Journal of Materials Science

, Volume 54, Issue 6, pp 4732–4741 | Cite as

Theoretical insight into the optoelectronic properties of lead-free perovskite derivatives of Cs3Sb2X9 (X = Cl, Br, I)

  • Yu-Liang Liu
  • Chuan-Lu YangEmail author
  • Mei-Shan Wang
  • Xiao-Guang Ma
  • You-Gen Yi


The lead-free perovskites derivatives of Cs3Sb2X9 (X = Cl, Br, I) have been synthesized, but their photocatalytic properties are not explored. To evaluate the feasibility for the visible light catalytic performance, we calculate the structural, electronic, optical and charge transfer properties of Cs3Sb2X9, based on the hybrid density functional theory of HSE06 with the projector augmented wave potential. The results show the decrease of band energy gaps and the redshift of absorption edges from X = Cl to I. The absolute potential of the valence band maximum and conduction band minimum is determined to justify the feasibility of the photocatalytic water splitting or CO2 reduction. The calculated carrier mobilities reveal that the high electron mobilities of Cs3Sb2I9 are beneficial to the reducing powers for hydrogen generation and CO2 reduction. The present results indicate that Cs3Sb2I9 is appropriate for the photocatalytic water splitting to produce hydrogen or the CO2 reduction driven by the visible light.



This work was supported by the National Natural Science Foundation of China (NSFC) under Grant Nos. NSFC-11874192 and NSFC-11574125, as well as the Taishan Scholars Project of Shandong Province (ts201511055).

Supplementary material

10853_2018_3162_MOESM1_ESM.docx (180 kb)
Supplementary material 1 (DOCX 180 kb)


