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  • ReceivedMay 9, 2017
  • AcceptedMay 10, 2017
  • PublishedJul 14, 2017

Abstract

As the large single-crystalline silicon wafers have revolutionized many industries including electronics and solar cells, it is envisioned that the availability of large single-crystalline perovskite crystals and wafers will revolutionize its broad applications in photovoltaics, optoelectronics, lasers, photodetectors, light emitting diodes (LEDs), etc. Here we report a method to grow large single-crystalline perovskites including single-halide crystals: CH3NH3PbX3 (X=I, Br, Cl), and dual-halide ones: CH3NH3Pb(ClxBr1−x)3 and CH3NH3Pb(BrxI1−x)3, with the largest crystal being 120 mm in length. Meanwhile, we have advanced a process to slice the large perovskite crystals into thin wafers. It is found that the wafers exhibit remarkable features: (1) its trap-state density is a million times smaller than that in the microcrystalline perovskite thin films (MPTF); (2) its carrier mobility is 410 times higher than its most popular organic counterpart P3HT; (3) its optical absorption is expanded to as high as 910 nm comparing to 797 nm for the MPTF; (4) while MPTF decomposes at 150 °C, the wafer is stable at high temperature up to 270 °C; (5) when exposed to high humidity (75% RH), MPTF decomposes in 5 h while the wafer shows no change for overnight; (6) its photocurrent response is 250 times higher than its MPTF counterpart. A few electronic devices have been fabricated using the crystalline wafers. Among them, the Hall test gives low carrier concentration with high mobility. The trap-state density is measured much lower than common semiconductors. Moreover, the large SC-wafer is found particularly useful for mass production of integrated circuits. By adjusting the halide composition, both the optical absorption and the light emission can be fine-tuned across the entire visible spectrum from 400 nm to 800 nm. It is envisioned that a range of visible lasers and LEDs may be developed using the dual-halide perovskites. With fewer trap states, high mobility, broader absorption, and humidity resistance, it is expected that solar cells with high stable efficiency maybe attainable using the crystalline wafers.


Funded by

National Key Research Project MOST(2016YFA0202400)

National Natural Science Foundation of China(61604090,61604091,61674098)

National University Research Fund(GK261001009,GK201603107)

Changjiang Scholar and Innovative Research Team(IRT_14R33)

111 Project(B14041)

Chinese National 1000-talent-plan Program(1110010341)

and the Innovation Funds of Graduate Programs

SNNU(2015CXS047)


Acknowledgment

This work was supported by the National Key Research Project MOST (2016YFA0202400), the National Natural Science Foundation of China (61604090, 61604091, 61674098), National University Research Fund (GK261001009, GK201603107), the Changjiang Scholar and Innovative Research Team (IRT_14R33), the 111 Project (B14041), the Chinese National 1000-talent-plan Program (1110010341), and the Innovation Funds of Graduate Programs, SNNU (2015CXS047). The authors would like to thank Prof. Ming Liu at the Xi’an Jiaotong University for the high resolution X-ray diffraction measurement and Prof. Yong Zhang at The University of North Carolina at Charlotte for insightful discussion.


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

These authors contributed equally to this work.


Supplement

The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


References

[1] Wehrenfennig C, Eperon GE, Johnston MB, Snaith HJ, Herz LM. Adv Mater, 2014, 26: 1584-1589 CrossRef Google Scholar

[2] Shi D, Adinolfi V, Comin R, Yuan M, Alarousu E, Buin A, Chen Y, Hoogland S, Rothenberger A, Katsiev K, Losovyj Y, Zhang X, Dowben PA, Mohammed OF, Sargent EH, Bakr OM. Science, 2015, 347: 519-522 CrossRef PubMed ADS Google Scholar

[3] Dong Q, Fang Y, Shao Y, Mulligan P, Qiu J, Cao L, Huang J. Science, 2015, 347: 967-970 CrossRef PubMed ADS Google Scholar

[4] Best. Research Cell Efficiency Records, Nation Renewable Energy Laboratory (NREL). http://www.nrel.gov/ncpv/images/efficiency_chart.jpg, accessed on 2017. Google Scholar

[5] Kumawat NK, Dey A, Narasimhan KL, Kabra D. ACS Photonics, 2015, 2: 349-354 CrossRef Google Scholar

[6] Kim YH, Cho H, Heo JH, Kim TS, Myoung NS, Lee CL, Im SH, Lee TW. Adv Mater, 2015, 27: 1248-1254 CrossRef PubMed Google Scholar

