Nanoscale Bilayer Mechanical Lithography Using Water as Developer.

Sustainability has become a critical concern in the semiconductor industry as hazardous wastes released during the manufacturing process of semiconductor devices have an adverse impact on human beings and the environment. The use of hazardous solvents in existing fabrication processes also restricts the use of polymer substrates because of their low chemical resistance to such solvents. Here, we demonstrate an environmentally friendly mechanical, bilayer lithography that uses just water for development and lift-off. We show that we are able to create arbitrary patterns achieving resolution down to 310 nm. We then demonstrate the use of this technique to create functional devices by fabricating a MoS2 photodetector on a polyethylene terephthalate (PET) substrate with measured response times down to 42 ms.

Filamentary High-Resolution Electrical Probes for Nanoengineering.

Confining electric fields to a nanoscale region is challenging yet crucial for applications such as high-resolution probing of electrical properties of materials and electric-field manipulation of nanoparticles. State-of-the-art techniques involving atomic force microscopy typically have a lateral resolution limit of tens of nanometers due to limitations in the probe geometry and stray electric fields that extend over space. Engineering the probes is the most direct approach to improving this resolution limit. However, current methods to fabricate high-resolution probes, which can effectively confine the electric fields laterally, involve expensive and sophisticated probe manipulation, which has limited the use of this approach. Here, we demonstrate that nanoscale phase switching of configurable thin films on probes can result in high-resolution electrical probes. These configurable coatings can be both germanium-antimony-tellurium (GST) as well as amorphous-carbon, materials known to undergo electric field-induced nonvolatile, yet reversible switching. By forming a localized conductive filament through phase transition, we demonstrate a spatial resolution of electrical field beyond the geometrical limitations of commercial platinum probes (i.e., an improvement of ∼48%). We then utilize these confined electric fields to manipulate nanoparticles with single nanoparticle precision via dielectrophoresis. Our results advance the field of nanomanufacturing and metrology with direct applications for pick and place assembly at the nanoscale.

Direct Laser Patterning and Phase Transformation of 2D PdSe2 Films for On-Demand Device Fabrication.

Heterophase homojunction formation in atomically thin 2D layers is of great importance for next-generation nanoelectronics and optoelectronics applications. Technologically challenging, controllable transformation between the semiconducting and metallic phases of transition metal chalcogenides is of particular importance. Here, we demonstrate that controlled laser irradiation can be used to directly ablate PdSe2 thin films using high power or trigger the local transformation of PdSe2 into a metallic phase PdSe2-x using lower laser power. Such transformations are possible due to the low decomposition temperature of PdSe2 and a variety of stable phases compared to other 2D transition metal dichalcogenides. Scanning transmission electron microscopy is used to reveal the laser-induced Se-deficient phases of PdSe2 material. The process sensitivity to the laser power allows patterning flexibility for resist-free device fabrication. The laser-patterned devices demonstrate that a laser-induced metallic phase PdSe2-x is stable with increased conductivity by a factor of about 20 compared to PdSe2. These findings contribute to the development of nanoscale devices with homojunctions and scalable methods to achieve structural transformations in 2D materials.

Chemical Vapor Deposition Growth of Two-Dimensional Monolayer Gallium Sulfide Crystals Using Hydrogen Reduction of Ga2S3.

Two-dimensional gallium sulfide (GaS) crystals are synthesized by a simple and efficient ambient pressure chemical vapor deposition (CVD) method using a single-source precursor of Ga2S3. The synthesized GaS structures involve triangular monolayer domains and multilayer flakes with thickness of 1 and 15 nm, respectively. Regions of continuous films of GaS are also achieved with about 0.7 cm2 uniform coverage. This is achieved by using hydrogen carrier gas and the horizontally placed SiO2/Si substrates. Electron microscopy and spectroscopic measurements are used to characteristic the CVD-grown materials. This provides important insights into novel approaches for enlarging the domain size of GaS crystals and understanding of the growth mechanism using this precursor system.

High-Performance All 2D-Layered Tin Disulfide: Graphene Photodetecting Transistors with Thickness-Controlled Interface Dynamics.

Tin disulfide crystals with layered two-dimensional (2D) sheets are grown by chemical vapor deposition using a novel precursor approach and integrated into all 2D transistors with graphene (Gr) electrodes. The Gr:SnS2:Gr transistors exhibit excellent photodetector response with high detectivity and photoresponsivity. We show that the response of the all 2D photodetectors depends upon charge trapping at the interface and the Schottky barrier modulation. The thickness-dependent SnS2 measurements in devices reveal a transition from the interface-dominated response for thin crystals to bulklike response for the thicker SnS2 crystals, showing the sensitivity of devices fabricated using layered materials on the number of layers. These results show that SnS2 has photosensing performance when combined with Gr electrodes that is comparable to other 2D transition metal dichalcogenides of MoS2 and WS2.

Revealing Strain-Induced Effects in Ultrathin Heterostructures at the Nanoscale.

