All-Optical and Label-Free Stimulation of Action Potentials in Neurons and Cardiomyocytes by Plasmonic Porous Metamaterials.

Optical stimulation technologies are gaining great consideration in cardiology, neuroscience studies, and drug discovery pathways by providing control over cell activity with high spatio-temporal resolution. However, this high precision requires manipulation of biological processes at genetic level concealing its development from broad scale application. Therefore, translating these technologies into tools for medical or pharmacological applications remains a challenge. Here, an all-optical nongenetic method for the modulation of electrogenic cells is introduced. It is demonstrated that plasmonic metamaterials can be used to elicit action potentials by converting near infrared laser pulses into stimulatory currents. The suggested approach allows for the stimulation of cardiomyocytes and neurons directly on commercial complementary metal-oxide semiconductor microelectrode arrays coupled with ultrafast pulsed laser, providing both stimulation and network-level recordings on the same device.

Nanoengineering InP Quantum Dot-Based Photoactive Biointerfaces for Optical Control of Neurons.

Light-activated biointerfaces provide a non-genetic route for effective control of neural activity. InP quantum dots (QDs) have a high potential for such biomedical applications due to their uniquely tunable electronic properties, photostability, toxic-heavy-metal-free content, heterostructuring, and solution-processing ability. However, the effect of QD nanostructure and biointerface architecture on the photoelectrical cellular interfacing remained unexplored. Here, we unravel the control of the photoelectrical response of InP QD-based biointerfaces via nanoengineering from QD to device-level. At QD level, thin ZnS shell growth (∼0.65 nm) enhances the current level of biointerfaces over an order of magnitude with respect to only InP core QDs. At device-level, band alignment engineering allows for the bidirectional photoelectrochemical current generation, which enables light-induced temporally precise and rapidly reversible action potential generation and hyperpolarization on primary hippocampal neurons. Our findings show that nanoengineering QD-based biointerfaces hold great promise for next-generation neurostimulation devices.

Cadmium-Free and Efficient Type-II InP/ZnO/ZnS Quantum Dots and Their Application for LEDs.

It is a generally accepted perspective that type-II nanocrystal quantum dots (QDs) have low quantum yield due to the separation of the electron and hole wavefunctions. Recently, high quantum yield levels were reported for cadmium-based type-II QDs. Hence, the quest for finding non-toxic and efficient type-II QDs is continuing. Herein, we demonstrate environmentally benign type-II InP/ZnO/ZnS core/shell/shell QDs that reach a high quantum yield of ∼91%. For this, ZnO layer was grown on core InP QDs by thermal decomposition, which was followed by a ZnS layer via successive ionic layer adsorption. The small-angle X-ray scattering shows that spherical InP core and InP/ZnO core/shell QDs turn into elliptical particles with the growth of the ZnS shell. To conserve the quantum efficiency of QDs in device architectures, InP/ZnO/ZnS QDs were integrated in the liquid state on blue light-emitting diodes (LEDs) as down-converters that led to an external quantum efficiency of 9.4% and a power conversion efficiency of 6.8%, respectively, which is the most efficient QD-LED using type-II QDs. This study pointed out that cadmium-free type-II QDs can reach high efficiency levels, which can stimulate novel forms of devices and nanomaterials for bioimaging, display, and lighting.

Quantum dot and electron acceptor nano-heterojunction for photo-induced capacitive charge-transfer.

Capacitive charge transfer at the electrode/electrolyte interface is a biocompatible mechanism for the stimulation of neurons. Although quantum dots showed their potential for photostimulation device architectures, dominant photoelectrochemical charge transfer combined with heavy-metal content in such architectures hinders their safe use. In this study, we demonstrate heavy-metal-free quantum dot-based nano-heterojunction devices that generate capacitive photoresponse. For that, we formed a novel form of nano-heterojunctions using type-II InP/ZnO/ZnS core/shell/shell quantum dot as the donor and a fullerene derivative of PCBM as the electron acceptor. The reduced electron-hole wavefunction overlap of 0.52 due to type-II band alignment of the quantum dot and the passivation of the trap states indicated by the high photoluminescence quantum yield of 70% led to the domination of photoinduced capacitive charge transfer at an optimum donor-acceptor ratio. This study paves the way toward safe and efficient nanoengineered quantum dot-based next-generation photostimulation devices.

