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Letter
Modeling the Interaction of Molecular Iodine with MAPbI3:
A Probe of Lead-Halide Perovskites Defect Chemistry
Daniele Meggiolaro, Edoardo Mosconi, and Filippo De Angelis
ACS Energy Lett., Just Accepted Manuscript • DOI: 10.1021/acsenergylett.7b01244 • Publication Date (Web): 18 Jan 2018
Downloaded from http://pubs.acs.org on January 18, 2018

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3 Modeling the Interaction of Molecular Iodine with MAPbI3: A
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Probe of Lead-Halide Perovskites Defect Chemistry
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10 Daniele Meggiolaro,a,b Edoardo Mosconi,a,c * Filippo De Angelis a,b,c *
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16 Computational Laboratory for Hybrid/Organic Photovoltaics (CLHYO), CNR-ISTM, Via Elce di
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18 Sotto 8, 06123, Perugia, Italy.
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D3-CompuNet, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy.
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24 Consortium for Computational Molecular and Materials Sciences (CMS)2, Via Elce di Sotto, 8,
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26 06123 Perugia, Italy.
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3 Abstract
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6 Understanding the defect chemistry of lead-halide perovskites is of paramount importance to further
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8 progress towards exploitation of these materials. Here we combine recent experimental observations
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10 on the behavior of MAPbI3 upon exposure to I2 vapor with first-principles calculations to extract a
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12 global picture of defect chemistry in lead-halide perovskites. By matching the reported
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14 experimental observables we disclose the origin of the p-doping observed upon exposing MAPbI3
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to I2 and highlight its consequences on the charge/ion transport and trapping activity. Electron/hole
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19 traps related to positive/negative interstitial iodine dominate the defect chemistry in intrinsic
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21 conditions, while in p-doped MAPbI3 electrons are mainly trapped by positive interstitial iodine and
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23 neutral lead vacancies. I2 spontaneously dissociates on iodine vacancies, leading to vacancy
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25 passivation and to the formation of positive interstitial iodine. I2 spontaneously dissociates on non-
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27 defective MAPbI3 (001) surfaces to form pairs of negative/positive interstitial iodine. Upon trapping
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29 a hole/electron pair at negative/positive interstitial iodine, I2 release becomes thermodynamically
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favored possibly representing a photo-induced trap curing mechanism.
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3 Understanding the defect chemistry of lead-halide perovskites is of paramount importance to further
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5 progress with the practical solar cell exploitation of this outstanding class of materials. The long
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7 lifetimes and diffusion lengths of photogenerated charge carriers in MAPbI3 and related perovskites
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9 are suggestive of an apparently low density of charge traps. Clearly, a distinction should be made
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between defects and traps, since most of typical defects in conventional perovskites turn out to be
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14 only shallow traps in MAPbI3.1-4 This, coupled to large polarons protecting photogenerated charge
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16 carriers,5, 6 has generated the concept of the what is generically referred to as “perovskite defect
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18 tolerance”. One must recognize that defect tolerance, in the general meaning, is a fundamental
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20 ingredient of the astonishing properties of this materials class, which would otherwise probably
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22 only have a mere academic interest.
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Most experimental investigations provide indirect hints on defects, mainly determining the
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27 density of trap states through electrical conductivity measurements. Very low trap densities of
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29 ∼1010-1011 cm-3 have been reported for MAPbI3 single crystals,7, 8 increasing up to ∼1016 cm-3 for
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31 polycrystalline thin films.8-10 Disclosing the properties of defects in a semiconductor with atomistic
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33 resolution can be accessed through first-principles calculations, which are however limited by the
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35 scale of employed models and the intrinsic accuracy the underlying electronic structure theory. Here
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we sought to combine a survey of recent experimental observations on the behavior of MAPbI3
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40 upon exposure to molecular iodine vapor with high level first-principles calculations to extract a
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42 global picture of defect chemistry in lead-halide perovskites. We thus use the effect of I2 exposure
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44 to MAPbI3 as a probe of the underlying material defect chemistry. By matching the reported
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46 experimental observables to our model defect chemistry, we disclose the origin of the observed p-
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48 doping upon I2 exposure and highlight its consequences on the charge/ion transport and trapping
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activity.
