Low temperature open-air plasma deposition of amorphous tin oxide for perovskite solar cells
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La 0.7 Sr 0.2 Ni 0.2 Fe 0.8 O 3 (LSNF), having thermochemical stability, superior ionic and electronic conductivity, and structural flexibility, was investigated as a cathode in SOECs.
Dunfield et al. discuss various options for satisfying the ISOS light stability series (ISOS-L-#) of tests, a homebuilt testing apparatus and software suite for such tests, and a case study.
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Metal halide perovskites have garnered a great deal of attention for their applications in photovoltaics, LEDs, and radiation detection. The ease of solution processing high-quality perovskite semiconductors with large absorption coefficients and tolerance to native defects is decidedly attractive. Additionally, the ability to precisely tune the band gap of halide perovskites through compositional alloying of the halide ion is of particular interest for a range of applications, especially for tandem solar cells. However, under steady state light irradiation, an initially homogeneous mixed halide perovskite (MHP) will form local domains that are rich in one halide ion (e.g., Br or I). This light-induced phase segregation in MHPs forms iodide-rich domains that act as charge carrier traps and lowers the efficiency of perovskite-based devices. Thus, phase segregation poses a serious challenge to the implementation of MHPs in real-world device settings. Interestingly, when a phase segregated MHP film is placed in the dark, entropic driving forces become dominant and the segregated perovskite remixes and returns to its initially homogeneous state. Several key mechanistic details of phase segregation have been elucidated over the years. However, there are still aspects of halide segregation that are not clear, and there is ongoing debate in the literature as to what are the key factors that contribute to the mechanism. This Account discusses recent results that point to the specific role of hole trapping in phase segregation. Interestingly, generation of holes through above-band-gap excitation or through electrochemical injection increases ion migration and leads to phase segregation. The thermodynamic and redox properties of halide perovskites provide a strong driving force for hole trapping and oxidation of iodide species in MHPs. However, mobile halide species within the perovskite lattice take time to migrate and generate halide-rich domains. When in contact with a nonpolar solvent, the migration of iodine species is further extended to expulsion of iodine from the perovskite film. Thus, the mobility of halides and their susceptibility to hole-induced oxidation play a crucial role in determining the long-term stability of metal halide perovskites. Strategies to gain kinetic control over ion migration to slow phase segregation are needed to overcome these hurdles and achieve stable mixed halide perovskites. Modification of the perovskite composition through introduction of different cations or halide ions, or introduction of low-dimensional perovskite phases may suppress phase segregation. Furthermore, in achieving stability and improving the efficiency of perovskite solar cells and light emitting devices with minimal impacts, suppression of segregation remains the key factor.
Perovskite oxides continue to attract huge interest due to their fascinating and wide-ranging properties for diverse applications. The tunability of these properties may be further enhanced by increasing their compositional complexity via double perovskite-ordered configurations containing multiple cations. In this work, we focus on an exhaustive chemical space of single and double oxide perovskites and optimally explore this space to identify novel compositions that are likely to form stable compounds. Critically, we examine the relationship between formability, the practical ability to synthesize a compound, and stability, the thermodynamic preference to form the structure. Our formability and stability training data sets were enumerated from the available experimental literature and in-house density functional theory computations and contained 1505 and 3469 examples, respectively, representing state-of-the-art in the current open literature in perovskite and double perovskite compounds. Subsequently, cross-validated and highly accurate machine learning classification models are built using these training data sets and employed to screen for novel stable oxide perovskites. The study identifies (1) atomic features relevant to prediction of formability and stability in perovskite and double perovskite compounds, (2) the importance of including energy contributions due to local structural relaxations going beyond the high symmetry perovskite phase, and (3) 437,828 double perovskite compounds that are likely to be stable and 891,188 compounds that are likely to be formable. From the intersection of this large chemical space of formable and stable oxide perovskites, 414 compositions are identified as the most promising candidates for future experimental synthesis of novel oxide perovskites. The developed models may be generalized and have implications beyond perovskite discovery if applied to other families of compounds.
