Skip to main content
Log in

Partially reversible photochromic behavior of organic-inorganic perovskites with copper(II) chloride

  • Published:
Journal of Zhejiang University-SCIENCE A Aims and scope Submit manuscript

Abstract

We report that the ultraviolet (UV) light induced photochromic behavior of layered organic-inorganic perovskite material of (C4H9NH3)2CuCl4, changed from yellow to brown after irradiation with UV light (10 mW/cm2) and partially recovered through storage in the dark. (C4H9NH3)2CuCl4 exhibited two distinct absorption bands centered at 286 nm (band I) and 384 nm (band II), which were attributed to the photo-induced exciton formed in 2D inorganic layers sandwiched by organic layers. The blue shift of band I from 287 to 269 nm as well as the decrease of the intensity of band I and band II could be found when samples were irradiated under UV light for different length of time. The simultaneous weakening of the intensity of the N-H⋯Cl hydrogen bond as well as the vibration of the long Cu-Cl bond in the distorted CuCl6 4− octahedron could be detected from the Fourier transform infrared (FTIR) spectra, which resulted the change of charge distribution of the dissymmetric Cl-Cu⋯Cl bond and the resulting photochromic behavior.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Cheng, Z.Y., Wang, Z., Xing, R.B., Han, Y.C., Lin, J., 2003. Patterning and photoluminescent properties of perovskite-type organic/inorganic hybrid luminescent films by soft lithography. Chemical Physics Letters, 376(3—4):481–486. [doi:10.1016/S0009-2614(03)01017-0]

    Article  Google Scholar 

  • Geraud, E., Mohwald, H., Shchukin, D.G., 2008. Templating of perovskite-related films using layer-by-layer assemblies and nanoparticle building blocks. Chemistry of Materials, 20(16):5139–5145. [doi:10.1021/cm7020559]

    Article  Google Scholar 

  • Jain, P., Dalal, N.S., Toby, B.H., Kroto, H.W., Cheetham, A.K., 2008. Order-disorder antiferroelectric phase transition in a hybrid inorganic-organic framework with the perovskite architecture. Journal of the American Chemical Society, 130(32):10450-10451. [doi:10.1021/ja801952e]

    Google Scholar 

  • Li, Y., Zheng, G., Lin, C., Lin, J., 2008. New organic-inorganic perovskite materials with different optical properties modulated by different inorganic sheets. Crystal Growth & Design, 8(6):1990–1996. [doi:10.1021/cg800047p]

    Article  Google Scholar 

  • Mitzi, D.B., 1996. Synthesis, crystal structure, and optical and thermal properties of (C4H9NH3)2MI4 (M=Ge, Sn, Pb). Chemistry of Materials 8:791–800. [doi:10.1021/cm9505097]

    Article  Google Scholar 

  • Mitzi, D.B., 2001. Thin-film deposition of organic-inorganic hybrid materials. Chemistry of Materials, 13(10): 3283–3298. [doi:10.1021/cm0101677]

    Article  Google Scholar 

  • Mitzi, D.B., 2004. Solution-processed inorganic semiconductors. Journal of Materials Chemistry, 14(15):2355–2365. [doi:10.1039/b403482a]

    Article  Google Scholar 

  • Myles, A.J., Wigglesworth, T.J., Branda, N.R., 2003. A multi-addressable photochromic 1,2-dithienylcyclopentene-phenoxynaphthacenequinone hybrid. Advanced Materials, 15(9):745–748. [doi:10.1002/adma.200304917]

    Article  Google Scholar 

  • Rodriguez, F., Aguado, F., Valiente, R., Hanfland, M., Itie, J.P., 2007. Variation of the Jahn-Teller distortion with pressure in perovskite layers A2CuCl4. Influence on the charge-transfer band. Physica Status Solidi (B), 24:156–161. [doi:10.1002/pssb.200672506]

    Article  Google Scholar 

  • Sourisseau, S., Louvain, N., Bi, W.H., Mercier, N., Rondeau, D., Buzare, J.Y., Legein, C., 2007. Hybrid perovskite resulting from the solid-state reaction between the organic cations and perovskite layers of α1-(Br-(CH2)2-NH3)2PbI4. Inorganic Chemistry, 46:6148–6154. [doi:10.1021/ic070240g]

    Article  Google Scholar 

  • Smith, D.W., 1976. Chlorocuprates(II). Coordination Chemistry Reviews, 21(2–3):93–260. [doi:10.1016/S0010-8545(00)80445-2]

    Article  Google Scholar 

  • Valiente, R., Rodriguez, F., 1996. Polarized electronic spectra of the (CH3NH3)2Cd1-x MnxCl4 (x=0∼1) perovskite layer doped with Cu2+: Study of the Cl→Cu2+ charge transfer intensity enhancement along the series. Journal of Physics and Chemistry of Solids, 57:571–578.

    Article  Google Scholar 

  • Valiente, R., Rodriguez, F., 1999. Electron-phonon coupling in charge-transfer and crystal-field states of Jahn-Teller CuCl6 4−. systems. Physical Review B, 60(13):9423–9429. [doi:10.1103/PhysRevB.60.9423]

    Article  Google Scholar 

  • Valiente, R., Rodriguez, F., Moreno, M., Hitchman, M., 1999. Effect of pressure on the Cl→Cu2+ charge transfer in A2CuCl4 layer perovskites (A=CnH2n+1NH3, n=2, 3) and (3-Chloroanilinium)8[CuCl6]Cl4: structural correlations. Physica B: Condensed Matter, 265(1–4):176–180. [doi:10.1016/S0921-4526(98)01365-9]

    Article  Google Scholar 

  • Wselucha-Birczynska, A., Pluszkiewicz, C., Borzecka-Prolop, B., 2003. FTIR and XRD studies of the temperature changes in copper(II)-cinchoninium compound: the importance of the sample preparation. Journal of Molecular Structure, 651:525–531.

    Article  Google Scholar 

  • Xu, H.P., Sun, J.Z., Qin, A.J., 2006. Functional perovskite hybrid of polyacetylene ammonium and lead bromide: synthesis, light emission, and fluorescence imagining. The Journal of Physical Chemistry B, 110(43):21701–21709. [doi:10.1021/jp0646269]

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Gang Wu.

Additional information

Project supported by the National Natural Science Foundation of China (Nos. 50318001, 50433020, 50503021 and 50520150165), and the Developing Program of Changjiang Scholar and Innovation Team from Ministry of Education of China (No. IRT0651)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Pan, Xw., Wu, G., Wang, M. et al. Partially reversible photochromic behavior of organic-inorganic perovskites with copper(II) chloride. J. Zhejiang Univ. Sci. A 10, 710–715 (2009). https://doi.org/10.1631/jzus.A0820736

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1631/jzus.A0820736

Key words

CLC number

Navigation