Lead halide perovskites have attracted increasing interest for their exciting potential in diverse optoelectronic devices. However, their charge transport properties remain elusive, plagued by the issues of excessive contact resistance and large hysteresis in ambient conditions. Here we report a van der Waals integration approach for creating high-performance contacts on monocrystalline halide perovskite thin films with minimum interfacial damage and an atomically clean interface. Compared to the deposited contacts, our van der Waals contacts exhibit two to three orders of magnitude lower contact resistance, enabling systematic transport studies in a wide temperature range. We report a Hall mobility exceeding 2,000 cm2 V–1 s–1 at around 80 K, an ultralow bimolecular recombination coefficient of 3.5 × 10–15 cm3 s–1 and a photocurrent gain >106 in the perovskite thin films. Furthermore, magnetotransport studies reveal a quantum-interference-induced weak localization behaviour with a phase coherence length up to 49 nm at 3.5 K. Our results lay the foundation for exploring new physics in this class of ‘soft-lattice’ materials.
Subscribe to Journal
Get full journal access for 1 year
only $15.58 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
The data that support the findings of this study are available from the corresponding author on reasonable request.
Nie, W. et al. High-efficiency solution-processed perovskite solar cells with millimeter-scale grains. Science 347, 522–525 (2015).
Cao, Y. et al. Perovskite light-emitting diodes based on spontaneously formed submicrometre-scale structures. Nature 562, 249–253 (2018).
Fang, Y., Dong, Q., Shao, Y., Yuan, Y. & Huang, J. Highly narrowband perovskite single-crystal photodetectors enabled by surface-charge recombination. Nat. Photonics 9, 679–686 (2015).
Spicer, W., Chye, P., Garner, C., Lindau, I. & Pianetta, P. The surface electronic structure of 3–5 compounds and the mechanism of Fermi level pinning by oxygen (passivation) and metals (Schottky barriers). Surf. Sci. 86, 763–788 (1979).
Haick, H., Ambrico, M., Ghabboun, J., Ligonzo, T. & Cahen, D. Contacting organic molecules by metal evaporation. Phys. Chem. Chem. Phys. 6, 4538–4541 (2004).
Miyata, K., Atallah, T. L. & Zhu, X. Lead halide perovskites: crystal-liquid duality, phonon glass electron crystals, and large polaron formation. Sci. Adv. 3, e1701469 (2017).
Mott, N. F. & Gurney, R. W. Electronic Processes in Ionic Crystals (Oxford Univeristy Press, 1940).
Herz, L. M. Charge-carrier mobilities in metal halide perovskites: fundamental mechanisms and limits. ACS Energy Lett. 2, 1539–1548 (2017).
Green, M. A. Intrinsic concentration, effective densities of states, and effective mass in silicon. J. Appl. Phys. 67, 2944–2954 (1990).
Manfra, M. J. Molecular beam epitaxy of ultra-high-quality AlGaAs/GaAs heterostructures: enabling physics in low-dimensional electronic systems. Annu. Rev. Condens. Matter Phys. 5, 347–373 (2014).
Chen, Y. et al. Extended carrier lifetimes and diffusion in hybrid perovskites revealed by Hall effect and photoconductivity measurements. Nat. Commun. 7, 12253 (2016).
Yi, H. T., Wu, X., Zhu, X. & Podzorov, V. Intrinsic charge transport across phase transitions in hybrid organo‐inorganic perovskites. Adv. Mater. 28, 6509–6514 (2016).
Sze, S. M. & Ng, K. K. Physics of Semiconductor Devices. (Wiley, 2006).
Liu, Y. et al. Approaching the Schottky–Mott limit in van der Waals metal–semiconductor junctions. Nature 557, 696–700 (2018).
Liu, Y., Huang, Y. & Duan, X. Van der Waals integration before and beyond two-dimensional materials. Nature 567, 323–333 (2019).
Du, Y., Neal, A. T., Zhou, H. & Peide, D. Y. Weak localization in few-layer black phosphorus. 2D Mater. 3, 024003 (2016).
Zeng, J. et al. Gate-tunable weak antilocalization in a few-layer InSe. Phys. Rev. B 98, 125414 (2018).
Eaton, S. W. et al. Lasing in robust cesium lead halide perovskite nanowires. Proc. Natl Acad. Sci. USA 113, 1993–1998 (2016).
Imran, M. et al. Simultaneous cationic and anionic ligand exchange for colloidally stable CsPbBr3 nanocrystals. ACS Energy Lett. 4, 819–824 (2019).
Milot, R. L., Eperon, G. E., Snaith, H. J., Johnston, M. B. & Herz, L. M. Temperature‐dependent charge‐carrier dynamics in CH3NH3PbI3 perovskite thin films. Adv. Funct. Mater. 25, 6218–6227 (2015).
Azarhoosh, P. et al. Research update: Relativistic origin of slow electron-hole recombination in hybrid halide perovskite solar cells. APL Mater. 4, 091501 (2016).
Zhu, X. & Podzorov, V. Charge carriers in hybrid organic-inorganic lead halide perovskites might be protected as large polarons. J. Phys. Chem. Lett. 6, 4758–4761 (2015).
Zhu, H. et al. Screening in crystalline liquids protects energetic carriers in hybrid perovskites. Science 353, 1409–1413 (2016).
