Heteronanostructured Field-Effect Transistors for Enhancing Entropy and Parameter Space in Electrical Unclonable Primitives.

Hardware security is not a new problem but is ever-growing in consumer and medical domains owing to hyperconnectivity. A physical unclonable function (PUF) offers a promising hardware security solution for cryptographic key generation, identification, and authentication. However, electrical PUFs using nanomaterials or two-dimensional (2D) transition metal dichalcogenides (TMDCs) often have limited entropy and parameter space sources, both of which increase the vulnerability to attacks and act as bottlenecks for practical applications. We report an electrical PUF with enhanced entropy as well as parameter space by incorporating 2D TMDC heteronanostructures into field-effect transistors (FETs). Lateral heteronanostructures of 2D molybdenum disulfide and tungsten disulfide serve as a potent entropy source. The variable feature of FETs is further leveraged to enhance the parameter space that provides multiple challenge-response pairs, which are essential for PUFs. This combination results in stably repeatable yet highly variable FET characteristics as alternative electrical PUFs. Comprehensive PUF performance analyses validate the bit uniformity, reproducibility, uniqueness, randomness, false rates, and encoding capacity. The 2D material heteronanostructure-driven electrical PUFs with strong FET-to-FET variability can potentially be augmented as an immediately deployable and scalable security solution for various hardware devices.

mHealth hyperspectral learning for instantaneous spatiospectral imaging of hemodynamics.

Hyperspectral imaging acquires data in both the spatial and frequency domains to offer abundant physical or biological information. However, conventional hyperspectral imaging has intrinsic limitations of bulky instruments, slow data acquisition rate, and spatiospectral trade-off. Here we introduce hyperspectral learning for snapshot hyperspectral imaging in which sampled hyperspectral data in a small subarea are incorporated into a learning algorithm to recover the hypercube. Hyperspectral learning exploits the idea that a photograph is more than merely a picture and contains detailed spectral information. A small sampling of hyperspectral data enables spectrally informed learning to recover a hypercube from a red-green-blue (RGB) image without complete hyperspectral measurements. Hyperspectral learning is capable of recovering full spectroscopic resolution in the hypercube, comparable to high spectral resolutions of scientific spectrometers. Hyperspectral learning also enables ultrafast dynamic imaging, leveraging ultraslow video recording in an off-the-shelf smartphone, given that a video comprises a time series of multiple RGB images. To demonstrate its versatility, an experimental model of vascular development is used to extract hemodynamic parameters via statistical and deep learning approaches. Subsequently, the hemodynamics of peripheral microcirculation is assessed at an ultrafast temporal resolution up to a millisecond, using a conventional smartphone camera. This spectrally informed learning method is analogous to compressed sensing; however, it further allows for reliable hypercube recovery and key feature extractions with a transparent learning algorithm. This learning-powered snapshot hyperspectral imaging method yields high spectral and temporal resolutions and eliminates the spatiospectral trade-off, offering simple hardware requirements and potential applications of various machine learning techniques.

Edible Matrix Code with Photogenic Silk Proteins.

Counterfeit medicines are a healthcare security problem, posing not only a direct threat to patient safety and public health but also causing heavy economic losses. Current anticounterfeiting methods are limited due to the toxicity of the constituent materials and the focus of secondary packaging level protections. We introduce an edible, imperceptible, and scalable matrix code of information representation and data storage for pharmaceutical products. This matrix code is digestible as it is composed of silk fibroin genetically encoded with fluorescent proteins produced by ecofriendly, sustainable silkworm farming. Three distinct fluorescence emission colors are incorporated into a multidimensional parameter space with a variable encoding capacity in a format of matrix arrays. This code is smartphone-readable to extract a digitized security key augmented by a deep neural network for overcoming fabrication imperfections and a cryptographic hash function for enhanced security. The biocompatibility, photostability, thermal stability, long-term reliability, and low bit error ratio of the code support the immediate feasibility for dosage-level anticounterfeit measures and authentication features. The edible code affixed to each medicine can serve as serialization, track and trace, and authentication at the dosage level, empowering every patient to play a role in combating illicit pharmaceuticals.

