Cilia metasurfaces for electronically programmable microfluidic manipulation.

Cilial pumping is a powerful strategy used by biological organisms to control and manipulate fluids at the microscale. However, despite numerous recent advances in optically, magnetically and electrically driven actuation, development of an engineered cilial platform with the potential for applications has remained difficult to realize1-6. Here we report on active metasurfaces of electronically actuated artificial cilia that can create arbitrary flow patterns in liquids near a surface. We first create voltage-actuated cilia that generate non-reciprocal motions to drive surface flows at tens of microns per second at actuation voltages of 1 volt. We then show that a cilia unit cell can locally create a range of elemental flow geometries. By combining these unit cells, we create an active cilia metasurface that can generate and switch between any desired surface flow pattern. Finally, we integrate the cilia with a light-powered complementary metal-oxide-semiconductor (CMOS) clock circuit to demonstrate wireless operation. As a proof of concept, we use this circuit to output voltage pulses with various phase delays to demonstrate improved pumping efficiency using metachronal waves. These powerful results, demonstrated experimentally and confirmed using theoretical computations, illustrate a pathway towards fine-scale microfluidic manipulation, with applications from microfluidic pumping to microrobotic locomotion.

Electronically integrated, mass-manufactured, microscopic robots.

Fifty years of Moore's law scaling in microelectronics have brought remarkable opportunities for the rapidly evolving field of microscopic robotics1-5. Electronic, magnetic and optical systems now offer an unprecedented combination of complexity, small size and low cost6,7, and could be readily appropriated for robots that are smaller than the resolution limit of human vision (less than a hundred micrometres)8-11. However, a major roadblock exists: there is no micrometre-scale actuator system that seamlessly integrates with semiconductor processing and responds to standard electronic control signals. Here we overcome this barrier by developing a new class of voltage-controllable electrochemical actuators that operate at low voltages (200 microvolts), low power (10 nanowatts) and are completely compatible with silicon processing. To demonstrate their potential, we develop lithographic fabrication-and-release protocols to prototype sub-hundred-micrometre walking robots. Every step in this process is performed in parallel, allowing us to produce over one million robots per four-inch wafer. These results are an important advance towards mass-manufactured, silicon-based, functional robots that are too small to be resolved by the naked eye.

Bifurcation instructed design of multistate machines.

We propose a design paradigm for multistate machines where transitions from one state to another are organized by bifurcations of multiple equilibria of the energy landscape describing the collective interactions of the machine components. This design paradigm is attractive since, near bifurcations, small variations in a few control parameters can result in large changes to the system's state providing an emergent lever mechanism. Further, the topological configuration of transitions between states near such bifurcations ensures robust operation, making the machine less sensitive to fabrication errors and noise. To design such machines, we develop and implement a new efficient algorithm that searches for interactions between the machine components that give rise to energy landscapes with these bifurcation structures. We demonstrate a proof of concept for this approach by designing magnetoelastic machines whose motions are primarily guided by their magnetic energy landscapes and show that by operating near bifurcations we can achieve multiple transition pathways between states. This proof of concept demonstration illustrates the power of this approach, which could be especially useful for soft robotics and at the microscale where typical macroscale designs are difficult to implement.

Gas-phase microactuation using kinetically controlled surface states of ultrathin catalytic sheets.

Biological systems convert chemical energy into mechanical work by using protein catalysts that assume kinetically controlled conformational states. Synthetic chemomechanical systems using chemical catalysis have been reported, but they are slow, require high temperatures to operate, or indirectly perform work by harnessing reaction products in liquids (e.g., heat or protons). Here, we introduce a bioinspired chemical strategy for gas-phase chemomechanical transduction that sequences the elementary steps of catalytic reactions on ultrathin (<10 nm) platinum sheets to generate surface stresses that directly drive microactuation (bending radii of 700 nm) at ambient conditions (T = 20 °C; Ptotal = 1 atm). When fueled by hydrogen gas and either oxygen or ozone gas, we show how kinetically controlled surface states of the catalyst can be exploited to achieve fast actuation (600 ms/cycle) at 20 °C. We also show that the approach can integrate photochemically controlled reactions and can be used to drive the reconfiguration of microhinges and complex origami- and kirigami-based microstructures.

Real-time vibrations of a carbon nanotube.

The field of miniature mechanical oscillators is rapidly evolving, with emerging applications including signal processing, biological detection1 and fundamental tests of quantum mechanics2. As the dimensions of a mechanical oscillator shrink to the molecular scale, such as in a carbon nanotube resonator3-7, their vibrations become increasingly coupled and strongly interacting8,9 until even weak thermal fluctuations could make the oscillator nonlinear10-13. The mechanics at this scale possesses rich dynamics, unexplored because an efficient way of detecting the motion in real time is lacking. Here we directly measure the thermal vibrations of a carbon nanotube in real time using a high-finesse micrometre-scale silicon nitride optical cavity as a sensitive photonic microscope. With the high displacement sensitivity of 700 fm Hz-1/2 and the fine time resolution of this technique, we were able to discover a realm of dynamics undetected by previous time-averaged measurements and a room-temperature coherence that is nearly three orders of magnitude longer than previously reported. We find that the discrepancy in the coherence stems from long-time non-equilibrium dynamics, analogous to the Fermi-Pasta-Ulam-Tsingou recurrence seen in nonlinear systems14. Our data unveil the emergence of a weakly chaotic mechanical breather15, in which vibrational energy is recurrently shared among several resonance modes-dynamics that we are able to reproduce using a simple numerical model. These experiments open up the study of nonlinear mechanical systems in the Brownian limit (that is, when a system is driven solely by thermal fluctuations) and present an integrated, sensitive, high-bandwidth nanophotonic interface for carbon nanotube resonators.