Electrospray deposition technique has been reported previously for fabricating effective and stable perovskite thin film, leading to efficient perovskite solar cells. Here, in this work, a comprehensive investigation of the formation mechanism of methylammonium lead iodide perovskite (CH 3 NH 3 PbI 3 ) film by electrospray technique is demonstrated and compared to the formation mechanism through the conventional spin coating technique. In the electrospray process, charged MAI nanoparticles are gradually introduced onto the PbI 2 film, intercalating within the PbI 2 structure to produce the perovskite film. In contrast, the spin-coating method involves supplying the MAI solution in bulk, leading to perovskite crystal formation through the dissolution of the PbI 2 layer by the MAI solution, followed by recrystallization into perovskite oriented in the [110] direction, 30° inclined to the substrate. The impact of charge and the electric field on the formation of perovskite film using the electrospray is explored. Furthermore, the intrinsic stability of perovskite films is monitored in real-time in a highly humid environment (≥80 % relative humidity (RH)) using in-situ Grazing Incidence Wide Angle X-ray Scattering (GIWAXS), and a degradation mechanism is proposed to enhance the durability of the perovskite-based devices. The study further delves into the comparison of the stability of electrosprayed and spin-coated perovskite film, and the impact of humidity level and the presence of a hole-transporting layer on the stability of the perovskite layer. Overall, this work provides a detailed understanding of the formation and humidity-induced degradation mechanism of electrosprayed perovskite films, offering insights that can extend to various applications of perovskite materials.
Tin-lead perovskites have low band gaps (1.2 eV - 1.4 eV) that offer complementary absorption spectra to mixed halide perovskites with band gaps in the range of 1.6 eV - 1.85 eV. In combination, tin-lead and mixed halide perovskites can be used to make efficient all-perovskite tandem solar cells. While these can achieve high efficiency, they are hampered by the unproven longterm stability of tin-containing perovskites. We make the first demonstration of tin-lead perovskite solar cells that pass benchmark 1000-hour tests of stability under stressors of heat, light, and atmospheric exposure. We identify that mixed tin-lead perovskites oxidise by a different chemical pathway, one that is much less favourable, than the oxidation pathway followed by pure tin perovskites, making them significantly more stable. Fortuitously, mixed tin-lead perovskites also have band gaps that are close to ideal for the rear cell of an all-perovskite monolithic two-junction tandem. Beyond selecting the composition of the perovskite to be one that has inherently suppressed tendency to oxidise, we also fabricate a novel heterojunction-based architecture that eliminates the commonly used acidic PEDOT:PSS layer, which leads to enhanced stability. By packaging the resulting solar cell in a glass-on-glass package with a pliable low-elastic-modulus polyolefin encapsulant and a butyl rubber edge seal, we also demonstrate that the low band gap perovskite solar cell that passes the IEC damp heat test for thin film solar cells - a milestone that demonstrates the removal of a significant impediment to the commercialization of high efficiency perovskite tandem solar cells.
The D″ region of the lower mantle, which lies just above the core–mantle boundary, is distinct from the bulk of the lower mantle in that it exhibits complex seismic heterogeneity and seismic anisotropy. Seismic anisotropy in this region is likely to be largely due to the deformation-induced texture (crystallographic preferred orientation) development of the constituent mineral phases. Thus, seismic anisotropy can provide a marker for deformation processes occurring in this dynamic region of the Earth. Post-perovskite-structured (Mg,Fe)SiO3 is believed to be the dominant mineral phase in many regions of the D”. As such, understanding deformation mechanisms and texture development in post-perovskite is important for the interpretation of observed seismic anisotropy. Here, we report on high-pressure diamond anvil cell deformation experiments on NaMgF3 neighborite (perovskite structure) and post-perovskite. During deformation, neighborite develops a 100 texture, as has been previously observed, both in NaMgF3 and MgSiO3 perovskite. Upon transformation to the post-perovskite phase, an initial texture of {130} at high angles to compression is observed, indicating that the {100} planes of perovskite become the ~{130} planes of post-perovskite. Further compression results in the development of a shoulder towards (001) in the inverse pole figure. Plasticity modeling using the elasto-viscoplastic self-consistent code shows this texture evolution to be most consistent with deformation on (001)[100] with some contribution of glide on (100)[010] and (001)<110> in NaMgF3 post-perovskite. The transformation and deformation mechanisms observed in this study in the NaMgF3 system are consistent with the behavior generally observed in other perovskite–post-perovskite systems, including the MgSiO3 system. This shows that NaMgF3 is a good analog for the mantle bridgmanite and MgSiO3 post-perovskite.