Cation exchange mediated synthesis of bright Au@ZnTe core-shell nanocrystals.

The synthesis of heterostructured core-shell nanocrystals has attracted significant attention due to their wide range of applications in energy, medicine and environment. To further extend the possible nanostructures, non-epitaxial growth is introduced to form heterostructures with large lattice mismatches, which cannot be achieved by classical epitaxial growth techniques. Here, we report the synthetic procedure of Au@ZnTe core-shell nanostructures by cation exchange reaction for the first time. For that, bimetallic Au@Ag heterostructures were synthesized by using PDDA as stabilizer and shape-controller. Then, by addition of Te and Zn precursors in a step-wise reaction, the zinc and silver cation exchange was performed and Au@ZnTe nanocrystals were obtained. Structural and optical characterization confirmed the formation of the Au@ZnTe nanocrystals. The optimization of the synthesis led to the bright nanocrystals with a photoluminescence quantum yield up to 27%. The non-toxic, versatile synthetic route, and bright emission of the synthesized Au@ZnTe nanocrystals offer significant potential for future bio-imaging and optoelectronic applications.

Bidirectional optical neuromodulation using capacitive charge-transfer.

Artificial control of neural activity allows for understanding complex neural networks and improving therapy of neurological disorders. Here, we demonstrate that utilization of photovoltaic biointerfaces combined with light waveform shaping can generate safe capacitive currents for bidirectional modulation of neurons. The differential photoresponse of the biointerface due to double layer capacitance facilitates the direction control of capacitive currents depending on the slope of light intensity. Moreover, the strength of capacitive currents is controlled by changing the rise and fall time slope of light intensity. This approach allows for high-level control of the hyperpolarization and depolarization of membrane potential at single-cell level. Our results pave the way toward advanced bioelectronic functionalities for wireless and safe control of neural activity.

Efficient photocapacitors via ternary hybrid photovoltaic optimization for photostimulation of neurons.

Optoelectronic photoelectrodes based on capacitive charge-transfer offer an attractive route to develop safe and effective neuromodulators. Here, we demonstrate efficient optoelectronic photoelectrodes that are based on the incorporation of quantum dots (QDs) into poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-Phenyl-C61-butyric acid methyl ester (PCBM) bulk heterojunction. We control the performance of the photoelectrode by the blend ratio, thickness, and nanomorphology of the ternary bulk heterojunction. The optimization led to a photocapacitor that has a photovoltage of 450 mV under a light intensity level of 20 mW.cm-2 and a responsivity of 99 mA/W corresponding to the most light-sensitive organic photoelectrode reported to date. The photocapacitor can facilitate action potential generation by hippocampal neurons via burst waveforms at an intensity level of 20 mW.cm-2. Therefore, the results point to an alternative direction in the engineering of safe and ultra-light-sensitive neural interfaces.

Organic Photovoltaic Pseudocapacitors for Neurostimulation.

Neural interfaces are the fundamental tools to understand the brain and cure many nervous-system diseases. For proper interfacing, seamless integration, efficient and safe digital-to-biological signal transduction, and long operational lifetime are required. Here, we devised a wireless optoelectronic pseudocapacitor converting the optical energy to safe capacitive currents by dissociating the photogenerated excitons in the photovoltaic unit and effectively routing the holes to the supercapacitor electrode and the pseudocapacitive electrode-electrolyte interfacial layer of PEDOT:PSS for reversible faradic reactions. The biointerface showed high peak capacitive currents of ∼3 mA·cm-2 with total charge injection of ∼1 µC·cm-2 at responsivity of 30 mA·W-1, generating high photovoltages over 400 mV for the main eye photoreception colors of blue, green, and red. Moreover, modification of PEDOT:PSS controls the charging/discharging phases leading to rapid capacitive photoresponse of 50 µs and effective membrane depolarization at the single-cell level. The neural interface has a device lifetime of over 1.5 years in the aqueous environment and showed stability without significant performance decrease after sterilization steps. Our results demonstrate that adopting the pseudocapacitance phenomenon on organic photovoltaics paves an ultraefficient, safe, and robust way toward communicating with biological systems.

