A biomaterial-silicon junction for photodetection.

Bio-integrated optoelectronics can be interfaced with biological tissues, thereby offering opportunities for clinical diagnosis and therapy. However, finding a suitable biomaterial-based semiconductor to interface with electronics is still challenging. In this study, a semiconducting layer is assembled comprising a silk protein hydrogel and melanin nanoparticles (NPs). The silk protein hydrogel provides a water-rich environment for the melanin NPs that maximizes their ionic conductivity and bio-friendliness. An efficient photodetector is produced by forming a junction between melanin NP-silk and a p-type Si (p-Si) semiconductor. The observed charge accumulation/transport behavior at the melanin NP-silk/p-Si junction is associated with the ionic conductive state of the melanin NP-silk composite. The melanin NP-silk semiconducting layer is printed as an array on an Si substrate. The photodetector array exhibits uniform photo-response to illumination at various wavelengths, thus providing broadband photodetection. Efficient charge transfer between melanin NP-silk and Si provides fast photo-switching with rise and decay constants of 0.44 â€‹s and 0.19 â€‹s, respectively. The photodetector with a biotic interface comprising an Ag nanowire-incorporated silk layer as the top contact can operate when underneath biological tissue. The photo-responsive biomaterial-Si semiconductor junction using light as a stimulus offers a bio-friendly and versatile platform for artificial electronic skin/tissue.

Engineering Silk Protein to Modulate Polymorphic Transitions for Green Lithography Resists.

Silk protein is being increasingly introduced as a prospective material for biomedical devices. However, a limited locus to intervene in nature-oriented silk protein makes it challenging to implement on-demand functions to silk. Here, we report how polymorphic transitions are related with molecular structures of artificially synthesized silk protein and design principles to construct a green-lithographic and high-performative protein resist. The repetition number and ratio of two major building blocks in synthesized silk protein are essential to determine the size and content of ß-sheet crystallites, and radicals resulting from tyrosine cleavages by the 193 nm laser irradiation induce the ß-sheet to α-helix transition. Synthesized silk is designed to exclusively comprise homogeneous building blocks and exhibit high crystallization and tyrosine-richness, thus constituting an excellent basis for developing a high-performance deep-UV photoresist. Additionally, our findings can be conjugated to design an electron-beam resist governed by the different irradiation-protein interaction mechanisms. All synthesis and lithography processes are fully water-based, promising green lithography. Using the engineered silk, a nanopatterned planar color filter showing the reduced angle dependence can be obtained. Our study provides insights into the industrial scale production of silk protein with on-demand functions.

Multifunctional and Ultrathin Electronic Tattoo for On-Skin Diagnostic and Therapeutic Applications.

Epidermal electronic systems for detecting electrophysiological signals, sensing, therapy, and drug delivery are at the frontier in man-machine interfacing for healthcare. However, it is still a challenge to develop multifunctional bioapplications with minimal invasiveness, biocompatibility, and stable electrical performance under various mechanical deformations of biological tissues. In this study, a natural silk protein with carbon nanotubes (CNTs) is utilized to realize an epidermal electronic tattoo (E-tattoo) system for multifunctional applications that address these challenging issues through dispersing highly conductive CNTs onto the biocompatible silk nanofibrous networks with porous nature to construct skin-adhesive ultrathin electronic patches. Individual components that incorporate electrically and optically active heaters, a temperature sensor (temperature coefficient of resistance of 5.2 × 10-3  °C-1 ), a stimulator for drug delivery (>500 µm penetration depth in skin), and real-time electrophysiological signal detectors are described. This strategy of E-tattoos integrated onto human skin can open a new route to a next-generation electronic platform for wearable and epidermal bioapplications.

Light Trapping-Mediated Room-Temperature Gas Sensing by Ordered ZnO Nano Structures Decorated with Plasmonic Au Nanoparticles.