The recent observation of broadband white-light emission from the inorganic sheets of certain layered lead-bromide perovskites has instigated a multitude of studies on this unusual phenomenon. However, the vast majority of layered bromide perovskites have flat (001) inorganic sheets and display a narrow photoluminescence at room temperature. A handful of heavily distorted (001) perovskites display broad emission, but to date, there is no method of predicting which perovskites will produce white light at room temperature prior to screening different organic molecules that can template 2D perovskites and crystallizing and analyzing the material. By studying ten Pb–Cl perovskites, we find that they all exhibit a broad yellow emission, which is strikingly invariant despite different distortions in the inorganic framework seen across the series. We postulate that this broad emission is intrinsic to all layered Pb–Cl perovskites. Although broad, the emission is not white. By adding Br to the Pb–Cl perovskites we obtain both the narrow emission and the broad emission such that the combined emission color smoothly varies from yellow to warm white to cold white as a function of the halide ratio. Thus, alloying Br to Pb–Cl perovskites appears to be a simple and general strategy for reliably obtaining white light at room temperature from (001) perovskites, regardless of the templating effects of the organic molecules, which should greatly expand the number of white-light-emitting layered perovskites.
Perovskite solar modules have been attracting increasing attention due to their market potential, yet publications concerned with theintrinsic scale-up potential of different perovskite compositions remain relatively scarce. On the other hand, while great success is being made towards improving the power conversion efficiency (PCE) of perovskite solar cells (PSCs) by cesium cation (Cs + ) doping of the perovskite, more attention is being paid to the perovskite phase stabilization effect of Cs + doping, and less to other properties that are critical to understand and futher improve the PSC's. In this work, moderately-Cs-doped MAPbI 3 was employed as a model perovskite material in order to exclude the phase stabilization effect. Our systematic study revealed the influence of Cs + in organic-inorganic hybrid perovskites on the crystal structure, crystallization process, trap state density, band structure and charge (i.e., ions or photo-carriers) transport. Markedly, it has been observed that Cs + doping can greatly increase the carrier diffusion length in the perovskite films, thus improving the potential to scale-up PSC's.The PCE of small area devices (0.09 cm 2 ) was increased to 21.72% from 19.73%, with decreased hysteresis behavior and increased operational stability (T85 = 1000 h) after Cs + doped, where T85 refers to the retention of 85% of the initial PCE. Moreover, a PCE of 21.08% was obtained for a Cs + -containing perovskite module with an active area > 30 cm 2 , which demonstrates a better "reproducibility" than the reference sample (MAPbI3-based perovskite modules, PCE = 18.26%).
Lower dimensional or 2D halide perovskites with their versatile structural and functional properties, are known to improve the performance and room temperature stability of perovskite solar cells. One would expect 2D perovskites to be more resistant to ion migration compared to their 3D counterparts because of the presence of bulky organic cations. However, recent findings show ion migration indeed is prevalent in 2D halide perovskites similar to 3D perovskites. Halide ion migration in 2D perovskites manifests itself as halide ion segregation under photoirradiation as well as in halide exchange between physically paired films of 2D perovskites with different halide ions. Besides halide ion migration, cation migration of spacer cations and A-site cation is also seen when 2D/3D perovskite films are subjected to light and thermal stress. It is important to recognize the importance of ion migration while incorporating 2D perovskites in solar cells and other optoelectronic devices as it can be detrimental for achieving streamlined performance and long-term stability Furthermore, this perspective discusses recent reports on ion migration in 2D and in 2D/3D halide perovskite films under the operational conditions (at elevated temperature and given in-built bias) and presents a few mitigating strategies.
As the perovskite technology is ramping up into commercialization, reliable and accurate power rating of large-size perovskite modules becomes a prominent aspect for its future deployment in the PV market. It is known that the performance calibration of perovskite PV devices is very challenging due to its complex dynamic response during a conventional current-voltage (IV) measurement. PV researchers have previously proposed several steady-state performance calibration methods to reliably extract PV efficiencies, but mostly focus on small area research-type cells. In this paper, we emphasize the importance of reliable performance calibration on large-size perovskite modules. Extending the NREL Cell and Module Performance (CMP) group's steady-state performance calibration protocol (i.e., Asymptotic P MAX Scan) for perovskite cells to modules, we justify the necessity of reporting steady-state efficiencies for perovskite cells and discuss the challenges of applying this protocol to modules. We also present our protocol for Maximum Power Point Tracking (MPPT), which is a technique often used for performance calibration of perovskite cells and modules, and show a comparison between MPPT and Asymptotic P MAX . Using MPPT we demonstrate the interplay between metastability and degradation in perovskite modules, and emphasize the necessity to develop preconditioning protocols for stabilizing these devices. Our aim is to promote development of consensus protocols for performance calibration of perovskite modules, and to advance their credible power ratings, which will be beneficial to the growth of perovskite technology in the PV market.