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2 Highly Air-Stable Single-Crystalline β-CsPbI3 Nanorods: A 1
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Platform for Inverted Perovskite Solar Cells 3

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Somnath Mahato, Arup Ghorai, Sanjeev Kumar Srivastava, Mantu Modak,

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Q1 8 Sudarshan Singh, and Samit K. Ray* 8
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12 coefficient (105 cm), excellent charge trans- 12
13 The synthesis of single-crystalline β-CsPbI3 perovskite nanorods (NRs) using port properties, and high photo­stability.[2–5] 13
14 a colloidal process is reported, exhibiting their improved photostability CsPbI3 exists in four phases; α-cubic (black 14

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15 under 45–55% humid condition. The crystal structure of CsPbI3 NRs films color) is only stable at a high temperature 15
16 (>320 °C), β-tetragonal and γ-orthorhombic 16
is investigated using Rietveld refined X-ray diffraction (XRD) patterns to
17 phases are stable at low temperatures, and 17
18 determine crystallographic parameters and the phase transformation from δ-orthorhombic (yellow color) is the non- 18
19 orthorhombic (γ-CsPbI3) to tetragonal (β-CsPbI3) one on annealing at 150 °C. perovskite phase that is an optically inactive 19
20 Atomic resolution transmission electron microscopy images are utilized to semiconductor. It has been predicted that 20
21 determine the probable atomic distribution of Cs, Pb, and I atoms in a single the crystal structure of tetragonal β-phase 21
22 is more stable than the cubic α-phase.[6,7] 22
β-phase CsPbI3 NR, in agreement with the XRD structure and selected area

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23 However, all stable phases can convert into 23
24 electron diffraction pattern, indicating a growth of single crystalline β-CsPbI3 a yellow non-perovskite one on prolonged 24
25 NR. The calculation of electronic band structure of tetragonal β-CsPbI3 using exposure to humid condition. Therefore, 25
26 density functional theory (DFT) reveals a direct transition with lower band the realization of long-term stability of 26
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27 gap and higher absorption coefficient in the solar spectrum, as compared to CsPbI3, especially in high humidity and 27
28 its γ-phase. An air-stable (45–55% humidity) inverted perovskite solar cell, temperature, is a challenging task.[8,9] 28
29 Recently, Wang et  al.[6] have reported the 29
employing β-CsPbI3 NRs without any encapsulation, yields an efficiency
30 synthesis of tetragonal β-CsPbI3 thin 30
31 of 7.3% with 78% enhancement over the γ-phase, showing its potential for films, which exhibited higher stability and 31
32 future low cost photovoltaic devices. a more suitable band gap, giving rise to 32 Q4
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33 photovoltaic conversion efficiency (PCE) of 33

34 15% without any surface passivation. 34
35 1. Introduction In addition to thin films, different nanocrystals of perov- 35
36 skites have been investigated extensively in recent years due 36
37 All inorganic perovskites (CsPbX3: X = Cl, Br, and I) are very to their size-dependent properties useful for optical devices 37
38 promising for the development of next-generation optoelec- with enhanced performance and stability.[10–13] However the 38
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39 tronic and photovoltaic (PV) devices.[1] From application point fundamental atomic structures imaging of all inorganic halide 39
40 of view, CsPbI3 is one of the most important inorganic perov- perovskites in real-space is difficult to extract by atomic reso- 40
41 skites due to its high diffusion length (>1 µm), high absorption lution transmission electron microscopy (TEM) because of the 41
42 sensitivity of their structures to the destructive electron beam. 42
43 As a result, such atomic resolution imaging[14–16] is very impor- 43
S. Mahato, A. Ghorai
44 School of Nano Science and Technology tant for the understanding of novel and unique properties of 44
45 Indian Institute of Technology Kharagpur CsPbI3. CsPbI3 nanocrystals have a tunable band gap (from ≈1.7 45
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Q2 46 Kharagpur, West Bengal 721803, India to ≈2.8 eV), excellent photoluminescence, and outstanding light 46
47 S. Mahato, S. K. Srivastava, S. Singh, S. K. Ray harvesting properties.[17–20] Therefore, they have triggered wide 47
48 Department of Physics and exciting applications in high-performance optoelectronic 48
Indian Institute of Technology Kharagpur
49 Kharagpur, West Bengal 721302, India devices.[21–24] Besides the photodetectors and light-emitting 49
50 E-mail: physkr@phy.iitkgp.ac.in devices (LEDs), they possess a great potential for PV applica- 50
51 M. Modak tions requiring them to be synthesized using a low cost process. 51
52 Saha Institute of Nuclear Physics Among different shapes, 1D nanostructures (nanorods (NRs)/ 52
Q3 53 1/AF Bidhannagar, Kolkata, West Bengal 700064, India 53
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nanowires) are potentially attractive due to their high crystal-

