Heterostructures formed from interfaces between materials with complementary properties often display unconventional physics. Of especial interest are heterostructures formed with ferroelectric materials. These are mostly formed by combining thin layers in vertical stacks. Here the first in situ molecular beam epitaxial growth and scanning tunneling microscopy characterization of atomically sharp lateral heterostructures between a ferroelectric SnTe monolayer and a paraelectric PbTe monolayer are reported. The bias voltage dependence of the apparent heights of SnTe and PbTe monolayers, which are closely related to the type‐II band alignment of the heterostructure, is investigated. Remarkably, it is discovered that the ferroelectric domains in the SnTe surrounding a PbTe core form either clockwise or counterclockwise vortex‐oriented quadrant configurations. In addition, when there is a finite angle between the polarization and the interface, the perpendicular component of the polarization always points from SnTe to PbTe. Supported by first‐principles calculation, the mechanism of vortex formation and preferred polarization direction is identified in the interaction between the polarization, the space charge, and the strain effect at the horizontal heterointerface. The studies bring the application of 2D group‐IV monochalcogenides on in‐plane ferroelectric heterostructures a step closer.
Two-dimensional halide perovskite lateral epitaxial heterostructures
Epitaxial heterostructures based on oxide perovskites and III–V, II–VI and transition metal dichalcogenide semiconductors form the foundation of modern electronics and optoelectronics. Halide perovskites—an emerging family of tunable semiconductors with desirable properties—are attractive for applications such as solution-processed solar cells, light-emitting diodes, detectors and lasers. Their inherently soft crystal lattice allows greater tolerance to lattice mismatch, making them promising for heterostructure formation and semiconductor integration. Atomically sharp epitaxial interfaces are necessary to improve performance and for device miniaturization. However, epitaxial growth of atomically sharp heterostructures of halide perovskites has not yet been achieved, owing to their high intrinsic ion mobility, which leads to interdiffusion and large junction widths, and owing to their poor chemical stability, which leads to decomposition of prior layers
during the fabrication of subsequent layers. Therefore, understanding the origins of this instability and identifying effective approaches to suppress ion diffusion are of great importance22–26. Here we report an effective strategy to substantially inhibit in-plane ion diffusion in two-dimensional halide perovskites by incorporating rigid π-conjugated organic ligands. We demonstrate highly stable and tunable lateral epitaxial heterostructures, multiheterostructures and superlattices. Near-atomically sharp interfaces and epitaxial growth are revealed by low-dose aberration-corrected high-resolution transmission electron microscopy. Molecular dynamics simulations confirm the reduced heterostructure disorder and larger vacancy formation energies of the two-dimensional perovskites in the presence of conjugated ligands. These findings provide insights into the immobilization and stabilization of halide perovskite semiconductors and demonstrate a materials platform for complex and molecularly thin superlattices, devices and integrated circuits.
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- Award ID(s):
- 1939986
- NSF-PAR ID:
- 10191207
- Date Published:
- Journal Name:
- Nature
- Volume:
- 580
- ISSN:
- 1476-4687
- Page Range / eLocation ID:
- 614-620
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract The growth of epitaxial semiconductors and oxides has long since revolutionized the electronics and optics fields, and continues to be exploited to uncover new physics stemming from quantum interactions. While the recent emergence of halide perovskites offers exciting new opportunities for a range of thin‐film electronics, the principles of epitaxy have yet to be applied to this new class of materials and the full potential of these materials is still not yet known. In this work, single‐domain inorganic halide perovskite epitaxy is demonstrated. This is enabled by reactive vapor phase deposition onto single crystal metal halide substrates with congruent ionic interactions. For the archetypical halide perovskite, cesium tin bromide, two epitaxial phases, a cubic phase and tetragonal phase, are uncovered which emerge via stoichiometry control that are both stabilized with vastly differing lattice constants and accommodated via epitaxial rotation. This epitaxial growth is exploited to demonstrate multilayer 2D quantum wells of a halide‐perovskite system. This work ultimately unlocks new routes to push halide perovskites to their full potential.
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1038/s41586-020-2219-7
