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Article
Lead-Free Perovskite Semiconductors Based on Germanium-
Tin Solid Solutions: Structural and Optoelectronic Properties
Satyawan Nagane, Dibyajyoti Ghosh, Robert Hoye, Baodan Zhao, Shahab Ahmad,
Alison B. Walker, M. Saiful Islam, Satishchandra Ogale, and Aditya Sadhanala
J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.8b00480 • Publication Date (Web): 28 Feb 2018
Downloaded from http://pubs.acs.org on February 28, 2018

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The Journal of Physical Chemistry C is published by the American Chemical Society.

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Published by American Chemical Society. Copyright © American Chemical Society.
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Page 1 of 29 The Journal of Physical Chemistry

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Lead-Free Perovskite Semiconductors Based on
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Germanium-Tin Solid Solutions: Structural and
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Optoelectronic Properties
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Satyawan Nagane,1 Dibyajyoti Ghosh,2,5 Robert L. Z. Hoye,3 Baodan Zhao,3 Shahab Ahmad,4
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23 Alison B. Walker,2 M. Saiful Islam,5* Satishchandra Ogale1* and Aditya Sadhanala3*
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26 Department of Physics and Centre for Energy Science, Indian Institute of Science Education and
27 Research (IISER), Dr. Homi Bhabha Road, Pune 411 008, India.
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Department of Physics, University of Bath, Bath BA2 7AY, United Kingdom.
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Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, CB3 0HE, Cambridge,
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Institute for Manufacturing, Department of Engineering, University of Cambridge, 17 Charles
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Babbage Road, Cambridge CB3 0FS, United Kingdom.
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Department of Chemistry, University of Bath, Bath BA2 7AY, United Kingdom.
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49 AUTHOR INFORMATION
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52 Corresponding Author
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55 *m.s.islam@bath.ac.uk, *satishogale@iiserpune.ac.in, *as2233@cam.ac.uk
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ABSTRACT Solar cells and optoelectronics based on lead halide perovskites are generating
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9 considerable interest, but face challenges with the use of toxic lead. Here, we fabricate and
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11 characterize lead-free perovskites based on germanium and tin solid solutions, CH3NH3Sn(1-
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x)GexI3 (0 ≤ x ≤ 1). We show that these perovskite compounds possess bandgaps from 2.0 to 1.3
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16 eV, which are suitable for a range of optoelectronic applications, from single junction devices
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18 and top cells for tandems to light emitting layers. Their thermodynamic stability and electronic
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20 properties are calculated for all compositions and agree well with our experimental
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23 measurements. Our findings demonstrate an attractive family of lead-free perovskite
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25 semiconductors with a favorable bandgap range for efficient single junction solar cells.
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29 KEYWORDS Lead-free hybrid perovskite, Tin-Germanium (Sn-Ge) perovskite, band tuning,
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31 amplified spontaneous emission (ASE) and mixed metal/alloy hybrid perovskite.
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Page 3 of 29 The Journal of Physical Chemistry

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3 INTRODUCTION
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Organic-inorganic hybrid perovskites have attracted a great deal of attention in the scientific and
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9 industrial communities due to their phenomenal performance in solar cells and light emitting
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11 diodes (LEDs)1–3. Their superior optoelectronic properties and long carrier diffusion lengths have
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13 produced a sharp rise in power conversion efficiencies (PCEs) from below 10% to 22.1% in a
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16 few years4–7. The attributes that make perovskite-based optoelectronics especially attractive are
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18 the ambipolar nature of charge transport 8, long carrier diffusion lengths 9, high molar extinction
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20 coefficient 10
, easy bandgap tunability and simple thin-film processability 11,12
. Nevertheless,
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perovskite-based technologies are not yet attractive for commercial use due, for example, to the
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25 inclusion of lead in the highest performing perovskite, CH3NH3PbI3, which is highly toxic and
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27 could enter the soil and groundwater 13. Lead-free alternatives focusing on Sn-based perovskites
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29 14–19
have been considered. Other replacements for lead in the perovskite semiconductor include
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32 Bi 20, Cu 21, Ag 22 and Sb 21, amongst several elements discussed by Hoye et. al.23 The aim with
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34 these lead-free perovskites is to achieve similar or better optoelectronic properties and stability,
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36 as compared to their lead-based perovskite counterparts.
