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Physical Insights into Energy Science

Incorporation of Vanadium (V) Oxide in Hybrid Hole Transport Layer
Enables Long-Term Operational Stability of Perovskite Solar Cells
Marina M. Tepliakova, Aleksandra N. Mikheeva, Lyubov Frolova, Aleksandra G. Boldyreva,
Aly Elakshar, Artyom V. Novikov, Sergey A. Tsarev, Marina I. Ustinova, Olga R. Yamilova,
Albert G. Nasibulin, Sergey M. Aldoshin, Keith J. Stevenson, and Pavel A Troshin
J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.0c01600 • Publication Date (Web): 22 Jun 2020
Downloaded from pubs.acs.org on June 22, 2020

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Incorporation of Vanadium (V) Oxide in Hybrid
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Hole Transport Layer Enables Long-term
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Operational Stability of Perovskite Solar Cells
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20 Marina M. Tepliakova1,2, Aleksandra N. Miheeva1,3, Lyubov A. Frolova1,2, Aleksandra G. Boldyreva1, Aly
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22 Elakshar1, Artyom V. Novikov1,2, Sergey A. Tsarev1, Marina I. Ustinova1,2, Olga R. Yamilova1,2, Albert G.
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24 Nasibulin1,4, Sergey M. Aldoshin2, Keith J. Stevenson1, and Pavel A. Troshin*1,2
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27 1 Skolkovo Institute of Science and Technology, Nobel st. 3, 143026 Moscow, Russia
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Institute for Problems of Chemical Physics of Russian Academy of Sciences (IPCP RAS),
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32 Semenov av. 1, 142432, Chernogolovka, Moscow region, Russia
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34 3 Mendeleev University of Chemical Technology of Russia (MUCTR), Miusskaya sq. 9,
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125947, Moscow, Russia
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4 Aalto University, P.O. Box 16100, FI-00076 Aalto, Espoo, Finland
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41 AUTHOR INFORMATION
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44 Corresponding Author
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* Pavel A. Troshin. E-mail: p.troshin@skoltech.ru
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3 ABSTRACT
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6 Recent studies have shown that charge transport interlayers with low gas permeability can
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increase operational lifetime of perovskite solar cells serving as a barrier for migration of
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11 volatile decomposition products from the photoactive layer. Herein we present a hybrid hole-
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13 transport layer (HTL) comprised of p-type polytriarylamine (PTAA) polymer and vanadium
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15 (V) oxide (VOx). Devices with PTAA/VOx top HTL reach up to 20% efficiency and
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18 demonstrate negligible degradation after 4500 h of light soaking, whereas reference cells using
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20 PTAA/MoOx as HTL lose ~50% of their initial efficiency under the same aging conditions. It
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22 was shown, that the main origin of the enhanced device stability lies in the higher tolerance of
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VOx towards MAPbI3 compared to the MoOx interlayer, which tends to facilitate perovskite
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27 decomposition. Our results demonstrate that the application of PTAA/VOx hybrid HTL enables
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29 long-term operational stability of perovskite solar cells thus bringing them closer to
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commercial applications.
