hazardous solvent with a yield >93%. We compared powders obtained with low-purity lead iodide sources and those from conventional high-purity precursors (CsFAPI-hp) used for small-area cells and mini-module fabrication. Here, all the layers (except for gold) in both small area (0.5 cm2 active area) and minimodules (12.5 cm2 active area) devices were deposited in ambient air by blade coating technique, with a commendable efficiency for small area (0.5 cm2) cells of 19.4% and 19.2% obtained from CsxFA1−xPbI3 pre-synthetized powder and conventional precursor route, respectively. The perovskite films obtained with the powder method exhibit superior performances in terms of efficiency, stability (ISOS-D1), and reproducibility. We then selected CsFAPI-pw for mini-module fabrication and the device measured 18.5% (less than 5% losses with respect to the small area cell) on a 12.5 cm2 active area.
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| Fig. 1 CsFAPI powder synthesis steps (a); black CsFAPI powder (b); process routine for CsFAPI perovskite deposition in ambient air with blade coating technique (c). | ||
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| Fig. 2 Particle size distribution for CsFAPI-hp (a) and CSFAPI-pw solution, and (b) measure by dynamic light scattering technique. | ||
To compare the quality of CsFAPI-pw to the CsFAPI-hp, we fabricated and characterized a small area (0.5 cm2 a.a.) PSCs and films coated on a 5 × 5 cm2 substrate, and were cut into four smaller pieces (2.5 × 2.5 cm2) prior to the thermal evaporation of the back electrode. The morphological analysis (Fig. 3) indicates that the CsFAPI-pw exhibits superior uniformity compared to the CsFAPI-hp. Micron-size grains are detected for CsFAPI-pw presenting a compact and pinholes-free (Fig. 3a and b) film due to the different crystallization profiles of nucleation rate and crystal growth. On the other hand, CsFAPI-hp shows smaller grains and the presence of unreacted PbI2 (Fig. 3c and d) that can compromise the film quality and stability over time. The X-ray diffraction (XRD) patterns for both CsFAPI films (Fig. 3e) show peaks at 2θ = 14° and 28°, which are indicative of perovskite orientation along (00h) facets that have been identified as the desired orientation for solar cell applications.38 It should be notice that lead iodide signal at 12.6° is still present for CsFAPI-pw even if there are not possible excess in the stoichiometry of the solution. The reason of that behave in the antisolvent quenching. Infact IPA it's a well know green antisolvent and recently integrated also as passivator additive in other antisolvent system (i.e. chlorobenzene) and eventually used as a washing step to provoke the 2D crystals reorganization on the surface of 3D perovskite.39–41 In this work bare IPA is used as antisolvent and of curse a large excess of IPA in the antisolvent system can produce some lead iodide39–42 that is treated and washed out with the passivation strategy with PEAI to form 2D perovskite and wash out the unreacted lead iodide as we already described in a previous work on passivation strategy.43
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| Fig. 3 SEM top view of CsFAPI-pw (a and b) and CsFAPI-hp (c and d) at lower and higher magnification, respectively; red circles in Fig. 2d highlight unreacted PbI2; XRD diffraction pattern of CsFAPI-hp and CsFAPI-pw deposited by blade coating on bare FTO (e). | ||
While the intensity of diffraction peaks is higher for the CsFAPI-pw as compared to CsFAPI-hp suggesting an enhanced crystallinity as well as a larger lattice constant as indicated by the shift toward lower 2θ in the diffractograms (Fig. 3e). In a previous work, we attributed the enhanced crystallinity of the powder-processed FAPbI3 films deposited by the spin coating technique, to their conventional counterpart to reduced microstrain.18 To assess the impact of the microstrain on the blade-coated thin films and to evaluate how it translates to large-scale fabrications, we performed a detailed analysis of the diffraction peaks employing the Williamson–Hall21 equation
![]() | (1) |
cos
θ as a function of 4
sin
θ, and the slope calculated from the linear fitting was estimated as the microstrains (Fig. S1†). We found that, besides the enhanced crystallinity, the CsFAPI-pw film displays a lower microstrain value of 6 × 10−4, while the conventional CsFAPI-hp counterpart shows a higher value of 6.54 × 10−4 (Fig. S1†). The reduced microstrain will induce long-term stability and the efficiency of CsFAPI-pw devices due to the impact of microstrain on structural stability, defect generation, charge carrier dynamics, and local disorder near the band edges.18,21,44,45