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We have synthesized perovskites with Sn and Ge that absorb strongly in the visible region with
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42 absorption coefficients in the range of 2 – 5 x 104 cm-1. The CH3NH3SnI3 perovskite has a
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44 bandgap lower than ~1.3 eV, much smaller than the 2.0 eV bandgap of the CH3NH3GeI3
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46 perovskite 24,25
. Solar cells with thin-films of these perovskites as active layers produce power
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49 conversion efficiencies (PCEs) of ~ 6% and ~ 0.1% respectively . This poor performance
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51 compared to the Pb based perovskite cells has been attributed to poor atmospheric stability and
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53 film coverage 28. In order to improve the stability, a new strategy was evolved to introduce lead
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56 into tin-based perovskites to form a Pb-Sn mixed metal perovskite solid solution 29. These new
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3 Pb-Sn based perovskite solid solutions have delivered excellent solar cell performance and
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6 stability, showing the possibilities of multi-metal based perovskite solid solutions 30. Moreover,
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8 these Pb-Sn based solid solutions possess advanced optoelectronic properties and bandgaps
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10 smaller than that of the single metal containing perovskites, for example <1.2 eV for
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CH3NH3Sn0.75Pb0.25I3 30–33 that are suitable for perovskite-perovskite tandems 34.
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19 RESULTS AND DISCUSSION
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22 In this paper, we report the design, synthesis and optoelectronic characterization of Sn-Ge solid
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24 solution hybrid perovskites where we have replaced Pb with Ge in the Pb-Sn solid solutions, and
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fabricated Sn-Ge based perovskites by simple solution processing and vapor deposition methods.
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29 We have varied the metal ion composition (Sn to Ge ratio) in the perovskite matrix and
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31 investigated the effect on structural geometry and optoelectronic properties.
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34 First of all, for the synthesis of Sn-Ge mixed alloy hybrid perovskites, we applied the
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well-known single-step solution processing method. In brief, we prepared a 0.5 mmol stock
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39 solution of CH3NH3SnI3 (using equimolar ratios of CH3NH3I and SnI2) and CH3NH3GeI3 (using
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41 equimolar ratios of CH3NH3I and GeI2) in N, N-dimethylformamide (DMF) and mixed these
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solutions according the required ratios of metal elements viz. Sn and Ge in the perovskite matrix.
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46 These solutions form the desired perovskite phase on casting into thin-films. Full details of the
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48 synthesis methods and diffraction measurements are given in the SI. Recently, Ju et. al. predicted
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50 the possibility of realizing a series of mixed Sn-Ge perovskites and calculated the band structures
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53 of different combinations such as CsSn0.5Ge0.5I3, CH3NH3Sn0.5Ge0.5I3,
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55 Cs0.5(CH3NH3)0.5Sn0.5Ge0.5I3, Cs0.5(CH(NH2)2)0.5Sn0.5Ge0.5I3 and RbSn0.5Ge0.5I3. Amongst these
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3 materials, RbSn0.5Ge0.5I3 was shown to cover almost the whole solar spectrum as does
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6 CH3NH3PbI3 35.