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34 TOC GRAPHICS
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3 Perovskite solar cells (PSCs) demonstrated rapid improvement in the light power conversion
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6 efficiency (PCE) since the first reported 3.8% in 20091 to the current record of 25.2%.2 The
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8 technology owes this rapid progress to the simplicity of manufacturing of the absorber films
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10 using various processing techniques3, combined with the exceptional properties of the lead
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halide perovskite materials such as high absorbance, bandgap tunability, good charge transport
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15 properties and remarkable defect tolerance.4–6 Nevertheless, there are several obstacles to
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17 commercialization of PSCs7 with the insufficient operational stability being the most important
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among them.8
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22 PSCs are comprised of APbX3 absorber material with the perovskite crystal structure (where
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24 A is a univalent cation and X is halide anion) placed between charge transport interlayers that
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26 selectively extract and transport charges to the opposite electrodes. It is well documented now
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29 that lead halide perovskites incorporating organic cations can decompose with the formation
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31 of volatile byproducts under the action of stress factors such as elevated temperature, light, or
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33 electric bias.9 However, most of these decomposition reactions can be reversed if volatile
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components do not leave the active layer of the device, which can lead to at least partial
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38 restoration of the device efficiency in the dark e.g. during day/night cycling.10 Therefore, the
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40 most severe degradation pathways of PSCs can be suppressed if we block migration and loss
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of volatile aging products from the photoactive layer by using appropriate adjacent charge
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45 transport interlayers. In other words, charge transport interlayers have to function as
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47 encapsulation for perovskite absorber, so they are supposed to be composed of the materials
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49 with low gas-permeability. In case of conventional n-i-p PSCs architecture,11 the hole-transport
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52 layer (HTL) deposited atop the perovskite absorber film plays the most crucial role. Metal
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54 oxides are known to have good barrier properties for volatile perovskite decomposition
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56 products. For example, using an ALD-grown SnO2 electron-transport interlayer in combination
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with a 150 nm thick layer of ITO was reported to boost the stability of p-i-n devices at 85°C
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3 for up to 1000 h.12 Furthermore, the introduction of a bilayer composed of aluminum-doped
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6 zinc oxide (AZO) and SnO2 layer under the metal electrode tends to preserve perovskite
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8 decomposition products in the structure leading to improved thermal and ambient stability.13
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10 Using vanadium oxide as HTL component in n-i-p PSCs enabled decent efficiencies of up to
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16.8% and provided reasonable device stability under ambient conditions and at elevated
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15 temperatures, while the operational stability of the devices under light exposure was not
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17 investigated.14–15
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Spectacular improvement in the operational stability of n-i-p PSCs was achieved by
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22 incorporation of just 15 nm of MoOx oxide interlayer between organic HTL and the aluminum
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24 top electrode.16 In particular, non-encapsulated devices with MoOx/Al electrode maintained
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26 91% of the starting efficiency after 1000 h of continuous operation under 1 sun equivalent and
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29 using MPP tracking regime.17 However, such an impressive result was reached using low
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31 humidity (RH<20%) in combination with vigorous external device cooling to preserve the
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33 sample temperature at ~30°C. These results show that while using the MoOx interlayer as HTL
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component greatly improves the operational stability of PSCs, the problem of heat sensitivity
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38 of this system still has to be addressed.
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40 While this work was in preparation for publication, using VOx as a more suitable replacement
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for MoOx oxide interlayer in combination with a low molecular weight HTL material18 was
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45 reported at NanoGe conference.19 In particular, it was shown that MoOx tends to delaminate
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47 and forms wrinkles at elevated temperature of 70°C, which was suggested to be the main reason
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49 for a drop in the current density of the degraded devices.
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52 In this paper, we show that using MoOx as HTL component is challenged by intrinsic properties
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54 of this oxide since it rapidly degrades lead halide perovskites at elevated temperatures on the
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56 contrary to vanadium pentoxide (VOx), which was shown to be much less aggressive. The
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combination of VOx with polytriarylamine (PTAA) enabled high efficiencies of n-i-p PSCs
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3 approaching 20% and their much superior operational stability as compared to the reference
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6 cells comprising MoOx/PTAA as HTL.
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8 The concept pursued (Figure 1a) is based on the different nature of defects in organic and
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10 inorganic materials, therefore their combination is expected to have low gas permeability and
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good encapsulation properties, which are commonly exploited in designing plastic barrier foils.
