Crumpled graphene films are broadly used, for instance in electronics1, energy storage2, 3, composites4, 5, and biomedicine6. Although it is known that the degree of crumpling affects graphene's properties and the performance of graphene-based devices and materials3, 5, 7, the controlled folding and unfolding of crumpled graphene films has not been demonstrated. Here we report an approach to reversibly control the crumpling and unfolding of large-area graphene sheets. We show with experiments, atomistic simulations and theory that, by harnessing the mechanical instabilities of graphene adhered on a biaxially pre-stretched polymer substrate and by controlling the relaxation of the pre-strains in a particular order, graphene films can be crumpled into tailored self-organized hierarchical structures that mimic superhydrophobic leaves. The approach enables us to fabricate large-area conductive coatings and electrodes showing superhydrophobicity, high transparency, and tunable wettability and transmittance. We also demonstrate that crumpled graphene-polymer laminates can be used as artificial-muscle actuators.

A series of two-dimensional (2D) hybrid organic-inorganic perovskite (HOIP) crystals, based on acene alkylamine cations (i.e., phenylmethylammonium (PMA), 2-phenylethylammonium (PEA), 1-(2-naphthyl)methanammonium (NMA), and 2-(2-naphthyl)ethanammonium (NEA)) and lead(II) halide (i.e., PbX, X = Cl, Br, and I) frameworks, and their corresponding thin films were fabricated and examined for structure-property relationship. Several new or redetermined crystal structures are reported, including those for (NEA)PbI, (NEA)PbBr, (NMA)PbBr, (PMA)PbBr, and (PEA)PbI. Non-centrosymmetric structures from among these 2D HOIPs were confirmed by piezoresponse force microscopy-especially noteworthy is the structure of (PMA)PbBr, which was previously reported as centrosymmetric. Examination of the impact of organic cation and inorganic layer choice on the exciton absorption/emission properties, among the set of compounds considered, reveals that perovskite layer distortion (i.e., Pb-I-Pb bond angle between adjacent PbI octahedra) has a more global effect on the exciton properties than octahedral distortion (i.e., variation of I-Pb-I bond angles and discrepancy among Pb-I bond lengths within each PbI octahedron). In addition to the characteristic sharp exciton emission for each perovskite, (PMA)PbCl, (PEA)PbCl, (NMA)PbCl, and (PMA)PbBr exhibit separate, broad "white" emission in the long wavelength range. Piezoelectric compounds identified from these 2D HOIPs may be considered for future piezoresponse-type energy or electronic applications.

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The unique hybrid nature of 2D Ruddlesden–Popper (R–P) perovskites has bestowed upon them not only tunability of their electronic properties but also high-performance electronic devices with improved environmental stability as compared to their 3D analogs. However, there is limited information about their inherent heat, light, and air stability and how different parameters such as the inorganic layer number and length of organic spacer molecule affect stability. To gain deeper understanding on the matter we have expanded the family of 2D R–P perovskites, by utilizing pentylamine (PA)2(MA) n−1Pb n I3n+1 (n = 1–5, PA = CH3(CH2)4NH3 +, C5) and hexylamine (HA)2(MA) n−1Pb n I3n+1 (n = 1–4, HA = CH3(CH2)5NH3 +, C6) as the organic spacer molecules between the inorganic slabs, creating two new series of layered materials, for up to n = 5 and 4 layers, respectively. The resulting compounds were extensively characterized through a combination of physical and spectroscopic methods, including single crystal X-ray analysis. High resolution powder X-ray diffraction studies using synchrotron radiation shed light for the first time to the phase transitions of the higher layer 2D R–P perovskites. The increase in the length of the organic spacer molecules did not affect their optical properties; however, it has a pronounced effect on the air, heat, and light stability of the fabricated thin films. An extensive study of heat, light, and air stability with and without encapsulation revealed that specific compounds can be air stable (relative humidity (RH) = 20–80% ± 5%) for more than 450 days, while heat and light stability in air can be exponentially increased by encapsulating the corresponding films. Evaluation of the out-of-plane mechanical properties of the corresponding materials showed that their soft and flexible nature can be compared to current commercially available polymer substrates (e.g., PMMA), rendering them suitable for fabricating flexible and wearable electronic devices.

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