Journal of Physics D: Applied Physics

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Atmospherically induced defects in (FASnI3)0.6(MAPbI3-3xCl3x)0.4

perovskites
To cite this article before publication: Maxwell M Junda et al 2019 J. Phys. D: Appl. Phys. in press https://doi.org/10.1088/1361-6463/ab05b2

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Page 1 of 8 AUTHOR SUBMITTED MANUSCRIPT - JPhysD-119159.R1

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4 Atmospherically induced defects in (FASnI3)0.6(MAPbI3-

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6 3xCl3x)0.4 perovskites
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8 Maxwell M. Junda, Dewei Zhao, Biwas Subedi, Changlei Wang, Cong Chen, Yanfa Yan, and Nikolas J.
9 Podraza

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10 Department of Physics & Astronomy and The Wright Center for Photovoltaics Innovation &
11 Commercialization, University of Toledo, Toledo, OH 43606 USA
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14 Abstract
15 The effects of brief atmospheric exposure are assessed for mixed composition perovskites
16 comprised of a combination of formamidinium tin iodide (FASnI3) and methylammonium lead iodide +

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17 chloride (MAPbI3-3xCl3x) as well as MA0.7FA0.3PbI3 perovskite for use as absorber layers in high-efficiency
18 thin film solar cells. Photothermal deflection spectroscopy (PDS) is employed to probe the relative defect
19 density of all films by way of extracting the Urbach energy characterizing the width of the sub-bandgap
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absorption tail. Exposure to atmosphere for ~3 minutes prior to PDS measurement is found to degrade
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mixed composition films such that exposed films had an average increase of 36% in Urbach energies
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compared to those that are fully kept out of atmosphere through immersion in inert C6F14 liquid. By
contrast, the same exposure to atmosphere induced no change in Urbach energy for MA0.7FA0.3PbI3. These
results demonstrate the influence of ambient exposure on perovskites, particularly those containing Sn, and
highlight the fact that handling procedure itself throughout all fabrication and subsequent characterization
steps influences the measured results.
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29 Introduction
30 The rapid improvement in world record efficiencies for inorganic-organic halide perovskite-based
31 solar cells from single digits to over 20% in less than a decade1-3 has generated substantial interest in
32 understanding and optimizing the properties of such materials. The assembly of multijunction solar cells
33 provides the opportunity to achieve even higher efficiencies using a stack of multiple individual subcell
34 junctions containing absorber layers with different optical bandgaps (Egs) to more effectively make use of
35 the AM 1.5 solar irradiance spectrum. Fabrication of mixed composition perovskites 4-8 has been
36 demonstrated to be capable of producing films with a range of Eg and, thus, the possibility of creating
37 multijunction solar cells with all perovskite absorbers. One well-known complication for characterizing
38 these perovskites is instability in atmosphere8-11 such that even brief exposure can result in degradation and
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39 the formation of defects. An ever-growing body of research is examining both the sources of defects and
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their impact on devices. In general, the formation of defects in perovskite materials has been attributed to
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a variety of factors including exposure to oxygen, moisture, light, heat, and electric fields 9,10. In the case
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of point defects, theoretical work employing density functional theory12 and Monte Carlo simulations13
44 have probed the effects of various point defects on carrier transport properties in perovskite materials. Other
45 experimental work has measured the energies of specific trap states14 and identified the role interfaces with
46 other materials play on defects and ultimately carrier mobility15. Most work to date has determined that the
dominant point defects are shallow12 and, therefore, can be tolerated in reasonable concentrations by solar
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48 cell devices. Upon extended atmospheric exposure, perovskite materials are shown to decompose11 with
49 the level of atmospheric sensitivity being composition-dependant8. As a result of the wide-ranging defect
50 susceptibility, properties determined from measurements of individual perovskite films exposed to
51 atmosphere are not necessarily the same as properties of films fabricated under identical conditions but
52 encapsulated within a full solar cell device. At present, much literature describing characterization of
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53 perovskite thin films generally either fully disregards or cannot account for the effects of measurement
54 ambient, thereby reducing the relevance of such results with respect to similarly processed layers in full
55 photovoltaic devices. This work demonstrates the relative effects of brief ~3 minute exposure to laboratory
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3 ambient on the Urbach energies characterizing the sub-bandgap optical absorption in mixed-cation-halide
4 perovskite films by comparing those films that were exposed to atmosphere to those that were not. In doing

