Export file:


  • RIS(for EndNote,Reference Manager,ProCite)
  • BibTex
  • Text


  • Citation Only
  • Citation and Abstract

Inorganic alkali lead iodide semiconducting APbI3 (A = Li, Na, K, Cs) and NH4PbI3 films prepared from solution: Structure, morphology, and electronic structure

Materials Science Department, Technische Universitaet Darmstadt, Jovanka-Bontschits-Strasse 2, D-64287, Darmstadt, Germany

Topical Section: Thin films, surfaces and interfaces

APbI3 alkali lead iodides were prepared from aqueous (A= Na, Cs, ammonium NH4+, and methyl­ammonium CH3NH3+) and acetone (A= Li, K) solutions by a self-organization low temperature process. Diffraction analysis revealed that the methylammonium-containing system (MAPbI3) crystallizes into a tetragonal perovskite structure, whereas the alkali and NH4+ systems adopt orthorhombic structures. Morphological inspection confirmed the influence of the cation on the growth mechanism: for A = Cs and NH4+, needle-like crystallites with lengths up to 3–4 mm; for A = K, thin stripes with lengths up to 5–6 mm; and for A = MA+, dodecahedral crystallites were observed. For A = Li and Na, the APbI3 systems typically resulted in polycrystalline aggregates. Optical absorption measurements demonstrated large energy band gaps for the alkali and ammonium systems with values between 2.19 and 2.40 eV. For electronic and chemical characterization by photoelectron spectroscopy, the as-prepared powders were dissolved in di-methylformamide and re-crystallized as thin films on F:SnO2 substrates by spin-coating. The binding energy differences between Pb4f and I3d core levels are highly similar in the investigated systems and close to the value measured for PbI2, indicating similar relative partial charges and formal oxidation states. The binding energies of the alkali ions are in accordance with oxidation state +1. The X-ray excited valence band spectra of the investigated APbI3 systems exhibited similar line shapes in the region between the valence band maximum and 4.5 eV higher binding energy due to common PbI6 octahedra which dominate the electronic structure. While the ionization energy values are quite similar (6.15 ±
0.25 eV), the Fermi-level positions of the unintentionally doped materials vary for different cations and different batches of the same material, which indicates that the position of the Fermi level can be influenced by changing the process parameters.
  Article Metrics

Keywords solution process; alkali lead iodide; ammonium lead iodide; X-ray photoelectron spectroscopy; ultra-violet photoelectron spectroscopy

Citation: Lucangelo Dimesso, Michael Wussler, Thomas Mayer, Eric Mankel, Wolfram Jaegermann. Inorganic alkali lead iodide semiconducting APbI3 (A = Li, Na, K, Cs) and NH4PbI3 films prepared from solution: Structure, morphology, and electronic structure. AIMS Materials Science, 2016, 3(3): 737-755. doi: 10.3934/matersci.2016.3.737


