Additive Lithography-Organic Monolayer Patterning Coupled with an Area-Selective Deposition.

The combination of area-selective deposition (ASD) with a patternable organic monolayer provides a versatile additive lithography platform, enabling the generation of a variety of nanoscale feature geometries. Stearate hydroxamic acid self-assembled monolayers (SAMs) were patterned with extreme ultraviolet (λ = 13.5 nm) or electron beam irradiation and developed with ASD to achieve line space patterns as small as 50 nm. Density functional theory was employed to aid in the synthesis of hydroxamic acid derivatives with optimized packing density to enhance the imaging contrast and improve dose sensitivity. Near-edge X-ray absorption fine structure spectroscopy and infrared spectroscopy reveal that the imaging mechanism is based on improved deposition inhibition provided by the cross-linking of the SAM to produce a more effective barrier during a subsequent deposition step. With patterned substrates composed of coplanar copper lines and silicon spacers, hydroxamic acids selectively formed monolayers on the metal portions and could undergo a pattern-wise exposure followed by ASD in the first combination of a patternable monolayer with ASD. This material system presents an additional capability compared to traditional ASD approaches that generally reflect a starting patterned surface. Furthermore, this bottoms-up additive approach to lithography may be a viable alternative to subtractive nanoscale feature generation.

A three-dimensional micro-electrode array for in-vitro neuronal interfacing.

OBJECTIVE: In this paper, we report on the development of an easy-to-fabricate three-dimensional Micro-Electrode Array (3D-MEA) specifically designed for brain-on-a-dish applications. APPROACH: The proposed device consists of pillar-shaped gold microelectrodes realized by electroplating directly on top of a standard MEA, making this approach highly versatile and convenient for batch fabrication. Moreover, with this simple technique, it is possible to obtain electrodes with a height of more than 100 µm onto different kind of substrates, ranging from glass to flexible plastic ones. MAIN RESULTS: This novel 3D-MEA structure has been validated with acute brain slices, successfully recording both epileptiform-like discharges (upon the administration of 4-AP), and electrically-evoked neuronal activity. The preliminary validation showed a substantial improvement in the signals amplitude with respect to both commercial and custom planar electrodes thanks to a better coupling offered by the peculiar shape of the three-dimensional electrodes. SIGNIFICANCE: Beside the versatility of the fabrication approach, which allows to obtain 3D MEA devices onto both rigid and flexible substrates, the reported validation showed how the pillar approach can outperform standard planar MEA recordings in terms of signal amplitude. Moreover, thanks to the possibility of obtaining multi-level 3D structures within the same device, the proposed fabrication technique offers an interesting and flexible approach for the development of a new family of electrophysiological tools for 3D in vitro electrophysiology, in particular for acute brain slices and 3D neuronal cultures for brain-on-a-dish applications.

Precise pitch-scaling of carbon nanotube arrays within three-dimensional DNA nanotrenches.

Precise fabrication of semiconducting carbon nanotubes (CNTs) into densely aligned evenly spaced arrays is required for ultrascaled technology nodes. We report the precise scaling of inter-CNT pitch using a supramolecular assembly method called spatially hindered integration of nanotube electronics. Specifically, by using DNA brick crystal-based nanotrenches to align DNA-wrapped CNTs through DNA hybridization, we constructed parallel CNT arrays with a uniform pitch as small as 10.4 nanometers, at an angular deviation <2° and an assembly yield >95%.

Spatial Control of the Self-assembled Block Copolymer Domain Orientation and Alignment on Photopatterned Surfaces.

Polarity-switching photopatternable guidelines can be directly used to both orient and direct the self-assembly of block copolymers. We report the orientation and alignment of poly(styrene-block-4-trimethylsilylstyrene) (PS-b-PTMSS) with a domain periodicity, L0, of 44 nm on thin photopatternable grafting surface treatments (pGSTs) and cross-linkable surface treatments (pXSTs), containing acid-labile 4-tert-butoxystyrene monomer units. The surface treatment was exposed using electron beam lithography to create well-defined linear arrays of neutral and preferential regions. Directed self-assembly (DSA) of PS-b-PTMSS with much lower defectivity was observed on pXST than on pGST guidelines. The study of the effect of film thickness on photoacid diffusion by Fourier transform infrared spectroscopy and near-edge X-ray absorption fine structure spectroscopy suggested slower diffusion in thinner films, potentially enabling production of guidelines with sharper interfaces between the unexposed and exposed lines, and thus, the DSA of PS-b-PTMSS on thinner pXST guidelines resulted in better alignment control.

Surface Initiated Polymer Thin Films for the Area Selective Deposition and Etching of Metal Oxides.

