Journal of Materials Science

, Volume 52, Issue 1, pp 276–284 | Cite as

High-quality inorganic–organic perovskite CH3NH3PbI3 single crystals for photo-detector applications

  • Jianxu DingEmail author
  • Songjie Du
  • Ying Zhao
  • Xiaojun Zhang
  • Zhiyuan ZuoEmail author
  • Hongzhi CuiEmail author
  • Xiaoyuan Zhan
  • Yijie Gu
  • Haiqing Sun
Original Paper


Single crystals of organolead trihalide perovskites (CH3NH3PbI3) are supposed to be one of the most promising materials as photo-detectors. Because of their large absorption coefficient, long-range balanced electron, and hole-transport lengths, it is considered to break through the responsivity and efficiency. To systematically investigate the potentiality as photo-detector, high-quality CH3NH3PbI3 single crystals with large size are highly demanded. In the paper, large CH3NH3PbI3 single crystals with various crystal shapes were grown from γ-butyrolactone. At optimized precursor concentration and growth temperature, the growth rate was fixed at about 0.2 mm h−1. Under such growth conditions, the growth steps, originated from screw dislocation on (100) facet, were revealed to be about 0.45 nm. This value is corresponded to half of the unit cell, implying the slow growth rate of (100) facet. With slow growth rate, the absorption edge of the CH3NH3PbI3 single crystal was extended to 860 nm, correlated with a calculated bandgap of ~1.44 eV. By depositing a pair of Au electrodes, a metal–semiconductor–metal (MSM) photo-detector on the basis of the CH3NH3PbI3 single crystal active layer (3 mm) was fabricated and its photo-response features were investigated systematically. About 2.531 A W−1 responsivity was obtained from the device under 780 nm laser illumination, while the external quantum efficiency reached to 396.20 %, better than some GaN, GaAs, and GaP photo-detectors with a MSM device structure.


External Quantum Efficiency Seed Crystal PbI2 Growth Step High Responsivity 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



This work was financially supported by the National Natural Science Foundation of China (No. 51202131), the Scientific Research Foundation of Shandong University of Science and Technology for Recruited Talent (No. 2014RCJJ001), the Fund of State Key Laboratory of Crystal Materials in Shandong University (No. KF1504), the SDUST Research Fund and Joint Innovative Center for Safe and Effective Mining Technology, the Fundamental Research Funds of Shandong University, and Equipment of Coal Resources, Shandong Province (No. 2014JQJH102).

Supplementary material

10853_2016_329_MOESM1_ESM.docx (11.6 mb)
Supplementary material 1 (DOCX 11860 kb)