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53 To our knowledge, four studies have reported on the interaction between I2 vapors and
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55 MAPbI3.11-14 Here we briefly summarize the main findings of these studies which are relevant to the
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57 present work:
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3 1) Formation of metallic lead, as revealed by XPS, related to degradation of the perovskite.11
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5 2) 150 mV shift of the Fermi energy towards the valence band, indicative of p-doping.13
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7 3) Irreversibility of the p-doping.11, 13
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9 4) Quenching of the photoluminescence quantum yield.12
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5) Increase of electrical conductivity due to holes. 14
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14 6) Decrease of the ionic conductivity.14
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18 We begin by re-investigating native defects in MAPbI3 by state of the art first-principles
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20 calculations in 2x2x1 tetragonal supercells using hybrid DFT, including dispersion corrections and
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22 spin-orbit coupling (SOC). We use the modified HSE06 exchange-correlation functional including
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43% exact exchange proposed in Ref. 15, which provides band edge energetics comparable to high-
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27 level GW-SOC calculations.16 Hybrid functionals are important to characterize defects with
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29 unpaired electrons,17, 18 such as the neutral Ii0 and VI0 defects. The central quantity to our discussion
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31 is the Defect Formation Energy (DFE), see Supplementary Information. Knowledge of the DFE of
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33 relevant defects in different charge states allows one to calculate: i) the thermodynamic ionization
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35 levels, correspond to oxidation and reduction potentials of the defective system, whose energy with
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37 respect to the band edges determine the defect trapping activity; ii) the defect density; and iii) the
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native Fermi level of the system.19
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42 The DFE diagram of MAPbI3 grown in iodine medium (corresponding to 1:1 ratio of the
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44 PbI2 and MAI precursors) and excess I2 vapors are reported in Figure 1a and 1b, respectively; the
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46 associated thermodynamic ionization levels are reported in Figure 1c.
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23 Figure 1. DFEs diagrams calculated by SOC-HSE06 in iodine medium conditions (a) and under a
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25 simulated I2 pressure of 10-4 atm (b); c) Thermodynamic transition levels, which are independent of
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27 the growth conditions.
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30 In iodine-medium conditions the most stable defects are MA interstitials (MAi+), negative
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32 interstitial iodine (Ii-) and lead vacancies (VPb2-), which pin the Fermi level at mid-gap (0.71 eV
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34 above VBM over a 1.58 eV calculated band gap), Figure 1a. Positive interstitial iodine (Ii+) and
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iodine vacancy (VI+) have a ∼0.2 eV higher DFE, while interstitial lead (Pbi2+) lies at much higher
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39 DFE. The close to mid-gap native Fermi level is consistent with the intrinsic (or mildly p-doped)
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41 nature of MAPbI3,13, 20 while thin films show n-doping related to a Pb-rich surface environment.21
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43 To properly account for defect activity, the defect activation energy to migration should be taken
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45 into account, since the presence of defects with high activation energy could be kinetically limited.
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Defects related to I and MA ions are the major migrating species,22-24 with I faster than MA, faster
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50 than Pb migration.25 Recent X-ray and neutron diffraction measurements on MAPbI3 revealed
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52 significant structural disorder associated to interstitial iodine in MAPbI3 films.26
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3 Table 1. DFEs and defect densities calculated in iodine-medium and at I2 partial pressure of 10-4
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5 atm.