54 S. K. Ray line, large surface-to-volume ratio, and capability of having both 54
55 S. N. Bose National Centre for Basic Sciences horizontal and vertical device configurations. To date, several 55
Kolkata, West Bengal 700106, India
56 groups[25–27] have developed techniques for synthesizing 1D 56
The ORCID identification number(s) for the author(s) of this article
57 can be found under https://doi.org/10.1002/aenm.202001305. CsPbI3 nanocrystals for electronic and optoelectronic devices 57
58 but all studies till date are focused on γ- and α-CsPbI3 nanocrys- 58
59 DOI: 10.1002/aenm.202001305 tals or quantum dots-based high-temperature conventional 59

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1 (n-i-p architecture) perovskite solar cells. However, the fabrica- In this work, single-crystalline CsPbI3 NRs were synthe- 1
2 tion of β-CsPbI3 NR- based inverted perovskite solar cells (p-i-n sized using a cheap, colloidal synthesis process. Detailed syn- 2
3 architecture) is challenging and, to the best of our knowledge, thesis process has been described in the previous work.[28] 3

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4 not yet reported so far. Figure  1a represents a freshly prepared CsPbI3 solution that 4
5 Herein, we first report a novel, low-cost colloidal synthesis was stable for more than 90 days. The freshly prepared solu- 5
6 of high-quality single-crystalline β-CsPbI3 NRs thin film that is tion was deposited on glass substrates by spin coating with a 6

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7 kinetically stable at room temperature in presence of humidity spinning rate of 1000  rpm for 40 s followed by annealing at 7
8 (45−55%) and showing remarkable stability up to 15 days different temperatures for a constant duration of 3 min, as 8
9 without any passivation. Rietveld refinement of X-ray diffrac- shown in Figure  1b. The as-deposited film was stable only for 9
10 tion (XRD) results confirmed that an as-deposited thin film a few days but showed a significant improvement in stability 10
11 has an orthorhombic (γ-CsPbI3) phase, which is converted to a on annealing at an optimized temperature ≈150  °C. The uni- 11
12 tetragonal (β-CsPbI3) one on annealing at 150 °C for 3 min. The formity and quality of CsPbI3 NRs films were found to degrade 12
13 calculation of electronic band structure and density of states on annealing at a higher temperature (≥175  °C), as shown in 13
14 (DOS) using the refined structure revealed that 150 °C annealed Figure S1, Supporting Information. Figure  1c schematically 14

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15 CsPbI3 NRs indeed have a direct band gap with tetragonal depicts a proposed thermal phase relation of CsPbI3 based on 15
16 phase. We visualized for the first time, the probable atomic our observations and reported work.[29] 16
17 arrangements of Cs, Pb, and I atoms in a single β-CsPbI3 NR 17
18 by using atomic resolution TEM micrograph and selected area 18
19 electron diffraction (SAED) pattern indicates a high-quality 2. Results and Discussions 19
20 single crystalline CsPbI3 NR. To demonstrate the proof of con- 20
21 cept, air-stable β-CsPbI3 NR-based inverted perovskite solar To determine the phase of as-deposited and annealed CsPbI3 21
22 cells (IPSCs), without any use of glovebox or encapsulation, films, we have performed XRD measurements at room tem- 22

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23 having a moderately high efficiency (7.3%) is also reported. perature and the pattern for a fresh as-deposited CsPbI3 film 23
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Figure 1.  Photographs of a) a freshly prepared CsPbI3 solution and b) as-deposited and annealed thin films of CsPbI3 at 45–55% relative humidity.
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c) Schematic diagram illustrating phase transitions of studied CsPbI3 thin films. d) Rietveld refinements (double phase fitting) of the XRD pattern of
57 150 °C annealed thin films with the inset showing the 3D visualization of β-tetragonal crystal structure of CsPbI3. e) Broad scan XPS spectra of as- 57
58 deposited and annealed thin films with the inset showing deconvoluted fitted curves for different cation oxidation states of Cs-3d, Pb-4f, and I-3d core 58
59 electrons for the annealed sample. 59

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1 is shown in Figure S2, Supporting Information. XRD peaks Supporting Information. TEM micrographs reveal that NRs 1
2 located at 2θ  = 14.24°, 20.34°, 24.33°, 26.37°, 30.68°, 32.61°, become smoother and perfectly aligned in a particular direction 2
3 33.48°, and 34.82° represent the crystallographic planes of (110), after annealing. HRTEM micrographs presented in Figure 2a,b 3