Biodegradable silicon nanoneedles for ocular drug delivery.

Ocular drug delivery remains a grand challenge due to the complex structure of the eye. Here, we introduce a unique platform of ocular drug delivery through the integration of silicon nanoneedles with a tear-soluble contact lens. The silicon nanoneedles can penetrate into the cornea in a minimally invasive manner and then undergo gradual degradation over the course of months, enabling painless and long-term sustained delivery of ocular drugs. The tear-soluble contact lens can fit a variety of corneal sizes and then quickly dissolve in tear fluid within a minute, enabling an initial burst release of anti-inflammatory drugs. We demonstrated the utility of this platform in effectively treating a chronic ocular disease, such as corneal neovascularization, in a rabbit model without showing a notable side effect over current standard therapies. This platform could also be useful in treating other chronic ocular diseases.

Revisiting silk: a lens-free optical physical unclonable function.

For modern security, devices, individuals, and communications require unprecedentedly unique identifiers and cryptographic keys. One emerging method for guaranteeing digital security is to take advantage of a physical unclonable function. Surprisingly, native silk, which has been commonly utilized in everyday life as textiles, can be applied as a unique tag material, thereby removing the necessary apparatus for optical physical unclonable functions, such as an objective lens or a coherent light source. Randomly distributed fibers in silk generate spatially chaotic diffractions, forming self-focused spots on the millimeter scale. The silk-based physical unclonable function has a self-focusing, low-cost, and eco-friendly feature without relying on pre-/post-process for security tag creation. Using these properties, we implement a lens-free, optical, and portable physical unclonable function with silk identification cards and study its characteristics and reliability in a systemic manner. We further demonstrate the feasibility of the physical unclonable functions in two modes: authentication and data encryption.

Fractal Web Design of a Hemispherical Photodetector Array with Organic-Dye-Sensitized Graphene Hybrid Composites.

The vision system of arthropods consists of a dense array of individual photodetecting elements across a curvilinear surface. This compound-eye architecture could be a useful model for optoelectronic sensing devices that require a large field of view and high sensitivity to motion. Strategies that aim to mimic the compound-eye architecture involve integrating photodetector pixels with a curved microlens, but their fabrication on a curvilinear surface is challenged by the use of standard microfabrication processes that are traditionally designed for planar, rigid substrates (e.g., Si wafers). Here, a fractal web design of a hemispherical photodetector array that contains an organic-dye-sensitized graphene hybrid composite is reported to serve as an effective photoactive component with enhanced light-absorbing capabilities. The device is first fabricated on a planar Si wafer at the microscale and then transferred to transparent hemispherical domes with different curvatures in a deterministic manner. The unique structural property of the fractal web design provides protection of the device from damage by effectively tolerating various external loads. Comprehensive experimental and computational studies reveal the essential design features and optoelectronic properties of the device, followed by the evaluation of its utility in the measurement of both the direction and intensity of incident light.

Photoelectric Silk via Genetic Encoding and Bioassisted Plasmonics.

Genetically encoded photoelectric silk that can convert photons to electrons (light to electricity) over a wide visible range in a self-power mode is reported. As silk is a versatile host material with electrical conductivity, biocompatibility, and processability, a photoelectric protein is genetically fused with silk by silkworm transgenesis. Specifically, mKate2, which is conventionally known as a far-red fluorescent protein, is used as a photoelectric protein. Characterization of the electrochemical and optical properties of mKate2 silk allows designing a photoelectric measurement system. A series of in situ photocurrent experiments support the sensitive and stable performance of photoelectric conversion. In addition, as a plasmonic nanomaterial with a broad spectral resonance, titanium nitride (TiN) nanoparticles are biologically hybridized into the silk glands, taking full advantage of the silkworms' open circulatory system as well as the absorption band of mKate2 silk. This biological hybridization via direct feeding of TiN nanoparticles further enhances the overall photoelectric conversion ability of mKate2 silk. It is envisioned that the biologically derived photoelectric protein, its ecofriendly scalable production by transgenic silkworms, and the bioassisted plasmonic hybridization can potentially broaden the biomaterial choices for developing next-generation biosensing, retina prosthesis, and neurostimulation applications.