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15 Both polymeric PTAA and inorganic VOx films have relatively small roughness (Figure 1b–c),
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17 therefore, they can be combined to form the hybrid bilayer HTL. In addition, we expected that
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donor-acceptor interactions between the electron-deficient metal oxide and electron-rich amine
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22 centers in the polymer structure will enable excellent fusion between these two layers, while
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43 Figure 1. The concept of n-i-p PSCs with hybrid organic-inorganic HTL with low gas-
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45 permeability and excellent barrier properties with respect to the volatile perovskite
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47 decomposition products (a). Molecular structure of p-type transport polymer PTAA and
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50 topography of the spin-coated thin film of this material on glass (b). Linked pyramid-based
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52 structure and the topography of the evaporated 30 nm thick film of vanadium pentoxide on
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54 glass (c)
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57 At the first stage of this work, the thickness of VOx layer was optimized and it was shown that
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60 30–45 nm deliver the best performance in n-i-p devices with the

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3 ITO/SnO2/PCBA/MAPbI3/PTAA/VOx/Ag configuration (Figure S1, Supporting information,
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6 SI). It should be emphasized that using single-layer HTLs based on either PTAA or VOx leads
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8 to low device characteristics and poor reproducibility (Figure S2, SI). Therefore, combining
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inorganic and organic materials in one hybrid HTL is crucially important for reaching superior
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13 device performance.
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15 Afterward, we explored the performance of PTAA/VOx binary hybrid HTL in PSCs using a
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panel of different absorber and electron transport materials. The current-voltage (J-V)
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20 characteristics of devices with various configurations were obtained (Figure 2a–d, the
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22 configurations are shown in the insets). The current densities were confirmed with external
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24 quantum efficiency (EQE) spectra (Figure S3, SI), and the performance parameters reached for
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27 all studied configurations are summarized in Table 1.
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29 Table 1. Characteristics of perovskite solar cells using VOx as HTL component
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31 Device configuration 2
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mV mA/cm % %
33 average±standard deviation (top)
34 ITO/SnO2/PCBA(a)/CsFAPbI3(b)/MAI(c)/PTAA/VOx/Ag 1021±47 23.7±1.0 76±2 18.1±1.2
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36 (1044) (24.6) (78) (20.1)
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38 1029±12 21.0±0.8 76±4 16.3±1.1
ITO/SnO2/PCBA/MAPbI3/PTA/PS(d)/VOx/Ag
39 (1032) (22.1) (80) (18.3)
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41 960±11 23.7±0.7 70±3 16.0±1.1
42 FTO/TiO2/PCBM/CsFAPbI3/PTA/VOx/Ag
(974) (24.0) (76) (17.7)
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44 994± 23.6± 1.8 58±6 13.1±2
45 ITO/SnO2/PCBA/CsFAPbI3/PTAA/VOx/Ag
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47 1022±9 22.8±1.3 72±6 15.3±1.4
48 ITO/ZnO/PCBA/CsFAPbI3/MAI/PTA/VOx/Ag
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1012±23 22.0±2.4 53±7 10.4±2.0
ITO/ZnO/PCBA/CsFAPbI3/PTA/VOx/Ag
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55 a) PCBA –Phenyl C61 butyric acid20, 21, (Figure S4, SI); b) CsFAPbI3 stands here and below for
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Cs0.12FA0.88PbI3; c) MAI stand for CH3NH3I d) PS stands for polystyrene
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26 Figure 2. Current-voltage characteristics of the devices comprising VOx as a component of
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bilayer hybrid HTL
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32 Devices comprising VOx as an inorganic component of the hybrid bilayer HTL demonstrated
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34 good performances while using different perovskite formulations such as CsFAPbI3 and
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39 PCBM or PCBA passivation coatings.21 It should be noted that PTAA was replaced in some
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41 cases by very similar PTA analog having fewer methyl groups (Figure S4, SI)22 and hence
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43 demonstrating improved charge transport characteristics. The best PCE was achieved for the
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device incorporating CsFAPbI3 photoactive layer additionally covered with a thin layer of
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50 at the grain boundaries of the perovskite material23, which is also reflected in improved open-
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52 circuit voltage (VOC =1035–1044 mV, Figure 2d) compared to the cells with a similar
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3 At the next stage, we explored the impact of PTAA/VOx hybrid HTL on the operational
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6 stability of n-i-p PSCs assembled using ZnO and CsFAPbI3 as ETL and light absorber
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8 components, respectively (Figure 3a). While using Ag and Au top electrodes is preferable for
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10 achieving high power conversion efficiencies, it was shown that such electrodes might
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compromise device operational stability due to the tendency of these metals to diffuse and react
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15 with the lead halide perovskite.24 Following previous reports, we used Al top electrodes, which
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17 slightly decreased the PSCs efficiency while contributing to their superior stability.16, 25 Thus,
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the best devices assembled in configuration ITO/ZnO/CsFAPbI3/PTAA/VOx/Al showed PCEs
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22 of 16.2 and 14.5% for reverse and forward scans, respectively (Figure 3b, Table 1).