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4 (112), (022), (122), (221), (310), (311), and (024), respectively, show the lattice fringes of NRs, providing additional informa- 4
5 for an orthorhombic phase (γ-phase) of CsPbI3 in agreement tion on the growth direction and crystallinity. In the annealed 5
6 with reported results.[17,30] On optimized annealing at 150  °C sample (Figure 2b), sharper lattice fringes indicate an improved 6

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7 (Figure  1d), the peaks at 30.68°, 32.61°, 33.48°, and 34.82° are crystalline quality with reduced grain boundaries, as compared 7
8 suppressed and the main peak is shifted to 2θ = 14.85° (shown to the as-deposited sample in Figure 2a. The fast Fourier trans- 8
9 in Figure S3, Supporting Information) corresponding to (110) form (FFT) patterns (Figure  2e,f) are obtained from the red 9
10 plane. This high intense peak represents a very good crystalline dotted squares on HRTEM images of Figure 2a,b and indexed 10
11 quality of CsPbI3 NRs with the growth along [110] direction. properly. The crystal planes reveal that the as-deposited CsPbI3 11
12 To determine the phase and space group of CsPbI3 thin films, NR has an orthorhombic phase viewed from [ 201] zone axis and 12
13 we performed the Rietveld refinement by using a FullProf pro- annealed CsPbI3 NR exhibits a tetragonal phase viewed from 13
14 gram. It is evident that most of the as-deposited XRD peaks [102] zone axis. However, a few additional diffraction spots 14

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15 match with the orthorhombic phase having space group Pnma, not belonging to the CsPbI3 are also observed in Figure  2e,f. 15
16 no. 62. On the other hand, the annealed film shows a mixture These additional spots are attributed to the presence of a finite 16
17 of tetragonal (space group P4/mbm, no. 127) and orthorhombic amount of PbI2 and CsI, which may be formed due to the 17
18 phases (space group Pnma, no. 62). Using Rietveld refinement, surface decomposition of the sample at a high electron beam 18
19 we have calculated the tetragonal to orthorhombic phase ratio dose.[12] The decomposition of the sample at a high dose also 19
20 using double phase fitting of 150 °C annealed CsPbI3 film to be gives rise to a few bubbles in HRTEM images of CsPbI3 NRs. 20
21 10:1. The obtained crystallographic parameters are summarized Bubbles-free HRTEM images recorded for as-deposited and 21
22 in Table ST1, Supporting Information. Using calculated lattice annealed CsPbI3 samples before any degradation are presented 22