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8 iodine-medium P(I2) = 10-4 atm
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11 Defect DFE (eV) Density (cm-3) DFE (eV) Density (cm-3)
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14 VPb2- 0.66 ∼ 1010 0.44 ∼ 1014
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17 VPb0 1.10 ∼ 103 0.71 ∼ 1010
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20 MAi+ 0.57 ∼ 1012 0.69 ∼ 1010
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23 Ii+ 0.72 ∼ 1010 0.44 ∼ 1014
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Ii- 0.60 ∼ 1012 0.49 ∼ 1014
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30 VI + 0.87 ∼ 107 0.98 ∼ 106
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33 Pbi2+ 1.16 ∼ 102 1.38 ∼0
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40 Interstitial iodine is an amphoteric defect that can trap both electrons and holes with +/0 and
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42 0/- ionization levels placed at 0.57 and 0.30 eV below and above the CB and VB edges, Figure 1c.
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44 Notice that the neutral state of interstitial iodine is unstable, 15 similar to the typical iodine chemistry
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46 whereby I2- (or a neutral I atom) is unstable with respect to I- and I3-.27 The metastable nature of Ii0
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implies that Ii- should trap two holes to convert to Ii+, with the (-/+) transition placed at mid-gap; the
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51 two-electron nature of the process, however, imparts it a vanishingly small cross section since the
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53 probability of two consecutive trapping events at the same defect site is vanishingly small. VI+ has a
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55 transition level resonant with the CB, thus although showing a low activation energy to migration,28
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57 it can at most represent a shallow trapping site in bulk crystals. VPb is stable in the 2- charge state in
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3 a wide range of Fermi energies, thus this defect can trap holes by the (-/2-) transition level whose
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5 energy falls 0.15 eV above the VBM, suggesting a shallow trapping activity. The (0/2-) transition
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7 implies the trapping of two holes on the same defect site, and as such it has a vanishingly small
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9 capture cross section. The deep (0/-) transition falling at mid-gap is not active in iodine-medium
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conditions due to the low density of VPb0, see Table 1. Notably, VPb0 decomposes into VPb2- + Ii+ +
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14 VI+ on the same site, which is more stable than the simple neutral Pb vacancy by 0.40 eV. The (0/-)
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16 ionization level of VPb is thus the analogous of the (+/0) transition of Ii, falling approximately in
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18 the same energy range. As previously mentioned, lead vacancies have a large (∼1 eV) migration
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20 barrier,28 thus their formation could be kinetically limited. In iodine-medium conditions the main
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deep electron and hole traps among native defects are thus related to interstitial iodine. The match
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between the calculated Ii+/- density (~1010-1012 cm-3, see Table 1) and the measured trap density
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27 points at Ii+ and Ii- as the experimentally observed electron and hole traps in MAPbI3 single
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29 crystals.7
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32 By increasing the iodine partial pressure, mimicking experiments in which the perovskite is
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34 exposed to I2 vapors, we are shifting the equilibrium towards iodine-rich conditions. To quantify the
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36 chemical potential shift due to exposure of MAPbI3 to I2 pressures of the order of ∼10-4 atm
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employed in experiments,13, 14
we calculated the variation of I2 chemical potential induced by
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41 pressure referred to iodine rich conditions as:
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44 ∆µ= -RT ln(P/P0) -T∆St (2)
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47 where P is the actual pressure referred to the standard P0=1 atm, T is the absolute temperature (300
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49 K here), and ∆St is the variation of translation entropy of I2 gas with pressure estimated assuming an
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51 ideal gas behavior, see Table S1, Supporting Information. We verified that other terms in the Gibbs
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53 free energy (e.g. thermal contributions to enthalpy due to vibrations, and rotational-vibrational
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contributions to entropy) remain roughly constant in the explored pressure variation range. Notice
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3 that variation of the chemical potential of a gaseous species in a sizable range (0.2 eV or more) is
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5 easily achieved by varying its partial pressure, while tuning the chemical potential of a species in
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7 solution by a factor ∼2.3 RT (∼0.06 eV) implies variation of its activity (concentration) by 1 order
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of magnitude, a situation which can be hardly realized in standard perovskite synthetic conditions.
