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Ultrathin freestanding films with well-defined micro/nanostructures and robust mechanical properties are applied in many engineering applications including microelectronics, optics, filtration and separation, biomedical engineering, and nanotechnology. Although considerable efforts have been made toward the fabrication of freestanding thin films, it is still a significant challenge to develop a simple and reliable process for producing freestanding films with ultrathin thickness, well-regulated micro/nanopatterns, robust mechanical properties, macroscopic coverage area, and multi-layered composite structures. In this work, a significant advancement is reported in this regard. This study shows a new sacrificial-layer-free (SLF) lifting-off process, integrated with conventional micro- and nanolithography, enabling the release of micro- and nanopatterned photoresist (PR) films from the supporting substrate with unprecedented pattern coverage and structure characteristics. The freestanding PR film is resilient, can withstand significant bending and deformation, and is sufficiently flexible to be transferred onto substrates with 3D topography as a conformal soft stencil for further technological processing and applications. Moreover, the SLF lifting-off process provides a simple approach to prepare single-layered and multi-layered freestanding composite films. The results suggest that the novel SLF lifting-off process can significantly extend the capability of 3D micro-/nanofabrication.
DNA double helices containing metal-mediated DNA (mmDNA) base pairs are constructed from Ag + and Hg 2+ ions between pyrimidine:pyrimidine pairs with the promise of nanoelectronics. Rational design of mmDNA nanomaterials is impractical without a complete lexical and structural description. Here, in this study, the programmability of structural DNA nanotechnology toward its founding mission of self-assembling a diffraction platform for biomolecular structure determination is explored. The tensegrity triangle is employed to build a comprehensive structural library of mmDNA pairs via X-ray diffraction and generalized design rules for mmDNA construction are elucidated. Two binding modes are uncovered: N3-dominant, centrosymmetric pairs and major groove binders driven by 5-position ring modifications. Energy gap calculations show additional levels in the lowest unoccupied molecular orbitals (LUMO) of mmDNA structures, rendering them attractive molecular electronic candidates.
In this study, iron-nitrogen-carbon (Fe-N-C) single-atom catalysts are promising sustainable alternatives to the costly and scarce platinum (Pt) to catalyze the oxygen reduction reactions (ORR) at the cathode of proton exchange membrane fuel cells (PEMFCs). However, Fe-N-C cathodes for PEMFC are made thicker than Pt/C ones, in order to compensate for the lower intrinsic ORR activity and site density of Fe-N-C materials. The thick electrodes are bound with mass transport issues that limit their performance at high current densities, especially in H 2 /air PEMFCs. Practical Fe-N-C electrodes must combine high intrinsic ORR activity, high site density, and fast mass transport. Herein, it has achieved an improved combination of these properties with a Fe-N-C catalyst prepared via a two-step synthesis approach, constructing first a porous zinc-nitrogen-carbon (Zn-N-C) substrate, followed by transmetallating Zn by Fe via chemical vapor deposition. A cathode comprising this Fe-N-C catalyst has exhibited a maximum power density of 0.53 W cm -2 in H 2 /air PEMFC at 80 °C. The improved power density is associated with the hierarchical porosity of the Zn-N-C substrate of this work, which is achieved by epitaxial growth of ZIF-8 onto g-C 3 N 4 , leading to a micro-mesoporous substrate.
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Advanced manufacturing has received considerable attention as a tool for the fabrication of cell scaffolds however, finding ideal biocompatible and biodegradable materials that fit the correct parameters for 3D printing and guide cells to align remain a challenge. Herein, a photocrosslinkable smectic-A (Sm-A) liquid crystal elastomer (LCE) designed for 3D printing is presented, that promotes cell proliferation but most importantly induces cell anisotropy. The LCE-based bio-ink allows the 3D duplication of a highly complex brain structure generated from an animal model. Vascular tissue models are generated from fluorescently stained mouse tissue spatially imaged using confocal microscopy and subsequently processed to create a digital 3D model suitable for printing. The 3D structure is reproduced using a Digital Light Processing (DLP) stereolithography (SLA) desktop 3D printer. Synchrotron Small-Angle X-ray Diffraction (SAXD) data reveal a strong alignment of the LCE layering within the struts of the printed 3D scaffold. The resultant anisotropy of the LCE struts is then shown to direct cell growth. This study offers a simple approach to produce model tissues built within hours that promote cellular alignment.