  1. 1.
    Dou L, Yang YM, You J, Hong Z, Chang WH, Li G (2013) Solution-processed hybrid perovskite photodetectors with high detectivity. Nat Commun 5:5404Google Scholar
  2. 2.
    Fang Y, Huang J (2015) Resolving weak light of sub-picowatt per square centimeter by hybrid perovskite photodetectors enabled by noise reduction. Adv Mater 27:2804–2810Google Scholar
  3. 3.
    Li G, Tan ZK, Di D, Lai ML, Jiang L, Lim JH (2015) efficient light-emitting diodes based on nano-crystalline perovskite in a dielectric polymer matrix. Nano Lett 15:2640–2644Google Scholar
  4. 4.
    Kim YH, Cho H, Heo JH, Kim TS, Myoung NS, Lee CL (2015) multicolored organic/inorganic hybrid perovskite light-emitting diodes. Adv Mater 27:1248–1254Google Scholar
  5. 5.
    Gao G, Xi Q, Zhou H, Zhao Y, Wu C, Wang L (2017) Novel inorganic perovskite quantum dots for photocatalysis. Nanoscale 33:12032–12038Google Scholar
  6. 6.
    Lim SC, Lin HP, Tsai WL, Lin HW, Hsu YT, Tuan HY (2017) Binary halide, ternary perovskite-like, and perovskite-derivative nanostructures: hot injection synthesis and optical and photocatalytic properties. Nanoscale 9:3747–3751Google Scholar
  7. 7.
    Schünemann S, Van GM, Tüysüz H (2018) A CsPbBr3/TiO2 composite for visible-light driven photocatalytic benzyl alcohol oxidation. Chemsuschem 13:2057–2061Google Scholar
  8. 8.
    Xu YF, Yang MZ, Chen BX, Wang XD, Chen HY, Kuang DB (2017) A CsPbBr3 perovskite quantum dot/graphene oxide composite for photocatalytic CO2 reduction. J Am Chem Soc 139:5660Google Scholar
  9. 9.
    Park S, Chang WJ, Chan WL, Park S, Ahn HY, Nam KT (2016) Photocatalytic hydrogen generation from hydriodic acid using methylammonium lead iodide in dynamic equilibrium with aqueous solution. Nat Energy 2:16185Google Scholar
  10. 10.
    Wang X, Wang H, Zhang H, Yu W, Wang X, Zhao Y (2018) Dynamic interaction between methylammonium lead iodide and TiO2 nanocrystals leads to enhanced photocatalytic H2 evolution from HI splitting. Acs Energy Lett 5:1159–1164Google Scholar
  11. 11.
    Filippetti A, Mattoni A (2014) Hybrid perovskites for photovoltaics: insights from first principles. Phys Rev B 89:231–236Google Scholar
  12. 12.
    Kang J, Wang LW (2017) High defect tolerance in lead halide perovskite CsPbBr3. J Phys Chem Lett 8:489–493Google Scholar
  13. 13.
    Kim J, Lee SH, Lee JH, Hong KH (2014) The role of intrinsic defects in methylammonium lead iodide perovskite. J Phys Chem Lett 5:1312–1317Google Scholar
  14. 14.
    Yin WJ, Shi T, Yan Y (2014) Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber. Appl Phys Lett 104:063903Google Scholar
  15. 15.
    Zakutayev A, Caskey CM, Fioretti AN, Ginley DS, Vidal J, Stevanovic V (2014) Defect tolerant semiconductors for solar energy conversion. J Phys Chem Lett 5:1117–1125Google Scholar
  16. 16.
    Hebig JC, Kühn I, Flohre J, Kirchartz T (2016) Optoelectronic properties of (CH3NH3)3Sb2I9 thin films for photovoltaic applications. Acs Energy Lett 1:309–314Google Scholar
  17. 17.
    Yang B, Li YJ, Tang YX, Mao X, Luo C, Wang MS (2018) Constructing sensitive and fast lead-free single-crystalline perovskite photodetectors. J Phys Chem Lett 9:3087–3092Google Scholar
  18. 18.
    Harikesh PC, Mulmudi HK, Ghosh B, Goh TW, Teng YT, Thirumal K (2016) Rb as an alternative cation for templating inorganic lead-free perovskites for solution processed photovoltaics. Chem Mater 28:7496–7504Google Scholar
  19. 19.
    Zuo C, Ding L (2017) Lead-free perovskite materials (NH4)3Sb2IxBr9−x. Angew Chem 129:6628–6632Google Scholar
  20. 20.
    Adonin SA, Frolova LA, Sokolov MN, Shilov GV, Korchagin DV, Fedin VP, Aldoshin SM, Stevenson KJ, Troshin PA (2018) Antimony (V) complex halides: lead-free perovskite-like materials for hybrid solar cells. Adv Energy Mater 8:1701140Google Scholar
  21. 21.
    Adonin SA, Bondarenko MA, Abramov PA, Novikov AS, Plyusnin PE, Sokolov MN, Fedin VP (2018) Bromo- and polybromoantimonates(V): structural and theoretical studies of hybrid halogen-rich halometalate frameworks. Chem Eur J 24:10165–10170Google Scholar
  22. 22.
    Adonin SA, Udalova LI, Abramov PA, Novikov AS, Yushina IV, Korolkov IV, Semitut EY, Derzhavskaya TA, Stevenson KJ, Troshin PA, Sokolov MN, Fedin VP (2018) A novel family of polyiodo-bromoantimonate(III) complexes: cation-driven self-assembly of photoconductive metal-polyhalide frameworks. Chem Eur J 24:14707–14711Google Scholar
  23. 23.
    Zemnukhova LA, Kuznetsov SI, Fedorishcheva GA, Davidovich RL (2000) The temperature dependence of 121,123Sb, 35Cl, 79,81Br and 127I NQR spectra in complexes Cs3Sb2X9 (X = Cl, Br, I). Z Naturforsch 55:134–138Google Scholar
  24. 24.
    Saparov B, Hong F, Sun JP, Duan HS, Meng W, Cameron S (2015) Thin-film preparation and characterization of Cs3Sb2I9: a lead-free layered perovskite semiconductor. Chem Mater 27:5622–5632Google Scholar
  25. 25.