  • 1. Papavassiliou GC (1997) Three- and low-dimensional inorganic semiconductors. Prog Solid St Chem 25: 125–270.
  • 2. Billing DG, Lemmerer A (2009) Inorganic-organic hybrid materials incorporating primary cyclic ammonium cations: The lead bromide and chloride series. Cryst Eng Comm 11: 1549–1562.    
  • 3. Brgoch J, Lehner AJ, Chabinyc M (2014) Ab initio calculations of band gaps and absolute band positions of polymorphs of RbPbI3 and CsPbI3: Implications for main-group halide perovskite photovoltaics. J Phys Chem C 118: 27721–27727.    
  • 4. Baibarac M, Preda N, Mihut L (2004) On the optical properties of micro- and nanometric size PbI2 particles. J Phys Condens Matter 16: 2345–2356.
  • 5. Stranks SD, Eperon GE, Grancini G (2013) Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342: 341–344.    
  • 6. Xing G, Mathews N, Sun S (2013) Long-range balanced electron- and hole-transport lengths in organic-inorganic CH3NH3PbI3. Science 342: 344–347.
  • 7. Frost JM, Butler KT, Brivio F (2014) Atomistic origins of high-performance in hybrid halide perovskite solar cells. Nano Lett 14: 2584–2590.    
  • 8. Du MH (2014) Efficient carrier transport in halide perovskites: theoretical perspectives. J Mater Chem A 2: 9091–9098.    
  • 9. Burschka J, Pellet N, Moon SJ (2013) Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature 499: 316–319.    
  • 10. Yang WS, Noh JH, Jeon NJ (2015) High-performance photovoltaic perovskite layers fabricated through intramolecular exchange. Science 348: 1234–1237.    
  • 11. Oxton IA, Knop O, Duncan JL (1977) The Infrared Spectrum and Force Field of the Methylammonium ion in (CH3NH3)2PtCl6. J Mol Struct 38: 25–32.    
  • 12. Chung I, Song JH, Im J (2012) CsSnI3: Semiconductor or Metal? High electrical conductivity and strong Near-Infrared Photoluminescence from a single material. High hole mobility and phase-transitions. J Am Chem Soc 134: 8579–8587.
  • 13. Shirane G, Yamada Y (1969) Lattice-dynamical study of the 110K phase transition in SrTiO3. Phys Rev 177: 858–863.    
  • 14. Prokert F (1981) Neutron Scattering Studies on phase transitions and phonon dispersion in CsSrCl3. Phys Status Solidi (b) 104: 261–265.    
  • 15. Rubin J, Palacios E, Bartolome J, et al. (1995) A single-crystal neutron diffraction study of NH4MnF3. J Phys Condens Matter 7: 563–575.
  • 16. Poglitsch A, Weber D (1987) Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter-wave spectroscopy. J Chem Phys 87: 6373–6378.    
  • 17. Knop O, Wasylishem RE, White M (1990) Alkylammonium lead halides. Part2. CH3NH3PbX3 (X = C1, Br, I) perovskites: cuboctahedral halide cages with isotropic cation reorientation. Can J Chem 68: 412–422.
  • 18. Swainson IP, Hammond RP, Soulliere C (2003) Phase transitions in the perovskite methylammonium lead bromide, CH3ND3PbBr3. J Solid State Chem 176: 97–104.    
  • 19. Mitzi DB, Liang K (1997) Synthesis, resistivity, and thermal properties of the cubic perovskite NH2CH=NH2SnI3 and related systems. J Solid State Chem 134: 376–381.    
  • 20. Lee Y, Mitzi DB, Barnes PW (2003) Pressure-induced phase transitions and templating effect in three-dimensional organic-inorganic hybrid perovskites. Phys Rev B 68: 366–369.
  • 21. Baikie T, Fang Y, Kadro JM (2013) Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications. J Mater Chem A 1: 5628–5641.
  • 22. Protesescu L, Yakunin S, Bodnarchuk MI (2015) Nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I): Novel optoelectronic materials showing bright emission with wide color gamut. Nano Lett 15: 3692–3696.    
  • 23. Shum K, Chen Z, Qureshi J (2010) Synthesis and characterization of CsSnI3 thin films. Appl Phys Lett 96: 221903.    
  • 24. Dimesso L, Dimamay M, Hamburger M (2014) Properties of CH3NH3PbX3 (X = I, Br, Cl) powders as precursors for organic/inorganic solar cells. Chem Mater 26: 6762–6770.    
  • 25. Wells LH (1893) Über die Cäsium- und Kalium-Blei halogenide. Z anorg Chemie 3: 195–210.    
  • 26. Kortüm G, Braun W, Herzog G (1963) Prinzip und Meßmethodik der diffusen Reflexionsspektroskopie. Angew Chem 75: 653–661.    
  • 27. McCarthy TJ, Tanzer TA, Kanatzidis MG (1995) A new metastable three-dimensional bismuth sulfide with large tunnels: Synthesis, structural characterization, ion-exchange properties, and reactivity of KBi3S5. J Am Chem Soc 117: 1294–1301.    
  • 28. Dimesso L, Quintilla A, Kim YM (2015) Investigation of formamidinium and guanidinium lead tri-iodide powders as precursors for solar cells. Mater Sci Eng B 204: 27–33.
  • 29. Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr A 32: 751–767.    
  • 30. Trots DM, Myagkota SV (2008) High-temperature structural evolution of caesium and rubidium triiodoplumbates. J Phys Chem Solids 69: 2520–2526.    
