The organic metal halide perovskite material is capable of high throughput manufacturing via traditional deposition processes used in roll-to-roll, yet thermal annealing post deposition may require long ovens. We report rapid annealed perovskite thin films using intense pulsed light (IPL) to initiate a radiative thermal response that is enabled by an alkyl halide additive that collectively improves the performance of a device processed in an ambient environment from a baseline of 10 to 16.5% efficiency. Previous reports on CH 3 NH 3 PbI 3 perovskite films using IPL processing achieved functional devices in milli-second time scales and are promising for high throughput manufacturing processes under ambient conditions. In this study, we found that the addition of diiodomethane (CH 2 I 2 ) as an additive to the methylammonium iodide (MAI)/lead iodide (PbI 2 ) precursor ink chemistry and subsequent IPL thermal annealing are inter-dependent. The concentration of CH 2 I 2 and IPL processing parameters have a direct effect on the surface morphology of the films and performance within a perovskite solar cell (PSC). The CH 2 I 2 dissociates under exposure to ultraviolet (UV) radiation from the IPL source liberating iodine ions in the film, influencing the perovskite formation and reducing the defect states. We anticipate that these results can be utilized to further develop different ink formulations using alkyl halides for the IPL technique to improve the performance of perovskite solar cells processed in ambient conditions.
more »
« less
Energy-distinguishable bipolar UV photoelectron injection from LiCl-promoted FAPbCl 3 perovskite nanorods
High-performance optoelectronic devices, such as solar cells and light-emitting diodes, have been fabricated with lead halide perovskites owing to their superior carrier properties. However, charge transport in such optoelectronics is intrinsically directional due to the existence of p–n junctions, which thus lacks the potential to elucidate any perturbations in light or electricity during energy conversion. Here, with the presence of a LiCl additive in a formamidinium chloride (FACl) solution, the as-grown LiCl:FAPbCl 3 nanorods demonstrate greatly enhanced crystallinity and UV photoresponse as compared to pristine FAPbCl 3 nanostructures without the LiCl additive. Most importantly, the LiCl:FAPbCl 3 nanorod film exhibits unprecedented distinguishability to UV photons with different energies and oscillating intensities, in the form of bipolar and periodically oscillatory photocurrents. This work could advance the fundamental understanding of photoinduced carrier processes in halide perovskites and facilitate the development of novel UV-based optical communications.
more »
« less
- Award ID(s):
- 1806152
- NSF-PAR ID:
- 10097251
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 7
- Issue:
- 21
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 13043 to 13049
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Abstract The two‐step conversion process consisting of metal halide deposition followed by conversion to hybrid perovskite has been successfully applied toward producing high‐quality solar cells of the archetypal MAPbI3hybrid perovskite, but the conversion of other halide perovskites, such as the lower bandgap FAPbI3, is more challenging and tends to be hampered by the formation of hexagonal nonperovskite polymorph of FAPbI3, requiring Cs addition and/or extensive thermal annealing. Here, an efficient room‐temperature conversion route of PbI2into the α‐FAPbI3perovskite phase without the use of cesium is demonstrated. Using in situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) and quartz crystal microbalance with dissipation (QCM‐D), the conversion behaviors of the PbI2precursor from its different states are compared. α‐FAPbI3forms spontaneously and efficiently at room temperature from P2(ordered solvated polymorphs with DMF) without hexagonal phase formation and leads to complete conversion after thermal annealing. The average power conversion efficiency (PCE) of the fabricated solar cells is greatly improved from 16.0(±0.32)% (conversion from annealed PbI2) to 17.23(±0.28)% (from solvated PbI2) with a champion device PCE > 18% due to reduction of carrier recombination rate. This work provides new design rules toward the room‐temperature phase transformation and processing of hybrid perovskite films based on FA+cation without the need for Cs+or mixed halide formulation.