[7] Lee Y, Kwon J, Hwang E, Ra CH, Yoo WJ, Ahn JH, Park JH, Cho JH. Adv Mater, 2015, 27: 41-46 CrossRef PubMed Google Scholar

[8] Dong R, Fang Y, Chae J, Dai J, Xiao Z, Dong Q, Yuan Y, Centrone A, Zeng XC, Huang J. Adv Mater, 2015, 27: 1912-1918 CrossRef PubMed Google Scholar

[9] Xia HR, Li J, Sun WT, Peng LM. Chem Commun, 2014, 50: 13695-13697 CrossRef PubMed Google Scholar

[10] Xing G, Mathews N, Lim SS, Yantara N, Liu X, Sabba D, Grätzel M, Mhaisalkar S, Sum TC. Nat Mater, 2014, 13: 476-480 CrossRef PubMed ADS Google Scholar

[11] Deschler F, Price M, Pathak S, Klintberg LE, Jarausch DD, Higler R, Hüttner S, Leijtens T, Stranks SD, Snaith HJ, Atatüre M, Phillips RT, Friend RH. J Phys Chem Lett, 2014, 5: 1421-1426 CrossRef PubMed Google Scholar

[12] Shao Y, Xiao Z, Bi C, Yuan Y, Huang J. Nat Commun, 2014, 5: 5784 CrossRef PubMed ADS Google Scholar

[13] Wetzelaer GJAH, Scheepers M, Sempere AM, Momblona C, Ávila J, Bolink HJ. Adv Mater, 2015, 27: 1837-1841 CrossRef PubMed Google Scholar

[14] Nelson RJ, Sobers RG. J Appl Phys, 1978, 49: 6103-6108 CrossRef ADS Google Scholar

[15] Barnard ES, Hoke ET, Connor ST, Groves JR, Kuykendall T, Yan Z, Samulon EC, Bourret-Courchesne ED, Aloni S, Schuck PJ, Peters CH, Hardin BE. Sci Rep, 2013, 3: 2098 CrossRef PubMed ADS Google Scholar

[16] Metzger WK, Repins IL, Contreras MA. Appl Phys Lett, 2008, 93: 022110 CrossRef ADS Google Scholar

[17] Saidaminov MI, Abdelhady AL, Murali B, Alarousu E, Burlakov VM, Peng W, Dursun I, Wang L, He Y, Maculan G, Goriely A, Wu T, Mohammed OF, Bakr OM. Nat Commun, 2015, 6: 7586 CrossRef PubMed ADS Google Scholar

[18] Dang Y, Liu Y, Sun Y, Yuan D, Liu X, Lu W, Liu G, Xia H, Tao X. CrystEngComm, 2015, 17: 665-670 CrossRef Google Scholar

[19] Liu Y, Yang Z, Cui D, Ren X, Sun J, Liu X, Zhang J, Wei Q, Fan H, Yu F, Zhang X, Zhao C, Liu SF. Adv Mater, 2015, 27: 5176-5183 CrossRef PubMed Google Scholar

[20] Baikie T, Fang Y, Kadro JM, Schreyer M, Wei F, Mhaisalkar SG, Graetzel M, White TJ. J Mater Chem A, 2013, 1: 5628-5641 CrossRef Google Scholar

[21] Sheng R, Ho-Baillie A, Huang S, Chen S, Wen X, Hao X, Green MA. J Phys Chem C, 2015, 119: 3545-3549 CrossRef Google Scholar

[22] Tanaka K, Takahashi T, Ban T, Kondo T, Uchida K, Miura N. Solid State Commun, 2003, 127: 619-623 CrossRef ADS Google Scholar

[23] Bube RH. J Appl Phys, 1962, 33: 1733-1737 CrossRef ADS Google Scholar

[24] Poglitsch A, Weber D. J Chem Phys, 1987, 87: 6373-6378 CrossRef ADS Google Scholar

[25] Jiang XM, Österbacka R, Korovyanko O, An CP, Horovitz B, Janssen RAJ, Vardeny ZV. Adv Funct Mater, 2002, 12: 587-597 CrossRef Google Scholar

[26] Dualeh A, Tétreault N, Moehl T, Gao P, Nazeeruddin MK, Grätzel M. Adv Funct Mater, 2014, 24: 3250-3258 CrossRef Google Scholar

[27] Dualeh A, Gao P, Seok SI, Nazeeruddin MK, Grätzel M. Chem Mater, 2014, 26: 6160-6164 CrossRef Google Scholar