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12 Upon exposing MAPbI3 to I2 the most notable effect is the stabilization of positive
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interstitial iodine and lead vacancies, Figure 1b, with a consequent p-doping of the material.
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17 Accordingly, the calculated Fermi level shifts by 80 meV, from 0.71 to 0.63 eV above the VBM,
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19 consistent with the 150 mV work function increase measured by Zohar et al.13. The increase in
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21 electric conductivity associated to hole transport observed by Senocrate et al.14 is also readily
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23 explained since holes are the dominant free carriers under p-doped conditions and their
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25 concentration is predicted to increase by ~3 orders of magnitudes a consequence of the observed p-
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doping. Our results are also consistent with the formation of metallic lead observed by Wang et al.
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30 upon exposure of MAPbI3 to I2,11 related to the stabilization of lead vacancies, i.e. the expulsion of
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32 lead from its bulk crystal site. Under p-doped conditions the main charge trap is now Ii+ (and to a
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34 lesser extent VPb0) whose density increases by several orders of magnitude compared to intrinsic
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36 conditions, see Table 1. Both defects can effectively trap electrons, thereby explaining the
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38 photoluminescence quenching observed by Li et al. after MAPbI3 interaction with I2.12
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41 Our model has so far allowed us to rationalize most of the experimental observations related
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to I2 exposure, with the exception of the decreased ionic conductivity measured by Senocrate et al.14
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46 These authors ascribed such behavior to the saturation of iodine vacancies, implying a mechanism
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48 of iodine incorporation mediated by vacancies. This seems a perfectly reasonable explanation, since
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50 iodine vacancy sites would “attract” mobile iodine atoms from I2 to restore a perfect crystal
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52 lattice. Ion conductivity is a function of both the density of ionic migrating species and their
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54 migration energy barrier. A decrease in ionic conductivity can be either caused by a reduction of the
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density of migrating defects (e.g. iodine vacancies) or by an increase of the migration energy
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3 barrier, or both. In this respect, one should notice that iodine vacancies are stable in their positive
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5 charge state in all conditions, meaning that to preserve electroneutrality I2 dissociation in a vacancy
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7 should also imply formation of a positive interstitial iodine, as:
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10 VI+ + I2→perf + Ii+ (3)
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13 where perf means the perfect crystal. We first calculated the thermodynamics for reaction (3) in a
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15 tetragonal 2x2x2 bulk MAPbI3 supercell, finding it favorable by 0.39 (0.72) eV with no corrections
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(including dispersion and entropic corrections, see Computational Details). Thus vacancy filling by
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20 I2 is in all cases a thermodynamically favored reaction which produces Ii+. The question is now
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22 whether positive interstitial iodine has a higher migration energy barrier than a positive iodine
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24 vacancy. To check this point we searched for the minimum energy pathway to Ii+ migration, by
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26 scanning the potential energy surface along a displacement coordinate, followed by short ab initio
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28 molecular dynamics simulations to properly allow for local atomic rearrangement.22 This procedure
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is expected to deliver lower activation energies than standard calculations by virtue of the effective
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33 relaxation around the migration pathway. In Table 2 we report migration energy barriers for
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35 relevant defects calculated at the SR-PBE level used for geometry optimizations and refined by
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37 SOC-HSE06.
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40 Table 2. Migration energy barriers (eV) calculated by SR-PBE and SOC-HSE06 levels of theory on
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42 the SR-PBE optimized geometries.
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45 SR-PBE SOC-HSE06
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48 VI + 0.09 0.11
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51 Ii+ 0.19 0.24
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54 Ii- 0.08 0.06
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3 As it can be noticed, SR-PBE and SOC-HSE06 levels of theory provide similar activation energies.
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5 Notably, while VI+ and Ii- have roughly the same energy barrier, we predict a factor 2 increase in the
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7 migration energy barrier for Ii+ compared to VI+, from ∼0.1 to ∼0.2 eV, consistent with the decrease
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of ionic conductivity experimentally measured in Ref. . This points at saturation of iodine
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12 vacancies by I2 leaving behind an Ii+ defect, further contributing to p-doping and
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14 photoluminescence quenching.