-
more » « less
Abstract Hybrid halide 2D perovskites deserve special attention because they exhibit superior environmental stability compared with their 3D analogs. The closer interlayer distance discovered in 2D Dion–Jacobson (DJ) type of halide perovskites relative to 2D Ruddlesden–Popper (RP) perovskites implies better carrier charge transport and superior performance in solar cells. Here, the structure and properties of 2D DJ perovskites employing 3‐(aminomethyl)piperidinium (3AMP2+) as the spacing cation and a mixture of methylammonium (MA+) and formamidinium (FA+) cations in the perovskite cages are presented. Using single‐crystal X‐ray crystallography, it is found that the mixed‐cation (3AMP)(MA0.75FA0.25)3Pb4I13perovskite has a narrower bandgap, less distorted inorganic framework, and larger PbIPb angles than the single‐cation (3AMP)(MA)3Pb4I13. Furthermore, the (3AMP)(MA0.75FA0.25)3Pb4I13films made by a solvent‐engineering method with a small amount of hydriodic acid have a much better film morphology and crystalline quality and more preferred perpendicular orientation. As a result, the (3AMP)(MA0.75FA0.25)3Pb4I13‐based solar cells exhibit a champion power conversion efficiency of 12.04% with a high fill factor of 81.04% and a 50% average efficiency improvement compared to the pristine (3AMP)(MA)3Pb4I13cells. Most importantly, the 2D DJ 3AMP‐based perovskite films and devices show better air and light stability than the 2D RP butylammonium‐based perovskites and their 3D analogs.
-
more » « less
Abstract Halide perovskites are revolutionizing the renewable energy sector owing to their high photovoltaic efficiency, low manufacturing cost, and flexibility. Their remarkable mobility and long carrier lifetime are also valuable for information technology, but fundamental challenges like poor stability under an electric field prevent realistic applications of halide perovskites in electronics. Here, it is discovered that valleytronics is a promising route to leverage the advantages of halide perovskites and derivatives for information storage and processing. The synthesized all‐inorganic lead‐free perovskite derivative, Cs3Bi2I9, exhibits strong light–matter interaction and parity‐dependent optically addressable valley degree of freedom. Robust optical helicity in all odd‐layer‐number crystals with inversion symmetry breaking is observed, indicating excitonic coherence extending well beyond 11 layers. The excellent optical and valley properties of Cs3Bi2I9arise from the unique parallel bands, according to first principles calculations. This discovery points to new materials design principles for scalable valleytronic devices and demonstrates the promise of perovskite derivatives beyond energy applications.
-
more » « less
Abstract Blue electroluminescence is highly desired for emerging light‐emitting devices for display applications and optoelectronics in general. However, saturated, efficient, and stable blue emission has been challenging to achieve, particularly in mixed‐halide perovskites, where intrinsic ion motion and halide segregation compromises spectral purity. Here, CsPbBr3−
x Clx perovskites, polyelectrolytes, and a salt additive are leveraged to demonstrate pure blue emission from single‐layer light‐emitting electrochemical cells (LECs). The electrolytes transport the ions from salt additives, enhancing charge injection and stabilizing the inherent perovskite emissive lattice for highly pure and sustained blue emission. Substituting Cl into CsPbBr3tunes the perovskite luminescence from green through blue. Sky blue and saturated blue devices produce International Commission on Illumination coordinates of (0.105, 0.129) and (0.136, 0.068), respectively, with the latter meeting the US National Television Committee standard for the blue primary. Likewise, maximum luminances of 2900 and 1000 cd m−2, external quantum efficiencies (EQEs) of 4.3% and 3.9%, and luminance half‐lives of 5.7 and 4.9 h are obtained for sky blue and saturated blue devices, respectively. Polymer and LiPF6inclusion increases photoluminescence efficiency, suppresses halide segregation, induces thin‐film smoothness and uniformity, and reduces crystallite size. Overall, these devices show superior performance among blue perovskite light‐emitting diodes (PeLEDs) and general LECs.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C9TA01160A
