Synthesis and Excited-State Properties of Donor-Acceptor Azahelical Coumarins.

A set of three donor-acceptor azahelical coumarins (DA-AHCs), namely, H-AHC, Me-AHC, and Ph-AHC, were rationally designed and synthesized, and their excited-state properties were comprehensively investigated. All three DA-AHCs are shown to display very high fluorosolvatochromic shifts as a result of significant intramolecular charge transfer in their excited states. The para-quinoidal forms of the latter apparently contribute predominantly to large dipole moments in their excited states. By virtue of the fact that these helical systems structurally incorporate a highly fluorescent coumarin dye, they exhibit high quantum yields in both solution and solid states. Indeed, their emission behaviors in the crystalline media are shown to be remarkably correlated with their respective crystal packings. Incisive analyses demonstrate (i) strengthening of hydrogen bonding in the excited state promotes quenching (H-AHC), (ii) efficient crystal packing promotes high emission (Me-AHC) by precluding deactivations via vibrational motions, and (iii) loose crystal packing contributes to excited-state deactivation to account for low quantum yields of emission (Ph-AHC).

Engineering Complex Synaptic Behaviors in a Single Device: Emulating Consolidation of Short-term Memory to Long-term Memory in Artificial Synapses via Dielectric Band Engineering.

As one of the key neuronal activities associated with memory in the human brain, memory consolidation is the process of the transition of short-term memory (STM) to long-term memory (LTM), which transforms an external stimulus to permanently stored information. Here, we report the emulation of this complex synaptic function, consolidation of STM to LTM, in a single-crystal indium phosphide (InP) field effect transistor (FET)-based artificial synapse. This behavior is achieved via the dielectric band and charge trap lifetime engineering in a dielectric gate heterostructure of aluminum oxide and titanium oxide. We analyze the behavior of these complex synaptic functions by engineering a variety of action potential parameters, and the devices exhibit good endurance, long retention time (>105 s), and high uniformity. Uniquely, this approach utilizes growth and device fabrication techniques which are scalable and back-end CMOS compatible, making this InP synaptic device a potential building block for neuromorphic computing.

High Quantum Efficiency Hot Electron Electrochemistry.

Using hot electrons to drive electrochemical reactions has drawn considerable interest in driving high-barrier reactions and enabling efficient solar to fuel conversion. However, the conversion efficiency from hot electrons to electrochemical products is typically low due to high hot electron scattering rates. Here, it is shown that the hydrogen evolution reaction (HER) in an acidic solution can be efficiently modulated by hot electrons injected into a thin gold film by an Au-Al2O3-Si metal-insulator-semiconductor (MIS) junction. Despite the large scattering rates in gold, it is shown that the hot electron driven HER can reach quantum efficiencies as high as ∼85% with a shift in the onset of hydrogen evolution by ∼0.6 V. By simultaneously measuring the currents from the solution, gold, and silicon terminals during the experiments, we find that the HER rate can be decomposed into three components: (i) thermal electron, corresponding to the thermal electron distribution in gold; (ii) hot electron, corresponding to electrons injected from silicon into gold which drive the HER before fully thermalizing; and (iii) silicon direct injection, corresponding to electrons injected from Si into gold that drive the HER before electron-electron scattering occurs. Through a series of control experiments, we eliminate the possibility of the observed HER rate modulation coming from lateral resistivity of the thin gold film, pinholes in the gold, oxidation of the MIS device, and measurement circuit artifacts. Next, we theoretically evaluate the feasibility of hot electron injection modifying the available supply of electrons. Considering electron-electron and electron-phonon scattering, we track how hot electrons injected at different energies interact with the gold-solution interface as they scatter and thermalize. The simulator is first used to reproduce other published experimental pump-probe hot electron measurements, and then simulate the experimental conditions used here. These simulations predict that hot electron injection first increases the supply of electrons to the gold-solution interface at higher energies by several orders of magnitude and causes a peaked electron interaction with the gold-solution interface at the electron injection energy. The first prediction corresponds to the observed hot electron electrochemical current, while the second prediction corresponds to the observed silicon direct injection current. These results indicate that MIS devices offer a versatile platform for hot electron sources that can efficiently drive electrochemical reactions.

Light-assisted, templated self-assembly of gold nanoparticle chains.

