Abstract
The remarkable optoelectronic and especially photovoltaic performance of hybrid organic-inorganic perovskite (HOIP) materials drives efforts to connect materials properties to this performance. From nano-indentation experiments on solution-grown single crystals we obtain elastic modulus and nano-hardness values of APbX3 (A = Cs, CH3NH3; X = I, Br). The Young’s moduli are ≈14, 19.5, and 16 GPa, for CH3NH3Pbl3, CH3NH3PbBr3, and CsPbBr3, respectively, lending credence to theoretically calculated values. We discuss the possible relevance of our results to suggested “self-healing”, ion diffusion, and ease of manufacturing. Using our results, together with literature data on elastic moduli, we classified HOIPs amongst the relevant material groups, based on their elastomechanical properties.
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.References
M. Kulbak, D. Cahen, and G. Hodes: How important is the organic part of lead halide perovskite photovoltaic cells? efficient CsPbBr3 cells. J. Phys. Chem. Lett. 6, 2452–2456 (2015).
M.A. Green, K. Emery, Y. Hishikawa, W. Warta, and E.D. Dunlop: Solar cell efficiency tables (version 44). Prog. Photovolt. Res. Appl. 22, 701–710 (2014).
W.-J. Yin, T. Shi, and Y. Yan: Unusual defect physics in CH3NH3Pbl3 perovskite solar cell absorber. Appl. Phys. Lett. 104, 063903 (2014).
D. Shi, V. Adinolfi, R. Comin, M. Yuan, E. Alarousu, A. Buin, Y. Chen, S. Hoogland, A. Rothenberger, K. Katsiev, Y. Losovyj, X. Zhang, P.A. Dowben, O.F. Mohammed, E.H. Sargent, and O.M. Bakr: Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals. Science 347, 519–522 (2015).
W. Tress, N. Marinova, T. Moehl, S.M. Zakeeruddin, M.K. Nazeeruddin, and M. Gratzel: Understanding the rate-dependent J-V hysteresis, slow time component, and aging in CH3NH3Pbl3 perovskite solar cells: the role of a compensated electric field. Energy Environ. Sci. 8, 995–1004 (2015).
T.-Y. Yang, G. Gregori, N. Pellet, M. Gratzel, and J. Maier: The significance of ion conduction in a hybrid organic-inorganic lead-iodide-based perovskite photosensitizer. Angew. Chem. 127, 8016–8021 (2015).
C. Eames, J.M. Frost, P.R.F. Barnes, B.C. O’Regan, A. Walsh, and M. S. Islam: Ionic transport in hybrid lead iodide perovskite solar cells. Nat. Commun. B, (2015).
Z. Xiao, Y. Yuan, Y. Shao, Q. Wang, Q. Dong, C. Bi, P. Sharma, A. Gruverman, and J. Huang: Giant switchable photovoltaic effect in organometal trihalide perovskite devices. Nat. Mater. 14, 193–198 (2015).
9. J. Beilsten-Edmands, G.E. Eperon, R.D. Johnson, H.J. Snaith, and P. G. Radaelli: Non-ferroelectric nature of the conductance hysteresis in CH3NH3Pbl3 perovskite-based photovoltaic devices. Appl. Phys. Lett. 106, 173502 (2015).
Y. Kawamura, H. Mashiyama, and K. Hasebe: Structural study on cubic-tetragonal transition of CH3NH3Pbl3. J. Phys. Soc. Jpn. 71, 1694–1697 (2002).
H. Mashiyama, Y. Kawamura, E. Magome.and Y. Kubota: Displacive character of the cubic-tetragonal transition in CH3NH3PbA3. J. Korean Phys. Soc. 42, S1026–S1029 (2003).
W.C. Oliver and G.M. Pharr: An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. J. Mater. Res. 7, 1564–1583 (1992).
Q. Dong, Y. Fang, Y. Shao, P. Mulligan, J. Qiu, L. Cao, and J. Huang: Electron-hole diffusion lengths >175 μm in solution grown CH3NH3Pbl3 single crystals. Science 347, 967–970 (2015).
Y. Dang, Y. Liu, Y. Sun, D. Yuan, X. Liu, W. Lu, G. Liu, H. Xia, and X. Tao: Bulk crystal growth of hybrid perovskite material CH3NH3Pbl3. CrystEngComm, 17, 665–670 (2014).
Y. Tidhar, E. Edri, H. Weissman, D. Zohar, G. Hodes, D. Cahen, B. Rybtchinski, and S. Kirmayer: Crystallization of methyl ammonium lead halide perovskites: implications for photovoltaic applications. J. Am. Chem. Soc. 136, 13249–13256 (2014).