  • 31. Bedlivy D, Mereiter K (1980) The structure of potassium lead triiodide dihydrate and ammonium Lead Triiodide Dyhydrate. Acta Cryst B 36: 782–785.    
  • 32. Fan LQ, Wu JH (2007) (IUCr) Poly[diaquatris([mu]4-isophthalato)dilanthanum(III)]. Acta Cryst E 63: 189.
  • 33. Ziger E, Kukol' V, Babich G (1980) New three-component compounds based on alkali metal, Lead and Bismuth Iodides. Russ J Inorg Chem (Engl Transl) 25: 1201–1203.
  • 34. Roger M (1944) Abstract of Engineer Doctor Work (Paris).
  • 35. Condeles JF, Lofrano RCZ, Rosolen JM (2006) Stoichiometry, surface and structural characterization of Lead Iodide thin films. Brazilian J Phys 36: 320–323.
  • 36. Chihara H, Kawakami T, Soda G (1969) The NMR study of the disorder in Lithium Iodide Monohydrate and Monodeuterate. J Magn Res 1: 75–88.
  • 37. Ghobadi N (2013) Band gap determination using absorption spectrum fitting procedure. Inter Nano Lett 3: 2.    
  • 38. Ferreira da Silva A, Veissid N, An CY (1996) Optical determination of the direct band gap energy of lead iodide crystals. Appl Phys Lett 69: 1930–1932.    
  • 39. Salvador P (1982) Analysis of the physical properties of TiO2-Be electrodes in the photoassisted oxidation of qater. Sol En Mater 6: 241–250.    
  • 40. Tsunekawa S, Fukuda T, Kasuya A (2000) Blue shift in ultraviolet absorption spectra of monodisperse CeO2−x nanoparticles. J Appl Phys 87: 1318–1321.    
  • 41. Tauc J (1968) Optical properties and electronic structure of amorphous Ge and Si Optical properties and electronic structure of amorphous Ge and Si Optical properties and electronic structure of amorphous Ge and Si. Mater Res Bull 3: 37–46.    
  • 42. Clark SJ, Donaldson JD, Harvey JA (1995) Evidence for the direct population of solid-state bands by nonbonding electron pairs in compounds of the type CsM"X, (MI' = Ge, Sn, Pb; X = CI, Br, I). J Mater Chem 5: 1813–1818.
  • 43. Moller CK (1958) Crystal structure and photoconductivity of Caesium Plumbohalides. Nature 182: 1436.
  • 44. Stoumpos CC, Malliakas CD, Kanatzidis MG (2013) Semiconducting Tin and Lead Iodide Perovskites with organic cations: Phase transitions, high mobilities, and Near-Infrared Photoluminescent properties. Inorg Chem 52: 9019–9038.    
  • 45. Talmadge JM (1897) On Potassium Lead Iodid. J Phys Chem 1: 493–498.    
  • 46. Salau AM (1980) Fundamental absorption edge in PbI2:KI alloys. Sol En Mater 2: 327–332.    
  • 47. Baltog I, Marculescu L, Mihut L (1980) Optical properties of Na:Pb single crystals. Phys Stat Sol (a) 61: 573–578.    
  • 48. Filip MR, Verdi C, Giustino F (2015) GW band structures and carrier effective masses of CH3NH3PbI3 and hypothetical perovskites of the type APbI3: A = NH4, PH4, AsH4, and SbH4. J Phys Chem C 119: 25209−25219.
  • 49. Lindblad R, Bi DQ, Park BW (2014) Electronic structure of TiO2/CH3NH3PbI3 perovskite solar cell interfaces. J Phys Chem Lett 5: 648–653.
  • 50. Repoux M (1992) Comparison of background removal methods for XPS. Surf Interface Anal 18: 567–570.    
  • 51. Emara J, Schnier T, Pourdavoud N (2016) Impact of film stoichiometry on the ionization energy and electronic structure of CH3NH3PbI3 perovskites. Adv Mater 28: 553–559.    
  • 52. Moulder JF, Stickle WF, Sebol PE (1995) Handbook of XPS, Physical Electronics Inc.
  • 53. Morgan WE, Van Wazer JR, Stec WJ (1973) Inner-orbital photoelectron spectroscopy of the alkali metal halides, perchlorates, phosphates, and pyrophosphates. J Am Chem Soc 95: 751–755.    
  • 54. Yeh JJ, Lindau I (1985) Atomic subshell photoionization cross sections and asymmetry parameters: 1 ≤ Z ≤ 103. Atom Data Nucl Data 32: 1–155.
  • 55. Giorgi G, Fujisawa J, Segawa H (2014) Cation role in structural and electronic properties of 3D organic−inorganic Halide Perovskites: A DFT Analysis. J Phys Chem C 118: 12176–12183.
  • 56. Miller EM, Zhao Y, Mercado CC (2014) Substrate-controlled band positions in CH3NH3PbI3 perovskite films. Phys Chem Chem Phys 16: 22122–22130.    
  • 57. Brivio F, Walker AB, Walsh A (2013) Structural and electronic properties of hybrid perovskites for high-efficiency thin-film photovoltaics from first-principles. Appl Phys Lett Mater 1: 042111.
  • 58. Conings B, Drijkoningen J, Gauquelin N (2015) Intrinsic thermal instability of Methylammonium Lead Trihalide Perovskite. Adv Energy Mater 5: 1500477.
  • 59. Schulz P, Edri E, Kirmayer S (2014) Interface energetics in organo-metal halide perovskite-based photovoltaic cells. Energy Environ Sci 7: 1377–1381.    
  • 60. Liu X , Wang C, Lyu L, et al. (2015) Electronic structures at the interface between Au and CH3NH3PbI3 in organometal trihalide perovskite-based solar cells. Phys Chem Chem Phys 17: 896–902.    