[28] Christians JA, Miranda Herrera PA, Kamat PV. J Am Chem Soc, 2015, 137: 1530-1538 CrossRef PubMed Google Scholar

[29] You J, Yang YM, Hong Z, Song TB, Meng L, Liu Y, Jiang C, Zhou H, Chang WH, Li G, Yang Y. Appl Phys Lett, 2014, 105: 183902 CrossRef ADS Google Scholar

[30] Kumawat NK, Dey A, Kumar A, Gopinathan SP, Narasimhan KL, Kabra D. ACS Appl Mater Interfaces, 2015, 7: 13119-13124 CrossRef Google Scholar

[31] Jang DM, Park K, Kim DH, Park J, Shojaei F, Kang HS, Ahn JP, Lee JW, Song JK. Nano Lett, 2015, 15: 5191-5199 CrossRef PubMed ADS Google Scholar

[32] Noh JH, Im SH, Heo JH, Mandal TN, Seok SI. Nano Lett, 2013, 13: 1764-1769 CrossRef PubMed Google Scholar

[33] Vegard L. Z Physik, 1921, 5: 17-26 CrossRef ADS Google Scholar

[34] Butler KT, Frost JM, Walsh A. Mater Horiz, 2015, 2: 228-231 CrossRef Google Scholar

[35] Buin A, Comin R, Xu J, Ip AH, Sargent EH. Chem Mater, 2015, 27: 4405-4412 CrossRef Google Scholar

  • Figure 1

    Characterization of materials. (a) Photograph taken from a CH3NH3PbI3 crystal in growth solution; (b) X-ray diffraction pattern of the PGC (~50 μm) and 2θ scan for the large perovskite CH3NH3PbI3 crystal with the X-ray rocking curve shown in the upper-left inset for the (112) plane; (c) the schematic illustration of the wafer slicing process; (d) the perovskite CH3NH3PbI3 crystalline wafers sliced at LONGI Silicon (the world’s largest SC Si wafer provider), planar and cross-sectional view (color online).

  • Figure 2

    Characterization of the SC perovskite material. (a) UV-Vis-NIR absorption spectra for a MPTF CH3NH3PbI3, CH3NH3PbI3 PGC, a LSC and a SCW; (b) PL spectra for the CH3NH3PbI3 MPTF, CH3NH3PbI3 PGC, a LSC and a SCW; (c) PL spectra from 14 different locations, as labeled in Figure S4 (Supporting Information online); (d) I-V curve of the Au/(perovskite CH3NH3PbI3 crystalline wafer)/Au all-hole device measured under dark exhibiting VTFL kink-point behavior; (e) the picture of a 53.5 mm×34.5 mm×1.4 mm CH3NH3PbI3 crystalline wafer used for PL uniformity measurement; (f) the picture taken from the device (16.6 mm×11.7 mm×3.4 mm) used for the trap-state density measurement; (g) the picture taken from the device (9.1 mm×9.1 mm×2.4 mm) used for the hall effect measurement (color online).

  • Figure 3

    Photographs of SC perovskite. (a) CH3NH3Pb(BryI1−y)3 (y=0–1); (b) CH3NH3Pb(ClxBr1−x)3 (x=0–1); (c) XRD of CH3NH3Pb(ClxBr1−x)3; (d) XRD of CH3NH3Pb(BryI1−y)3 (color online).

  • Figure 4

    Optical Characterization. (a) UV-Vis-NIR absorption spectra of CH3NH3Pb(ClxBr1−x)3 and CH3NH3Pb(BryI1−y)3 powder; (b) PL spectra of CH3NH3Pb(ClxBr1−x)3 and CH3NH3Pb(BryI1−y)3 powder; (c) energy alignment of halide perovskites referenced to CH3NH3PbI3 (color online).

  • Figure 5

    Characterization of the single crystalline perovskite wafer and microcrystalline perovskite thin film photodetector. (a, b) Photographs of 24 and 28 planar-type photodetectors fabricated on single-crystalline perovskite wafers; (c, d) photocurrent response of the detectors measured at different bias voltages of 1, 2, 4, 6, 8, 10 and 12 V with the illumination turned on-and-off (AM 1.5G, 100 mW/cm2) for a single-crystalline perovskite wafer and a typical microcrystalline perovskite thin film planar-type photodetector; (e) the comparison of photocurrent response between a single-crystalline perovskite wafer and microcrystalline perovskite thin film planar-type photodetector at bias voltage of 6 V with and without light illumination (900 nm,13.2 mW/cm2) (color online).

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