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    Universal and scalable fabrication of plasmonic nanocrystals for ultrasensitive SERS
    Surface-enhanced Raman spectroscopy (SERS) enables the detection of molecular signatures at extremely low concentrations, even down to a single molecule, by using plasmonic nanostructures that support localized surface plasmon resonances (LSPRs). Nonetheless, fabricating highly sensitive nanostructures typically requires complex, time-consuming, and costly fabrication processes with limited scalability. In this work, we present a simple and universally applicable single-step method to fabricate plasmonic nanocrystals (NCs) from metals, such as Al, Ag, and Au. These NCs are directly grown over large surface areas on various substrates through heat-assisted growth from e-beam or magnetron sputter depositions. The LSPRs of the NCs can be tailored by selecting the metal, nanocrystal size, and surface morphology. The heat-assisted growth strategy enables the formation of NC matrices capable of detecting analyte molecules at ultralow, down to zeptomolar, concentrations via SERS, particularly when using Ag NCs. This versatile, cost-effective fabrication approach opens new opportunities for large-area plasmonic platforms in sensing, photocatalysis, and optoelectronic applications.
    Publicationtype: Journal Article
      17
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    Switchable 3D Photonic Crystals Based on the Insulator-to-Metal Transition in VO2
    (American Chemical Society (ACS), 2024-12-11)
    Peng, Jun
    ;
    ; ; ;
    Photonic crystals (PhCs) are optical structures characterized by the spatial modulation of the dielectric function, which results in the formation of a photonic band gap (PBG) in the frequency spectrum. This PBG blocks the propagation of light, enabling filtering, confinement, and manipulation of light. Most of the research in this field has concentrated on static PhCs, which have fixed structural and material parameters, leading to a constant PBG. However, the growing demand for adaptive photonic devices has led to an increased interest in switchable PhCs, where the PBG can be reversibly activated or shifted. Vanadium dioxide (VO2) is particularly notable for its near-room-temperature insulator-to-metal transition (IMT), which is accompanied by significant changes in its optical properties. Here, we demonstrate a fabrication strategy for switchable three-dimensional (3D) PhCs, involving sacrificial templates and a VO2 atomic layer deposition (ALD) process in combination with an accurately controlled annealing procedure. The resulting VO2 inverse opal (IO) PhC achieves substantial control over PBG in the near-infrared (NIR) region. Specifically, the synthesized VO2 IO PhC exhibits PBGs near 1.49 and 1.03 μm in the dielectric and metallic states of the VO2 material, respectively, which can be reversibly switched by adjusting the external temperature. Furthermore, a temperature-dependent switch from a narrow-band NIR reflector to a broad-band absorber is revealed. This work highlights the potential of integrating VO2 into 3D templates in the development of switchable photonics with complex 3D structures, offering a promising avenue for the advancement of photonic devices with adaptable functionalities.
    Publicationtype: Review Article
      26  23
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    Enhanced Photocatalytic Properties and Photoinduced Crystallization of TiO2–Fe2O3 Inverse Opals Fabricated by Atomic Layer Deposition
    The use of solar energy for photocatalysis holds great potential for sustainable pollution reduction. Titanium dioxide (TiO2) is a benchmark material, effective under ultraviolet light but limited in visible light utilization, restricting its application in solar-driven photocatalysis. Previous studies have shown that semiconductor heterojunctions and nanostructuring can broaden the TiO2’s photocatalytic spectral range. Semiconductor heterojunctions are interfaces formed between two different semiconductor materials that can be engineered. Especially, type II heterojunctions facilitate charge separation, and they can be obtained by combining TiO2 with, for example, iron(III) oxide (Fe2O3). Nanostructuring in the form of 3D inverse opals (IOs) demonstrated increased TiO2 light absorption efficiency of the material, by tailoring light-matter interactions through their photonic crystal structure and specifically their photonic stopband, which can give rise to a slow photon effect. Such effect is hypothesized to enhance the generation of free charges. This work focuses on the above-described effects simultaneously, through the synthesis of TiO2-Fe2O3 IOs via multilayer atomic layer deposition (ALD) and the characterization of their photocatalytic activities. Our results reveal that the complete functionalization of TiO2 IOs with Fe2O3 increases the photocatalytic activity through the slow photon effect and semiconductor heterojunction formation. We systematically explore the influence of Fe2O3 thickness on photocatalytic performance, and a maximum photocatalytic rate constant of 1.38 ± 0.09 h-1 is observed for a 252 nm template TiO2-Fe2O3 bilayer IO consisting of 16 nm TiO2 and 2 nm Fe2O3. Further tailoring the performance by overcoating with additional TiO2 layers enhances photoinduced crystallization and tunes photocatalytic properties. These findings highlight the potential of TiO2-Fe2O3 IOs for efficient water pollutant removal and the importance of precise nanostructuring and heterojunction engineering in advancing photocatalytic technologies.