The area selective growth of polymers and their use as inhibiting layers for inorganic film depositions may provide a valuable self-aligned process for fabrication. Polynorbornene (PNB) thin films were grown from surface-bound initiators and show inhibitory properties against the atomic layer deposition (ALD) of ZnO and TiO2. Area selective control of the polymerization was achieved through the synthesis of initiators that incorporate surface-binding ligands, enabling their selective attachment to metal oxide features versus silicon dielectrics, which were then used to initiate surface polymerizations. The subsequent use of these films in an ALD process enabled the area selective deposition (ASD) of up to 39 nm of ZnO. In addition, polymer thickness was found to play a key role, where films that underwent longer polymerization times were more effective at inhibiting higher numbers of ALD cycles. Finally, while the ASD of a TiO2 film was not achieved despite blanket studies showing inhibition, the ALD deposition on polymer regions of a patterned film produced a different quality metal oxide and therefore altered its etch resistance. This property was exploited in the area selective etch of a metal feature. This demonstration of an area selective surface-grown polymer to enable ASD and selective etch has implications for the fabrication of both micro- and nanoscale features and surfaces.

Role of Micromagnetic States on Spin-Orbit Torque-Switching Schemes.

Three-terminal spintronic memory devices based on the controlled manipulation of the proximate magnetization of a magnetic nanoelement using spin-orbit torques (SOTs) have attracted growing interest recently. These devices are nonvolatile, can operate at high speeds with low error rates, and have essentially infinite endurance, making them promising candidates for high-speed cache memory. Typically, the magnetization and spin polarization in these devices are collinear to one another, leading to a finite incubation time associated with the switching process. While switching can also be achieved when the magnetization easy axis and spin polarization are noncollinear, this requires the application of an external magnetic field for deterministic switching. Here, we demonstrate a novel SOT scheme that exploits non-uniform micromagnetic states to achieve deterministic switching when the spin polarization and magnetic moment axis are noncollinear to one another in the absence of external magnetic field. We also explore the use of a highly efficient SOT generator, oxygen-doped tungsten in the three-terminal device geometry, confirming its -50% spin Hall angle. Lastly, we illustrate how this scheme may potentially be useful for nanomagnetic logic applications.

Highly Asymmetric Chiral Domain-Wall Velocities in Y-Shaped Junctions.

Recent developments in spin-orbit torques allow for highly efficient current-driven domain wall (DW) motion in nanowires with perpendicular magnetic anisotropy. Here, we show that chiral DWs can be driven into nonequilibrium states that can persist over tens of nanoseconds in Y-shaped magnetic nanowire junctions that have an input and two symmetric outputs. A single DW that is injected into the input splits and travels at very different velocities in the two output branches until it reaches its steady-state velocity. We find that this is due to the disparity between the fast temporal evolution of the spin current derived spin-orbit torque and a much-slower temporal evolution of the DMI-derived torque. Changing the DW polarity inverts the velocity asymmetry in the two output branches, a property that we use to demonstrate the sorting of domains.

Ensemble-averaged Rabi oscillations in a ferromagnetic CoFeB film.

Rabi oscillations describe the process whereby electromagnetic radiation interacts coherently with spin states in a non-equilibrium interaction. To date, Rabi oscillations have not been studied in one of the most common spin ensembles in nature: spins in ferromagnets. Here, using a combination of femtosecond laser pulses and microwave excitations, we report the classical analogue of Rabi oscillations in ensemble-averaged spins of a ferromagnet. The microwave stimuli are shown to extend the coherence-time resulting in resonant spin amplification. The results we present in a dense magnetic system are qualitatively similar to those reported previously in semiconductors which have five orders of magnitude fewer spins and which require resonant optical excitations to spin-polarize the ensemble. Our study is a step towards connecting concepts used in quantum processing with spin-transport effects in ferromagnets. For example, coherent control may become possible without the complications of driving an electromagnetic field but rather by using spin-polarized currents.

Evidence for Ionic Liquid Gate-Induced Metallization of Vanadium Dioxide Bars over Micron Length Scales.

It has recently been shown that the metal-insulator transition in vanadium dioxide epitaxial films can be suppressed and the material made metallic to low temperatures by ionic liquid gating due to migration of oxygen. The gating is only possible on certain crystal facets where volume channels along the VO2's rutile c-axis intersect the surface. Here, we fabricate bars with the c-axis in plane and oriented parallel to or perpendicular to the length of the bars. We show that only bars with the c-axis perpendicular to the bars, for which the volume channels are accessible from the sides of the bar, can be metallized by ionic liquid gating. Moreover, we find that bars up to at least 0.5 µm wide can be fully gated, demonstrating the possibility of the electric field induced migration of oxygen over very long distances, ∼5 times longer than previously observed.