Miyata, K. et al. Large polarons in lead halide perovskites. Sci. Adv. 3, e1701217 (2017).
Oga, H., Saeki, A., Ogomi, Y., Hayase, S. & Seki, S. Improved understanding of the electronic and energetic landscapes of perovskite solar cells: high local charge carrier mobility, reduced recombination, and extremely shallow traps. J. Am. Chem. Soc. 136, 13818–13825 (2014).
Wehrenfennig, C., Liu, M., Snaith, H. J., Johnston, M. B. & Herz, L. M. Charge-carrier dynamics in vapour-deposited films of the organolead halide perovskite CH3NH3PbI3-xClx. Energy Environ. Sci. 7, 2269–2275 (2014).
Dong, Q. et al. Electron-hole diffusion lengths > 175 μm in solution-grown CH3NH3PbI3 single crystals. Science 347, 967–970 (2015).
Ihn, T. Semiconductor Nanostructures: Quantum States and Electronic Transport (Oxford University Press, 2010).
Hendry, E., Koeberg, M., Pijpers, J. & Bonn, M. Reduction of carrier mobility in semiconductors caused by charge-charge interactions. Phys. Rev. B 75, 233202 (2007).
Zhao, T., Shi, W., Xi, J., Wang, D. & Shuai, Z. Intrinsic and extrinsic charge transport in CH3NH3PbI3 perovskites predicted from first-principles. Sci. Rep. 6, 19968 (2016).
Mante, P. A., Stoumpos, C. C., Kanatzidis, M. G. & Yartsev, A. Electron–acoustic phonon coupling in single crystal CH3NH3PbI3 perovskites revealed by coherent acoustic phonons. Nat. Commun. 8, 14398 (2017).
He, Y. & Galli, G. Perovskites for solar thermoelectric applications: a first principle study of CH3NH3AI3 (A = Pb and Sn). Chem. Mater. 26, 5394–5400 (2014).
Wang, Y., Zhang, Y., Zhang, P. & Zhang, W. High intrinsic carrier mobility and photon absorption in the perovskite CH3NH3PbI3. Phys. Chem. Chem. Phys. 17, 11516–11520 (2015).
Zhang, M., Zhang, X., Huang, L., Lin, H. & Lu, G. Charge transport in hybrid halide perovskites. Phys. Rev. B 96, 195203 (2017).
Frost, J. M. Calculating polaron mobility in halide perovskites. Phys. Rev. B 96, 195202 (2017).
Kawabata, A. Theory of negative magnetoresistance in three-dimensional systems. Solid State Commun. 34, 431–432 (1980).
Lee, P. A. & Ramakrishnan, T. Disordered electronic systems. Rev. Mod. Phys. 57, 287 (1985).
Kepenekian, M. & Even, J. Rashba and Dresselhaus couplings in halide perovskites: accomplishments and opportunities for spintronics and spin-orbitronics. J. Phys. Chem. Lett. 8, 3362–3370 (2017).
Niesner, D. et al. Giant Rashba splitting in CH3NH3PbBr3 organic-inorganic perovskite. Phys. Rev. Lett. 117, 126401 (2016).
Wang, Y., Shi, Y., Xin, G., Lian, J. & Shi, J. Two-dimensional van der Waals epitaxy kinetics in a three-dimensional perovskite halide. Cryst. Growth Des. 15, 4741–4749 (2015).
Zhang, Q. et al. High-quality whispering‐gallery‐mode lasing from cesium lead halide perovskite nanoplatelets. Adv. Funct. Mater. 26, 6238–6245 (2016).
Chen, J. et al. Vapor-phase epitaxial growth of aligned nanowire networks of cesium lead halide perovskites (CsPbX3, X = Cl, Br, I). Nano Lett. 17, 460–466 (2017).
Chen, J. et al. Single-crystal thin films of cesium lead bromide perovskite epitaxially grown on metal oxide perovskite (SrTiO3). J. Am. Chem. Soc. 139, 13525–13532 (2017).
Jiang, J. et al. Carrier lifetime enhancement in halide perovskite via remote epitaxy. Nat. Commun. 10, 4145 (2019).
Eperon, G. E. et al. Formamidinium lead trihalide: a broadly tunable perovskite for efficient planar heterojunction solar cells. Energy Environ. Sci. 7, 982–988 (2014).
We thank T. Atallah and J. Caram for discussions. X.D. acknowledges support by the Office of Naval Research through grant no. N00014-18-1-2707 for device fabrications and characterizations, and the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering through award DE-SC0018828 for materials growth. Y.H. acknowledges support by the National Science Foundation EFRI-1433541 for partial support of material preparation. Y. Z. acknowledges support by National Key Research and Development Program of China through grant no. 2018YFA0703503 and National Natural Science Foundation of China through grant no. 51991342 for materials characterizations. I.S. acknowledges the support by the International Scientific Partnership Program at King Saud University (ISPP-148). We acknowledge the Electron Imaging Center at UCLA for transmission electron microscopy technical support and the Nanoelectronics Research Facility at UCLA for device fabrication technical support.
The authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Wang, Y., Wan, Z., Qian, Q. et al. Probing photoelectrical transport in lead halide perovskites with van der Waals contacts. Nat. Nanotechnol. (2020). https://doi.org/10.1038/s41565-020-0729-y