Transgenic and Diet-Enhanced Silk Production for Reinforced Biomaterials: A Metamaterial Perspective.

Silk fibers, which are protein-based biopolymers produced by spiders and silkworms, are fascinating biomaterials that have been extensively studied for numerous biomedical applications. Silk fibers often have remarkable physical and biological properties that typical synthetic materials do not exhibit. These attributes have prompted a wide variety of silk research, including genetic engineering, biotechnological synthesis, and bioinspired fiber spinning, to produce silk proteins on a large scale and to further enhance their properties. In this review, we describe the basic properties of spider silk and silkworm silk and the important production methods for silk proteins. We discuss recent advances in reinforced silk using silkworm transgenesis and functional additive diets with a focus on biomedical applications. We also explain that reinforced silk has an analogy with metamaterials such that user-designed atypical responses can be engineered beyond what naturally occurring materials offer. These insights into reinforced silk can guide better engineering of superior synthetic biomaterials and lead to discoveries of unexplored biological and medical applications of silk.

Edible unclonable functions.

Counterfeit medicines are a fundamental security problem. Counterfeiting medication poses a tremendous threat to patient safety, public health, and the economy in developed and less developed countries. Current solutions are often vulnerable due to the limited security levels. We propose that the highest protection against counterfeit medicines would be a combination of a physically unclonable function (PUF) with on-dose authentication. A PUF can provide a digital fingerprint with multiple pairs of input challenges and output responses. On-dose authentication can verify every individual pill without removing the identification tag. Here, we report on-dose PUFs that can be directly attached onto the surface of medicines, be swallowed, and digested. Fluorescent proteins and silk proteins serve as edible photonic biomaterials and the photoluminescent properties provide parametric support of challenge-response pairs. Such edible cryptographic primitives can play an important role in pharmaceutical anti-counterfeiting and other security applications requiring immediate destruction or vanishing features.

Green-Light-Activated Photoreaction via Genetic Hybridization of Far-Red Fluorescent Protein and Silk.

Fluorescent proteins often result in phototoxicity and cytotoxicity, in particular because some red fluorescent proteins produce and release reactive oxygen species (ROS). The photogeneration of ROS is considered as a detrimental side effect in cellular imaging or is proactively utilized for ablating cancerous tissue. As ancient textiles or biomaterials, silk produced by silkworms can directly be used as fabrics or be processed into materials and structures to host other functional nanomaterials. It is reported that transgenic fusion of far-red fluorescent protein (mKate2) with silk provides a photosensitizer hybridization platform for photoinducible control of ROS. Taking advantage of green (visible) light activation, native and regenerated mKate2 silk can produce and release superoxide and singlet oxygen, in a comparable manner of visible light-driven plasmonic photocatalysis. Thus, the genetic expression of mKate2 in silk offers immediately exploitable and scalable photocatalyst-like biomaterials. It is further envisioned that mKate2 silk can potentially rule out hazardous concerns associated with foreign semiconductor photocatalytic nanomaterials.

Plasmonic photocatalyst-like fluorescent proteins for generating reactive oxygen species.

