DRop-on demand flexible Optoelectronics & Photovoltaics by means of Lead-Free halide perovskITes

Project Information

DROP-IT

Grant agreement ID: 862656

DOI

10.3030/862656

Project closed

EC signature date 30 August 2019

Start date 1 November 2019

End date 30 April 2023

Funded under

• EXCELLENT SCIENCE - Future and Emerging Technologies (FET)

Total cost

€ 3 461 345,00

EU contribution

€ 3 461 344,00

Coordinated by

UNIVERSITAT DE VALENCIA
Spain

Periodic Reporting for period 3 - DROP-IT (DRop-on demand flexible Optoelectronics & Photovoltaics by means of Lead-Free halide perovskITes)

Reporting period: 2021-11-01 to 2023-04-30

Summary of the context and overall objectives of the project

DROP-IT proposes a drop-on demand inkjet technology platform of novel lead-free metal halide perovskites (LFPs) on flexible substrates, as the most promising route to revolutionize the fields of printed flexible photovoltaics, optoelectronics & photonics (Fig. 1).
DROP-IT proposes four main objectives:
1) Synthesis of LFPs in the form of nanoparticles and polycrystalline films: a theoretical screening of novel LFP compounds.
2) Formulation of suitable inks of LFPs and adequate charge transport layers.
3) Inkjet printing and processing of LFPs as thin films in different configurations for optimizing optoelectronic properties.
4) Validation of the technology by three proofs of concept in photovoltaics and integrated optoelectronics & photonics.

Work performed from the beginning of the project to the end of the period covered by the report and main results achieved so far

Along the project we have proposed and tested many perovskite materials. We focused on several of them:
(1) 2D/3D perovskite compounds (R0.5,BA0.5)2FA9Sn10I31 with R = PEA, TEA, DIP cations for allowing crystallization and stabilize the tin-perovskite phase for doctor blade and inkjet printing deposition techniques.
(2) PEA2SnI4, (4F-PEA)2SnX4 (X: I, I-Br) and TEA2SnI4 for red and orange emitting LEDs and photonics (emitting devices and photodetectors)
(3) Cs3Cu2Cl5 CsCu2Cl3 Rb3InCl6:Sb for green and blue LEDs.
(4) Cs2SnI6: spectacular nonlinear optical properties.

PdOx formulated with several precursors and obtaining sufficiently high conductivity under low processing temperatures (patent application).

In photovoltaic devices, important advances were achieved: world record efficiency for flexible lead-free perovskite solar modules of 5.7 % under 1-sun and an impressive 9.4% for 2000 lx. This was possible through the in-situ synthesis of SnI2 (patent applicatioon).

For lead-free LEDs: (i)-(ii) First inkjet-printed Pb-free perovskite LED emitting at red wavelengths and first on a flexible substrate, (iii) First orange emitting Pb-free perovskite LED, (iv) Fabrication of a Pb-free perovskite LED with the highest reported brightness (300 cd·m-2). The latter advances were possible by using a two-step recrystallization method, which is patent-pending.

Several advances were achieved in photonics: (1) Vertical lasing and near single-mode operation were observed for inkjet-printed films of a 2D/3D LFP, (ii) This 2D/3D LFP also leads to good flexible photodetector performances (iii) inkjet-printed films of 2D tin-perovskites (TEA2SnI4 among them) are exhibiting efficient two photon absorption mechanism at room temperature and also leading to efficient photodetectors.

Progress beyond the state of the art and expected potential impact (including the socio-economic impact and the wider societal implications of the project so far)