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5 so, we describe a methodology by which atmospheric exposure can be eliminated from influencing
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measurement results with applicability to a variety of optical measurements.
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Methods

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10 Film fabrication follows a solution-based approach within a N2 filled glove box as is described in
11 more detail in Ref. 16. Initially, formamidinium tin iodide (FASnI3), methylammonium lead iodide
12 (MAPbI3), and methylammonium lead iodide + chloride (MAPbI3-3xCl3x) precursor solutions in a mixed
13 N,N-dimethylmethanamide and dimethyl sulfoxide solvent are combined in stoichiometric amounts to form
14 both (FASnI3)0.6(MAPbI3)0.4 and (FASnI3)0.6(MAPbIyCl3-y)0.4 (0 < y < 3). These two mixtures are then
15 combined in varying proportions to produce (FASnI3)0.6(MAPbI3-3xCl3x)0.4 precursors with various Cl
16 proportions in solution of 0, 1.25, 2.5, 5, and 10% (i.e. x = 0, 0.0125, 0.025, 0.05, and 0.1) relative to I in

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17 the MAPbI3-3xCl3x component. With the final precursor solutions prepared, films are fabricated via spin-
18 casting onto glass substrates rotated at 5000 rpm for 60 s. During spin-casting, diethyl ether is dripped onto
19 the surface for the purposes of solvent engineering17. Film fabrication is completed by annealing at 100ºC
20 for 7 minutes in the N2 fabrication ambient. Henceforth, the films will be identified by the MAPbI3-3xCl3x
21 precursor Cl percentages for simplicity, however it should be noted that such percentages do not accurately
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describe the Cl content of the final films. These films can serve as the bottom subcell absorber in a tandem
device structure already shown to achieve nearly 21% efficiency16. Film fabrication took place in an N2-
purged glove box to prevent exposure to the laboratory ambient air. Additionally, high quality
MA0.7FA0.3PbI3 perovskite films that have been used in solar cells achieving >20% efficiency18-21 are
fabricated using the same procedure for the purposes of comparison to their mixed-metal, mixed-halide
perovskite counterparts. Photothermal deflection spectroscopy (PDS) measurements are collected over the
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0.89 – 1.55 eV photon energy spectral range for each film immediately following fabrication to compare
30 optical absorption below Eg for these compositions (PTDS-3-PTD, Sciencetech Inc.). During the PDS
31 measurement for approximately 5 hours, the films are in a quartz cuvette, immersed in inert C6F14 (3M
32 Fluorinert FC-72, Synquest Laboratories) deflecting fluid that prevents contact with the laboratory ambient
33 air. However, two separate procedures have been followed for transferring films into the C6F14 prior to each
34 PDS measurement. One series of films are transferred into the C6F14 fluid before removal from the N2
35 environment glove box. Thus, these PDS measurements are those of pristine films that had never been
36 exposed to laboratory ambient atmosphere. As a comparison, two films (0 and 2.5% Cl proportion) are
37 removed from the N2 environment into the atmosphere for ~3 minutes before being immersed in C6F14.
38 Directly after the PDS measurement, each film is removed from the C6F14 for measurement of optical
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39 response by spectroscopic ellipsometry (SE) and unpolarized transmittance over the 0.74 – 5.9 eV photon
40 energy spectral range in the laboratory ambient for a total of ~5 minutes atmospheric exposure (M-2000FI,
41 J. A. Woollam Co., Inc.).
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43 Results & Discussion
44 A single optical model is used to fit SE and transmittance measurements simultaneously in a way
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similar to that described in Ref. 22 in order to determine the spectroscopic absorption coefficient (α) of
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each film. In particular, the structural model consists of a glass substrate / interfacial layer / bulk perovskite
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film / surface roughness. Both the interfacial layer and surface roughness are described by Bruggeman
49 effective medium approximations23 with variable void fractions. All films had effective thicknesses of
50 between 650 – 710 nm. The optical response of the perovskite is initially described by a sum of Tauc-
51 Lorentz oscillators24,25, and finalized by applying a numerical inversion procedure26 to the measured data
52 assuming layer thicknesses obtained from the parametric model. Standard Tauc plots are constructed of
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53 (αhν)2 to obtain Eg of each film by way of finding the intersection of a linear fit over the range of (2 – 5) ×
54 108 eV2cm-2 with the abscissa. An example as applied to the 2.5% Cl film is shown in Fig. 1(a). The
55 resulting Eg for the (FASnI3)0.6(MAPbI3-3xCl3x)0.4 films that received no atmospheric exposure prior to PDS
56 measurement are plotted as a function of Cl content in Fig. 1(b). The variation in Eg for each film is found
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3 to be <1%, demonstrating that Cl content over a range of 0 – 10% has only a minor effect on Eg. For the
4 MA0.7FA0.3PbI3 sample, Eg is expectedly higher at 1.57 eV. As is nearly always the case with Tauc plots,