P. Zhao, J. Xu, X. Dong, L. Wang, W. Ren, L. Bian, and A. Chang: Large-size CH3NH3PbBr3 single crystal: growth and in situ characterization of the photophysics properties. J. Phys. Chem. Lett. 6, 2622–2628 (2015). doi: 10.1021/acs.jpclett.5b01017.
C.C. Stoumpos, C.D. Malliakas, J.A. Peters, Z. Liu, M. Sebastian, J. Im, T.C. Chasapis, A.C. Wibowo, D.Y. Chung, A.J. Freeman, B.W. Wessels, and M.G. Kanatzidis: Crystal growth of the perovskite semiconductor CsPbBr3: a new material for high-energy radiation detection. Cryst. Growth Des. 13, 2722–2727 (2013).
X. Li and B. Bhushan: A review of nanoindentation continuous stiffness measurement technique and its applications. Mater. Charact. 48, 11–36 (2002).
S. Sun, Y. Fang, G. Kieslich, T.J. White, and A.K. Cheetham: Mechanical properties of organic-inorganic halide perovskites, CH3NH3PbX3 (X=I, Br and CI), by nanoindentation. J. Mater. Chem. A 3, 18450–18455 (2015). doi: 10.1039/C5TA03331D.
L.P. Swainson, M.G. Tucker, D.J. Wilson, B. Winkler, and V. Milman: Pressure response of an organic-inorganic perovskite: methylammo-nium lead bromide. Chem. Mater. 19, 2401–2405 (2007).
S. Hirotsu, T. Suzuki, and S. Sawada: Ultrasonic velocity around the successive phase transition points of CsPbBr3. J. Phys. Soc. Jpn. 43, 575 (1977).
M. Rodová, J. Brožek, K. Knfžek, and K. Nitsch: Phase transitions in ternary caesium lead bromide. J. Therm. Anal. Calorim. 71, 667–673 (2003).
M.F. Ashby: Materials Selection in Mechanical Design (Elsevier/ Butterworth-Heinemann, Amsterdam, 2011).
D.A. Egger and L. Kronik: Role of dispersive interactions in determining structural properties of organic-inorganic halide perovskites: insights from first-principles calculations. J. Phys. Chem. Lett. 5, 2728–2733 (2014).
J. Feng: Mechanical properties of hybrid organic-inorganic CH3NH3BX3 (B = Sn, Pb; X=Br, I) perovskites for solar cell absorbers. APL Mater. 2, 081801 (2014).
G. Murtaza and I. Ahmad: First principle study of the structural and optoelectronic properties of cubic perovskites CsPbM3 (M=CI, Br, I). Phys. B: Condens. Maffer 406, 3222–3229 (2011).
Y.-R. Luo: Comprehensive Handbook of Chemical Bond Energies (CRC Press, Boca Raton, FL, 2007).
W. Veiga and C.M. Lepienski: Nanomechanical properties of lead iodide (Pbl2) layered crystals. Mater. Sci. Eng. A 335, 6–13 (2002).
M.J. Weber: CRC Handbook of Laser Science and Technology Supplement 2: Optical Materials (CRC Press, Boca Raton, FL, 1994).
V.S. Bhadram, D. Swain, R. Dhanya, M. Polentarutti, A. Sundaresan, and C. Narayana: Effect of pressure on octahedral distortions in RCrO3 (R = Lu, Tb, Gd, Eu, Sm): the role of R-ion size and its implications. Mater. Res. Express 1, 026111 (2014).
A.S. Verma and A. Kumar: Bulk modulus of cubic perovskites. J. Alloys Compd. 541, 210–214 (2012).
A. Pisoni, J. Jaćimović, O.S. Barisic, M. Spina, R. Gaal, L. Forró, and E. Horváth: Ultra-low thermal conductivity in organic-inorganic hybrid perovskite CH3NH3Pbl3. J. Phys. Chem. Lett. 5, 2488–2492 (2014).
K. Nakamura, S. Yamada, and T. Ohnuma: Energetic stability and thermoelectric property of alkali-metal-encapsulated type-l silicon-clathrate from first-principles calculation. Mater. Trans. 54, 276–285 (2013).
F. Sui, H. He, S. Bobev, J. Zhao, F.E. Osterloh, and S.M. Kauzlarich: Synthesis, structure, thermoelectric properties, and band gaps of alkali metal containing type I clathrates: A8Ga8Si38 (A=K, Rb, Cs) and K8Al8Si38. Chem. Mater. 27, 2812–2820 (2015).
A.J. Karttunen, V.J. Härkönen, M. Linnolahti, and T.A. Pakkanen: Mechanical properties and low elastic anisotropy of semiconducting group 14 Clathrate frameworks. J. Phys. Chem. C 115, 19925–19930 (2011).