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23 parameters, we have drawn 3D crystal structure and generated in Figure S7, Supporting Information. 23
24 XRD pattern of γ- and β-phases of CsPbI3 using a 3D visualiza- To further investigate the precise arrangement of atoms 24
25 tion VESTA program (Figure S4, Supporting Information). The in a single CsPbI3 NRs using a “polyhedral” model, we have 25
26 structure shown in the inset of Figure 1d is in excellent agree- used magnified atomic resolution images shown in Figure 2c,d 26
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27 ment with our experimental high-resolution TEM (HRTEM) processed by a Digital Micrograph software. In as-deposited 27
28 analysis to be discussed later. X-ray photoelectron spectroscopy sample (Figure  2c), it is difficult to identify the atoms due to 28
29 (XPS) has been carried out to investigate the effect of annealing lattice distortion,[33–35] which is in well-agreement with the 3D 29
30 on chemical composition of CsPbI3. XPS survey scans of as- crystal structure shown in Figure S4a , Supporting Information. 30
31 deposited and annealed samples are shown in Figure  1e, with In our synthesis, we have not used any kind of polar solvent 31
32 the figure insets showing deconvoluted Cs 3d, I 3d, and Pb 4f for the lattice distortion. The annealing resulted in the phase 32
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33 core level spectra corresponding to the doublets of Cs 3d5/2, transition and stability of CsPbI3 perovskite by suppressing 33
34 Cs 3d3/2, I 3d5/2, I 3d3/2, Pb 4f7/2, and Pb 4f5/2 electrons for the lattice distortion. XRD patterns presented in Figure S3, 34
35 the annealed sample.[31,32] Neither any additional peaks due to Supporting Information, showing a large peak shift for the 35
36 impurity phases nor any significant shift of the binding energy annealed film discussed earlier, corroborate thermally induced 36
37 peak for Cs 3d, Pb 4f, and I 3d (Figure S5, Supporting Infor- phase transition of CsPbI3. This is in agreement with previous 37
38 mation) electrons are detected on annealing the sample at reports on thermal phase relation of CsPbI3 using synchrotron- 38
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39 150 °C. This indicates that the change of crystal structure (from based, grazing incidence and wide-angle X-ray scattering 39
40 orthorhombic to tetragonal) improves only the material stability analy­ses along with the theoretical support.[29,30] In our synthesis, 40
41 without any change in the chemical composition of CsPbI3. we have used olive oil as a substitution of oleic acid (OA). 41
42 The surface morphology of CsPbI3 NRs films has been Compared to OA, olive oil has better stability in air and being 42
43 studied using field-emission scanning electron microscopy edible can be obtained easily from a supermarket, as reported 43
44 (FESEM). From the micrographs (Figure S6a,b, Supporting by Xu et al.[36] Sun et al.[33] reported that as-synthesized CsPbI3 44
45 Information), it is observed that as-deposited and annealed colloidal solution can be stabilized by the ligands. However, 45
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46 films (150 °C) are continuous and composed of 1D structures of these ligands are not favorable for efficient charge transport in 46
47 nonuniform size. It may be noted that the diameter and length the material. So, unwanted ligands (fatty acids or oleyl ammine) 47 Q5
48 of grown nanostructures vary from 20 to 200 nm and 200 nm to or by-products have been eliminated by centrifugation of the 48
49 2 µm, respectively. A relatively higher aspect ratio (diameter-to- solution several times using excess hexane. However, even after 49
50 length ratio) of 1D structure indicates that the grown samples repeated centrifugation process, there may be a trace amount 50
51 are indeed nanorods, rather than nanowires with extremely of oleyl ammine or fatty acids, which will be helpful to improve 51
52 long length or very low aspect ratio. All NRs are homogene- the stability of the final product in ambient condition. While 52
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ously distributed over the surface though the as-deposited film
54 appears to be rough, which may lead to the increased recom-
55 bination of charge carriers. On the other hand, the annealed
56 film exhibits better uniformity and smoother surface that
57 are desirable to minimize charge carrier recombination. For
58 a closer look into the micro-structural properties of CsPbI3
59 NRs, we have studied TEM analysis as shown in Figure S6c,d,
remaining in the solution phase for a few hours, highly con-
centrated CsPbI3 nanocrystals are attached together side-by-side 54
and self-assembled in lateral direction to form uneven NRs with 55
a lattice distortion in as-synthesized sample.[33,37] We calculated 56
the lattice distortion using the VESTA structure, as shown in 57
Figure S4a,b, Supporting Information. In as-deposited γ-CsPbI3 58
NRs, the I-Pb-I bond angle of PbI6 octahedra is 88.44°, which 59