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17 Besides the vacancy saturation pathway, I2 could possibly interact with both the intact
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19 perovskite bulk and surfaces. A recent computational study reported the favorable interaction of I2
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21 with MAPbI3 surfaces, leading to split iodine interstitials.30 To investigate the energetics and
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23 structural features of this processes in the bulk and on surfaces, we explicitly added one I2 molecule
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25 to a bulk 2x2x2 MAPbI3 tetragonal supercell and to MAI-terminated 2x2x3 slabs exposing (001)
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and (110) facets, see Figure 2 and Supporting Information. In these cases the MA cations were
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30 initially aligned antiparallel to quench the molecular dipole. Most notably, I2 is not stable in its
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32 molecular form and spontaneously dissociates into a positive and a negative interstitial iodine (Ii+
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34 and Ii-), similarly to what found by Zhang et al. 30, being stabilized by the bond with I and Pb atoms,
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36 respectively, see Figure 2.
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50 Figure 2. a) Starting bulk MAPbI3 structure with added I2 (yellow atoms) and b) final relaxed
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structures. Notice in b) the formation of the typical Ii+ trimer and Ii- dimer. c) Optimized structure
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55 of I2 added at the MAI-terminated MAPbI3 surface (001) facet, delivering the same Ii+/ Ii- pair. I-I
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57 distances (Å) are also reported.
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3 I2 incorporation into bulk MAPbI3 is unfavorable (favorable) by 0.40 (0.02) eV with no corrections
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5 (including dispersion and entropic corrections), so we expect the vacancy-mediated I2 incorporation
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7 mechanism to dominate the bulk chemistry. The Ii+ / Ii- intimate defect couple is more stable than
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9 the non-interacting Ii+ and Ii- defects by ~0.15 eV. This means that formation of interacting Ii+ and
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Ii- defects, which is possible due to their low barriers to migration, could increase their density in
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14 bulk MAPbI3.
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I2 dissociation becomes thermodynamically favorable by 0.73 (0.16) eV on MAPbI3 (001)
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19 facets with no corrections (with corrections) forming the same Ii+ / Ii- interacting defect couple, see
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21 Figure 2c.30 Notably, I2 dissociation is unfavorable by 0.10 eV on the (110) facet, see Supporting
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23 Information, suggesting a different reactivity of the various MAPbI3 surfaces. I2 dissociation at
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25 surfaces could thus still represent a pathway of VI+ saturation. The calculated thermodynamics is
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27 consistent with the irreversibility of the p-doping observed in Ref. 12
. This is at variance with
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MAPbI3 interaction with O2, which is characterized by a much smaller interaction energy,
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32 accounting for the reversibility of the reaction.31
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35 Finally, it is interesting to notice that the energetics of I2 dissociation and incorporation at
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37 surfaces can be reverted when introducing an electron/hole pair into the system. By simulating the
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39 lowest triplet state of the MAPbI3 (001) surface with the Ii+ / Ii- interacting defect couple, we find
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41 that destabilization of neutral interstitial iodine by electron/hole trapping at Ii+ / Ii-, respectively,
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43 leads to spontaneous I2 release from the surface, which is now favorable by 0.19 (0.74) eV with no
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corrections (with corrections). This I2 formation pathway following electron/hole capture may
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48 constitute a source of light-induced trap annihilation, analogously to the previously proposed
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50 Frenkel (vacancy/interstitial) mediated pathway.28 The main difference between the two
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52 mechanisms is that since I2 would remain close to the perovskite surface, unless it is evacuated as a
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54 gas, it may reversibly re-dissociate to reform the electron/hole Ii+ / Ii- trapping defects. In a typical
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56 experiment in which MAPbI3 is exposed to inert atmosphere (by e.g. N2) while irradiating the
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3 sample, we thus predict that increasing (decreasing) the pressure of N2 will lead to a decrease
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5 (increase) of the effectiveness of light-induced trap annihilation, by disfavoring (favoring) the exit
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7 of gaseous I2. At the same time, removing the formed I2 by e.g. fluxing N2 could lead to more
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9 effective and partly irreversible decrease in the material trap density.
