skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Impact of cesium on the phase and device stability of triple cation Pb–Sn double halide perovskite films and solar cells
Triple cation Cs/methylammonium (MA)/formamidinium (FA) and double halide Br/I lead perovskites improved the stability and efficiency of perovskite solar cells (PVSCs). However, their effects on alloyed Pb–Sn perovskites are unexplored. In this work, perovskite thin films with the composition Cs x (MA 0.17 FA 0.83 ) 1−x Pb 1−y Sn y (I 0.83 Br 0.17 ) 3 are synthesized utilizing a one-step solution process plus an anti-solvent wash technique and deployed in PVSCs with an inverted architecture. All films show a cubic crystal structure, demonstrating that compositional tuning of both the tolerance factor and crystallization rate allows for dense, single phase formation. The band gaps, affected by both lattice constriction and octahedral tilting, show opposite trends in Pb-rich or Sn-rich perovskites with the increase of Cs for fixed Sn compositions. The Cs 0.05 (MA 0.17 FA 0.83 ) 0.95 Pb 0.25 Sn 0.75 (I 0.83 Br 0.17 ) 3 PVSCs achieve a power conversion efficiency (PCE) of 11.05%, a record for any PVSC containing 75% Sn perovskites, and the Cs 0.10 (MA 0.17 FA 0.83 ) 0.90 Pb 0.75 Sn 0.25 (I 0.83 Br 0.17 ) 3 PVSCs reach a record PCE of 15.78%. Moreover, the triple cation and double halide alloyed Pb–Sn perovskites exhibit improved device stability under inert and ambient conditions. This study, which illustrates the impact of cation and halide tuning on alloyed Pb–Sn perovskites, can be used to further eliminate Pb and improve device performance of high Sn PVSCs and other optoelectronic devices.  more » « less
Award ID(s):
1661660 1748101
PAR ID:
10101029
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Journal of Materials Chemistry A
Volume:
6
Issue:
36
ISSN:
2050-7488
Page Range / eLocation ID:
17426 to 17436
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. One of the organic components in the perovskite photo-absorber, the methylammonium cation, has been suggested to be a roadblock to the long-term operation of organic–inorganic hybrid perovskite-based solar cells. In this work we systematically explore the crystallographic and optical properties of the compositional space of mixed cation and mixed halide lead perovskites, where formamidinium (FA + ) is gradually replaced by cesium (Cs + ), and iodide (I − ) is substituted by bromide (Br − ), i.e. , Cs y FA 1− y Pb(Br x I 1− x ) 3 . Higher tolerance factors lead to more cubic structures, whereas lower tolerance factors lead to more orthorhombic structures. We find that while some correlation exists between the tolerance factor and structure, the tolerance factor does not provide a holistic understanding of whether or not a perovskite structure will fully form. By screening 26 solar cells with different compositions, our results show that Cs 1/6 FA 5/6 PbI 3 delivers the highest efficiency and long-term stability among the I-rich compositions. This work sheds light on the fundamental structure–property relationships in the Cs y FA 1− y Pb(Br x I 1− x ) 3 compositional space, providing vital insight to the design of durable perovskite materials. Our approach provides a library of structural and optoelectronic information for this compositional space. 
    more » « less
  2. Perovskite solar cells (PSCs) have attracted significant research efforts due to their remarkable performance. However, most perovskite films are prepared by the antisolvent method which is not suitable for practical applications. Herein, a (FA0.83MA0.17)0.95Cs0.05Pb(I0.83Br0.17)3(CsFAMA) perovskite film fabrication technique is developed using solvent volatilization without any antisolvents. The films are formed through recrystallization via the intermediate phase CsMAFAPbIxClyBrzduring annealing, leading to high‐quality perovskite films. The perovskite growth mechanism is investigated in terms of controlling the amount of formamidinium iodide and methylammonium chloride in the precursor solutions. The oriental growth of the films via the intermediate phase is confirmed by the grazing‐incidence wide‐angle X‐ray scattering measurements. The photovoltaic properties of the perovskite films are investigated. The PSCs based on the films fabricated using the method exhibit a high efficiency of 20.6%. The method developed in this work is based on solvent volatilization, which exhibits significant potential in high reproducibility, facile operation, and large‐scale production. 
    more » « less
  3. null (Ed.)