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5 the primary source of uncertainty in Eg arises from the selection of (αhν)2 range to which a line is fit. As
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shown in Fig. 1(a) the selected range of (2 – 5) × 108 eV2cm-2 is the lowest realistically linear region of
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data. For each film, (αhν)2 is qualitatively similar to that shown for 2.5% Cl proportion in Fig. 1(a) so that
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applying the same range of extrapolation is a sensible solution to minimizing errors in comparing extracted
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10 Eg for each film.
11 The experimental PDS signal, S, is converted to absorption coefficient27 via α = –ln(1–S/S0)/d,
12 where S0 is the saturation signal at the highest measured energies and d is the effective film thickness. In
13 the region below Eg, the absorption due to defect states can be described by an Urbach tail28 using α =
14 αgexp[(E–Eg)/Eu], where αg is the value of α at Eg and Eu is the Urbach energy describing the width of the
15 band tail and providing a relative measure of the defect concentration. Thus, Eu is taken to be the inverse
16 slope of a linear fit to ln(α/αg). Fig. 2 shows an example of one such fit for the 2.5% Cl film. The Eu results

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17 from all PDS measurements on (FASnI3)0.6(MAPbI3-3xCl3x)0.4 films are shown in Fig. 3. The effects of even
18 brief ~3 minute atmospheric exposure while transferring the films to the C6F14-filled cuvette are evident in
19 the substantially higher Eu when compared to the corresponding composition films transferred in a pure N2
20 ambient for both 0 and 2.5% Cl. By comparison, PDS measurements of two MA0.7FA0.3PbI3 films handled
21 in the same way found Eu of 18.8 ± 0.2 and 18.7 ± 0.5 meV for a film transferred in N2 and a film exposed
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to atmosphere, respectively. This finding demonstrates that these mixed-metal, mixed-halide
(FASnI3)0.6(MAPbI3-3xCl3x)0.4 perovskite thin films differ from their more stable, less-mixed counterparts in
that the measurement ambient can substantially influence the results obtained. The Eu of all samples studied
here are generally consistent with trends in PDS results for various perovskite compositions reported
elsewhere in that less mixing of constituent cations and anions results in lower Eu and vice versa. As an
example, high quality MAPbI3 has consistently been shown29,30 to have Eu of approximately 15 meV, which
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is close to the nearly 19 meV of MA0.7FA0.3PbI3 measured here. Although the authors are unaware of any
30 published PDS results for (FASnI3)0.6(MAPbI3-3xCl3x)0.4 specifically, similar mixed-metal and/or mixed-
31 halide perovskites31-35 have reported Eu in range of ~20-40 meV.
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53 FIG. 1. (a) Example Tauc plot used for Eg extrapolation for the 2.5% Cl proportion film. (b) Bandgap energy, Eg, as a function of
54 Cl content percent for all (FASnI3)0.6(MAPbI3-3xCl3x)0.4 films that received no atmospheric exposure prior to photothermal
55 deflection spectroscopic (PDS) measurement.
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21 FIG. 2. Example of linear fit to ln(α/αg) below Eg for the 2.5% Cl (FASnI3)0.6(MAPbI3-3xCl3x)0.4 film using data from PDS
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measurements. These fits allow for the determination of Eu, which is the inverse of the fit line slope.