Plasmon-Coupled Photocapacitor Neuromodulators.

Efficient transduction of optical energy to bioelectrical stimuli is an important goal for effective communication with biological systems. For that, plasmonics has a significant potential via boosting the light-matter interactions. However, plasmonics has been primarily used for heat-induced cell stimulation due to membrane capacitance change (i.e., optocapacitance). Instead, here, we demonstrate that plasmonic coupling to photocapacitor biointerfaces improves safe and efficacious neuromodulating displacement charges for an average of 185% in the entire visible spectrum while maintaining the faradic currents below 1%. Hot-electron injection dominantly leads the enhancement of displacement current in the blue spectral window, and the nanoantenna effect is mainly responsible for the improvement in the red spectral region. The plasmonic photocapacitor facilitates wireless modulation of single cells at three orders of magnitude below the maximum retinal intensity levels, corresponding to one of the most sensitive optoelectronic neural interfaces. This study introduces a new way of using plasmonics for safe and effective photostimulation of neurons and paves the way toward ultrasensitive plasmon-assisted neurostimulation devices.

High-Performance, Large-Area, and Ecofriendly Luminescent Solar Concentrators Using Copper-Doped InP Quantum Dots.

Colloidal quantum dots (QDs) are promising building blocks for luminescent solar concentrators (LSCs). For their widespread use, they need to simultaneously satisfy non-toxic material content, low reabsorption, high photoluminescence quantum yield, and large-scale production. Here, copper doping of zinc carboxylate-passivated InP core and nano-engineering of ZnSe shell facilitated high in-device quantum efficiency of QDs over 80%, having well-matched spectral emission profile with the photo-response of silicon solar cells. The optimized QD-LSCs showed an optical quantum efficiency of 37% and an internal concentration factor of 4.7 for a 10 × 10-cm2 device area under solar illumination, which is comparable with the state-of-the-art LSCs based on cadmium-containing QDs and lead-containing perovskites. Synthesis of the copper-doped InP/ZnSe QDs in gram-scale and large-area deposition (3,000 cm2) onto commercial window glasses via doctor-blade technique showed their scalability for mass production. These results position InP-based QDs as a promising alternative for efficient solar energy harvesting.

Silk as a biodegradable resist for field-emission scanning probe lithography.

The patterning of silk allows for manufacturing various structures with advanced functionalities for optical and tissue engineering and drug delivery applications. Here, we propose a high-resolution nanoscale patterning method based on field-emission scanning probe lithography (FE-SPL) that crosslinks the biomaterial silk on conductive indium tin oxide (ITO) promoting the use of a biodegradable material as resist and water as a developer. During the lithographic process, Fowler-Nordheim electron emission from a sharp tip was used to manipulate the structure of silk fibroin from random coil to beta sheet and the emission formed nanoscale latent patterns with a critical dimension (CD) of ∼50 nm. To demonstrate the versatility of the method, we patterned standard and complex shapes. This method is particularly attractive due to its ease of operation without relying on a vacuum or a special gaseous environment and without any need for complex electronics or optics. Therefore, this study paves a practical and cost-effective way toward patterning biopolymers at ultra-high level resolution.

Biocompatible Quantum Funnels for Neural Photostimulation.

Neural photostimulation has high potential to understand the working principles of complex neural networks and develop novel therapeutic methods for neurological disorders. A key issue in the light-induced cell stimulation is the efficient conversion of light to bioelectrical stimuli. In photosynthetic systems developed in millions of years by nature, the absorbed energy by the photoabsorbers is transported via nonradiative energy transfer to the reaction centers. Inspired by these systems, neural interfaces based on biocompatible quantum funnels are developed that direct the photogenerated charge carriers toward the bionanojunction for effective photostimulation. Funnels are constructed with indium-based rainbow quantum dots that are assembled in a graded energy profile. Implementation of a quantum funnel enhances the generated photoelectrochemical current 215% per unit absorbance in comparison with ungraded energy profile in a wireless and free-standing mode and facilitates optical neuromodulation of a single cell. This study indicates that the control of charge transport at nanoscale can lead to unconventional and effective neural interfaces.