    Achieving efficient and stable tin-based perovskite solar cells remains challenging. In this work, we incorporate the ethylenediammonium diiodide (EDAI 2 ) additive into a cesium–guanidinium doped formamidinium tin triiodide perovskite with the composition of (CsGA) x FA 1−2x SnI 3 + y % EDAI 2 . This new perovskite utilizes the strong hydrogen bonding of the guanidinium cation and the lattice strain relaxation of the small cesium cation as well as the hollowing and passivation effects of the EDAI 2 additive. The EDAI 2 additive not only yields pinhole-free cubic phase perovskite films but also decreases both shallow and deep trap states in the perovskite films. These effects are pronounced with the increase of substitution of the pair of GA + and Cs + . The new perovskites are deployed in inverted planar solar cells. A maximum power conversion efficiency (PCE) of 5.01% is achieved with the (CsGA) 0.15 FA 0.70 SnI 3 + 0% EDAI 2 device but the device degrades after storage in a nitrogen-filled glove box for 30 days. Both performance and stability are improved with the addition of EDAI 2 . A maximum PCE of 5.72% is achieved with the (CsGA) 0.15 FA 0.70 SnI 3 + 1.0% EDAI 2 device. The (CsGA) 0.15 FA 0.70 SnI 3 + 1.5% EDAI 2 devices exhibit a maximum PCE of 5.69% and the performance is further increased to 6.39% after storage in a nitrogen-filled glove box for 4 days; 70% of the initial PCE is retained after 45 days. This study demonstrates the benefit of tuning cation sizes and introducing divalent cations to integrate stabilizing factors into pure Sn perovskites, creating new routes for efficient and stable lead-free perovskite solar cells. 
    more » « less
  4. The remarkable optoelectronic properties of metal halide perovskites have generated intense research interest over the last few years. The ability to control and manipulate the crystallisation and stoichiometry of perovskite thin-films has allowed for impressive strides in the development of highly efficient perovskite solar cells. However, being able to effectively modify the interfaces of metal halide perovskites, and to controllably p- or n-type dope the surfaces, may be key to further improvements in the efficiency and long-term stability of these devices. In this study, we use surface doping of the mixed-cation, mixed-halide perovskite FA 0.85 MA 0.15 Pb(I 0.85 Br 0.15 ) 3 (FA – formamidinium; MA – methylammonium) to improve the hole extraction from the perovskite solar cell. By treating the surface of the perovskite film with a strongly oxidizing molybdenum tris(dithiolene) complex, we achieve a shift in the work function that is indicative of p-doping, and a twofold increase in the total conductivity throughout the film. We probe the associated interfacial chemistry through photoelectron and solid-state nuclear magnetic resonance spectroscopies and confirm that charge-transfer occurs between the perovskite and dopant complex. The resulting p-doped interface constitutes a homojunction with increased hole-selectivity. With charge-selective layers, we show that this surface doping enhances the device performance of perovskite solar cells resulting in steady-state efficiencies approaching 21%. Finally, we demonstrate that a surface treatment with this dopant produces the same effect as the commonly employed additive 4- tert butylpyridine ( t BP), allowing us to achieve “ t BP-free” devices with steady-state efficiencies of over 20%, and enhanced thermal stability as compared to devices processed using t BP. Our findings therefore demonstrate that molecular doping is a feasible route to tune and control the surface properties of metal halide perovskites. 
    more » « less
  5. null (Ed.)
    The past decade has witnessed tremendous advances in synthesis of metal halide perovskites and their use for a rich variety of optoelectronics applications. Metal halide perovskite has the general formula ABX 3 , where A is a monovalent cation (which can be either organic ( e.g. , CH 3 NH 3 + (MA), CH(NH 2 ) 2 + (FA)) or inorganic ( e.g. , Cs + )), B is a divalent metal cation (usually Pb 2+ ), and X is a halogen anion (Cl − , Br − , I − ). Particularly, the photoluminescence (PL) properties of metal halide perovskites have garnered much attention due to the recent rapid development of perovskite nanocrystals. The introduction of capping ligands enables the synthesis of colloidal perovskite nanocrystals which offer new insight into dimension-dependent physical properties compared to their bulk counterparts. It is notable that doping and ion substitution represent effective strategies for tailoring the optoelectronic properties ( e.g. , absorption band gap, PL emission, and quantum yield (QY)) and stabilities of perovskite nanocrystals. The doping and ion substitution processes can be performed during or after the synthesis of colloidal nanocrystals by incorporating new A′, B′, or X′ site ions into the A, B, or X sites of ABX 3 perovskites. Interestingly, both isovalent and heterovalent doping and ion substitution can be conducted on colloidal perovskite nanocrystals. In this review, the general background of perovskite nanocrystals synthesis is first introduced. The effects of A-site, B-site, and X-site ionic doping and substitution on the optoelectronic properties and stabilities of colloidal metal halide perovskite nanocrystals are then detailed. Finally, possible applications and future research directions of doped and ion-substituted colloidal perovskite nanocrystals are also discussed. 
    more » « less