The recent advances in photocatalysis have opened a variety of new possibilities for energy and biomedical applications. In particular, plasmonic photocatalysis using hybridization of semiconductor materials and metal nanoparticles has recently facilitated the rapid progress in enhancing photocatalytic efficiency under visible or solar light. One critical underlying aspect of photocatalysis is that it generates and releases reactive oxygen species (ROS) as intermediate or final products upon light excitation or activation. Although plasmonic photocatalysis overcomes the limitation of UV irradiation, synthesized metal/semiconductor nanomaterial photocatalysts often bring up biohazardous and environmental issues. In this respect, this review article is centered in identifying natural photosensitizing organic materials that can generate similar types of ROS as those of plasmonic photocatalysis. In particular, we propose the idea of plasmonic photocatalyst-like fluorescent proteins for ROS generation under visible light irradiation. We recapitulate fluorescent proteins that have Type I and Type II photosensitization properties in a comparable manner to plasmonic photocatalysis. Plasmonic photocatalysis and protein photosensitization have not yet been compared systemically in terms of ROS photogeneration under visible light, although the phototoxicity and cytotoxicity of some fluorescent proteins are well recognized. A comprehensive understanding of plasmonic photocatalyst-like fluorescent proteins and their potential advantages will lead us to explore new environmental, biomedical, and defense applications.

Visible light biophotosensors using biliverdin from Antheraea yamamai.

We report an endogenous photoelectric biomolecule and demonstrate that such a biomolecule can be used to detect visible light. We identify the green pigment abundantly present in natural silk cocoons of Antheraea yamamai (Japanese oak silkmoth) as biliverdin, using mass spectroscopy and optical spectroscopy. Biliverdin extracted from the green silk cocoons generates photocurrent upon light illumination with distinct colors. We further characterize the basic performance, responsiveness, and stability of the biliverdin-based biophotosensors at a photovoltaic device level using blue, green, orange, and red light illumination. Biliverdin could potentially serve as an optoelectric biomolecule toward the development of next-generation implantable photosensors and artificial photoreceptors.

Hybrid Energy Cell with Hierarchical Nano/Micro-Architectured Polymer Film to Harvest Mechanical, Solar, and Wind Energies Individually/Simultaneously.

We report the creation of hybrid energy cells based on hierarchical nano/micro-architectured polydimethylsiloxane (HNMA-PDMS) films with multifunctionality to simultaneously harvest mechanical, solar, and wind energies. These films consist of nano/micro dual-scale architectures (i.e., nanonipples on inverted micropyramidal arrays) on the PDMS surface. The HNMA-PDMS is replicable by facile and cost-effective soft imprint lithography using a nanoporous anodic alumina oxide film formed on the micropyramidal-structured silicon substrate. The HNMA-PDMS film plays multifunctional roles as a triboelectric layer in nanogenerators and an antireflection layer for dye-sensitized solar cells (DSSCs), as well as a self-cleaning surface. This film is employed in triboelectric nanogenerator (TENG) devices, fabricated by laminating it on indium-tin oxide-coated polyethylene terephthalate (ITO/PET) as a bottom electrode. The large effective contact area that emerged from the densely packed hierarchical nano/micro-architectures of the PDMS film leads to the enhancement of TENG device performance. Moreover, the HNMA-PDMS/ITO/PET, with a high transmittance of >90%, also results in highly transparent TENG devices. By placing the HNMA-PDMS/ITO/PET, where the ITO/PET is coated with zinc oxide nanowires, as the top glass substrate of DSSCs, the device is able to add the functionality of TENG devices, thus creating a hybrid energy cell. The hybrid energy cell can successfully convert mechanical, solar, and wind energies into electricity, simultaneously or independently. To specify the device performance, the effects of external pushing frequency and load resistance on the output of TENG devices are also analyzed, including the photovoltaic performance of the hybrid energy cells.

An Ultrahigh-Performance Photodetector based on a Perovskite-Transition-Metal-Dichalcogenide Hybrid Structure.

An ultrahigh performance MoS2 photodetector with high photoresponsivity (1.94 × 10(6) A W(-1) ) and detectivity (1.29 × 10(12) Jones) under 520 nm and 4.63 pW laser exposure is demonstrated. This photodetector is based on a methyl-ammonium lead halide perovskite/MoS2 hybrid structure with (3-aminopropyl)triethoxysilane doping. The performance degradation caused by moisture is also minimized down to 20% by adopting a new encapsulation bilayer of octadecyltrichlorosilane/polymethyl methacrylate.

Nanoporous TiO2-Based Distributed Bragg Reflectors for Near-Infrared Wavelength Applications.