Ecofriendly and Efficient Luminescent Solar Concentrators Based on Fluorescent Proteins.

In recent years, luminescent solar concentrators (LSCs) have received renewed attention as a versatile platform for large-area, high-efficiency, and low-cost solar energy harvesting. So far, artificial or engineered optical materials, such as rare-earth ions, organic dyes, and colloidal quantum dots (QDs) have been incorporated into LSCs. Incorporation of nontoxic materials into efficient device architectures is critical for environmental sustainability and clean energy production. Here, we demonstrated LSCs based on fluorescent proteins, which are biologically produced, ecofriendly, and edible luminescent biomaterials along with exceptional optical properties. We synthesized mScarlet fluorescent proteins in Escherichia coli expression system, which is the brightest protein with a quantum yield of 61% in red spectral region that matches well with the spectral response of silicon solar cells. Moreover, we integrated fluorescent proteins in an aqueous medium into solar concentrators, which preserved their quantum efficiency in LSCs and separated luminescence and wave-guiding regions due to refractive index contrast for efficient energy harvesting. Solar concentrators based on mScarlet fluorescent proteins achieved an external LSC efficiency of 2.58%, and the integration at high concentrations increased their efficiency approaching to 5%, which may facilitate their use as "luminescent solar curtains" for in-house applications. The liquid-state integration of proteins paves a way toward efficient and "green" solar energy harvesting.

Excitonic Energy Transfer within InP/ZnS Quantum Dot Langmuir-Blodgett Assemblies.

Interparticle energy transfer offers great promise to a diverse range of applications ranging from artificial solar energy harvesting to nanoscale rulers in biology. Here, we assembled InP/ZnS core/shell quantum dot monolayers via the Langmuir-Blodgett technique and studied the effect of ZnS shell thickness on the excitonic energy transfer within these core/shell quantum dots. Three types of InP-based core/shell quantum dot Langmuir-Blodgett assemblies with different ZnS shell thicknesses were assembled. The structural and optical properties of colloidal quantum dots reveal the successful multiple ZnS shell growth, and atomic force microscopy studies show the smoothness of the assembled monolayers. Time-resolved photoluminescence (PL) and fluorescence lifetime imaging microscopy (FLIM) studies of the thick-shell QD monolayer reveal narrower lifetime distribution in comparison with the thin-shell QD monolayer. The interparticle excitonic energy transfer was studied by spectrally resolved PL traces, and higher energy transfer was observed for the thin-shell InP/1ZnS QD monolayer. Finally, we calculated the average exciton energy and indicated that the energy transfer induced exciton energy shift decreased significantly from 95 to 27 meV after multiple ZnS shell growth.

Silk-Based Aqueous Microcontact Printing.

Lithography, the transfer of patterns to a film or substrate, is the basis by which many modern technological devices and components are produced. However, established lithographic approaches generally use complex techniques, expensive equipment, and advanced materials. Here, we introduce a water-based microcontact printing method using silk that is simple, inexpensive, ecofriendly, and recyclable. Whereas the traditional microcontact printing technique facilitates only negative lithography, the synergetic interaction of the silk, water, and common chemicals in our technique enables both positive and negative patterning using a single stamp. Among diverse application possibilities, we exemplify a proof of concept of the method through optimizing its metal lift-off process and demonstrate the fabrication of electromagnetic metamaterial elements on both solid and flexible substrates. The results indicate that the method demonstrated herein is universally applicable to device production and technology development.

Structural control of InP/ZnS core/shell quantum dots enables high-quality white LEDs.