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32 Figure 2.  HRTEM images of a) as-deposited and b) annealed CsPbI3 NRs with an energy of 200 keV, and dose of ≈1.14 × 105 e– Å–2 for as-deposited 32
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and ≈1.59 × 105 e– Å–2 for annealed samples. c,d) The magnified view of the corresponding images in the selected white square region and e,f) the
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FFT pattern from a region marked by a red square on micrographs in (a) and (b), respectively. White circles are attributed to the diffraction spots of
34 CsPbI3 along [ 201] and [ 102] zone axes, while yellow circles belong to the PbI2 diffraction spots along [070] zone axis and the green ones correspond 34
35 to CsI diffraction spots. 35
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37 deviates by 1.56° from the original value of 90°. Whereas, in the visualization VESTA software shown in Figure  3c. From this 37
38 β-CsPbI3 NRs, I-Pb-I bond angle is exactly 90°.[38] Therefore, a structure, we have calculated the distance between two atoms 38
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39 clear lattice distortion is observed in the γ-CsPbI3 NRs whereas (Pb–Pb = 8.49  Å, Cs–Cs = 8.49  Å, and I–I = 4.17  Å). On the 39
40 β-CsPbI3 NRs has a distortion free PbI6 octahedra. Finally, on other hand, from HRTEM (shown in Figure 3a) image, we also 40
41 annealing at 150  °C, we obtained a highly oriented along [110] calculated the atomic distance by the Digital Micrograph soft- 41
42 direction and high crystalline β-CsPbI3 NRs with distortion free ware, as shown in the right panel of Figure  3b. The distance 42
43 unit cell by minimizing the surface energy.[39] Meanwhile, the between two atoms derived from XRD analysis is very close to 43
44 orientation force (dipole−dipole attraction) pulls atoms inside that calculated from HRTEM image, as shown in the bottom 44
45 the unit cell leading to the minimization of lattice distortion of panel of Figure  3b. Therefore, Figure  3b represents the pro­ 45
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46 PbI6 octahedra, which are well-visualized in the XRD structure bable atomic distribution of Cs, Pb, and I atoms in a single 46
47 (Figure S4b, Supporting Information). Once the atomic arrange- β-CsPbI3 NRs based on both XRD and HRTEM data. The 47
48 ments are perfectly ordered, the unit cell volume is minimized experimentally (XRD) extracted tetragonal β-CsPbI3 (Pb−I−Pb 48
49 resulting in the long-term stability of β-CsPbI3 NRs even bond angle 162.71°) phase shows a lower octahedral to octahe- 49
50 under humid conditions. The experimentally extracted unit- dral inclination in the lattice as compared to the orthorhombic 50
51 cell volume of the annealed sample from XRD data is almost γ-CsPbI3 (Pb−I−Pb bond angle 153.20°) phase, which is attrib- 51
52 half of the value for as-deposited one shown in Table ST1, Sup- uted to the antibonding and bonding character of the orbital 52
53 porting Information. Through our analysis, we observe that the Pb−I overlaps.[40] Hence a single crystalline, distortion-free, 53
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54 annealing process not only reduces the ligand density but also and lower octahedral inclined β-CsPbI3 NRs formed along [110] 54
55 significantly affects the stability of CsPbI3 NRs. direction with different diameter (112 and 157 nm) is shown in 55
56 For detailed analysis of the atomic distribution, we have per- Figure  3d. This is presumed to be responsible for obtaining 56
57 formed XRD measurements and calculated all crystallographic high-performance, air-stable PV devices. To compare the crys- 57
58 parameters by Rietveld refinement analysis. Using these tallinity of CsPbI3 NRs, we have further recorded SAED pat- 58
59 parameters, we have drawn a crystal structure of CsPbI3 by 3D terns of individual nanorod from as-deposited and annealed 59

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38 Figure 3.  a) High-magnification TEM image of annealed CsPbI3 NRs. b) Green, red, and purple dots represent Cs, Pb, and I atoms, respectively and 38
inset shows the polyhedral models of β-CsPbI3 supporting the same β-CsPbI3 structure obtained from VESTA visualization software (using Rietveld
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39 refinement parameters) shown in (c). Right panel shows the atomic distance extracted from HRTEM image by Digital Micrograph software and the
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40 bottom panel presents the data in a single β-CsPbI3 NR based on both XRD and HRTEM measurements. d) TEM image of single annealed CsPbI3 NR 40
41 with an energy of 200 keV and a dose of ≈796.8 e– Å–2 and e) corresponding SAED pattern on the selected white circle on the NR of (d). 41
42 42
43 samples, which are presented in Figure S8, Supporting Infor- region and a strong peak observed around 590 nm can be attri­ 43
44 mation. The SAED pattern of annealed CsPbI3 NR has been buted to the transformation of nanocrystal to nanorods.[41] But 44
45 obtained from the white circle on the TEM image (Figure 3d), in β-CsPbI3, another broad hump is observed at around 620 nm 45
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46 which indicates well-defined diffraction spots indexed to (010), that gradually saturates in the red region. The optical band gap 46
47 (110), and (100) planes along [001] zone axis. The observation of γ and β-CsPbI3 phases are extracted from Tauc plots shown 47
48 of sharper and clean diffraction spots (Figure S8, Supporting in Figure 4b. The estimated value of β-CsPbI3 (1.94 eV) is found 48
49 Information) of the annealed NR, as compared to the as-depo­ to be lower compared to γ-CsPbI3 (2.03 eV) due to the transition 49
50 sited one, reveals the single crystalline nature of β-CsPbI3 NRs. from orthorhombic to tetragonal phase.[42,43] The absor­bance 50
51 However a weak reflection between the (100) and (110) spots in spectrum of β-CsPbI3 NRs films remains unchanged even 51
52 the annealed sample may arise from the presence of a finite after 15 days under 45–55% humidity condition, as shown in 52
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fraction of orthorhombic phase (≈10%), because our XRD and Figure 4a, indicating high air stability of annealed NRs.
54 Rietveld refinement analysis reveal that the annealed CsPbI3 We have studied the effect of annealing on the electronic band 54
55 NR is the combination of tetragonal and orthorhombic phases structure and DOS calculation of γ and β-CsPbI3 phases using 55
56 and not a pure tetragonal one. density functional theory (DFT). The electronic band structure 56
57 Figure  4a presents the optical absorbance spectra of thin (Figure  4c,d) is presented for the Γ-X-R-Z-Γ-X-R-A-M-X paths 57
58 films in γ (as-deposited) and β-CsPbI3 (150 °C annealed) phases. in the first Brillouin zone. For γ-CsPbI3, the direct band gap 58
59 Absorption features are observed around the UV to visible occurs at the Γ-point of the Brillouin zone. On the other hand, 59