Parametric Harmonic Generation as a Probe of Unconstrained Spin Magnetization Precession in the Shallow Barrier Limit.

We study the parametric excitation of high orders of magnetization precession in ultrathin films having perpendicular magnetic anisotropy. We observe that for a given driving field amplitude the harmonic generation can be increased by lowering the barrier with the application of an in-plane magnetic field in the manner of the Smit-Beljers effect. In this effect, the magnetic stiffness is reduced not by lowering the magnitude of the magnetic field upon which the spins precess, but rather by effectively releasing the field's "anchoring" point. This results in a shallow energy barrier where the electrons' spin is locally unconstrained. While the observation is unveiled in the form of nonlinear high harmonic generation, we believe that the physics whereby the barrier is suppressed by an external magnetic field may apply to other phenomena associated with ultrathin films. In these cases, such unconstrained motion may serve as a sensitive probe of the torques associated with proximate spin currents. Moreover, our approach may be used as a model system for the study of phase transitions in the field of nonlinear dynamics.

Giant thermal spin-torque-assisted magnetic tunnel junction switching.

Spin-polarized charge currents induce magnetic tunnel junction (MTJ) switching by virtue of spin-transfer torque (STT). Recently, by taking advantage of the spin-dependent thermoelectric properties of magnetic materials, novel means of generating spin currents from temperature gradients, and their associated thermal-spin torques (TSTs), have been proposed, but so far these TSTs have not been large enough to influence MTJ switching. Here we demonstrate significant TSTs in MTJs by generating large temperature gradients across ultrathin MgO tunnel barriers that considerably affect the switching fields of the MTJ. We attribute the origin of the TST to an asymmetry of the tunneling conductance across the zero-bias voltage of the MTJ. Remarkably, we estimate through magneto-Seebeck voltage measurements that the charge currents that would be generated due to the temperature gradient would give rise to STT that is a thousand times too small to account for the changes in switching fields that we observe.

Directed self-assembly of silicon-containing block copolymer thin films.

The directed self-assembly (DSA) of lamella-forming poly(styrene-block-trimethylsilylstyrene) (PS-PTMSS, L0=22 nm) was achieved using a combination of tailored top interfaces and lithographically defined patterned substrates. Chemo- and grapho-epitaxy, using hydrogen silsesquioxane (HSQ) based prepatterns, achieved density multiplications up to 6× and trench space subdivisions up to 7×, respectively. These results establish the compatibility of DSA techniques with a high etch contrast, Si-containing BCP that requires a top coat neutral layer to enable orientation.

Highly efficient in-line magnetic domain wall injector.

We demonstrate a highly efficient and simple scheme for injecting domain walls into magnetic nanowires. The spin transfer torque from nanosecond long, unipolar, current pulses that cross a 90° magnetization boundary together with the fringing magnetic fields inherently prevalent at the boundary, allow for the injection of single or a continual stream of domain walls. Remarkably, the currents needed for this "in-line" domain wall injection scheme are at least one hundred times smaller than conventional methods.

Enabling complex nanoscale pattern customization using directed self-assembly.

Block copolymer directed self-assembly is an attractive method to fabricate highly uniform nanoscale features for various technological applications, but the dense periodicity of block copolymer features limits the complexity of the resulting patterns and their potential utility. Therefore, customizability of nanoscale patterns has been a long-standing goal for using directed self-assembly in device fabrication. Here we show that a hybrid organic/inorganic chemical pattern serves as a guiding pattern for self-assembly as well as a self-aligned mask for pattern customization through cotransfer of aligned block copolymer features and an inorganic prepattern. As informed by a phenomenological model, deliberate process engineering is implemented to maintain global alignment of block copolymer features over arbitrarily shaped, 'masking' features incorporated into the chemical patterns. These hybrid chemical patterns with embedded customization information enable deterministic, complex two-dimensional nanoscale pattern customization through directed self-assembly.

Subnanosecond incubation times for electric-field-induced metallization of a correlated electron oxide.

Strong interactions, or correlations, between the d or f electrons in transition-metal oxides lead to various types of metal-insulator transitions that can be triggered by external parameters such as temperature, pressure, doping, magnetic fields and electric fields. Electric-field-induced metallization of such materials from their insulating states could enable a new class of ultrafast electronic switches and latches. However, significant questions remain about the detailed nature of the switching process. Here, we show, in the canonical metal-to-insulator transition system V2O3, that ultrafast voltage pulses result in its metallization only after an incubation time that ranges from ∼150 ps to many nanoseconds, depending on the electric field strength. We show that these incubation times can be accounted for by purely thermal effects and that intrinsic electronic-switching mechanisms may only be revealed using larger electric fields at even shorter timescales.