We experimentally demonstrate the technique of light-assisted, templated self-assembly (LATS) to trap and assemble 200 nm diameter gold nanoparticles. We excite a guided-resonance mode of a photonic-crystal slab with 1.55 µm laser light to create an array of optical traps. Unlike our previous demonstration of LATS with polystyrene particles, we find that the interparticle interactions play a significant role in the resulting particle patterns. Despite a two-dimensionally periodic intensity profile in the slab, the particles form one-dimensional chains whose orientations can be controlled by the incident polarization of the light. The formation of chains can be understood in terms of a competition between the gradient force due to the excitation of the mode in the slab and optical binding between particles.

Ultrasmall InGa(As)P Dielectric and Plasmonic Nanolasers.

Nanolasers have great potential for both on-chip light sources and optical barcoding particles. We demonstrate ultrasmall InGaP and InGaAsP disk lasers with diameters down to 360 nm (198 nm in height) in the red spectral range. Optically pumped, room-temperature, single-mode lasing was achieved from both disk-on-pillar and isolated particles. When isolated disks were placed on gold, plasmon polariton lasing was obtained with Purcell-enhanced stimulated emission. UV lithography and plasma ashing enabled wafer-scale fabrication of nanodisks with an intended random size variation. Silica-coated nanodisk particles generated stable subnanometer spectra from within biological cells across an 80 nm bandwidth from 635 to 715 nm.

Facile layer-by-layer fabrication of semiconductor microdisk laser particles.

Semiconductor-based laser particles (LPs) with exceptionally narrowband spectral emission have been used in biological systems for cell tagging purposes. Fabrication of these LPs typically requires highly specialized lithography and etching equipment, and is typically done in a cleanroom environment, hindering the broad adoption of this exciting new technology. Here, using only easily accessible laboratory equipment, we demonstrate a simple layer-by-layer fabrication strategy that overcomes this obstacle. We start from an indium phosphide (InP) substrate with multiple epitaxial indium gallium arsenide phosphide (InGaAsP) layers which are sequentially processed to yield LPs of various compositions and spectral properties. The LPs isolated from each layer are characterized, exhibiting excellent optical properties with lasing emission full width at half maximum as narrow as < 0.3 nm and typical thresholds of approximately 6 pJ upon excitation using a 3 ns pulse duration 1064 nm pump laser. The high quality of these particles renders them suitable for large-scale biological experiments including those requiring spectral multiplexing.

Contact photolithography-free integration of patterned and semi-transparent indium tin oxide stimulation electrodes into polydimethylsiloxane-based heart-on-a-chip devices for streamlining physiological recordings.

Controlled electrical stimulation is essential for evaluating the physiology of cardiac tissues engineered in heart-on-a-chip devices. However, existing stimulation techniques, such as external platinum electrodes or opaque microelectrode arrays patterned on glass substrates, have limited throughput, reproducibility, or compatibility with other desirable features of heart-on-a-chip systems, such as the use of tunable culture substrates, imaging accessibility, or enclosure in a microfluidic device. In this study, indium tin oxide (ITO), a conductive, semi-transparent, and biocompatible material, was deposited onto glass and polydimethylsiloxane (PDMS)-coated coverslips as parallel or point stimulation electrodes using laser-cut tape masks. ITO caused substrate discoloration but did not prevent brightfield imaging. ITO-patterned substrates were microcontact printed with arrayed lines of fibronectin and seeded with neonatal rat ventricular myocytes, which assembled into aligned cardiac tissues. ITO deposited as parallel or point electrodes was connected to an external stimulator and used to successfully stimulate micropatterned cardiac tissues to generate calcium transients or propagating calcium waves, respectively. ITO electrodes were also integrated into the cantilever-based muscular thin film (MTF) assay to stimulate and quantify the contraction of micropatterned cardiac tissues. To demonstrate the potential for multiple ITO electrodes to be integrated into larger, multiplexed systems, two sets of ITO electrodes were deposited onto a single substrate and used to stimulate the contraction of distinct micropatterned cardiac tissues independently. Collectively, these approaches for integrating ITO electrodes into heart-on-a-chip devices are relatively facile, modular, and scalable and could have diverse applications in microphysiological systems of excitable tissues.

Mimicking Biological Synaptic Functionality with an Indium Phosphide Synaptic Device on Silicon for Scalable Neuromorphic Computing.