We present a novel self-assembled monolayer (SAM)-based technique to make nanopinhole-enabled passivated contacts on silicon solar cells by tuning the SAM coverage area and etch selectivity. We deposit trimethyl-silyl Si(CH 3 ) 3 groups using hexamethyldisilazane (HMDS) as the precursor over passivating dielectric layers and their stacks (SiO 2 , SiN x , SiO 2 /SiN x ) and interrupt the HMDS attachment chemistry shortly before a full monolayer is formed on its surface. Subsequent etching in dilute HF produces pinholes through the dielectric layers due to the higher etch resistance of the SAM to HF etching. The pinhole areal density (10 4 –10 8 /cm 2 ) and size (10–1000 nm) can be tuned both by duration of HMDS attachment and HF etch time. Pinholes were characterized by atomic force microscopy, tetramethylammonium hydroxide (TMAH) selective etch, and Ag decoration by electroless plating. Polysilicon (poly-Si) passivated contacts enabled by pinholes were formed by subsequent deposition of doped amorphous silicon (a-Si:H) followed by thermal crystallization and dopant drive-in. At optimal areal pinhole density ≈10 7 /cm 2 , contacts exhibit both passivation and carrier transport via pinholes as evidenced by electron beam induced current, transmission line measurements, and carrier lifetime measurements. Solar cells based with these pinhole contacts show V oc = 723 mV and FF = 80.3%. The remaining SAM layer does not affect device performance.
DNA nanotechnology offers a wide toolkit of molecular functionalities and scales, including intricate motifs less than 10 nm and periodic structures exceeding 100 µm. At larger scales, however, there are often significant tradeoffs for DNA structures, namely stability and mechanical strength. This work describes the design, synthesis, and characterization of a functionalized DNA crystal. Using a ligated DNA crystal grants significant freedom for various functional materials to be applied, in this case, semiconducting cadmium sulfide and palladium metal. Properties investigated in this study include stability, mechanical strength, and optoelectronic properties such as photoluminescence (PL) and electric conductivity. Significant changes are observed based on the functional material applied to DNA crystals. The Young's modulus of the crystal varies by about five orders of magnitude when functionalized with palladium. PL and semiconductive behaviors were observed when cadmium sulfide was attached. These crystals represent an expansion of the capabilities of DNA structures at these length scales, and additionally a platform for future studies exchanging the materials or altering the ligation scheme.
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Numerous inorganic materials have been identified as potential candidates for high-performance photocatalysts. However, their solar-to-energy conversion efficiencies still fail to meet commercial requirements. Here, the main hurdle is the rapid recombination of photoexcited electrons and holes in single-phase materials. A viable predicted approach to suppress charge recombination is coupling two materials to form a two-dimensional (2D) heterostructure that physically separates photoinduced electrons and holes in different layers. In this work, the heterostructure-based paradigm was tested and a scalable solution synthesis of epitaxial ZnO-MoS 2 heterostructure was developed. A 2D ZnO-MoS 2 heterostructure was synthesized under hydrothermal conditions by stabilizing intermediate Zn-hydroxide states on a functionalized MoS 2 surface. Detailed characterization showed the formation of multilayer heterostructure with MoS 2 flakes intercalated between large size ZnO plates. The performance of this heterostructure was evaluated using photocatalytic degradation of rhodamine B. A degradation efficiency of 70% was measured within 90 minutes of visible-light irradiation, almost doubling the efficiency of the corresponding single-phase materials or their physical mixtures.
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