  1. 1.
    Liu YC, Yang Z, Cui D et al (2015) Two-inch-sized perovskite CH3NH3PbX3 (X = Cl, Br, I) crystals: growth and characterization. Adv Mater 27:5176–51783CrossRefGoogle Scholar
  2. 2.
    Lian ZP, Yan QF, Lv QR et al (2015) High-performance planar-type photodetector on 100 facet of MAPbI3 single crystal. Sci Rep 5:16563. doi: 10.1038/srep16563 CrossRefGoogle Scholar
  3. 3.
    Xing GC, Mathews N, Sun SY et al (2013) Long-range balanced electron and hole transport lengths in organic–inorganic CH3NH3PbI3. Science 342:344–347CrossRefGoogle Scholar
  4. 4.
    Shi D, Adinolfi V, Comin R et al (2015) Trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals. Science 30:519–522CrossRefGoogle Scholar
  5. 5.
    Tian WM, Zhao CY, Ment J et al (2015) Visualizing carrier diffusion in individual single-crystal organolead halide perovskite nanowires and nanoplates. J Am Chem Soc 137:12458–12461CrossRefGoogle Scholar
  6. 6.
    Stranks SD, Eperon GE, Grancini G et al (2013) Electron–hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342:341–344CrossRefGoogle Scholar
  7. 7.
    Nie WY, Tsai H, Asadpour R et al (2015) High-efficiency solution-processed perovskite solar cells with millimeter-scale grains. Science 347:522–525CrossRefGoogle Scholar
  8. 8.
    Saidaminov MI, Abdelhady AL, Murali B et al (2015) High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization. Nat Commun 6:7586. doi: 10.1038/ncomms8586 CrossRefGoogle Scholar
  9. 9.
    Guo Y, Liu C, Tanaka H et al (2015) Air-stable and solution-processable perovskite photodetectors for solar-blind UV and visible light. J Phys Chem Lett 6:535–539CrossRefGoogle Scholar
  10. 10.
    Chen HW, Sakai N et al (2015) Switchable high-sensitivity photodetecting and photovoltaic device with perovskite absorber. J Phys Chem Lett 6:1773–1779CrossRefGoogle Scholar
  11. 11.
    Dou L, Yang YM, You J et al (2014) Solution-processed hybrid perovskite photodetectors with high detectivity. Nat Commun 5:5404. doi: 10.1038/ncomms6404 CrossRefGoogle Scholar
  12. 12.
    Maculan G, Sheikh AD, Abdelhady AL et al (2015) CH3NH3PbCl3 single crystals: inverse temperature crystallization and visible-blind UV-photodetector. J Phys Chem Lett 6:3781–3786CrossRefGoogle Scholar
  13. 13.
    Yan KY, Long MZ, Zhang TK et al (2015) Hybrid halide perovskite solar cell precursors: colloidal chemistry and coordination engineering behind device processing for high efficiency. J Am Chem Soc 137:4460–4468CrossRefGoogle Scholar
  14. 14.
    Leguy AMA, Hu YH, Quiles MC et al (2015) Reversible hydration of CH3NH3PbI3 in films, single crystals, and solar cells. Chem Mater 27:3397–3407CrossRefGoogle Scholar
  15. 15.
    Kadro JM, Nonomura K, Gachet D et al (2015) Facile route to freestanding CH3NH3PbI3 crystals using inverse solubility. Sci Rep 5:11654. doi: 10.1038/srep11654 CrossRefGoogle Scholar
  16. 16.
    Su J, Chen DP, Lin CT (2015) Growth of large CH3NH3PbX3 (X = I, Br) single crystals in solution. J Cryst Growth 422:75–79CrossRefGoogle Scholar
  17. 17.
    Dang YY, Liu Y, Sun YX et al (2015) Bulk crystal growth of hybrid perovskite material CH3NH3PbI3. CrystEngComm 17:665–670CrossRefGoogle Scholar
  18. 18.
    She LM, Liu MZ, Zhong DY et al (2016) Atomic structures of CH3NH3PbI3 (001) surfaces. ACS Nano 10:1126–1131CrossRefGoogle Scholar
  19. 19.
    Dong QF, Fang YJ, Shao YC et al (2015) Electron–hole diffusion lengths >175 μm in solution-grown CH3NH3PbI3 single crystals. Science 27:967–970CrossRefGoogle Scholar
  20. 20.
    Kulkarni SA, Baikie T, Biox PP et al (2014) Band-gap tuning of lead halide perovskites using a sequential deposition process. J Mater Chem A 2:9221–9225CrossRefGoogle Scholar
  21. 21.
    Wang Q, Shao YC, Xie HP et al (2014) Qualifying composition dependent p and n self-doping in CH3NH3PbI3. Appl Phys Lett 105:163508. doi: 10.1063/1.4899051 CrossRefGoogle Scholar
  22. 22.
    As DJ, Schmilgus F, Wang C et al (1997) The near band edge photoluminescence of cubic GaN epilayers. Appl Phys Lett 70:1311–1313CrossRefGoogle Scholar
  23. 23.
    Warner HJ (1988) Schottky barrier and pn-junction I/V plots—small signal evaluation. Appl Phys A 47:291–300CrossRefGoogle Scholar
  24. 24.
    Averine SV, Kuznetzov PI, Zhitov VA et al (2006) Solar blind MSM-photodetectors based on AlxGa1−xN/GaN heterostructures grown by MOCVD. Solid State Electron 52:618–624CrossRefGoogle Scholar
  25. 25.
    Wang CK, Chang SJ, Su YK et al (2006) GaN MSM UV photodetectors with titanium tungsten transparent electrodes. IEEE Trans Electron Dev 53:38–42CrossRefGoogle Scholar
  26. 26.
    Koscielniak WC, Kolbas RM, Littlejohn MA (1988) Performance of a near-infrared GaAs metal–semiconductor–metal (MSM) photodetector with islands. IEEE Electron Dev Lett 9:485–487CrossRefGoogle Scholar
  27. 27.
    Kim JH, Griem HT, Friedman RA et al (1992) High-performance back-illuminated InGaAs/ln-AlAs MSM photodetector with a record responsivity of 0.96 A/W. IEEE Photon Technol Lett 4:1241–1244CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  1. 1.College of Materials Science and EngineeringShandong University of Science and TechnologyQingdaoChina
  2. 2.State Key Laboratory of Mining Disaster Prevention and Control Co-founded by Shandong Province and the Ministry of Science and TechnologyShandong University of Science and TechnologyQingdaoChina
  3. 3.Advanced Research Center for OpticsShandong UniversityJinanChina
  4. 4.State Key Laboratory of Crystal MaterialsShandong UniversityJinanChina

Personalised recommendations