Herein, we demonstrate that the structural and optical control of InP-based quantum dots (QDs) can lead to high-performance light-emitting diodes (LEDs). Zinc sulphide (ZnS) shells passivate the InP QD core and increase the quantum yield in green-emitting QDs by 13-fold and red-emitting QDs by 8-fold. The optimised QDs are integrated in the liquid state to eliminate aggregation-induced emission quenching and we fabricated white LEDs with a warm, neutral and cool-white appearance by the down-conversion mechanism. The QD-functionalized white LEDs achieve luminous efficiency (LE) up to 14.7 lm W-1 and colour-rendering index up to 80. The structural and optical control of InP/ZnS core/shell QDs enable 23-fold enhancement in LE of white LEDs compared to ones containing only QDs of InP core.

Stokes-Shift-Engineered Indium Phosphide Quantum Dots for Efficient Luminescent Solar Concentrators.

Luminescent solar concentrators (LSCs) show promise because of their potential for low-cost, large-area, and high-efficiency energy harvesting. Stokes shift engineering of luminescent quantum dots (QDs) is a favorable approach to suppress reabsorption losses in LSCs; however, the use of highly toxic heavy metals in QDs constitutes a serious concern for environmental sustainability. Here, we report LSCs based on cadmium-free InP/ZnO core/shell QDs with type-II band alignment that allow for the suppression of reabsorption by Stokes shift engineering. The spectral emission and absorption overlap was controlled by the growth of a ZnO shell on an InP core. At the same time, the ZnO layer also facilitates the photostability of the QDs within the host matrix. We analyzed the optical performance of indium-based LSCs and identified the optical efficiency as 1.45%. The transparency, flexibility, and cadmium-free content of the LSCs hold promise for solar window applications.

Biomaterial Disk Lasers by Suppressing the Coffee Ring Effect.

Inspired by the suppression of the coffee ring effect, we developed self-assembled disk lasers that can be formed with a wide variety of biomaterials. For proof of concept, we formed the disks with the natural protein silk fibroin or the synthetic biopolymer polyvinylpyrrolidone, which created a whispering gallery mode resonator that we combined with organic dyes for laser light generation. The lasers were flexible enough to bend around surfaces, physically transient in aqueous environments, and could be directly placed on various substrates. Moreover, the characteristics of laser emission could be modified by altering the size of the disk. Our results therefore highlight a new combination of materials that can be used in the environmentally friendly production of waste-free photonic devices.

Silk-hydrogel Lenses for Light-emitting Diodes.

Today the high demand for electronics leads to massive production of waste, thus green materials based electronic devices are becoming more important for environmental protection and sustainability. The biomaterial based hydrogels are widely used in tissue engineering, but their uses in photonics are limited. In this study, silk fibroin protein in hydrogel form is explored as a bio-friendly alternative to conventional polymers for lens applications in light-emitting diodes. The concentration of silk fibroin protein and crosslinking agent had direct effects on optical properties of silk hydrogel. The spatial radiation intensity distribution was controlled via dome- and crater-type silk-hydrogel lenses. The hydrogel lens showed a light extraction efficiency over 0.95 on a warm white LED. The stability of silk hydrogel lens is enhanced approximately three-folds by using a biocompatible/biodegradable poly(ester-urethane) coating and more than three orders of magnitude by using an edible paraffin wax coating. Therefore, biomaterial lenses show promise for green optoelectronic applications.

Fluorescent protein integrated white LEDs for displays.

The usage time of displays (e.g., TVs, mobile phones, etc) is in general shorter than their functional life time, which worsens the electronic waste (e-waste) problem around the world. The integration of biomaterials into electronics can help to reduce the e-waste problem. In this study, we demonstrate fluorescent protein integrated white LEDs to use as a backlight source for liquid crystal (LC) displays for the first time. We express and purify enhanced green fluorescent protein (eGFP) and monomeric Cherry protein (mCherry), and afterward we integrate these proteins as a wavelength-converter on a blue LED chip. The protein-integrated backlight exhibits a high luminous efficacy of 248 lm/Wopt and the area of the gamut covers 80% of the NTSC color gamut. The resultant colors and objects in the image on the display can be well observed and distinguished. Therefore, fluorescent proteins show promise for display applications.