An ordered array of 1D ZnO nanorods obtained by colloidal templating is shown to dramatically enhance the sensing response of NO x at room temperature by confining light and creating periodic structures. The sensitivity is measured for a concentration varying from 2 to 10 ppm (response 53% at 10 ppm) at room temperature under white light illumination with ≈225 nm hole diameter. In contrast, structures with ≈450 nm hole size show better sensing under (response 98% at 10 ppm) elevated temperatures in dark conditions, which is attributed to the increased surface chemical interactions with NO x molecules due to the porous nature and enhanced accessible surface area of ZnO nanorods. Further, the decoration of ZnO Nanorods with gold nanoparticles shows enhanced sensor performance (response 130% at 10 ppm) due to localized surface plasmon resonance under white light illumination. The findings may lead to new opportunities in the visible light-activated room-temperature NO x sensors for healthcare applications.

Enhanced performance of hybrid self-biased heterojunction photodetector on soft-lithographically patterned organic platform.

Nanopatterning of the active layer with feature size comparable to the wavelength of visible light is a popular strategy for improving the performance of optoelectronic devices, as these structures enhance the optical path length by light trapping due to combined contribution of multiple scattering, diffraction, and antireflection. Here, we report the fabrication of ZnO/CdS self-biased heterojunction photodetectors on soft lithographically patterned PEDOT:PSS layers with grating geometry. The present study combines the robustness of inorganic devices along with the convenience of easy patterning capability of an organic PEDOT:PSS layer. Patterns with two different line widths (L P = 350 nm, and Lp = 750 nm) have been used in this study to understand the influence of feature dimension on the device performance. We observe enhanced photoluminescence on patterned devices, in comparison to devices fabricated on flat PEDOT:PSS films, which is attributed to the increased interfacial area between the organic and inorganic layers. The spectral response [R( λ )] and specific detectivity [D * ( λ )] are found to be higher for the devices with Lp = 350 nm as compared to other devices due to enhanced absorption within the structures due to confinement of light, which also results in reduced reflectance in devices with Lp = 350 nm.

Plasmon mediated enhancement and tuning of optical emission properties of two dimensional graphitic carbon nitride nanosheets.

We demonstrate surface plasmon induced enhancement and tunablilty in optical emission properties of two dimensional graphitic carbon nitride (g-C3N4) nanosheets through the attachment of gold (Au) nanoparticles. Raman spectroscopy has revealed surface enhanced Raman scattering that arises due to the combined effect of the charge transfer process and localized surface plasmon induced enhancement in electromagnetic field, both occurring at the nanoparticle-nanosheet interface. Photoluminescence studies suggest that at an optimal concentration of nanoparticles, the emission intensity can be enhanced, which is maximum within the 500-525 nm region. Further, the fabricated electroluminescent devices reveal that the emission feature can be tuned from bluish-green to red (∼160 nm shift) upon attaching Au nanoparticles. We propose that the π*→π transition in g-C3N4 can trigger surface plasmon oscillation in Au, which subsequently increases the excitation process in the nanosheets and results in enhanced emission in the green region of the photoluminescence spectrum. On the other hand, electroluminescence of g-C3N4 can induce plasmon oscillation more efficiently and thus can lead to red emission from Au nanoparticles through the radiative damping of particle plasmons. The influence of nanoparticle size and coverage on the emission properties of two dimensional g-C3N4, nanosheets has also been studied in detail.

Gold nanoparticle-embedded silk protein-ZnO nanorod hybrids for flexible bio-photonic devices.

Silk protein has been used as a biopolymer substrate for flexible photonic devices. Here, we demonstrate ZnO nanorod array hybrid photodetectors on Au nanoparticle-embedded silk protein for flexible optoelectronics. Hybrid samples exhibit optical absorption at the band edge of ZnO as well as plasmonic energy due to Au nanoparticles, making them attractive for selective UV and visible wavelength detection. The device prepared on Au-silk protein shows a much lower dark current and a higher photo to dark-current ratio of ∼105 as compared to the control sample without Au nanoparticles. The hybrid device also exhibits a higher specific detectivity due to higher responsivity arising from the photo-generated hole trapping by Au nanoparticles. Sharp pulses in the transient photocurrent have been observed in devices prepared on glass and Au-silk protein substrates due to the light induced pyroelectric effect of ZnO, enabling the demonstration of self-powered photodetectors at zero bias. Flexible hybrid detectors have been demonstrated on Au-silk/polyethylene terephthalate substrates, exhibiting characteristics similar to those fabricated on rigid glass substrates. A study of the performance of photodetectors with different bending angles indicates very good mechanical stability of silk protein based flexible devices. This novel concept of ZnO nanorod array photodetectors on a natural silk protein platform provides an opportunity to realize integrated flexible and self-powered bio-photonic devices for medical applications in near future.