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38 FIG. 3. Urbach energies (Eu) of (FASnI3)0.6(MAPbI3-3xCl3x)0.4 perovskite thin films as a function of Cl proportion. Films exposed
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39 to atmosphere before PDS measurement and those not exposed are both shown for comparison. Eu describing the non-exposed 0%
40 and 1.25% Cl films are the same as those already reported in Ref. 16.
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43 The likely cause of such acute atmospheric instability in (FASnI3)0.6(MAPbI3-3xCl3x)0.4 is the well-
44 documented36-41 oxidation of Sn2+ to Sn4+ under atmospheric exposure for perovskite films containing Sn.
45 However, the recent reports of relatively stable performance16,38,42,43 under continuous illumination for solar
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cells incorporating Sn suggest that either intentional external encapsulation or the encapsulation occurring
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as a result of over-deposited solar cell layers is successful in mitigating much of the Sn-related degradation.
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This interpretation also provides context for understanding the mismatch of a factor of ~2 reported
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50 elsewhere34 between Eu determined by PDS and determined by external quantum efficiency measurements
51 for Sn-containing perovskites. Thus, if measurements of Sn-containing mixed composition perovskite thin
52 films are to be taken as representative of those contained in full device stacks, complete avoidance of
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53 atmosphere is paramount.
54 The non-exposed films shown in Fig. 3 also demonstrate that substitution of small quantities of Cl
55 (i.e. 1.25 or 2.5%) for I is effective in reducing the defect density as measured by Eu relative to films
56 fabricated with no Cl (0%). This is consistent with the fact that Cl inclusion is known to promote larger
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3 grain sizes and improved electronic quality16,44. Additionally, full solar cells fabricated incorporating
4 perovskite absorber layers of the compositions studied here are reported in Ref. 16. The highest and second

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5 highest cell efficiencies are observed in devices incorporating 2.5 and 1.25% Cl absorbers, respectively,
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which are the materials with lowest Eu. Despite the 2.5% Cl film having slightly higher Eu compared to
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1.25% Cl, we suspect that optimized cell performance with 2.5% Cl inclusion results from other factors
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such as aforementioned increased grain size with increased Cl. The cells fabricated with 0, 5, and 10% Cl
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10 all exhibit lower efficiency, suggesting that the defect densities characterized by Eu influence overall device
11 performance.
12 Fig. 4 compares α for 2.5% Cl mixed-halide films and MA0.7FA0.3PbI3 films determined from
13 various measurements. More specifically, it compares the PDS and SE+transmittance measurement results
14 for the films transferred into C6F14 in a N2 ambient as well as the PDS measurement of otherwise identical
15 films transferred into C6F14 in atmosphere. As expected for measurements of the same material, all three of
16 these measurements converge at energies above Eg for each of the two materials. However, substantial

