RESUMO
Stretchable barrier films capable of maintaining high levels of moisture- and gas-barrier performance under significant mechanical strains are a critical component for wearable/flexible electronics and other devices, but realization of stretchable moisture-barrier films has not been possible due to the inevitable issues of strain-induced rupturing compounded with moisture-induced swelling of a stretched barrier film. This study demonstrates nanolaminated polymer/metal oxide stretchable moisture-barrier films fabricated by a novel molecular layer deposition (MLD) process of polyamide-2,3 (PA-2,3) integrated with atomic layer deposition (ALD) metal oxide processes and an in situ surface-functionalization technique. The PA-2,3 surface upon in situ functionalization with H2O2 vapor offers adequate surface chemisorption sites for rapid nucleation of ALD oxides, minimizing defects at the PA-2,3/oxide interfaces in the nanolaminates. The integrated ALD/MLD process enables facile deposition and precise structural control of many-layered oxide/PA-2,3 nanolaminates, where the large number of PA-2,3 nanolayers provide high tolerance against mechanical stretching and flexing thanks to their defect-decoupling and stress-buffering functions, while the large number of oxide nanolayers shield against swelling by moisture. Specifically, a nanolaminate with 72 pairs of alternating 2 nm (5 cycles) PA-2,3 and 0.5 nm HfO2 (five cycles) maintains its water vapor transmission rate (WVTR) at the 10-6 g/m2 day level upon 10% tensile stretching and 2 mm-radius bending, a significant breakthrough for the wearable/flexible electronics technologies.
RESUMO
Thin films of Ag nanowires (NWs) offer many advantages as transparent electrodes for flexible electronics, but their applications are hindered by issues including poor stability/durability of Ag NWs, high processing temperatures, heterogeneity of surfaces, and lack of gas-barrier function. This study reports novel mechanisms through which a conductive Hf:ZnO (HZO) film by atomic layer deposition (ALD) can be integrated with a sprayed Ag NWs film to address the issues of Ag NWs. First, the ALD surface reactions can induce fusing of the Ag NWs into a connected network without the need for a thermal sintering process. Second, the ALD process can in situ functionalize the Ag NWs to yield defect-free (in terms of blocking gas permeation) coverage of the ALD HZO over the entire nanowire surfaces, which also enhances the ALD-induced fusing of Ag NWs. The composite HZO/Ag NWs films exhibit low sheet resistance (15 Ω sq-1), low water vapor transmission rate (WVTR) (5.1 × 10-6 g m-2 day-1), high optical transmission (92%), excellent flexibility (12.5 mm bending radius), high stability/durability (against an extensive set of degradation modes and photolithographic patterning processes), and low processing temperature (90 °C) and can be used in perovskite solar cells to obtain high power conversion efficiency (14.46%).