We reported the fabrication and characteristics of distributed Bragg reflectors (DBRs), made of titanium dioxide (TiO2) dense/nanoporous film stacks, operating in the near-infrared wavelength region of 0.8-1.1 µm. To form the nanoporous TiO2 films with a low refractive index (low-n), the oblique angle deposition (OAD) technique was employed at a high incident vapor flux angle of 80 degrees. For the fabricated DBRs consisting of TiO2 dense/nanoporous (high-n/low-n) thin films, the high reflectance band was gradually increased and the stop bandwidth was narrowed with increasing the number of DBR pairs. Particularly, the TiO2 DBR with only 6 pairs exhibited a normalized stop bandwidth (Δλ/λ(c)) of -11.6% at a center wavelength (λ(c)) of 0.96 µm as well as high reflectance values of > 95% over a wide mid-infrared wavelength region of 0.9-1.01 µm (i.e., Δλ = 0.111 µm). Furthermore, the reflectance characteristics were investigated at incident light angles of 20-70 degrees for different polarized lights. For theoretical optical analyses, the reflectance calculations were also performed by a rigorous coupled-wave analysis method, showing a similar tendency to the experimentally measured data.

Enhanced Photovoltaic Performance of Dye-Sensitized Solar Cells by Efficient Near-Infrared Sunlight Harvesting using Upconverting Y2O 3:Er (3+)/Yb (3+) Phosphor Nanoparticles.

We report the efficiency enhancement in dye-sensitized solar cells (DSSCs) using Er(3+)/Yb(3+)-co-doped Y2O3 (i.e., Y2O3:Er(3+)/Yb(3+)) phosphor nanoparticles, prepared by a simple and cost-effective urea-based homogeneous precipitation method, for efficient near-infrared (NIR) sunlight harvesting. Under the light excitation at a wavelength of 980 nm, the as-prepared samples exhibited strong upconversion emissions at green and red visible wavelengths. To investigate the influence of Y2O3:Er(3+)/Yb(3+) nanoparticles on the photovoltaic performance of DSSCs, the phosphor nanoparticles were incorporated into titanium dioxide films to form a composite photoelectrode. For the resulting DSSCs, the increased power conversion efficiency (PCE) of 6.68 % was obtained mainly by the increased photocurrent of J SC = 13.68 mA/cm(2) due to the light harvesting enhancement via the NIR-to-visible upconversion process (cf., PCE = 5.94 %, J SC = 12.74 mA/cm(2) for the reference DSSCs without phosphor nanoparticles), thus, indicating the PCE increment ratio of ~12.4 %.

Highly Transparent and Flexible Triboelectric Nanogenerators with Subwavelength-Architectured Polydimethylsiloxane by a Nanoporous Anodic Aluminum Oxide Template.

Highly transparent and flexible triboelectric nanogenerators (TENGs) were fabricated using the subwavelength-architectured (SWA) polydimethylsiloxane (PDMS) with a nanoporous anodic aluminum oxide (AAO) template as a replica mold. The SWA PDMS could be utilized as a multifunctional film for a triboelectric layer, an antireflection coating, and a self-cleaning surface. The nanopore arrays of AAO were formed by a simple, fast, and cost-effective electrochemical oxidation process of aluminum, which is relatively impressive for fabrication of the TENG device. For electrical contacts, the SWA PDMS was laminated on the indium tin oxide (ITO)-coated polyethylene terephthalate (PET) as a bottom electrode, and the bare ITO-coated PET (i.e., ITO/PET) was used for the top electrode. Compared to the ITO/PET, the SWA PDMS on the ITO/PET improved the transmittance from 80.5 to 83% in the visible wavelength region and also had high transmittances of >85% at wavelengths of 430-455 nm. The SWA PDMS also exhibited the hydrophobic surface with a water contact angle (θCA) of ∼115°, which can be useful for self-cleaning applications. The average transmittance (Tavg) of the entire TENG device was observed to be ∼70% over a broad wavelength range. At an external pushing frequency of 0.5 Hz, for the TENG device with the ITO top electrode, open-circuit voltage (VOC) and short-circuit current (ISC) values of ∼3.8 V and ∼0.8 µA were obtained instantaneously, respectively, which were higher than those (i.e., VOC ≈ 2.2 V, and ISC ≈ 0.4 µA) of the TENG device with a gold top electrode. The effect of external pushing force and frequency on the output device performance of the TENGs was investigated, including the device robustness. A theoretical optical analysis of SWA PDMS was also performed.