Two-dimensional materials are being increasingly studied, particularly for flexible and wearable technologies because of their inherent thickness and flexibility. Crucially, one aspect where our understanding is still limited is on the effect of mechanical strain, not on individual sheets of materials, but when stacked together as heterostructures in devices. In this paper, we demonstrate the use of Kelvin probe microscopy in capturing the influence of uniaxial tensile strain on the band-structures of graphene and WS2 (mono- and multilayered) based heterostructures at high resolution. We report a major advance in strain characterization tools through enabling a single-shot capture of strain defined changes in a heterogeneous system at the nanoscale, overcoming the limitations (materials, resolution, and substrate effects) of existing techniques such as optical spectroscopy. Using this technique, we observe that the work-functions of graphene and WS2 increase as a function of strain, which we attribute to the Fermi level lowering from increased p-doping. We also extract the nature of the interfacial heterojunctions and find that they get strongly modulated from strain. We observe that the strain-enhanced charge transfer with the substrate plays a dominant role, causing the heterostructures to behave differently from two-dimensional materials in their isolated forms.

Nanoparticle assembly enabled by EHD-printed monolayers.

Augmenting existing devices and structures at the nanoscale with unique functionalities is an exciting prospect. So is the ability to eventually enable at the nanoscale, a version of rapid prototyping via additive nanomanufacturing. Achieving this requires a step-up in manufacturing for industrial use of these devices through fast, inexpensive prototyping with nanoscale precision. In this paper, we combine two very promising techniques-self-assembly and printing-to achieve additively nanomanufactured structures. We start by showing that monolayers can drive the assembly of nanoparticles into pre-defined patterns with single-particle resolution; then crucially we demonstrate for the first time that molecular monolayers can be printed using electrohydrodynamic (EHD)-jet printing. The functionality and resolution of such printed monolayers then drives the self-assembly of nanoparticles, demonstrating the integration of EHD with self-assembly. This shows that such process combinations can lead towards more integrated process flows in nanomanufacturing. Furthermore, in-process metrology is a key requirement for any large-scale nanomanufacturing, and we show that Dual-Harmonic Kelvin Probe Microscopy provides a robust metrology technique to characterising these patterned structures through the convolution of geometrical and environmental constraints. These represent a first step toward combining different additive nanomanufacturing techniques and metrology techniques that could in future provide additively nanomanufactured devices and structures.

Design parameters for voltage-controllable directed assembly of single nanoparticles.

Techniques to reliably pick-and-place single nanoparticles into functional assemblies are required to incorporate exotic nanoparticles into standard electronic circuits. In this paper we explore the use of electric fields to drive and direct the assembly process, which has the advantage of being able to control the nano-assembly process at the single nanoparticle level. To achieve this, we design an electrostatic gating system, thus enabling a voltage-controllable nanoparticle picking technique. Simulating this system with the nonlinear Poisson-Boltzmann equation, we can successfully characterize the parameters required for single particle placement, the key being single particle selectivity, in effect designing a system that can achieve this controllably. We then present the optimum design parameters required for successful single nanoparticle placement at ambient temperature, an important requirement for nanomanufacturing processes.

Repeatedly pairing vagus nerve stimulation with a movement reorganizes primary motor cortex.

Although sensory and motor systems support different functions, both systems exhibit experience-dependent cortical plasticity under similar conditions. If mechanisms regulating cortical plasticity are common to sensory and motor cortices, then methods generating plasticity in sensory cortex should be effective in motor cortex. Repeatedly pairing a tone with a brief period of vagus nerve stimulation (VNS) increases the proportion of primary auditory cortex responding to the paired tone (Engineer ND, Riley JR, Seale JD, Vrana WA, Shetake J, Sudanagunta SP, Borland MS, Kilgard MP. 2011. Reversing pathological neural activity using targeted plasticity. Nature. 470:101-104). In this study, we predicted that repeatedly pairing VNS with a specific movement would result in an increased representation of that movement in primary motor cortex. To test this hypothesis, we paired VNS with movements of the distal or proximal forelimb in 2 groups of rats. After 5 days of VNS movement pairing, intracranial microstimulation was used to quantify the organization of primary motor cortex. Larger cortical areas were associated with movements paired with VNS. Rats receiving identical motor training without VNS pairing did not exhibit motor cortex map plasticity. These results suggest that pairing VNS with specific events may act as a general method for increasing cortical representations of those events. VNS movement pairing could provide a new approach for treating disorders associated with abnormal movement representations.

Discrimination of brief speech sounds is impaired in rats with auditory cortex lesions.