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24 The stability tests were performed using aging chamber integrated into the nitrogen-filled
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26 glovebox as described in detail previously (Figure 3a).9, 26 The samples were first exposed to
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29 the light of metal halide lamps (37±3 mW/cm2) at the temperature of 45±1 °C for 3200 h.
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31 Afterward, light soaking was continued for >1000 h using high-power LEDs as a light source
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33 (light flux 100±3 mW/cm2) at the temperature of 50±1 °C. No UV filters were used, while the
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devices were under open-circuit conditions throughout all aging experiment. The used aging
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38 conditions correspond to the recommended protocol ISOS-L-2I.27 The evolution of the device
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40 efficiencies under illumination was collected (Figure 3c). The reference cells assembled using
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PTAA/MoOx combination as HTL showed decent stability with ~24% drop in efficiency after
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45 3200h under 30 mW/cm2 and further ~25% decrease after 1300 h under 100 mW/cm2. The
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47 observed accelerated aging at the second stage was due to higher light power and temperature,
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49 which is critical for PSCs assembled with MoOx as it was mentioned above. The devices with
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52 PTAA/VOx HTL have demonstrated spectacular stability: no efficiency loss within the first
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54 3200 h of light soaking and relatively minor (~10%) decay after 1300 h at 100 mW/cm2. Thus,
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PSCs as compared to MoOx.
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hybrid HTLs under illumination (c)
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45 Improvement in operational stability of PSCs achieved by replacing MoOx with VOx might be
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47 attributed either to different phase behavior of their films as proposed recently19 or to the
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particular, previous studies suggested that MoOx can facilitate MAPbI3 decomposition and
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35 glass/metal oxide/PTAA/MAPbI3 (c–d) samples at 75–80oC within 18 h in dark. Insets show
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37 photographs of MoOx/MAPbI3 (a) and VOx/MAPbI3 (b) films after 18 h of annealing.
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To verify this hypothesis, we first investigated the behavior of glass/VOx/MAPbI3 and
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43 glass/MoOx/MAPbI3 stacks under thermal annealing at 75–80°C in dark. The rapid evolution
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45 of the absorption spectra of the glass/MoOx/MAPbI3 samples within 18 h and spectacular
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47 change of their color from dark brown to yellowish were observed (Figure 4a), thus evidencing
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50 poor thermal stability of this system. It is worthy to mention that the reference glass/MAPbI3
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57 glass/VOx/MAPbI3 samples were much more stable under the same conditions since no
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3 Incorporation of thin (~20 nm) organic PTAA layer between MoOx and MAPbI3 slowed down
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6 the rate of the perovskite decomposition but failed to prevent it completely (Figure 4c). Finally,
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8 the glass/VOx/PTAA/MAPbI3 stacks showed no signs of degradation (Figure 4d), which
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10 explains why the PSCs using PTAA/VOx material combination as HTL revealed superior
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operational stability. These results demonstrate that VOx has good compatibility with
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15 perovskite absorbers on the contrary to MoOx, which is quite aggressive and facilitates
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17 decomposition of lead halides most likely via redox pathway, due to a strong oxidizing nature
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of MoOx reagent implicating its possible reaction with I-.
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22 To summarize, in this work we introduced vanadium (V) oxide as a highly promising inorganic
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24 component of hybrid organic semiconductor/metal oxide HTLs delivering high efficiencies of
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26 up to 20% in n-i-p perovskite solar cells using various combinations of ETL and absorber
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29 materials. Most importantly, incorporation of VOx as HTL component enables impressive
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31 operational stability of perovskite solar cells over few thousands of hours under continuous
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33 illumination. We also showed that faster degradation of the reference cells using MoOx
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interlayer is associated with the aggressive chemistry occurring between this oxide and
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38 complex lead halides at elevated temperatures. On the contrary, VOx was shown to be much
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40 more chemically inert with respect to the oxidation of the absorber material, which accounts
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for the observed largely increased lifetime of PSCs assembled using this oxide material.