J.M. Azpiroz, E. Mosconi, J. Bisquert, and F.D. Angelis: Defect migration in methylammonium lead iodide and its role in perovskite solar cell operation. Energy Environ. Sci. 8, 2118–2127 (2015).
D.A. Egger, L. Kronik, and A.M. Rappe: Theory of hydrogen migration in organic-inorganic halide perovskites. Angew. Chem. Int. Ed. 54, 1–5 (2015). doi: 10.1002/anie.201502544.
C.C. Stoumpos, C.D. Malliakas, and M.G. Kanatzidis: Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties. Inorg. Chem. 52, 9019–9038 (2013).
Y. Lee, D.B. Mitzi, P.W. Barnes, and T. Vogt: Pressure-induced phase transitions and templating effect in three-dimensional organic-inorganic hybrid perovskites. Phys. Rev. B 68, 020103 (2003).
W.M. Sears, M.L. Klein, and J.A. Morrison: Polytypism and the vibrational properties of Pbl2. Phys. Rev. B 19, 2305–2313 (1979).
K. Nitsch and M. Rodová: Thermomechanical measurements of lead halide single crystals. Phys. Status Solidi B 234, 701–709 (2002).
J.E. Ni, E.D. Case, K.N. Khabir, R.C. Stewart, C.-I. Wu, T.P. Hogan, E.J. Timm, S.N. Girard, and M.G. Kanatzidis: Room temperature Young’s modulus, shear modulus, Poisson’s ratio and hardness of PbTe-PbS thermoelectric materials. Mater. Sci. Eng. B 170, 58–66 (2010).
M.S. Darrow, W.B. White, and R. Roy: Micro-indentation hardness variation as a function of composition for polycrystalline solutions in the systems PbS/PbTe, PbSe/PbTe, and PbS/PbSe. J. Mater. Sci. 4, 313–319 (1969).
B. Houston, R.E. Strakna, and H.S. Belson: Elastic constants, thermal expansion, and Debye temperature of lead telluride. J. Appl. Phys. 39, 3913–3916 (1968).
M. Pang, D.F. Bahr, and K.G. Lynn: Effects of Zn addition and thermal annealing on yield phenomena of CdTe and Cd0.96Zn0.04 Te single crystals by nanoindentation. Appl. Phys. Lett. 82, 1200–1202 (2003).
S. Luo, J.-H. Lee, C.-W. Liu, J.-M. Shieh, C.-H. Shen, T.-T. Wu, D. Jang, and J.R. Greer: Strength, stiffness, and microstructure of Cu(ln,Ga)Se2 thin films deposited via sputtering and co-evaporation. Appl. Phys. Lett. 105, 011907 (2014).
Y.-C. Lin, X.-Y. Peng, L.-C. Wang, Y.-L. Lin, C.-H. Wu, and S.-C Liang: Residual stress in CIGS thin film solar cells on polyimide: simulation and experiments. J. Mater. Sci. Mater. Electron. 25, 461–465 (2014).
S.E. Grillo, M. Ducarroir, M. Nadal, E. Tournié, and J.-P. Faurie: Nanoindentation of Si, GaP, GaAs and ZnSe single crystals. J. Phys. Appl. Phys. 36, L5 (2003).
L. Kinsler, A.R. Frey, A.B. Coppens, and J.V. Sanders: Fundamentals of Acoustics, 4th ed. (Wiley, New York, 2000) WW_marcado. Scribd at https://www.scribd.com/doc/39846878/Fundamentals-of-Acoustics-4th-Ed-L-Kinsler-Et-AI-Wiley-2000-WW-marcado (accessed August 10th, 2015).
Acknowledgments
D.C. thanks Leeor Kronik for drawing his attention to this experimental approach. We thank Milko van der Boom and Xiaomeng Sui for helpful discussions. This work was supported by the Israel Science Foundation, the Israel Ministry of Science, and the Israel National Nano-Initiative. D.C. holds the Sylvia and Rowland Schaefer Chair in Energy Research.
Author information
Authors and Affiliations
Corresponding authors
Supplementary materials
Supplementary materials
For supplementary material for this article, please visit http://dx.doi.org/10.1557/mrc.2015.69
Rights and permissions
About this article
Cite this article
Rakita, Y., Cohen, S.R., Kedem, N.K. et al. Mechanical properties of APbX3 (A = Cs or CH3NH3; X= I or Br) perovskite single crystals. MRS Communications 5, 623–629 (2015). https://doi.org/10.1557/mrc.2015.69
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1557/mrc.2015.69