    Publicationtype: Journal Article
      16  31
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    Achieving high-temperature stable structural color through nanostructuring in polymer-derived ceramics
    (American Chemical Society (ACS), 2024-04-18) ; ; ; ;
    Structural colors offer a myriad of advantages over conventional pigment-based colors, which often rely on toxic chemical substances that are prone to UV degradation. To take advantage of these benefits in demanding environments, there is growing interest in producing structural colors from ceramics. Polymer-derived ceramics (PDCs) emerge as a compelling choice, presenting two distinct advantages: their enhanced shape ability in their polymeric state associated with impressive temperature resistance once converted to ceramics. This study pioneers the fabrication of noniridescent structural colors from silicon oxycarbide (SiOC) PDC, enabled by the nanostructuring of an inverse photonic glass within the PDC material. This design, a functionally graded material with an inverse photonic glass (FGM-PhG) structure, leverages the innate light-absorbing properties of SiOC, yielding a vivid structural color that maintains its saturation even in white surroundings. This study elucidates the process−structure−properties relationship for the obtained structural colors by investigating each layer of the functionally graded material(FGM) in a stepwise coating deposition process. To further emphasize the exceptional processing flexibility of PDCs, the three-step process is later transferred to an additive manufacturing approach. Finally, the FGM-PhG structural colors are demonstrated to have remarkable thermal stability up to 1000 °C for 100 h, possibly making them the most thermally stable ceramic structural colors to date.
    Publicationtype: Journal Article
      32  65
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    Adsorption and Inactivation of SARS-CoV-2 on the Surface of Anatase TiO2(101)
    We investigated the adsorption of severe acute respiratory syndrome corona virus 2 (SARS-CoV-2), the virus responsible for the current pandemic, on the surface of the model catalyst TiO2(101) using atomic force microscopy, transmission electron microscopy, fluorescence microscopy, and X-ray photoelectron spectroscopy, accompanied by density functional theory calculations. Three different methods were employed to inactivate the virus after it was loaded on the surface of TiO2(101): (i) ethanol, (ii) thermal, and (iii) UV treatments. Microscopic studies demonstrate that the denatured spike proteins and other proteins in the virus structure readsorb on the surface of TiO2 under thermal and UV treatments. The interaction of the virus with the surface of TiO2 was different for the thermally and UV treated samples compared to the sample inactivated via ethanol treatment. AFM and TEM results on the UV-treated sample suggested that the adsorbed viral particles undergo damage and photocatalytic oxidation at the surface of TiO2(101) which can affect the structural proteins of SARS-CoV-2 and denature the spike proteins in 30 min. The role of Pd nanoparticles (NPs) was investigated in the interaction between SARS-CoV-2 and TiO2(101). The presence of Pd NPs enhanced the adsorption of the virus due to the possible interaction of the spike protein with the NPs. This study is the first investigation of the interaction of SARS-CoV-2 with the surface of single crystalline TiO2(101) as a potential candidate for virus deactivation applications. Clarification of the interaction of the virus with the surface of semiconductor oxides will aid in obtaining a deeper understanding of the chemical processes involved in photoinactivation of microorganisms, which is important for the design of effective photocatalysts for air purification and self-cleaning materials.