    Zhang J, Yang Y, Deng H, Farooq U, Yang X, Khan J (2017) High quantum yield blue emission from lead-free inorganic antimony halide perovskite colloidal quantum dots. ACS Nano 11:9294–9302Google Scholar
  26. 26.
    Zhou L, Xu YF, Chen BX, Kuang DB, Su CY (2018) Synthesis and photocatalytic application of stable lead-free Cs2AgBiBr6 perovskite nanocrystals. Small 14:1703762Google Scholar
  27. 27.
    Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865–3868Google Scholar
  28. 28.
    Le Bahers T, Rérat M, Sautet P (2014) Semiconductors used in photovoltaic and photocatalytic devices: assessing fundamental properties from DFT. J Phys Chem C 118:5997–6008Google Scholar
  29. 29.
    Melissen ST, Labat F, Sautet P, Le Bahers T (2015) Electronic properties of PbX3CH3NH3 (X = Cl, Br, I) compounds for photovoltaic and photocatalytic applications. Phys Chem Chem Phys 17:2199–2209Google Scholar
  30. 30.
    Lardhi S, Curutchet A, Cavallo L, Harb M, Le Bahers T (2017) Ab initio assessment of Bi1−xRExCuOS (RE = La, Gd, Y, Lu) solid solutions as a semiconductor for photochemical water splitting. Phys Chem Chem Phys 19:12321–12330Google Scholar
  31. 31.
    Heyd J (2003) Hybrid functionals based on a screened Coulomb potential. J Chem Phys 118:8207–8215Google Scholar
  32. 32.
    Kresse G, Furthmüller J (1996) Efficiency of ab initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput Mater Sci 6:15–50Google Scholar
  33. 33.
    Kresse G, Furthmüller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B Condens Matter 54:11169–11186Google Scholar
  34. 34.
    Blöchl PE (1994) Projector augmented-wave method. Phys Rev B Condens Matter 50:17953–17979Google Scholar
  35. 35.
    Yamada K, Sera H, Sawada S, Tada H, Okuda T, Tanaka H (1997) Reconstructive phase transformation and kinetics of Cs3Sb2I9 by means of rietveld analysis of X-Ray diffraction and 127I NQR. J Solid State Chem 134:319–325Google Scholar
  36. 36.
    Lv X, Wei W, Sun Q, Li F, Huang B, Dai Y (2017) Two-dimensional germanium monochalcogenides for photocatalytic water splitting with high carrier mobility. Appl Catal B 217:275–284Google Scholar
  37. 37.
    Liu X, Sohlberg K (2015) The influence of oxygen vacancies and La doping on the surface structure of NaTaO3. Comput Mater Sci 103:1–7Google Scholar
  38. 38.
    Timmermans CWM, Cholakh SO, Blasse G (1983) The luminescence of Cs3Bi2Cl9 and Cs3Sb2Cl9. J Solid State Chem 46:222–233Google Scholar
  39. 39.
    Pham TA, Ping Y, Galli G (2017) Modelling heterogeneous interfaces for solar water splitting. Nat Mater 16:401–408Google Scholar
  40. 40.
    Xu Y, Schoonen MAA (2000) The absolute energy positions of conduction and valence bands of selected semiconducting minerals. Am Mineral 85:543–556Google Scholar
  41. 41.
    Mulliken RS (1934) A new electroaffinity scale; together with data on valence states and on valence ionization potentials and electron affinities. J Chem Phys 2:782Google Scholar
  42. 42.
    Lin Y, Jiang Z, Zhu C, Hu X, Zhu H, Zhang X (2013) The optical absorption and hydrogen production by water splitting of (Si, Fe)-codoped anatase TiO2 photocatalyst. Int J Hydrogen Energy 38:5209–5214Google Scholar
  43. 43.
    Liu YL, Yang CL, Wang MS, Ma XG, Yi YG (2018) Te-doped perovskite NaTaO3 as a promising photocatalytic material for hydrogen production from water splitting driven by visible light. Mater Res Bull 107:125–131Google Scholar
  44. 44.
    He Y, Galli G (2014) Perovskites for solar thermoelectric applications: a first principle study of CH3NH3AI3 (A = Pb and Sn). Chem Mater 26:5394–5400Google Scholar
  45. 45.
    Wang H, Pei Y, Lalonde AD, Snyder GJ (2012) Weak electron-phonon coupling contributing to high thermoelectric performance in n-type PbSe. P Natl Acad Sci USA 109:9705–9709Google Scholar
  46. 46.
    Chin XY, Cortecchia D, Yin J, Bruno A, Soci C (2015) Lead iodide perovskite light-emitting field-effect transistor. Nat Commun 6:7383Google Scholar
  47. 47.
    Yettapu GR, Talukdar D, Sarkar S, Swarnkar A, Nag A, Ghosh P (2016) THz conductivity within colloidal CsPbBr3 perovskite nanocrystals: remarkably high carrier mobilities and large diffusion lengths. Nano Lett 16:4838–4848Google Scholar
  48. 48.
    Saidaminov MI, Haque MA, Almutlaq J, Sarmah S, Miao XH, Begum R (2017) Inorganic lead halide perovskite single crystals: phase-selective low-temperature growth, carrier transport properties, and self-powered photodetection. Adv Opt Mater 5:1600704Google Scholar

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Authors and Affiliations

  1. 1.School of Physics and Optoelectronics EngineeringLudong UniversityYantaiPeople’s Republic of China
  2. 2.Hunan Key Laboratory for High-Microstructure and Ultrafast Process, College of Physics and ElectronicsCentral South UniversityChangshaPeople’s Republic of China

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