# Fileset

[KOSEN-NIMS-2023.pdf](https://mdr.nims.go.jp/filesets/30c064a5-3c61-481a-a3b1-efff7263bf67/download)

## Creator

[KHADKA Dhruba Bahadur](https://orcid.org/0000-0001-9134-3890), [SHIRAI Yasuhiro](https://orcid.org/0000-0003-2164-5468), [YANAGIDA Masatoshi](https://orcid.org/0000-0002-8065-7875), [MIYANO Kenjiro](https://orcid.org/0000-0002-5869-3087)

## Rights

[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)

## Other metadata

[Molecular Passivation for High-Efficiency and Stable Methylammonium-Free Perovskite Solar Cells with Fluorinated Supramolecules](https://mdr.nims.go.jp/datasets/4be63ece-88e6-4823-84ff-98caeafe2503)

## Fulltext

1Molecular Passivation for High-Efficiency and Stable Methylammonium-Free Perovskite Solar Cells with Fluorinated SupramoleculesPhotovoltaic Materials GroupGlobal Research Center for Environment and Energy based on Nanomaterials Science(GREEN)National Institute for Materials Science (NIMS), Tsukuba, JapanDhruba B. Khadka, Yasuhiro Shirai, Masatoshi Yanagida, Terumasa Tadano, Kenjiro MiyanoMarch 1-2 , 20232Energy Demand and Renewable Energy PotentialSolar1.2 x 105 TW at Earth surface600 TW practicalhttp://www.eia.doe.govRef. Global Climate and Energy Project; Nate LewisGCEP Theme Leader –Solar Energy, Stanford UniversityCurrent demand; 15-18 TW[0.19% of  land area (540x540 km2)]PV cell having PCE of  10%To meet energy demand2040 energy demand; 30-35 TW[0.97% of land area (1200x1200 km2)]Potential of renewable energyA(E)= 5.7E7 sq miles /1.5E8 sq km[JPN-3,77,930 km2; ¾ of Jpn]3PV-technology development4Halide perovskite: promising material Eg=1.55 eV, 𝜶= 104-105 cm-1LD> 1𝝁, Eext< 𝒌𝑻, bipolar carriersCH3NH3PbI3 -Dieter Weber in 1978ABX3A- MA, FA, Cs, B- Pb, Sn, GeX- Cl, Br, IPCE- 4% CH3NH3PbBr3/TiO2 (solid line)CH3NH3PbI3/TiO2 (dashed line).Halide perovskite: promising for light harvesting2009: First perovskite solar cells; CsPbX3 (1892)Prof. Tsutomu Miyasaka ; Toin University of YokohamaDye sensitized structure: 4% efficiency52010 2013 2016 2019 2022 2025051015202530 Pb-PSCs Sn-PSCs Bi-PSCsPCE (%)Year<5%APbI3 ~25.7%~26.617~14.81%Halide Perovskite Solar Cells: Startling Progress6Energy Environ. Sci., 2015, 8, 995–1004J-V hysteresisDevice degradationPerovskite Solar Cell: Limitation Issue7Device Stability IssueEncapsulation~ 60 daysITO/PEDOTWith inorganic CTLsITO/NiOx• Adv. Energy Mater. 2016, 1600372;• Nature NanoTech. 