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9 Regarding the characterization of crystal structures, Figure. 1 shows the X-ray diffraction
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11 (XRD) patterns for CH3NH3SnI3, CH3NH3Sn0.75Ge0.25I3, CH3NH3Sn0.50Ge0.50I3,
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13 CH3NH3Sn0.25Ge0.75I3, and CH3NH3GeI3 perovskites. The XRD patterns for CH3NH3SnI3 and
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16 CH3NH3GeI3 perovskites are well matched with the reported data and show tetragonal (space
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18 group P4mm, no. 99) and trigonal (space group R3m, no. 160) unit cells, respectively. For
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20 powder samples with 0 – 50% Ge (from hereon this represents atomic % of Ge or Sn in the thin-
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films), we observed a monotonic shift in the peak positions with composition, along with a
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25 monotonic shift in the lattice parameters fit to the whole diffraction pattern using the Pawley
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27 method (Figure S6, SI)24,25. Note that this is true for the thin-film samples and for the powder
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samples we find the 50% Ge sample peaks slightly shifted away from this trend possibly due to
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32 displacement error. For the 75% Ge for the powder sample, we observe a transition to the
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34 trigonal phase from the splitting of the tetragonal (111) and (012) peaks to the trigonal (003),
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(201́), (113) and (211) peaks. There is also a non-monotonic change in the XRD patterns from
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39 CH3NH3SnI3 to CH3NH3Sn0.75Ge0.25I3 to CH3NH3GeI3 perovskites. This non-systematic shift in
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41 the peaks of XRD patterns is consistent with the change in crystal structure from tetragonal to
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43 trigonal due to incorporation of the comparatively smaller Ge2+ (ionic radius = 73pm)36 into a
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46 CH3NH3SnI3 perovskite matrix (Sn2+ ionic radius = 118pm)37, which leads to a distortion in the
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48 structure. From the XRD pattern we found that the (001), (002), (003) and (004) planes are intact
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53 perovskite shows more structural features similar to the pure germanium (100% Ge) based
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Figure 1. X-ray diffraction (XRD) patterns for 0% Ge (CH3NH3SnI3), 25% Ge
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2θ = 30˚ for the (b) powder and (d) thin film samples are also shown. *indicates small impurity
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Page 7 of 29 The Journal of Physical Chemistry

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3 It is known that we can test whether the Goldschmidt tolerance factor (t), a semi-empirical
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6 geometric parameter, can be linked to the structural stability of the ABX3 perovskite systems
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indication that mixed Sn-Ge perovskites can be created.
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16 A major obstacle for commercialization of hybrid perovskite solar cells is their long-term
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the perovskites over their decomposition products, for example, SnI2 and CH3NH3I for
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CH3NH3Sn(1-x)GexI3 system, which indicates favorable energetic stability of these materials in
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x)GexI3 at finite temperature (300K), we also performed ab initio molecular dynamics (AIMD)
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39 simulations extending our previous work.39,40 We find no sign of decomposition of their
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Ge perovskites at room temperature under inert atmosphere.
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Systems t ∆H (meV/f.u.)
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9 0% Ge (CH3NH3SnI3) 0.84 -166
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12 25% Ge (CH3NH3Sn0.75Ge0.25I3) 0.87 -55
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50% Ge (CH3NH3Sn0.5Ge0.5I3) 0.90 -48
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28 the optical properties of CH3NH3Sn(1-x)GexI3 [0 ≤ x ≤ 1] perovskite thin films fabricated on
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for the 0% Ge content sample (x = 1.0) and ~1.9eV for the 0% Sn sample (x = 1). With an
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seen in steady state photoluminescence (PL) measurements on films with a single optically
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47 The 0% Ge content perovskite, CH3NH3SnI3, exhibits a PL peak centered at 945 nm. We further
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Ge perovskite (CH3NH3GeI3), with 75%, 50% and 25% Ge samples demonstrating PL at peak
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3 and band gap of perovskites with varying Ge content. This comparison reveals the small bandgap
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6 bowing as observed previously in CH3NH3SnxPb1-xI3 [0 ≤ x ≤ 1] binary metal perovskites
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perovskites 30–33,41 This difference may be due to the way in which the orbitals of the Pb and Sn
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that observed by other Sn based systems . Further investigation might find possible
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3 Wavelength (nm)
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(a) Ge content (%)
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∝ (x 104)(cm-1)
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3 Figure 2. Optical properties with change in Ge content (0% to 100%), (a) absorption spectra,
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perovskites with change in Ge content (0% to 100%).
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16 Figure 3 shows the PL decay measured with varying germanium content in the perovskite. All
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bimolecular decay model and are listed in Table 2. We observe that the 0% Ge perovskite
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both show slow initial decays of more than half of the charge carriers followed by a delayed
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3 Table 2: Fitted lifetime values using a bimolecular decay model along with the respective %
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8 Samples τ1 (ps) τ2 (ps)
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10 0% Ge 140 ± 2 (90%) 620 ± 6 (10%)
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14 50% Ge 1620 ± 15 (54%) 390 ± 4 (46%)
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16 75% Ge 1300 ± 12 (62%) 270 ± 3 (38%)
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18 100% Ge 2100 ± 20 (55%) 360 ± 4 (45%)
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IRF 112 ± 2 (100%) -
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25 To analyze the quality of the perovskite formed, we performed photothermal deflection
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27 spectroscopy (PDS) measurements shown in Figure 4a that give the absorption in a
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30 semiconductor with a 4-5 orders of magnitude dynamic range sensitivity. This measurement
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34 all sub-band gap defect states arising from intrinsic doping as well as degradation in the
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materials 30. From Figure 4a we can see a steep drop in the absorption edges. The PDS spectrum
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39 for pure CH3NH3SnI3 perovskite shows the smallest bandgap and an Urbach energy of ~54 meV.