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35 Figure 4.  a) Optical absorbance of fresh as-deposited, annealed, and after 15 days CsPbI3 thin film. b) Optical band gap (Touc plot) calculated from
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36 transmittance spectrum. c,d) Electronic band structure and e,f) corresponding DOS of orthorhombic (as-deposited) and tetragonal (annealed) CsPbI3. 36
37 g) Calculated photoabsorption coefficients of γ and β-CsPbI3. 37
38 38
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39 the energy minima are shifted to the high-symmetry points of phases, showing a significantly higher absorption for the latter 39
40 the Brillouin zone (Z-point) for β-CsPbI3 phase due to dyna­ in the visible region of electromagnetic spectrum. For β-CsPbI3, 40
41 mical Rashba effect.[44] DFT results show that β-CsPbI3 also has since the band gap is lower (as obtained experimentally), the 41
42 a direct band gap, which is essential for its use in optoelectronic absorption edge is shifted to the red region in the solar spec- 42
43 and PV devices. The estimated band gap of β-CsPbI3 (0.93 eV) trum, which could be helpful as a better light harvesting mate- 43
44 is found to be lower than that of γ-CsPbI3 (1.63 eV), which can rial for PV applications. The band gap determined from DOS 44
45 be explained by the change of Pb-I bond length.[45] The Pb-I curve (1.63  eV for γ-CsPbI3 and 0.93  eV for β-CsPbI3) is in 45
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46 bond length of β-CsPbI3 (Pb-I1 = 3.11 Å, Pb-I2 = 3.04 Å) is lower excellent agreement with the photoabsorption edges at ≈1.64 eV 46
47 than that of γ-CsPbI3 (Pb-I1 = 3.18 Å, Pb-I2 = 3.20 Å). The cor- for γ-CsPbI3 and ≈0.94  eV for β-CsPbI3.[47] However, the esti- 47
48 responding total density of states (t-DOS) and partial density of mated band gaps from DFT are found to be underestimated 48
49 states (p-DOS) projected on s-Pb, p-Pb, s-I1, p-I1, s-I2, p-I2, s-Cs, as compared to the experimental data, which is also commonly 49
50 and p-Cs are shown in Figure 4e,f and Figure S9a,b, Supporting reported in literature,[6,17,48,49] since the calculations are based 50
51 Information. DOS curves clearly indicate that the band edge on Predew–Burke–Ernzerhof generalized gradient approxima- 51
52 states are dominated by the p and s orbitals of I and Pb atoms tion suggesting that further approximation is essential. 52
53 and not from the Cs, because band edge states of Cs atom are Finally, we have fabricated PV devices with inverted p-i-n 53
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54 far from the Fermi level.[46] In consequence, PbI6 octahedra configuration of ITO/PEDOT:PSS/CsPbI3/C60/BCP/Al and the 54
55 rotations are stabilized in the valence band maxima (VBM) details of the device fabrication are given in the Supporting 55
56 that is mainly contributed by the p-I orbital, and the conduc- Information. A cross-sectional FESEM micrograph of the fab- 56
57 tion band minima (CBM) is dominated by the p-Pb orbital. ricated device is shown in Figure S10, Supporting Information. 57
58 In Figure  4g, the optical absorption coefficient is plotted as a To understand the energy band alignment of the perovskite 58
59 function of photon energy (frequency) for both γ and β-CsPbI3 solar cell, we performed UV photoelectron spectroscopy (UPS) 59

Adv. Energy Mater. 2020, 2001305 2001305  (6 of 9) © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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32 32
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33 33
34 34
35 Figure 5.  UV photoelectron spectra corresponding to the a) secondary electron onset region and b) valence band region of as-deposited and annealed 35
36 CsPbI3 NR films, with the WF determined from the difference between the excitation energy and the binding energy at the position of the secondary 36
37 electron cutoff. c) Proposed energy band diagram exhibiting charge carriers transportation under illumination. d) External quantum efficiency spectra 37
38 showing a broadband response in the visible wavelength range and integrated JSC curve of fabricated solar cell devices. e) Current density versus 38
voltage curve of the inverted PV devices under 100 mW cm–2, AM 1.5 g standard solar illumination, and inset shows a typical photograph of fabricated
RR