    Publicationtype: Journal Article
      47
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    Tailoring disorder and quality of photonic glass templates for structural coloration by particle charge interactions
    (American Chemical Society (ACS), 2021-04-20) ; ; ; ;
    To obtain high-quality homogeneous photonic glass-based structural color films over large areas, it is essential to precisely control the degree of disorder of the spherical particles used and reduce the crack density within the films as much as possible. To tailor the disorder and quality of photonic glasses, a heteroaggregation-based process was developed by employing two oppositely charged equal-sized polystyrene (PS) particle types. The influence of the particle size ratio on the extent of heteroaggregation in the suspension mixes is investigated and correlated with both the morphology and the resultant optical properties of the films. The results show that the oppositely charged particle size ratio within the mix greatly influences the assembled structure in the films, affecting their roughness, crack density, and the coffee-ring formation. To better differentiate the morphology of the films, scanning electron microscopy images of the microstructures were classified by a supervised training of a deep convolutional neural network model to find distinctions that are inaccessible by conventional image analysis methods. Selected compositions were then infiltrated with TiO2 via atomic layer deposition, and after removal of the PS spheres, surfacelated inverse photonic glasses were obtained. Different color impressions and optical properties were obtained depending on the heteroaggregation level and thus the quality of the resultant films. The best results regarding the stability of the films and suppression of coffee-ring formation are obtained with a 35 wt % positively charged over negatively charged particle mix, which yielded enhanced structural coloration associated with improved film quality, tailored by the heteroaggregation fabrication process.
    Publicationtype: Journal Article
    Scopus© Citations 7  126  575
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    Mechanism of Hydration and Hydration Induced Structural Changes of Calcium Alginate Aerogel
    The most relevant properties of polysaccharide aerogels in practical applications are determined by their microstructures. Hydration has a dominant role in altering the microstructures of these hydrophilic porous materials. To understand the hydration induced structural changes of monolithic Ca-alginate aerogel, produced by drying fully cross-linked gels with supercritical CO2, the aerogel was gradually hydrated and characterized at different states of hydration by small-angle neutron scattering (SANS), liquid-state nuclear magnetic resonance (NMR) spectroscopy, and magic angle spinning (MAS) NMR spectroscopy. First, the incorporation of structural water and the formation of an extensive hydration sphere mobilize the Ca-alginate macromolecules and induce the rearrangement of the dry-state tertiary and quaternary structures. The primary fibrils of the original aerogel backbone form hydrated fibers and fascicles, resulting in the significant increase of pore size, the smoothing of the nanostructured surface, and the increase of the fractal dimension of the matrix. Because of the formation of these new superstructures in the hydrated backbone, the stiffness and the compressive strength of the aerogel significantly increase compared to its dry-state properties. Further elevation of the water content of the aerogel results in a critical hydration state. The Ca-alginate fibers of the backbone disintegrate into well-hydrated chains, which eventually form a quasi-homogeneous hydrogel-like network. Consequently, the porous structure collapses and the well-defined solid backbone ceases to exist. Even in this hydrogel-like state, the macroscopic integrity of the Ca-alginate monolith is intact. The postulated mechanism accounts for the modification of the macroscopic properties of Ca-alginate aerogel in relation to both humid and aqueous environments.