Improved biomolecular detection based on a plasmonic nanoporous gold film fabricated by oblique angle deposition.

We demonstrated an enhanced surface plasmon resonance (SPR) detection by incorporating a nanoporous gold film on a thin gold substrate. Nanoscale control of thickness and roughness of the nanoporous layer was successfully accomplished by oblique angle deposition. In biosensing experiments, the results obtained by biotin-streptavidin interaction showed that SPR samples with a nanoporous gold layer provided a notable sensitivity improvement compared to a conventional bare gold film, which is attributed to an excitation of local plasmon field and an increased surface reaction area. Imaging sensitivity enhancement factor was employed to estimate an overall sensor performance of the fabricated samples and an optimal SPR structure was determined. Our approach is intended to show the feasibility and extend the applicability of the nanoporous gold film-mediated SPR biosensor to diverse biomolecular binding events.

Inverted tetrahedron-pyramidal micropatterned polymer films for boosting light output power in flip-chip light-emitting diodes.

We report the improved light output power in gallium nitride-based green flip-chip light-emitting diodes (FCLEDs) employed with inverted tetrahedron-pyramidal micropatterned polydimethylsiloxane (ITPM PDMS) films as an encapsulation and protection layer. The micropatterns are transferred into the surface of PDMS films from the sapphire substrate master molds with two-dimensional periodic hexagonal TPM arrays by a soft imprint lithography method. The ITPM PDMS film laminated on the sapphire dramatically enhances the diffuse transmittance (T(D)) in a wavelength (λ) range of 400-650 nm, exhibiting the larger T(D) value of ~53% at λ = 525 nm, (cf., T(D) ~1% for planar sapphire). By introducing the ITPM PDMS film on the outer surface of sapphire in FCLEDs, the light output power is enhanced, indicating the increment percentage of ~11.1% at 500 mA of injection current compared to the reference FCLED without the ITPM PDMS film, together with better electroluminescence intensity and far-field radiation pattern.

Broadband high-reflective distributed Bragg reflectors based on amorphous silicon films for semiconductor laser facet coatings.

We fabricated amorphous silicon (a-Si)-based distributed Bragg reflectors (DBRs) consisting of alternating dense/porous films (i.e., pair) for a center wavelength (λ(c)) of 0.96 µm by oblique angle deposition (OAD) technique using an electron-beam evaporation system. The dense (high refractive index, i.e., high-n) and porous (low-n) a-Si films were deposited at two incident vapor flux angles of 0° and 80° in the OAD, respectively. Their optical reflectance characteristics were investigated in the wavelength range of 0.6-1.5 µm, including theoretical comparison using a rigorous coupled-wave analysis method. Above three pairs, the reflectivity (R) of a-Si DBRs was almost saturated at wavelengths around 0.96 µm, exhibiting R values of >97%. For the a-Si DBR with only three pairs, a broad normalized stop bandwidth (Δλ/λ(c)) of ∼22.5% was obtained at wavelengths of ∼0.87-1.085 µm, keeping high R values of >95%. To simply demonstrate the feasibility of device applications, the a-Si DBR with three pairs was coated as a high-reflection layer at the rear facet of GaAs/InGaAs quantum-well laser diodes (LDs) operating at λ=0.96 µm. For the LDs coated with three-pair a-Si DBR, external differential quantum efficiency (η(d)) was nearly doubled compared to the uncoated LDs, indicating the η(d) value of ∼50.6% (i.e., η(d)∼25.5% for the uncoated LDs).