39 39
PV devices with active area 0.5 × 0.5 cm2.
40 40
41 measurements, by using a He source emitting at an excitation electrons in the former. On the other hand, valance band 41
42 energy of 21.6 eV, to obtain the work function (WF) and valence maxima in β-CsPbI3 (−5.22  eV) lies below that of γ-CsPbI3 42
43 band maxima. Figure 5a shows the secondary cut-off region at (−4.99  eV), which is above the VBM of hole transport layer 43
44 17.87 and 17.91  eV for γ- and β-CsPbI3 NR films, respectively. (HTL). So the band alignment for γ-CsPbI3 layer is not suitable 44
45 The estimated WF is found to be 3.75 and 3.69  eV for γ- and for efficient hole injection into the HTL, as shown in Figure 5c. 45
CO

46 β-CsPbI3 NRs, respectively, which is in good agreement with In contrast, a favorable valence band alignment in β-CsPbI3 is 46
47 previously reported values.[6] On the other hand, the VBM (for beneficial for improved hole transport. So a higher open cir- 47
48 β-CsPbI3) is shifted by about 0.29 eV towards a higher binding cuit voltage (VOC) of 960  mV has been achieved for annealed 48
49 energy as compared to γ-CsPbI3 sample, which is illustrated β-CsPbI3 NRs due to higher crystalline quality, lesser grain 49
50 in Figure  5b. From the extracted values of WF, VBM position boundaries, and lower optical band gap. On the other hand, a 50
51 (relative to the Fermi level) and using the reported band gap favorable band alignment leads to the improvement in short- 51
52 for the materials (2.65 eV for PEDOT:PSS,[50] 1.7 eV for C60,[51] circuit current density (JSC) from 9.16 to 11.34  mA  cm–2 for 52
53 and 3.5  eV for BCP[52]), the proposed energy band diagram of 53
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54 the fabricated inverted PV device is presented Figure  5c. The Table 1.  Photovoltaic parameters obtained for the fabricated IPSCs. 54
55 deposited CsPbI3 NRs film behaves as n-type semiconduc- 55
IPSC VOC JSC FF PCE RS RSh
56 tors because the Fermi level is closer to the conduction band. [mV] [mA cm–2] [%] [%] [Ω cm2] [kΩ cm2] 56
57 Therefore, the conduction band offset (CBO) for β-CsPbI3 layer 57
β-CsPbI3 960 11.34 67.22 7.3 8.35 4.17
58 (0.41 eV) is closer to the Fermi level than that of γ-CsPbI3 one 58
γ-CsPbI3 753 9.16 59.63 4.1 14.77 5.56
59 (0.79 eV), which may lead to easier transport of photo-generated 59

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1 Table 2.  Comparison of device performance of CsPbI3-based photovoltaic devices reported in the literature. 1
2 2
3 Configuration Synthesis Architecture Humidity Area [cm2] Phase PCE Ref. 3

F
4 ITO/PEDOT:PSS/CsPbI3/C60/BCP/Al Colloidal synthesis: nanorods p-i-n 45–55% 0.25 β >7% This work 4
5 5
FTO/TiO2/CsPbI3/spiro/MoOx/Al Colloidal synthesis: quantum dots n-i-p 15–25% 0.1 α >10% [55]
6 6
FTO/TiO2/CsPbI3/PTAA/MoOx/Ag Colloidal synthesis: quantum dots n-i-p >10% – – >13% [56]

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7 7
8 FTO/TiO2/CsPbI3/spiro/Au CsI and PbI2 in DMF and DMSO solution n-i-p 45–55% 0.09 α >10% [57] 8
9 ITO/PTAA/CsPbI3/C60/BCP/Cu CsI and PbI2 are thermally evaporated p-i-n Inside glovebox 0.16 γ >12% [58] 9
10 10
11 β-CsPbI3 NRs, as shown in the current density−voltage (J−V) NRs exhibiting improved structural stability in comparison 11
12 characteristics in (Figure  5e). A significant enhancement in to as-deposited γ-CsPbI3 due to distortion free unit cell. DFT- 12
13 fill factor (FF) from 59.6% to 67.2% for β-CsPbI3 is attributed based calculations have been utilized to calculate the electronic 13
14 to a lower series resistance RS of 8.34 Ω cm2 in comparison to band structure and nature of bandgap of β-CsPbI3 phase. This 14