    Publicationtype: Journal Article
    Scopus© Citations 21  78
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    Heterostructured Monolayer MoS₂ Nanoparticles toward Water-Dispersible Catalysts
    MoS₂ is a 2D semiconductor where exfoliation to a single layer results in improved catalytic properties. However, its high surface energy can lead to extensive aggregation, resulting in degraded catalytic performance and stability. Combined with a lack of dispersibility in water, this represents a pitfall for catalysis in the aqueous phase. Herein, we present the use of nanoscopic layered silicates pillared with a cationic surfactant to template the growth of MoS₂ in the interlayer space. This provides heterostructured layered nanoparticles ∼25 nm wide by 3-8 nm thick containing isolated MoS₂ layers. The resulting nanohybrids retain the disc-like morphology and surface chemistry of the clays, providing good aqueous stability, while also providing access to the catalytic edge-sites of the MoS2 layer. In addition to significant enhancement of catalytic dye degradation, molecular aggregation on the highly charged clay interface is comparable to unmodified clays. These particles are ideal for studies of charge-transport properties in confined semiconductor layers, as well as hierarchical self-assembly into functional materials. This study paves the way to colloidal synthesis of nanoparticulate heterostructures with other functional layered materials, particularly where particle exfoliation, covalent modification, and aqueous stability are concerns.
    Publicationtype: Journal Article
      203
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    Cultivation of Exoelectrogenic Bacteria in Conductive DNA Nanocomposite Hydrogels Yields a Programmable Biohybrid Materials System
    The use of living microorganisms integrated within electrochemical devices is an expanding field of research, with applications in microbial fuel cells, microbial biosensors or bioreactors. We describe the use of porous nanocomposite materials prepared by DNA polymerization of carbon nanotubes (CNTs) and silica nanoparticles (SiNPs) for the construction of a programmable biohybrid system containing the exoelectrogenic bacterium Shewanella oneidensis. We initially demonstrate the electrical conductivity of the CNT-containing DNA composite by employment of chronopotentiometry, electrochemical impedance spectroscopy, and cyclic voltammetry. Cultivation of Shewanella oneidensis in the conductive materials shows that the exoelectrogenic bacteria populate the matrix of the conductive composite, while nonexoelectrogenic Escherichia coli remain on its surface. Moreover, the ability to use extracellular electron transfer pathways is positively correlated with the number of cells within the conductive synthetic biofilm matrix. The Shewanella-containing composite remains stable for several days and shows electrochemical activity, indicating that the conductive backbone is capable of extracting the metabolic electrons produced by the bacteria under strictly anoxic conditions and conducting them to the anode. Programmability of this biohybrid material system is demonstrated by on-demand release and degradation induced by a short-term enzymatic stimulus. We believe that the application possibilities of such biohybrid materials could even go beyond microbial biosensors, bioreactors, and fuel cell systems.
    Publicationtype: Journal Article
    Scopus© Citations 31  52
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    Revealing the photocharge-transfer mechanism at manganite-buffered LaAlO3/SrTiO3 interfaces by giant photoresponse
    (American Chemical Society (ACS), 2020-03-04) ;
    Butt, Mehwish Khalid
    ;
    Iqbal, Muhammad A.
    ;
    Wang, Shuanhu
    ;
    Ren, Lixia
    The photoinduced phase transition at complex oxides remains one of the very important issues because of the emergent physics and potential applications. In particular, the mechanism of charge transfer at interfaces under irradiation is challenging. Herein, the photoinduced properties of manganite-buffered LaAlO3/SrTiO3 interfaces with different thicknesses of the buffer layer are systematically investigated. The giant photoresponse is observed, and its relative change in resistance is about 6.24 × 106% at T = 20 K for the sample with a buffer layer thickness of 4.8 nm. Moreover, the transition temperature is enhanced by increasing the thickness of the buffer layer. More importantly, the dead layer effect at the interfaces has been suppressed by using light. All these results are attributed to the charge transfer because of the octahedral tilting at low temperatures and provide a new kind of oxide-based optical devices, such as ultraviolet detectors. This piece of work will pave the way toward two-dimensional electron gas-based optoelectronic devices.
    Publicationtype: Journal Article
      9