This article has been cited by

  • 1. Xing Huang, Su Huang, Pratim Biswas, Rohan Mishra, Band Gap Insensitivity to Large Chemical Pressures in Ternary Bismuth Iodides for Photovoltaic Applications, The Journal of Physical Chemistry C, 2016, 10.1021/acs.jpcc.6b09567
  • 2. Lucangelo Dimesso, Chittaranjan Das, Maximilian Stöhr, Wolfram Jaegermann, Investigation of cesium tin/lead iodide (CsSn1−xPbxI3) systems, Materials Research Bulletin, 2017, 85, 80, 10.1016/j.materresbull.2016.08.052
  • 3. Muhammad Muzammal uz Zaman, Muhammad Imran, Abida Saleem, Afzal Hussain Kamboh, Muhammad Arshad, Nawazish Ali Khan, Parvez Akhter, Potassium doped methylammonium lead iodide (MAPbI 3 ) thin films as a potential absorber for perovskite solar cells; structural, morphological, electronic and optoelectric properties, Physica B: Condensed Matter, 2017, 522, 57, 10.1016/j.physb.2017.07.067

Reader Comments

your name: *   your email: *  

Copyright Info: © 2016, Lucangelo Dimesso, et al., licensee AIMS Press. This is an open access article distributed under the terms of the Creative Commons Attribution Licese (http://creativecommons.org/licenses/by/4.0)

Download full text in PDF

Export Citation

Copyright © AIMS Press All Rights Reserved