ALREADY PUBLISHED RESULTS:
1. (INSA, ETHZ): S. Kahmann et al., Negative Thermal Quenching in FASnI3 Perovskite Single Crystals and Thin Films, ACS Energy Lett. 5, 2512-2519 (2020).
2. (UJI, UVEG): A. F. Gualdrón-Reyes et al., Sr-Doping Engineering for Enabling Long-Term Stable FAPb1 xSrxI3 Quantum Dots with 100% Photoluminescence Quantum Yield, J. Mat. Chem. C 9, 1555-1566 (2021).
3. (UVEG, UJI): J. Navarro-Arenas et al., Recycled Photons Traveling Several Millimeters in Waveguides Based on CsPbBr3 Perovskite Nanocrystals, Adv. Optical Mater. 9, 2021, 2100807 (2021).
4. (UJI, UVEG): S. Das Adhikari et al., V. Sans, and I. Mora-Seró, Continuous-Flow Synthesis of Orange Emitting Sn(II)-Doped CsBr Materials, Adv. Optical Mater. 2101024 (2021).
5. (INSA-RENNES): B. Cucco et al., Electronic structure and stability of Cs2TiX6 and Cs2ZrX6 (X = Br, I) vacancy ordered double perovskites, Applied Physics Letters 119, 181903 (2021).
6. (INSA-RENNES): A. Skorokhod et al., From Zero- to One-Dimensional, Opportunities and Caveats of Hybrid Iodobismuthates for Optoelectronic Applications, Inorganic Chemistry 60, 17123-17131 (2021).
7. (UJI, UVEG): S. Das Adhikari et al., White Light Emission from Lead-Free Mixed-Cation Doped Cs2SnCl6 Nanocrystals, Nanoscale, 14, 1468-1479 (2022).
8. (UJI, UVEG): J. Sanchez-Diaz et al., Tin perovskite solar cells with >1300 hours of operational stability in N2 through a synergistic chemical engineering approach, Joule 6, 861-883 (2022).
9. (UVEG, UJI): I. Suárez et al., Directional and polarized lasing action on Pb-free FASnI3 integrated in flexible optical waveguides, Advanced Optical Materials 10, 2200458 (1-11) (2022).
10. (UVEG, AVANTAMA): I. Suárez et al., Ecofriendly Perovskites with Giant Self-Defocusing Optical Response, Advanced Optical Materials 10, 2202120 (1-10) (2022).
11. (UB, UJI): G. Vescio et al., High Quality Inkjet Printed-Emissive Nanocrystalline Perovskite CsPbBr3 Layers for Color Conversion Layer and LEDs Applications, Advanced Materials Technologies 7, 2101525 (1-11) (2022).
12. (UB, UJI): G. Vescio et al., 2D PEA2SnI4 Inkjet-Printed Halide Perovskite LEDs on Rigid and Flexible Substrates, ACS Energy Letters 7, 3653–3655 (2022).
13. (UB, AVANTAMA) S. González et al., Inkjet-Printed p-NiO/n-ZnO Heterojunction Diodes for Photodetection Applications, Advanced Materials Interfaces 10, 2300035 (1-8) (2022).
14. (INSA-RENNES): B. Cucco et al., Silver–Bismuth Halide Double Salts for Lead-Free Photovoltaics: Insights from Symmetry-Based Modeling. Solar RRL 6, 2200718 (1-8) (2022).
15. (INSA-RENNES): P. Jiang et al., Pb-free halide perovskites for solar cells, light-emitting diodes, and photocatalysts, APL Materials 10, 060902 (1-19) (2022).
16. (ETHZ, INSA-RENNES): D. N. Dirin et al., Intrinsic formamidinium tin iodide nanocrystals by suppressing the Sn(IV) impurities, Nano Letters 23, 1914-1923 (2023).
17. (INSA-RENNES): B. Cucco et al., Fine Structure of Excitons in Vacancy-Ordered Halide Double Perovskites, ACS Materials Letters 5, 52-59 (2023).
18. (UVEG - UJI): V. S. Chirvony et al., Unusual Spectrally Reproducible and High Q-Factor Random Lasing in Polycrystalline Tin Perovskite Films, Advanced Materials 35, 2208293 (1-10) (2023).
19. (UB, UJI, AVANTAMA): G. Mathiazhagan et al., Fully Inkjet-printed PEDOT:PSS/NiO/Colloidal CsPbBr3/SnO2 Perovskite LED on Rigid and Flexible Substrates, under review.

Several publications will follow along the next weeks and few months, on the basis of LAST RESULTS OBTAINED ON
- Several synthesized LFP compounds still not published
- Achievements in solar cells and photovoltaic modules
- First orange emitting Pb-free perovskite LED.
- Fabrication of a Pb-free perovskite LED with the highest reported brightness (300 cd/m2).
- Vertical lasing action and near single-mode operation observed for inkjet-printed films of 2D/3D G-LFPs.
- Inkjet-printed films of 2D/3D G-LFPs also exhibits good performances for low-level light photodetection; flexible photodetectors also exhibit comparable performances.
- Inkjet-printed films of 2D tin-perovskites (TEA2SnI4 among them) are exhibiting efficient two photon absorption mechanism at room temperature
- Inkjet-printed photodetectors in glass and PET substrates based on 2D TEA2SnI4 with very low dark currents and good performance.

DROP-IT results can be of interest for future markets of flexible electronics, displays, photovoltaics and Internet of Things (IoT).

Strategy of the project