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41 The bandgap widens with increasing Ge content. The Urbach energy for the 25% Ge sample
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43 increases to 54 meV and decreases to 47 meV for the 50% Ge sample (Figure 4b). The Urbach
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46 energy further increases to 103 meV for the 75% Ge sample before dropping to 63 meV for
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3 We find that the 50% Ge content sample demonstrates the lowest Urbach energy amongst the
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6 CH3NH3Sn(1-x)GexI3 perovskites and with a decent photoluminescence quantum yield (PLQY) of
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two sets of measurements are consistent, indicating the dependence of the PL broadening on the
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we observe in the case of 50% Ge content sample, predicted in the recent work by Ju et.al 35.
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3 Wavelength (nm)
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3 We measured the PL quantum yield (PLQY) for the 50% Ge sample to yield a decent
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8 excitation densities, from a full width at half maxima (FWHM) of ~75 nm down to less than half
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10 ~40 nm, as shown in figure 5b, a possible demonstration of amplified spontaneous emission
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(ASE). The 50% Ge sample is a good candidate for various optoelectronic applications owing to
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15 its superior optical properties; these include a high absorption coefficient reaching 4 x 104 cm-1
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17 (Figure 2a), long charge carrier recombination, and a bandgap that covers the entire Vis-NIR
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spectrum similar to that shown by CH3NH3PbI3 and GaAs which is close to optimum for a single
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3 A key property for a material to be used as an efficient absorber for solar cells is the optical
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6 band-gap as well as its transition nature. Our ab initio DFT calculations show an increase in the
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8 band-gap when going from CH3NH3SnI3 to CH3NH3GeI3 (Table 3 and Figure 6(a)). The
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10 variation in band gap with Sn-Ge mixing is consistent with our experimental observations
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(Figure 2(c)). It should be noted that we also considered inclusion of spin-orbital coupling in our
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15 DFT simulations (Table S3 in SI), which significantly underestimates the experimental band gap
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17 values, although the trend from CH3NH3SnI3 to CH3NH3GeI3 remains unchanged. Exploring the
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band structures of all these perovskites (Figure S9), indicate that they are direct-gap
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22 semiconductors.
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25 Table 3. Calculated electronic band-gaps and carrier effective masses for CH3NH3Sn(1-x)GexI3
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27 perovskites (using GGA-PBEsol functionals).
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29 Systems Band Gap (eV) Effective Mass
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33 0% Ge (CH3NH3SnI3) 0.50 0.13
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35 25% Ge (CH3NH3Sn0.75Ge0.25I3) 0.56 0.12
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37 50% Ge (CH3NH3Sn0.5Ge0.5I3) 0.68 0.14
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39 75% Ge (CH3NH3Sn0.25GeO.75I3) 1.20 0.33
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41 100% Ge (CH3NH3GeI3) 1.38 0.37
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Another important factor which affects the overall performance of these solar cell materials is the
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49 transport of photo-generated charge carriers inside the device. We have derived the carrier
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51 effective mass (m*), which provides an indication of the carrier mobility (µ) (under a constant
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53 relaxation-time approximation,50–53 through the relation, µ = eτ/m* where e is the elementary
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3 carrier effective mass for pure and mixed Sn-Ge perovskites (with the lowest values for 0%, 25%
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6 and 50%), which suggests good hole transport properties and are important for promising solar
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8 cell materials. Despite the lack of experimental data for these compounds for direct comparison,
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10 these values are consistent with related hybrid perovskites.54
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13 Finally, to examine the nature of the valence and conduction bands of these Sn-Ge mixed
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15 perovskites, the density of states (DOS) have been simulated. As can be seen in Figure 6(b-d)
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(and Figure S10(a,b)), the valence band of the parent perovskite as well as mixed-metal
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20 compounds has dominant contributions from 5p orbitals of the I atoms, with additional
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22 contributions from the s-orbitals of the B-site metals (i.e. Sn and/or Ge). For the conduction
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band, the p-orbitals of B-site metal atoms (4p for Ge or 5p for Sn) largely contribute.