Neuromorphic or "brain-like" computation is a leading candidate for efficient, fault-tolerant processing of large-scale data as well as real-time sensing and transduction of complex multivariate systems and networks such as self-driving vehicles or Internet of Things applications. In biology, the synapse serves as an active memory unit in the neural system and is the component responsible for learning and memory. Electronically emulating this element via a compact, scalable technology which can be integrated in a three-dimensional (3-D) architecture is critical for future implementations of neuromorphic processors. However, present day 3-D transistor implementations of synapses are typically based on low-mobility semiconductor channels or technologies that are not scalable. Here, we demonstrate a crystalline indium phosphide (InP)-based artificial synapse for spiking neural networks that exhibits elasticity, short-term plasticity, long-term plasticity, metaplasticity, and spike timing-dependent plasticity, emulating the critical behaviors exhibited by biological synapses. Critically, we show that this crystalline InP device can be directly integrated via back-end processing on a Si wafer using a SiO2 buffer without the need for a crystalline seed, enabling neuromorphic devices that can be implemented in a scalable and 3-D architecture. Specifically, the device is a crystalline InP channel field-effect transistor that interacts with neuron spikes by modification of the population of filled traps in the MOS structure itself. Unlike other transistor-based implementations, we show that it is possible to mimic these biological functions without the use of external factors (e.g., surface adsorption of gas molecules) and without the need for the high electric fields necessary for traditional flash-based implementations. Finally, when exposed to neuronal spikes with a waveform similar to that observed in the brain, these devices exhibit the ability to learn without the need for any external potentiating/depressing circuits, mimicking the biological process of Hebbian learning.

Confined Liquid-Phase Growth of Crystalline Compound Semiconductors on Any Substrate.

The growth of crystalline compound semiconductors on amorphous and non-epitaxial substrates is a fundamental challenge for state-of-the-art thin-film epitaxial growth techniques. Direct growth of materials on technologically relevant amorphous surfaces, such as nitrides or oxides results in nanocrystalline thin films or nanowire-type structures, preventing growth and integration of high-performance devices and circuits on these surfaces. Here, we show crystalline compound semiconductors grown directly on technologically relevant amorphous and non-epitaxial substrates in geometries compatible with standard microfabrication technology. Furthermore, by removing the traditional epitaxial constraint, we demonstrate an atomically sharp lateral heterojunction between indium phosphide and tin phosphide, two materials with vastly different crystal structures, a structure that cannot be grown with standard vapor-phase growth approaches. Critically, this approach enables the growth and manufacturing of crystalline materials without requiring a nearly lattice-matched substrate, potentially impacting a wide range of fields, including electronics, photonics, and energy devices.

Scalable Indium Phosphide Thin-Film Nanophotonics Platform for Photovoltaic and Photoelectrochemical Devices.

Recent developments in nanophotonics have provided a clear roadmap for improving the efficiency of photonic devices through control over absorption and emission of devices. These advances could prove transformative for a wide variety of devices, such as photovoltaics, photoelectrochemical devices, photodetectors, and light-emitting diodes. However, it is often challenging to physically create the nanophotonic designs required to engineer the optical properties of devices. Here, we present a platform based on crystalline indium phosphide that enables thin-film nanophotonic structures with physical morphologies that are impossible to achieve through conventional state-of-the-art material growth techniques. Here, nanostructured InP thin films have been demonstrated on non-epitaxial alumina inverted nanocone (i-cone) substrates via a low-cost and scalable thin-film vapor-liquid-solid growth technique. In this process, indium films are first evaporated onto the i-cone structures in the desired morphology, followed by a high-temperature step that causes a phase transformation of the indium into indium phosphide, preserving the original morphology of the deposited indium. Through this approach, a wide variety of nanostructured film morphologies are accessible using only control over evaporation process variables. Critically, the as-grown nanotextured InP thin films demonstrate excellent optoelectronic properties, suggesting this platform is promising for future high-performance nanophotonic devices.

Bandgap Control via Structural and Chemical Tuning of Transition Metal Perovskite Chalcogenides.

Transition metal perovskite chalcogenides are a new class of versatile semiconductors with high absorption coefficient and luminescence efficiency. Polycrystalline materials synthesized by an iodine-catalyzed solid-state reaction show distinctive optical colors and tunable bandgaps across the visible range in photoluminescence, with one of the materials' external efficiency approaching the level of single-crystal InP and CdSe.