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15 14.77 Ω  cm2 for γ-CsPbI3. An overall PCE of 7.3% is achieved high-quality, single-crystalline β-CsPbI3 NRs thin films not only 15
16 for β-CsPbI3 NRs as compared to 4.1% in γ-CsPbI3 showing underscore the performance of PV devices with a moderately 16
17 an enhancement by 78% in the former. To further characterize efficiency (>7%) but also provide highly stable colloidal syn- 17
18 the performance of IPSC devices, we have performed external thesis of perovskite layers under 45–55% humid condition for 18
19 quantum efficiency (EQE) measurements and calculated inte- potential use of optoelectronic devices in future. 19
20 grated JSC values. The estimated current density in J–V curve 20
21 agrees well with the integrated current density extracted from 21
22 EQE, which is shown in Figure  5d. It is clear, that the EQE Supporting Information 22

D
23 response of β-CsPbI3-based device is superior to the γ-CsPbI3 23
24 based one, due to the enhanced light absorption in the visible Supporting Information is available from the Wiley Online Library or 24
from the author.
25 spectrum. The overall performance of β-CsPbI3-based PV device 25
26 including the cell parameters, viz., FF, and efficiency are found 26
27
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to be enhanced. However, we noticed a strong hysteresis effect 27
28 in forward and reverse scans in the β-CsPbI3 based IPSCs, as Acknowledgements 28
29 shown in Figure S11, Supporting Information. This kind of Authors are grateful to Prof. Manabendra Mukherjee and Mr. Goutam 29
30 hysteresis behavior has also been reported earlier in perov- Sarkar of Saha Institute of Nuclear Physics (Surface Physics and Material 30
31 skite solar cells.[53,54] The PV parameters of air stable IPSCs Science division), Kolkata, India for the UPS measurement. The authors 31
32 are summarized in Table 1, which shows that shunt resistance would like to thank Mr. Subhabrata Chakaraborty of Central Research 32
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33 β-CsPbI3 needs to be improved further. It may be noted that a Facility, IIT Kharagpur for the TEM measurement. The DST FIST facility 33
of IIT Kharagpur for XPS measurements is acknowledged. The financial
34 further optimization of device fabrication process needs to be 34
support received under the Meity NNETRA “SWI” project is gratefully
35 done with proper choice of electrodes to minimize the series acknowledged. 35
36 resistance, charge transport layers, contact metallizations, and 36
37 surface passivation, which will lead to achieve much higher 37
38 efficiency in β-CsPbI3 NR-based solar cells. The performance 38
Conflict of Interest
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39 of our colloidal synthesized β-CsPbI3 NR-based PV device is 39

40 compared with those previously reported in the literature using The authors declare no conflict of interest. 40
41 CsPbI3 nanocrystals of different phases under varying humidity 41
42 conditions in Table  2. It may be noted the device area is also 42
43 a critical parameter related to the efficiency, which was the Keywords 43
44 highest in our case. Our results indicate the great potential of 44
45 β-CsPbI3 NRs in laboratory humidity conditions for future low- CsPbI3, DFT, inverted perovskite solar cells, single-crystalline NRs 45
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46 cost, air-stable, all inorganic perovskite-based PV devices. Received: April 15, 2020
46
47 Revised: June 6, 2020 47
48 Published online: 48
49 3. Conclusions 49
50 50
51 In conclusion, we have reported that air-stable β-CsPbI3 NRs 51
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53 lowed by post-growth annealing of relatively unstable γ-CsPbI3 N.  Chen, T.  Lin, F.  Wang, C.  Li, J.  Wang, ACS Energy Lett. 2019, 4, 53
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2913.
54 thin films at 150  °C. Rietveld refinement indicates that the 54
[2] F.  Haque, M.  Wright, M. A.  Mahmud, H.  Yi, D.  Wang, L.  Duan,
55 annealing causes the movement of atoms inside the unit cell C. Xu, M. B. Upama, A. Uddin, ACS Omega 2018, 3, 11937.
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56 resulting in distortion free PbI6 octahedra, which could be visu- [3] B.  Li, Y.  Zhang, L.  Fu, L.  Zhang, Z.  Liu, L.  Yin, J. Mater. Chem. A 56
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59 found to be single crystalline in nature with perfectly oriented S. Dai, B. Xu, C. Cheng, NPG Asia Mater. 2018, 10, 552. 59

Adv. Energy Mater. 2020, 2001305 2001305  (8 of 9) © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Wiley-VCH Verlag GmbH & Co. KGaA – A company of John Wiley & Sons, Inc. -
Location of the Company: Weinheim - Trade Register: Mannheim, HRB 432833.
Chairman of the Supervisory Board: John Kritzmacher
General Partner: John Wiley & Sons GmbH, Location: Weinheim –
Trade Register Mannheim, HRB 432296 – Managing Director: Sabine Haag and Dr. Guido Herrmann