| V oc [V] | J sc [mA cm−2] | Fill factor [%] | PCE [%] | |
|---|---|---|---|---|
| CsFAPI-pw | 1.048 ± 0.004 | 23.000 ± 0.080 | 79.860 ± 0.079 | 19.141 ± 0.008 |
| CsFAPI-hp | 1.040 ± 0.007 | 22.800 ± 0.248 | 79.790 ± 0.902 | 18.304 ± 0.061 |
To investigate the improvement of average Voc in CsFAPI-pw concerning CsFAPI-hp and its relation with perovskite properties such as trap densities, we carried out space charge limit current (SCLC) and transient photoluminescence (TRPL) analyses to evaluate and compare the trap state densities of both perovskite films. SCLC measurements were carried out with an electron-only device architecture, namely FTO/SnO2/PVK/PCBM/Ag.46 The trap-filled limit (TFL) voltage (VTFL), (Fig. 5a), was determined from the change of slope between the ohmic region (n ≈ 1) and the TFL region (n > 2). CsFAPI-pw showed significantly reduced VTFL (0.233 V) for that of CsFAPI-hp (0.442 V). This proves the better quality of the film also in the bulk and it's reflected in the higher overall photovoltaic performances of the CsFAPI-pw devices. The trap state density (Ntrap) can be estimated with the following equation:47
![]() | (2) |
![]() | (3) |
![]() | (4) |
| Sample | A 1 | τ 1 [μs] | A 2 | τ 2 [μs] | τ ave [μs] | A 0 |
|---|---|---|---|---|---|---|
| CsFAPI-hp | 0.955 | 0.947 | 0.039 | 9.706 | 1.29 | 0.027 |
| CsFAPI-pw | 0.845 | 1.043 | 0.070 | 75.168 | 6.77 | 0.033 |
Assuming that τave is affected by the trap density and the corresponding lifetime of the free carriers generated into the film,49 is in agreement with SCLC analysis and with the higher peak of photoluminescence (performed on Glass/FTO/PVK sample, excitation wavelength 385 nm) on CsFAPI-pw with respect to the CsFAPI-hp (Fig. 5a–c).
Furthermore, we assess the shelf-life stability of both non-encapsulated perovskite devices performing ISOS-D1 at 30% RH in a UV-filtered environment.50 CsFAPI-hp-based perovskite shows a significant efficiency drop (Fig. 5d) in the first 100 hours and presents a large degradation trend starting from 600 hours with a reduction of 20% of initial efficiency (T80) of 1100 h. On the other hand, CsFAPI-pw based perovskite, which is characterized by a smooth and compact film with low defects and low content of unreacted species on its surface, can resist under 30% RH for more than 1200 hours, losing only less than 5% of its initial efficiency.
To further test the stability of the perovskite layer we conducted ISOS-L1 stability test in ambient air at 35/40 °C on encapsulated devices with UV-curable resin. The stack is (FTO/SnO2/PVK/PEAI/Spiro-OMeTAD/Au). As shown in the inset of Fig. 5d, the first drop in efficiency is visible for both perovskite formulations due to the burn-in effect and encapsulation process, which slightly decrease efficiency within the first 24 hours of light exposure.51,52 The CsFAPI-hp device reach the T80 only after 128 h of light exposure, as result of the poor crystallinity of the PVK film and the elevated lead iodide excess that affect the operational stability.53,54 In the CsFAPI-pw case, the stability is more than doubled (T80 = 317 h) respect to the CsFAPI-hp devices, highlighting the improved operational stability of the layer. Moreover, after 1000 h of test the CsFAPI-pw device lose a bit less than 40% of the initial efficiency where instead the CsFAPI-hp device efficiency dropped more than 80% respect the initial efficiency. PVK layer obtained from nano powder still suffers from the pinholes (smaller and in lower quantity, but stil present) into the PVK film as shown in the SEM top view images (Fig. 3a and b). The possible reasons of that can be found in the massive quantity of IPA used onto the supersaturated PVK film in the deposition process that extracts part of the formamidiunium that is highly soluble in alcoholic solvents.39,40,42 Should be pointed out that no additives are used in the PVK layer except for MACl that helps to stabilize the alpha phase in the deposition process.55 The stability obtained is in line with our previous work on PVK film obtained from powders with similar architecture18 but further improvements with antisolvent engineering and additives selection are needed to reach the optimal operational stability.