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17 differences exist in the “floor” values of α below Eg. The PDS floors (circles) for the MA0.7FA0.3PbI3 films
18 are quite similar, whereas the floor for the 2.5% Cl (FASnI3)0.6(MAPbI3-3xCl3x)0.4 films exposed to
19 atmosphere during transfer is ~3.5 times higher than the corresponding floor for the film transferred in N2.
20 This further suggests that MA0.7FA0.3PbI3 is relatively unaffected by brief atmospheric exposure while the
21 material defect density for (FASnI3)0.6(MAPbI3-3xCl3x)0.4 is increased upon exposure to atmosphere.
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However, another critical observation is that the PDS floors for both materials are nearly the same when
both are never exposed to atmosphere, indicating the effectiveness of N2 to C6F14 transfer in maintaining
pristine film quality comparable to films in full solar cell devices that have also never directly contacted
atmosphere. Additionally, the SE+transmittance result floors are approximately an order of magnitude (or
greater) larger than corresponding PDS results. All SE and transmittance measurements have been collected
in atmosphere which undoubtedly influences the magnitude of the floor observed in α, as discussed
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previously for the PDS results. However, rather than restricting the incident spectrum to a fairly narrow
30 range around Eg through the use of a monochromator as is the case in the PDS measurements, the
31 multichannel ellipsometer used for SE and transmittance measurements uses a broadband beam from a 150
32 W Xe arc-lamp with ample intensity extending well into the ultraviolet. In addition to the atmospheric
33 exposure, the known perovskite sensitivity to ultraviolet irradiation11,45,46 is likely an additional source of
34 degradation and defect formation accounting for the higher α floor relative to PDS for both materials. The
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52 FIG. 4. Comparison of α in the vicinity of Eg for (FASnI3)0.6(MAPbI3-3xCl3x)0.4 films with 2.5% Cl and MA0.7FA0.3PbI3 films.
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53 The open circles are from a films transferred into the C6F14-filled cuvette in N2 ambient (i.e. with no atmospheric exposure prior
54 to measurement), and then removed into atmosphere and measured by SE+transmittance (triangles). The closed circles are for
55 otherwise identical films that are transferred into the cuvette through laboratory atmosphere and measured by PDS. The data
56 point density of the SE+transmittance results have been reduced for clarity.
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4 interpretation of these floors is reasonable considering the sensitivity limits of the measurement techniques

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5 involved. Despite the fact that SE, transmittance, and PDS all involve different signal detection methods,
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the lowest values of α that each is sensitive to are all influenced by the film thickness. In the case here
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where SE and transmittance are modeled together, basic transmittance simulations indicate that a reasonable
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expected lower limit to α sensitivity is in the range of ~ 100 cm-1 for films of these thicknesses. For PDS,
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sensitivity to values of α as low as 10 – 100 cm-1 has been demonstrated for measurements of similar

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11 thickness thin films47-51. The ranges of α plotted in Fig. 4 are comparable to or above these expected lower
12 sensitivity limits, which further reinforces the interpretation of the floor values as real spectral features, as
13 opposed to artifacts arising from reaching each instrument’s lower detection limit.
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15 Conclusion
16 The findings of this work demonstrate the fact that handling of mixed composition perovskite thin

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17 films must be considered and managed throughout the full process of fabrication and characterization. In
18 particular, when interpreted in the context of existing literature, mixed composition perovskites containing
19 Sn are particularly vulnerable to degradation, whereas our results indicate that MA0.7FA0.3PbI3 perovskites
20 are relatively stable. Even brief exposure of (FASnI3)0.6(MAPbI3-3xCl3x)0.4 films to atmosphere on the order
21 of minutes is shown to result in an average increase of 36% to Eu compared to completely unexposed films.
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degradation effects.
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Immersion in C6F14 while still in the N2 fabrication ambient is shown to be an effective procedure for
maintaining temporary encapsulation sufficient for optical characterization free from atmospheric
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Acknowledgement
29 This work is funded by the U.S. Department of Energy (DOE) SunShot Initiative under the Next
30 Generation Photovoltaics 3 program (DE-FOA-0000990), the Office of Naval Research (N00014-17-1-
31 2223), Air Force Research Laboratory under Space Vehicles Directorate (FA9453-11-C-0253), and the
32 Ohio Department of Development (ODOD) Ohio Research Scholar Program.
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