Auditory cortex (AC) lesions impair complex sound discrimination. However, a recent study demonstrated spared performance on an acoustic startle response test of speech discrimination following AC lesions (Floody et al., 2010). The current study reports the effects of AC lesions on two operant speech discrimination tasks. AC lesions caused a modest and quickly recovered impairment in the ability of rats to discriminate consonant-vowel-consonant speech sounds. This result seems to suggest that AC does not play a role in speech discrimination. However, the speech sounds used in both studies differed in many acoustic dimensions and an adaptive change in discrimination strategy could allow the rats to use an acoustic difference that does not require an intact AC to discriminate. Based on our earlier observation that the first 40 ms of the spatiotemporal activity patterns elicited by speech sounds best correlate with behavioral discriminations of these sounds (Engineer et al., 2008), we predicted that eliminating additional cues by truncating speech sounds to the first 40 ms would render the stimuli indistinguishable to a rat with AC lesions. Although the initial discrimination of truncated sounds took longer to learn, the final performance paralleled rats using full-length consonant-vowel-consonant sounds. After 20 days of testing, half of the rats using speech onsets received bilateral AC lesions. Lesions severely impaired speech onset discrimination for at least one-month post lesion. These results support the hypothesis that auditory cortex is required to accurately discriminate the subtle differences between similar consonant and vowel sounds.

Effects of damage to auditory cortex on the discrimination of speech sounds by rats.

The intensity of a noise-induced startle response can be reduced by the presentation of an otherwise neutral stimulus immediately before the noise ("prepulse inhibition" or PPI). We used a form of PPI to study the effects of damage to auditory cortex on the discrimination of speech sounds by rats. Subjects underwent control surgery or treatment of the auditory cortex with the vasoconstrictor endothelin-1. This treatment caused damage concentrated in primary auditory cortex (A1). Both before and after lesions, subjects were tested on 5 tasks, most presenting a pair of human speech sounds (consonant-vowel syllables) so that the capacity for discrimination would be evident in the extent of PPI. Group comparisons failed to reveal any consistent lesion effect. At the same time, the analysis of individual differences in performance by multiple regression suggests that some of the temporal processing required to discriminate speech sounds is concentrated anteroventrally in the right A1. These results also confirm that PPI can be adapted to studies of the brain mechanisms involved in the processing of speech and other complex sounds.

Effect of the environment on the dendritic morphology of the rat auditory cortex.

The present study aimed to identify morphological correlates of environment-induced changes at excitatory synapses of the primary auditory cortex (A1). We used the Golgi-Cox stain technique to compare pyramidal cells dendritic properties of Sprague-Dawley rats exposed to different environmental manipulations. Sholl analysis, dendritic length measures, and spine density counts were used to monitor the effects of sensory deafness and an auditory version of environmental enrichment (EE). We found that deafness decreased apical dendritic length leaving basal dendritic length unchanged, whereas EE selectively increased basal dendritic length without changing apical dendritic length. On the contrary, deafness decreased while EE increased spine density in both basal and apical dendrites of A1 Layer 2/3 (LII/III) neurons. To determine whether stress contributed to the observed morphological changes in A1, we studied neural morphology in a restraint-induced model that lacked behaviorally relevant acoustic cues. We found that stress selectively decreased apical dendritic length in the auditory but not in the visual primary cortex. Similar to the acoustic manipulation, stress-induced changes in dendritic length possessed a layer-specific pattern displaying LII/III neurons from stressed animals with normal apical dendrites but shorter basal dendrites, while infragranular neurons (Layers V and VI) displayed shorter apical dendrites but normal basal dendrites. The same treatment did not induce similar changes in the visual cortex, demonstrating that the auditory cortex is an exquisitely sensitive target of neocortical plasticity, and that prolonged exposure to different acoustic as well as emotional environmental manipulation may produce specific changes in dendritic shape and spine density.

Chronic stress induces dendritic atrophy in the rat medial geniculate nucleus: effects on auditory conditioning.

Chronic stress induces dendritic atrophy in the inferior colliculus (IC, auditory mesencephalon) and impairs auditory avoidance conditioning. The aim of this study was to determine in Golgi preparations and in cued fear conditioning whether stress affects other auditory components, like the thalamic medial geniculate nucleus (MG) or the posterior thalamic nucleus (PO), in Sprague-Dawley rats. Chronic restraint stress produced a significant dendritic atrophy in the MG (stress: 407+/-55 microm; control: 808+/-120 microm; p<0.01) but did not affect auditory fear conditioning. The last result was in apparent contrast with the fact that stress impairs both the acquisition of auditory avoidance conditioned responses and the dendritic structure in two major nuclei of the auditory system. In order to analyze this disagreement, we investigated whether the stress-related freezing to tone occurring in the fear conditioning protocol corresponded to a conditioned or an unconditioned fear response, using changes in tone instead of light throughout conditioning trials. Chronic stress significantly enhanced visual fear conditioning in stressed animals compared to controls (stress: 58.9+/-8.42%, control: 23.31+/-8.01%; p<0.05), but this fear enhancement was related to unconditioned fear. Conversely, chronic stress did not affect the morphology of the PO (subserving both auditory and somatosensory information) or the corresponding auditory and somatosensory unconditioned responses (acoustic startle response and escape behavior). Our results suggest that the auditory conditioned stimulus can be processed in part independently of the IC and MG in the stressed animals, and sent to the amygdala via the PO inducing unconditioned fear. Comparable alterations could be produced in major depression.