Based on the remarkable results obtained on small-area cells, we scale up the fabrication process used in small-area cells to realize mini-modules. Considering the improved reproducibility and stability for CsFAPI-hp, we focused only on the CsFAPI-pw perovskite for such a study. The mini-module has a total active area of 12.5 cm2 and a geometrical fill factor (GFF) of 93%, giving an aperture area of 13.44 cm2. P1–P2–P3 laser scribing scheme56 was adopted during the fabrication process to guarantee the series Z connection among the 5 sub-cells (2.5 cm2 active area each) of the mini-module. The SEM/EDX and the scheme of the P1–P2–P3 laser process are presented (Fig. 6a and b). The relative small signal of lead, carbon, iodine, and the strong signal from tin and oxygen inside P2/P3 etching lines from the EDX mapping confirmed the good quality of the laser process in the removal of the stack without damaging TCO. The best-performing mini-module (Fig. 6c) displayed a Voc of 1064 mV for each cell, 52 mA of current, 76% FF, and a PCE of 18,46% (17.17% on aperture area) in the reverse scan. For the forward scan, the PCE was slightly improved to 18.5% (17.2%). Negligible hysteresis and high reproducibility achieved in this process attest to the potential of our powder engineering strategy for module fabrication. The optimization of the P2 laser process contributed to the high-quality contact with the TCO (75% fill factor of), negligible hysteresis, and less than 5% efficiency difference with small area devices.43,48,57,58
We made preliminary cost estimations for the CsFAPI-pw and CsFAPI-hp, and the data referred to the material usage are normalized to 1 g of perovskite. In the case of CsFAPI-pw, the costs of the solvents are considered for the reaction (acetonitrile, ACN) and for washing the synthesized product (diethyl ether) (Tables S1 and S2†). With a rough estimation of the costs and a yield set at 100% for CsFAPI-hp as estimated, considering the “direct synthesis” during the deposition, and 93% for CsFAPI-pw (empirically determined by weighing the converted black FAPI powder and extracting the moles of product useful for the yield calculation molesproduct/molesreagents × 100), the overall costs for 1 g of perovskites is one fourth for CsFAPI-pw compared to the cost of CsFAPI-hp. This demonstrates the economic sustainability of the FAPI powder made from low-purity lead iodide, which can play a game-changer role in the manufacturing costs. Further, CsFAPI-pw can be produced in a batch production eliminating the need for multiple powder weighing and possible manual errors that can occur in the process and affect the stoichiometry of the solution and will promote reproducibility.
The next crucial phase for perovskite solar cell technology is the industrial production of solar modules. In this context, it is essential to prioritise the optimisation of fabrication costs, economic viability and environmental sustainability, alongside the enhancement of device performance. This work represents the inaugural demonstration of the utilisation of low-cost materials, batch production, green solvents (for synthesis and for the antisolvent step), and scalable techniques under ambient conditions, all of which are indispensable elements for the industrialisation of perovskite technology. The powder engineering approach, which employs ambient blade coating, offers a promising pathway to addressing these challenges. The reliability and sustainability of the processes are further reinforced through the use of green solvents for perovskite precursor synthesis (ACN) and antisolvent quenching (Isoprpanol, IPA), as well as the use of low-purity precursors (lead iodide) and ambient air fabrication methods.
Footnote |
| † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d5el00032g |
| This journal is © The Royal Society of Chemistry 2025 |