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12 In summary, we have constructed a global picture of defect chemistry in lead-iodide
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perovskites. Under intrinsic conditions, i.e. when the Fermi level is close to mid-gap, positive and
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negative interstitial iodine constitute the main source of electron and hole traps, respectively. Upon
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19 exposing the material to I2 a Fermi level down shift is calculated, which closely matches the
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21 experimental work function variation. I2 dissociates on iodine vacancies restoring the pristine
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23 crystal but leaving behind positive interstitial iodine. The higher migration energy barrier of
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25 positive interstitial iodine compared to iodine vacancy accounts for the decreased ionic transport,
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27 while the associated p-doping increases the hole electrical conductivity. Notably, I2 dissociates both
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in the bulk and on surfaces to produce a pair of positive/negative interstitial iodine defects, with the
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32 reaction being strongly favored on (001) surfaces. Upon light irradiation, a hole and an electron can
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34 be trapped at the positive/negative interstitial iodine defect pair, leading to destabilization of the
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36 defect pair and I2 exit from the perovskite. This may represent an additional pathway of light-
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38 induced defect annihilation.
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41 Supporting Information Available: Computational Details, (110) structures, I2 chemical
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43 potentials.
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46 References:
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48 (1) Yin, W.-J.; Shi, T.; Yan, Y. Unusual defect physics in CH3NH3PbI3 perovskite solar cell
49 absorber. Appl. Phys. Lett. 2014, 104, 063903.
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(2) Buin, A.; Comin, R.; Xu, J.; Ip, A. H.; Sargent, E. H. Halide-Dependent Electronic Structure of
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Organolead Perovskite Materials. Chem. Mater. 2015, 27, 4405-4412.
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53 (3) Agiorgousis, M. L.; Sun, Y.-Y.; Zeng, H.; Zhang, S. Strong Covalency-Induced Recombination
54 Centers in Perovskite Solar Cell Material CH3NH3PbI3. J. Am. Chem. Soc. 2014, 136, 14570-14575.
55 (4) Walsh, A.; Scanlon, D. O.; Chen, S.; Gong, X. G.; Wei, S.-H. Self-Regulation Mechanism for
56 Charged Point Defects in Hybrid Halide Perovskites. Angew. Chem. Int. Ed. 2014, 53, 1-5.
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3 (5) Miyata, K.; Meggiolaro, D.; Trinh, M. T.; Joshi, P. P.; Mosconi, E.; Jones, S. C.; De Angelis, F.;
4 Zhu, X. Y. Large polarons in lead halide perovskites. Sci. Adv. 2017, 3.
5 (6) Zhu, X. Y.; Podzorov, V. Charge Carriers in Hybrid Organic–Inorganic Lead Halide Perovskites
6 Might Be Protected as Large Polarons. J. Phys. Chem. Lett. 2015, 6, 4758-4761.
7 (7) Adinolfi, V.; Yuan, M.; Comin, R.; Thibau, E. S.; Shi, D.; Saidaminov, M. I.; Kanjanaboos, P.;
8 Kopilovic, D.; Hoogland, S.; Lu, Z.-H.; Bakr, O. M.; Sargent, E. H. The In-Gap Electronic State
9 Spectrum of Methylammonium Lead Iodide Single-Crystal Perovskites. Adv. Mater. 2016, 28,
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(8) Chen, Y.; Yi, H. T.; Wu, X.; Haroldson, R.; Gartstein, Y. N.; Rodionov, Y. I.; Tikhonov, K. S.;
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Zakhidov, A.; Zhu, X. Y.; Podzorov, V. Extended carrier lifetimes and diffusion in hybrid
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