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45 Finally, we strongly believe that the application of hybrid HTLs utilizing vanadium (V) oxide
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47 as an inorganic component (e.g. explored PTA(A)/VOx systems) represents an important step
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49 towards increasing operational lifetime of perovskite photovoltaics which is essential for
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52 practical use of this technology.
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55 ASSOCIATED CONTENT
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58 Supporting Information Available: experimental procedures and figures S1–S4 with
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60 additional J-V characteristics and EQE spectra.

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3 AUTHOR INFORMATION
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6 The authors declare no competing financial interests.
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9 ACKNOWLEDGEMENTS
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11 This work was supported by Russian Science Foundation (project No. 19-73-30020) at IPCP
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RAS and Skolkovo Foundation grant at Skoltech.
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17 REFERENCES
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19 (1) Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. Organometal Halide Perovskites as
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Visible-Light Sensitizers for Photovoltaic Cells. J. Am. Chem. Soc. 2009, 131, 6050–
22 6051.
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24 (2) NREL Best Certified Research-Cell Efficiency Chart. https://www.nrel.gov/pv/cell-
25
26 efficiency.html (accessed 18 march).
27
(3) Frolova, L. A.; Anokhin, D. V.; Piryazev, A. A.; Luchkin, S. Y.; Dremova, N. N.;
28
29 Stevenson, K. J.; Troshin, P. A. Highly Efficient All-Inorganic Planar Heterojunction
30
31 Perovskite Solar Cells Produced by Thermal Coevaporation of CsI and PbI2. J. Phys.
32
33 Chem. Lett. 2017, 8, 67–72.
34 (4) Saliba, M.; Correa-Baena, J.-P.; Grätzel, M.; Hagfeldt, A.; Abate, A. Perovskite Solar
35
36 Cells: From the Atomic Level to Film Quality and Device Performance. Angew. Chem.
37
38 Int. Ed. 2018, 57, 2554–2569.
39
(5) Frolova, L. A.; Anokhin, D. V.; Gerasimov, K. L.; Dremova, N. N.; Troshin, P. A.
40
41 Exploring the Effects of the Pb2+ Substitution in MAPbI3 on the Photovoltaic
42
43 Performance of the Hybrid Perovskite Solar Cells. J. Phys. Chem. Lett. 2016, 7, 4353–
44
45 4357.
46 (6) Steirer, K. X.; Schulz, P.; Teeter, G.; Stevanovic, V.; Yang, M.; Zhu, K.; Berry, J. J.
47
48 Defect Tolerance in Methylammonium Lead Triiodide Perovskite. ACS Energy Lett.
49
50 2016, 1, 360–366.
51
52
(7) Yamilova, O. R.; Danilov, A. V.; Mangrulkar, M.; Fedotov, Y. S.; Luchkin, S. Y.;
53 Babenko, S. D.; Bredikhin, S. I.; Aldoshin, S. M.; Stevenson, K. J.; Troshin, P. A.
54
55 Reduction of Methylammonium Cations as a Major Electrochemical Degradation
56
57 Pathway in Mapbi3 Perovskite Solar Cells. J. Phys. Chem. Lett. 2020, 11, 221–228.
58
(8) Wali, Q.; Iftikhar, F. J.; Khan, M. E.; Ullah, A.; Iqbal, Y.; Jose, R. Advances in Stability
59
60 of Perovskite Solar Cells. Org. Electron. 2020, 78, 105590.