Observation of edge transport in the disordered regime of topologically insulating InAs/GaSb quantum wells.

We observe edge transport in the topologically insulating InAs/GaSb system in the disordered regime. Using asymmetric current paths we show that conduction occurs exclusively along the device edge, exhibiting a large Hall signal at zero magnetic fields, while for symmetric current paths, the conductance between the two mesoscopicly separated probes is quantized to 2e2/h. Both quantized and self-averaged transport show resilience to magnetic fields, and are temperature independent for temperatures between 20 mK and 1 K.

Programmable nanoparticle ensembles via high-throughput directed self-assembly.

We present a simple and facile strategy for the directed self-assembly of nanoparticles into complex geometries using a minimal set of post guiding features patterned on a substrate. This understanding is based on extensive studies of nanoparticle self-assembly into linear, dense-packed, circular, and star-shaped ensembles when coated onto patterned substrates of predefined post arrays. We determined the conditions under which nanoparticles assemble and "connect" two adjacent post features, thereby forming the desired shapes. We demonstrate that with rational design of the post patterns to enforce the required pairwise interactions with posts, we can create arbitrary arrangements of nanoparticles-for example, to write "IBM" in a deterministic manner. This demonstration of programmable, high-throughput directed self-assembly of nanoparticles shows an alternative route to generate functional nanoparticle assemblies.

Pattern placement accuracy in block copolymer directed self-assembly based on chemical epitaxy.

The realization of viable designs for circuit patterns using the dense features formed by block copolymer directed self-assembly (DSA) will require a precise and quantitative understanding of self-assembled feature registration to guiding templates or chemical prepatterns. Here we report measurements of DSA placement error for lamellar block copolymer domains indexed to specific lines in the surface chemical prepattern for spatial frequency tripling and quadrupling. These measurements are made possible by the use of an inorganic domain-selective prepattern material that may be imaged upon polymer removal after DSA and a prepattern design incorporating a single feature serving as an in situ registration mark that is identifiable by pattern symmetry in both the prepattern and resulting self-assembled pattern. The results indicate that DSA placement error is correlated with average prepattern line width as well as prepattern pitch uniformity. Finally, the magnitude of DSA placement error anticipated for a uniform, optimized prepattern is estimated.

In situ doping of catalyst-free InAs nanowires.

We report on in situ doping of InAs nanowires grown by metal-organic vapor-phase epitaxy without any catalyst particles. The effects of various dopant precursors (Si(2)H(6), H(2)S, DETe, CBr(4)) on the nanowire morphology and the axial and radial growth rates are investigated to select dopants that enable control of the conductivity in a broad range and that concomitantly lead to favorable nanowire growth. In addition, the resistivity of individual wires was measured for different gas-phase concentrations of the dopants selected, and the doping density and mobility were extracted. We find that by using Si(2)H(6) axially and radially uniform doping densities up to 7 × 10(19) cm(-3) can be obtained without affecting the morphology or growth rates. For sulfur-doped InAs nanowires, we find that the distribution coefficient depends on the growth conditions, making S doping more difficult to control than Si doping. Moreover, above a critical sulfur gas-phase concentration, compensation takes place, limiting the maximum doping level to 2 × 10(19) cm(-3). Finally, we extract the specific contact resistivity as a function of doping concentration for Ti and Ni contacts.

High-gradient nanomagnets on cantilevers for sensitive detection of nuclear magnetic resonance.

Detection of magnetic resonance as a force between a magnetic tip and nuclear spins has previously been shown to enable sub-10 nm resolution 1H imaging. Maximizing the spin force in such a magnetic resonance force microscopy (MRFM) experiment demands a high field gradient. In order to study a wide range of samples, it is equally desirable to locate the magnetic tip on the force sensor. Here we report the development of attonewton-sensitivity cantilevers with high-gradient cobalt nanomagnet tips. The damage layer thickness and saturation magnetization of the magnetic material were characterized by X-ray photoelectron spectroscopy and superconducting quantum interference device magnetometry. The coercive field and saturation magnetization of an individual tip were quantified in situ using frequency-shift cantilever magnetometry. Measurements of cantilever dissipation versus magnetic field and tip­sample separation were conducted. MRFM signals from protons in a polystyrene film were studied versus rf irradiation frequency and tip­sample separation, and from this data the tip field and tip-field gradient were evaluated. Magnetic tip performance was assessed by numerically modeling the frequency dependence of the magnetic resonance signal. We observed a tip-field gradient ∂B(z)(tip)/∂z estimated to be between 4.4 and 5.4 MT m(­1), which is comparable to the gradient used in recent 4 nm resolution 1H imaging experiments and larger by nearly an order of magnitude than the gradient achieved in prior magnet-on-cantilever MRFM experiments.