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27 Interestingly, as we move along the series from CH3NH3SnI3 to CH3NH3GeI3, the major
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29 contributing orbitals to the conduction band changes from Sn 5p-orbitals to Ge 4p-orbitals
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31 (shown in Figure 6(b-d) and Figure S10(a,b)). This seems to be the origin of the increase in the
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34 band-gap as the Ge content increases in the CH3NH3Sn(1-x)GexI3 perovskite solid solution. In
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36 addition, for Ge-rich systems, (i.e. x=0.75, 1) the trigonal distortion in the GeI6 octahedra, leads
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38 to half of the Ge-I bond-lengths increasing to ~3.5 Angstrom (Table S2), which reduces the
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orbital overlap between the B-metal and iodine. Since, the highly dispersive valence band in the
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43 halide perovskites appears from the strong metal halide orbital interactions, the elongation of Ge-
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45 I bonds leads to less dispersive valence band maxima for these solid-solutions (Figure S9(d)).
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Such a non-dispersive nature of the valence band also relates to the relatively higher effective
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50 mass for the Ge-rich perovskites as shown in Table 3.
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33 Figure 6. Electronic properties. (a) Variation in the calculated bandgaps by tuning the Ge
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35 content in CH3NH3Sn(1-x)GexI3 perovskites. Projected density of states (pDOS) of (b) 0% Ge
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37 (CH3NH3SnI3), (c) 50% Ge (CH3NH3Sn0.5Ge0.5I3), and (d) 100% Ge (CH3NH3GeI3) including
38 SOC.
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44 CONCLUSIONS
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47 In conclusion, we have successfully synthesized and characterized a new germanium-tin based
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perovskite family, CH3NH3Sn(1-x)GexI3 [0 ≤ x ≤ 1]. The addition of germanium to CH3NH3SnI3
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52 produces a systematic blue-shift in the band gap from 1.3 eV to 2.0 eV. We also observe
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54 simultaneous monotonic shifts in absorption and photoluminescence for the Ge-Sn mixed-metal
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3 perovskites. Ab initio simulations on their intrinsic stability and band gap properties agree well
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6 with the experimental observations. The insertion of Ge into CH3NH3SnI3 results in an amplified
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8 spontaneous emission from the 50% Ge perovskite thin-film. Moreover, the 50% Ge content
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10 perovskite also demonstrates the lowest disorder (Urbach energy of ~47 meV) amongst the entire
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family, while demonstrating a bandgap (~1.5 eV) that is ideal for fabricating an efficient single
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15 junction solar cell. We believe that the favorable optoelectronic properties of this family of
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17 germanium and tin perovskites will result in the fabrication of novel lead-free perovskite
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optoelectronics, as well as stimulating further research into alternative lead-free perovskite
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3 ASSOCIATED CONTENT
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7 Supporting Information. Contains molecular dynamics simulation data, energy dispersive X-
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9 ray data, SEM, fittings to the optical data and structural data. The Supporting Information is
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11 available free of charge on the ACS Publications website.
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17 AUTHOR INFORMATION
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Notes
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22 The authors declare no competing financial interests.
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25 ACKNOWLEDGMENT
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28 A.S. would like to thank Prof. Sir Richard Friend and Dr Michael De Volder for the useful
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30 discussions. A.S., S.N. and S.O would like to acknowledge the support from Indo-UK APEX
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32 project. A.S. would like to acknowledge the support from EPSRC. S.O. would like to
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acknowledge funding support from DST Nanomission Thematic Unit and DST-CERI programs,
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37 Govt. of India. D.G., S.I. and A.B.W. acknowledge the support from Energy oriented Centre of
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39 Excellence (EoCoE), grant agreement number 676629, funded within the Horizon2020
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framework of the European Union. S.N. and D.G. contributed equally to this work and they
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44 worked on performing most of the experiment and theoretical calculations. R. L. Z. H. and B. Z.
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46 helped with XRD sample preparation and analysis. S.A. helped in sensitive absorption
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48 measurements and SEM data collection. A.B.W. and M.S.I. supervised the theoretical
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51 calculations and their interpretation along with D.G. who formulated the calculations. A.S. and
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53 S.N. conceptualized the work. S.O. and A.S. further designed and supervised the entire work.
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