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3 (9) Akbulatov, A. F.; Luchkin, S. Y.; Frolova, L. A.; Dremova, N. N.; Gerasimov, K. L.;
4
5 Zhidkov, I. S.; Anokhin, D. V.; Kurmaev, E. Z.; Stevenson, K. J.; Troshin, P. A. Probing
6
7 the Intrinsic Thermal and Photochemical Stability of Hybrid and Inorganic Lead Halide
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9
Perovskites. J. Phys. Chem. Lett. 2017, 8, 1211–1218.
10 (10) Domanski, K.; Roose, B.; Matsui, T.; Saliba, M.; Turren-Cruz, S.-H.; Correa-Baena, J.-
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12 P.; Carmona, C. R.; Richardson, G.; Foster, J. M.; De Angelis, F., et al. Migration of
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14 Cations Induces Reversible Performance Losses over Day/Night Cycling in Perovskite
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Solar Cells. Energy Environ. Sci. 2017, 10, 604–613.
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17 (11) Ansari, M. I. H.; Qurashi, A.; Nazeeruddin, M. K. Frontiers, Opportunities, and
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19 Challenges in Perovskite Solar Cells: A Critical Review. J. Photoch. Photobio. C 2018,
20
21 35, 1–24.
22 (12) Boyd, C. C.; Cheacharoen, R.; Bush, K. A.; Prasanna, R.; Leijtens, T.; McGehee, M.
23
24 D. Barrier Design to Prevent Metal-Induced Degradation and Improve Thermal
25
26 Stability in Perovskite Solar Cells. ACS Energy Lett. 2018, 3, 1772–1778.
27
28
(13) Brinkmann, K. O.; Zhao, J.; Pourdavoud, N.; Becker, T.; Hu, T.; Olthof, S.; Meerholz,
29 K.; Hoffmann, L.; Gahlmann, T.; Heiderhoff, R., et al. Suppressed Decomposition of
30
31 Organometal Halide Perovskites by Impermeable Electron-Extraction Layers in
32
33 Inverted Solar Cells. Nature Commun. 2017, 8, 13938.
34
(14) Raiford, J. A.; Belisle, R. A.; Bush, K. A.; Prasanna, R.; Palmstrom, A. F.; McGehee,
35
36 M. D.; Bent, S. F. Atomic Layer Deposition of Vanadium Oxide to Reduce Parasitic
37
38 Absorption and Improve Stability in n-i-p Perovskite Solar Cells for Tandems. Sustain.
39
40 Energy Fuels 2019, 3, 1517–1525.
41 (15) Cheng, M.; Li, Y.; Safdari, M.; Chen, C.; Liu, P.; Kloo, L.; Sun, L. Solar Cells: Efficient
42
43 Perovskite Solar Cells Based on a Solution Processable Nickel(II) Phthalocyanine and
44
45 Vanadium Oxide Integrated Hole Transport Layer. Adv. Energy Mater. 2017, 7,
46
1602556.
47
48 (16) Sanehira, E. M.; Tremolet de Villers, B. J.; Schulz, P.; Reese, M. O.; Ferrere, S.; Zhu,
49
50 K.; Lin, L. Y.; Berry, J. J.; Luther, J. M. Influence of Electrode Interfaces on the
51
52 Stability of Perovskite Solar Cells: Reduced Degradation Using MoOx/Al for Hole
53 Collection. ACS Energy Lett. 2016, 1, 38–45.
54
55 (17) Christians, J. A.; Schulz, P.; Tinkham, J. S.; Schloemer, T. H.; Harvey, S. P.; Tremolet
56
57 de Villers, B. J.; Sellinger, A.; Berry, J. J.; Luther, J. M. Tailored Interfaces of
58
59
Unencapsulated Perovskite Solar Cells for >1,000 Hour Operational Stability. Nat.
60 Energy 2018, 3, 68–74.
13
ACS Paragon Plus Environment
 The Journal of Physical Chemistry Letters Page 14 of 15

1
2
3 (18) Schloemer, T. H.; Gehan, T. S.; Christians, J. A.; Mitchell, D. G.; Dixon, A.; Li, Z.;
4
5 Zhu, K.; Berry, J. J.; Luther, J. M.; Sellinger, A. Thermally Stable Perovskite Solar
6
7 Cells by Systematic Molecular Design of the Hole-Transport Layer. ACS Energy Lett.
8
9
2019, 4, 473–482.