2016, 11,75-81 ;~ 40 daysCu-electrodeAl-electrodeImpact of electrodeStandard: 85C/85%- RH; 1000 hoursInterfacial passivationAngew. Chem. Int. Ed. 2017, 56, 1190 – 12128Halide perovskite: Scientific issueMAPbX3Exploration on➢ Material properties➢ Interface quality with the    contact layer➢ Carrier dynamics➢ Ionic migration➢ Defect physicsUnderlying physics91. Perovskite Solar Cells: Vapor Surface treatmentFilm crystallization• Khadka et al., Sustain. Energy Fuels, 2017, 1, 755• Khadka et al., J. Mater. Chem. C, 2017, 5,8819PCE- ImprovedControl MACl-treatedDefect passivation100.0 0.2 0.4 0.6 0.8 1.0 1.201020J (mA/cm2)V (V)/  PTAA/  NiOxDevice/ParameterPTAA NiOxJsc(mAcm-2) 21.48 20.44Voc(V) 1.146 0.997FF 0.785 0.765η(%) 19.32 15.602. PSCs: Impact of carrier transport layer• Khadka et al. ACS Appl. Energy Mater. 2021, 4, 10, 11121• Khadka et al. ACS Appl. Mater. Interfaces, 2018, 11, 7055• Khadka et al,  ACS Appl. Mater. Interfaces, 2018,10, 22074• Khadka et al., J. Mater. Chem. C, 2018, 6, 162-170Device stability113. PSCs: NiOx-surface treatmentsMeO-2PACz• Miyano and co-workers, ACS Omega 2022, 7, 12147.✓ PCE: 15.60 → 17.2%✓ Certified PCE→16.3% @1 cm2✓ MAPI device with ~ 270 nmPhotothermal Deflection Spectroscopy: NiOx and NiOx/MeO-2PACzNiOx band gap: 3.5~3.7 eV12MeO-2PACzKhadka et al. Adv. Energy Mater. 2022, 12, 2202029✓ Two-step → One-step method; ~270nm → ~500nm✓MAPbI3 → FA0.84Cs0.12Rb0.04PbI3 18.1%＠1cm222.3%4. PSCs: Passivation on top and bottom of the perovskite layer 13Pb-HaP: 5F-PHZ treated: Device trend0 0.5 1 2 3 5 10141618202224PCE (%)5F-PHZ (mol%)mol%145F-PHZ treated: Effect on materials growth✓ 5F-PHZ additive: well coverage on the surfaceControl 3 mol% 10 mol%XRD results0 mol%Mixed precursor10 mol%155F-PHZ treated: Opto-physical properties ✓ PL characteristics peak✓ Blue shift with 5F-PHZ650 700 750 800 850 900 950PL intensity (a.u.)l (nm) Control 5F-PHZ500 600 700 800 900 Control  0.5 mol%  1 mol% 2 mol%  3 mol%  5 mol% 10 mol%Absorbance (a.u.)l (nm)750 780 810 840 870 900✓ Absorption spectra164. STEM images: Interface formation17PSCs-5F-PHZ: ToF-SIMS spectraToF-SIMS; 5F-PHZ 2D imagesControl 5F-PHZ180.4 0.8 1.2 1.6 2.00.20.40.60.81.01.2VOC (V)Ln(I) (mWcm-2)Control 5F-PHZ0 3000 6000 9000 12000 15000 18000PL IntesityTime (ns) Control 5F-PHZHaP Film𝛕𝟏 (ns) 𝛕𝟐 (ns)Control 142 6545F-PHZ 324 19821.35 kBT/q1.12 kBT/qVOC-I analysisTRPL resultsLonger carrier lifetime6. PSCs-surface treatments: PhotoPhysics/DFTTerumasa Tadano, Spin Theory GroupDFT calculations197. PSCs- Surface passivation: device stabilityKhadka et al. Adv. Energy Mater. 2022, 12, 2202029High Stability80%30%MPPT, 65℃90%50%MPPT, ~30℃Over 22 % @1 cm2Maintain 20% after 1000 hr20Report Summary5F-PHZ passivation in Pb-HaP➢ Interface modulation with fluoroarene functional derivatives➢ Form interfacial embedded 2D-layers ➢ Attenuate defect densities and suppress of ion migration➢ PCE increase from 18%  to > 22 % - with superior stability21Team/ AcknowledgementsPhotovoltaic Materials GroupOur team22 Slide 1 Slide 2 Slide 3 Slide 4 Slide 5 Slide 6 Slide 7 Slide 8 Slide 9 Slide 10 Slide 11 Slide 12 Slide 13 Slide 14 Slide 15 Slide 16 Slide 17 Slide 18 Slide 19 Slide 20 Slide 21 Slide 22