Highly Luminescent WS2 Quantum Dots/ZnO Heterojunctions for Light Emitting Devices.

Sonication induced vertical fragmentation of two-dimensional (2D) WS2 nanosheets into highly luminescent, monodispered, zero-dimensional (0D) quantum dots (QDs) is reported. The formation of 0D structures from 2D sheets and their surface/microstructure characterization are revealed from their microscopic and spectroscopic investigations. Size dependent optical properties of WS2 nanostructures have been explored by UV-vis absorption and photoluminescence spectroscopy. Interestingly, it is observed that, below a critical dimension (∼2 nm), comparable to the Bohr exciton radius, the tiny nanocrystals exhibit strong emission. Finally, the electroluminescence characteristics are demonstrated for the first time, by forming a heterojunction of stabilizer free WS2 QDs and ZnO thin films. The signature of white light emission in the light emitting device is attributed to the adequate intermixing of emission characteristics of WS2 QDs and ZnO. The observation of white electroluminescence may pave the way to fabricate prototype futuristic efficient light emitting devices.

Metal nanoparticles triggered persistent negative photoconductivity in silk protein hydrogels.

Silk protein is a natural biopolymer with intriguing properties, which are attractive for next generation bio-integrated electronic and photonic devices. Here, we demonstrate the negative photoconductive response of Bombyx mori silk protein fibroin hydrogels, triggered by Au nanoparticles. The room temperature electrical conductivity of Au-silk hydrogels is found to be enhanced with the incorporation of Au nanoparticles over the control sample, due to the increased charge transporting networks within the hydrogel. Au-silk lateral photoconductor devices show a unique negative photoconductive response under an illumination of 325 nm, with excitation energy higher than the characteristic metal plasmon resonance band. The enhanced photoconductance yield in the hydrogels over the silk protein is attributed to the photo-oxidation of amino groups in the ß-pleated sheets of the silk around the Au nanoparticles followed by the breaking of charge transport networks. The Au-silk nanocomposite does not show any photoresponse under visible illumination because of the localization of excited charges in Au nanoparticles. The negative photoconductive response of hybrid Au-silk under UV illumination may pave the way towards the utilization of silk for future bio-photonic devices using metal nanoparticle platforms.

Multifunctional Au-ZnO plasmonic nanostructures for enhanced UV photodetector and room temperature NO sensing devices.

In this study we report the enhancement of UV photodetection and wavelength tunable light induced NO gas sensing at room temperature using Au-ZnO nanocomposites synthesized by a simple photochemical process. Plasmonic Au-ZnO nanostructures with a size less than the incident wavelength have been found to exhibit a localized surface plasmon resonance (LSPR) that leads to a strong absorption, scattering and local field enhancement. The photoresponse of Au-ZnO nanocomposite can be effectively enhanced by 80 times at 335 nm over control ZnO. We also demonstrated Au-ZnO nanocomposite's application to wavelength tunable gas sensor operating at room temperature. The sensing response of Au-ZnO nancomposite is enhanced both in UV and visible region, as compared to control ZnO. The sensitivity is observed to be higher in the visible region due to the LSPR effect of Au NPs. The selectivity is found to be higher for NO gas over CO and some other volatile organic compounds (VOCs), with a minimum detection limit of 0.1 ppb for Au-ZnO sensor at 335 nm.

Transparent and flexible resistive switching memory devices with a very high ON/OFF ratio using gold nanoparticles embedded in a silk protein matrix.

The growing demand for biomaterials for electrical and optical devices is motivated by the need to make building blocks for the next generation of printable bio-electronic devices. In this study, transparent and flexible resistive memory devices with a very high ON/OFF ratio incorporating gold nanoparticles into the Bombyx mori silk protein fibroin biopolymer are demonstrated. The novel electronic memory effect is based on filamentary switching, which leads to the occurrence of bistable states with an ON=OFF ratio larger than six orders of magnitude. The mechanism of this process is attributed to the formation of conductive filaments through silk fibroin and gold nanoparticles in the nanocomposite. The proposed hybrid bio-inorganic devices show promise for use in future flexible and transparent nanoelectronic systems.