10 (19) Tracy H. Schloemer, J. A. R., Timothy S. Gehan, Sanjini Mamayakkara, Taylor Moot,
11
12 Steven Harvey, Rosemary C. Bramante, Sean Dunfield, Amy Louks, Annalise E.
13
14 Maughan, Lyle Bliss, Michael D. McGehee, Maikei F.A.M. van Hest, Matthew O.
15
Reese, Stacey F. Bent, Joseph J. Berry, Joseph M. Luther, Alan Sellinger, Vanadium
16
17 Oxide Interfacial Layer in Perovskite Solar Cells for High Temperature Operational
18
19 Stability of Unencapsulated Devices in Air. In NanoGe Online Meetup Conference,
20
21 2020.
22 (20) Tsarev, S.; Dubinina, T. S.; Luchkin, S. Y.; Zhidkov, I. S.; Kurmaev, E. Z.; Stevenson,
23
24 K. J.; Troshin, P. A. Phenyl-C61-Butyric Acid as an Interface Passivation Layer for
25
26 Highly Efficient and Stable Perovskite Solar Cells. J. Phys. Chem. C 2020, 124, 1872–
27
28
1877.
29 (21) Hummelen, J. C.; Knight, B. W.; LePeq, F.; Wudl, F.; Yao, J.; Wilkins, C. L.
30
31 Preparation and Characterization of Fulleroid and Methanofullerene Derivatives. J.
32
33 Org. Chem. 1995, 60, 532–538.
34
(22) Tsarev, S.; Yakushchenko, I. K.; Luchkin, S. Y.; Kuznetsov, P. M.; Timerbulatov, R.
35
36 S.; Dremova, N. N.; Frolova, L. A.; Stevenson, K. J.; Troshin, P. A. A New
37
38 Polytriarylamine Derivative for Dopant-Free High-Efficiency Perovskite Solar Cells.
39
40 Sustain. Energy Fuels 2019, 3, 2627–2632.
41 (23) Zhao, P.; Kim, B. J.; Jung, H. S. Passivation in Perovskite Solar Cells: A Review.
42
43 Mater. Today Energy 2018, 7, 267–286.
44
45 (24) Guerrero, A.; You, J.; Aranda, C.; Kang, Y. S.; Garcia-Belmonte, G.; Zhou, H.;
46
Bisquert, J.; Yang, Y. Interfacial Degradation of Planar Lead Halide Perovskite Solar
47
48 Cells. ACS Nano 2016, 10, 218–224.
49
50 (25) Zhao, Y.; Nardes, A. M.; Zhu, K. Effective Hole Extraction Using Moox-Al Contact in
51
52 Perovskite CH3NH3PbI3 Solar Cells. Appl. Phys. Lett. 2014, 104, 213906.
53 (26) Boldyreva, A. G.; Akbulatov, A. F.; Tsarev, S. A.; Luchkin, S. Y.; Zhidkov, I. S.;
54
55 Kurmaev, E. Z.; Stevenson, K. J.; Petrov, V. G.; Troshin, P. A. Gamma-Ray-Induced
56
57 Degradation in the Triple-Cation Perovskite Solar Cells. J. Phys. Chem. Lett. 2019, 10,
58
59
813–818.
60

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1
2
3 (27) Khenkin, M. V.; Katz, E. A.; Abate, A.; Bardizza, G.; Berry, J. J.; Brabec, C.; Brunetti,
4
5 F.; Bulović, V.; Burlingame, Q.; Di Carlo, A., et al. Consensus Statement for Stability
6
7 Assessment and Reporting for Perovskite Photovoltaics Based on Isos Procedures. Nat.
8
9
Energy 2020, 5, 35–49.
10 (28) Olthof, S.; Meerholz, K. Substrate-Dependent Electronic Structure and Film Formation
11
12 of MAPbI3 Perovskites. Sci. Rep. 2017, 7, 40267.
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
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