Nanocalorimetry using microscopic optical wireless integrated circuits.

We present in situ calorimetry, thermal conductivity, and thermal diffusivity measurements of materials using temperature-sensing optical wireless integrated circuits (OWiCs). These microscopic and untethered optical sensors eliminate input wires and reduce parasitic effects. Each OWiC has a mass of ∼100 ng, a 100-µm-scale footprint, and a thermal response time of microseconds. We demonstrate that they can measure the thermal properties of nearly any material, from aerogels to metals, on samples as small as 100 ng and over thermal diffusivities covering four orders of magnitude. They also function over a broad temperature range, and we present proof-of-concept measurements of the thermodynamic phase transitions in both liquid crystal 5CB and gadolinium.

Microscopic sensors using optical wireless integrated circuits.

We present a platform for parallel production of standalone, untethered electronic sensors that are truly microscopic, i.e., smaller than the resolution of the naked eye. This platform heterogeneously integrates silicon electronics and inorganic microlight emitting diodes (LEDs) into a 100-µm-scale package that is powered by and communicates with light. The devices are fabricated, packaged, and released in parallel using photolithographic techniques, resulting in ∼10,000 individual sensors per square inch. To illustrate their use, we show proof-of-concept measurements recording voltage, temperature, pressure, and conductivity in a variety of environments.

Programming interactions in magnetic handshake materials.

The ability to rapidly manufacture building blocks with specific binding interactions is a key aspect of programmable assembly. Recent developments in DNA nanotechnology and colloidal particle synthesis have significantly advanced our ability to create particle sets with programmable interactions, based on DNA or shape complementarity. The increasing miniaturization underlying magnetic storage offers a new path for engineering programmable components for self assembly, by printing magnetic dipole patterns on substrates using nanotechnology. How to efficiently design dipole patterns for programmable assembly remains an open question as the design space is combinatorially large. Here, we present design rules for programming these magnetic interactions. By optimizing the structure of the dipole pattern, we demonstrate that the number of independent building blocks scales super linearly with the number of printed domains. We test these design rules using computational simulations of self assembled blocks, and experimental realizations of the blocks at the mm scale, demonstrating that the designed blocks give high yield assembly. In addition, our design rules indicate that with current printing technology, micron sized magnetic panels could easily achieve hundreds of different building blocks.

Magnetic handshake materials as a scale-invariant platform for programmed self-assembly.

Programmable self-assembly of smart, digital, and structurally complex materials from simple components at size scales from the macro to the nano remains a long-standing goal of material science. Here, we introduce a platform based on magnetic encoding of information to drive programmable self-assembly that works across length scales. Our building blocks consist of panels with different patterns of magnetic dipoles that are capable of specific binding. Because the ratios of the different panel-binding energies are scale-invariant, this approach can, in principle, be applied down to the nanometer scale. Using a centimeter-sized version of these panels, we demonstrate 3 canonical hallmarks of assembly: controlled polymerization of individual building blocks; assembly of 1-dimensional strands made of panels connected by elastic backbones into secondary structures; and hierarchical assembly of 2-dimensional nets into 3-dimensional objects. We envision that magnetic encoding of assembly instructions into primary structures of panels, strands, and nets will lead to the formation of secondary and even tertiary structures that transmit information, act as mechanical elements, or function as machines on scales ranging from the nano to the macro.

Accurate Measurement of the Gap of Graphene/h-BN Moiré Superlattice through Photocurrent Spectroscopy.

Monolayer graphene aligned with hexagonal boron nitride (h-BN) develops a gap at the charge neutrality point (CNP). This gap has previously been extensively studied by electrical transport through thermal activation measurements. Here, we report the determination of the gap size at the CNP of graphene/h-BN superlattice through photocurrent spectroscopy study. We demonstrate two distinct measurement approaches to extract the gap size. A maximum of ∼14 meV gap is observed for devices with a twist angle of less than 1°. This value is significantly smaller than that obtained from thermal activation measurements, yet larger than the theoretically predicted single-particle gap. Our results suggest that lattice relaxation and moderate electron-electron interaction effects may enhance the CNP gap in graphene/h-BN superlattice.

Graphene kirigami.

For centuries, practitioners of origami ('ori', fold; 'kami', paper) and kirigami ('kiru', cut) have fashioned sheets of paper into beautiful and complex three-dimensional structures. Both techniques are scalable, and scientists and engineers are adapting them to different two-dimensional starting materials to create structures from the macro- to the microscale. Here we show that graphene is well suited for kirigami, allowing us to build robust microscale structures with tunable mechanical properties. The material parameter crucial for kirigami is the Föppl-von Kármán number γ: an indication of the ratio between in-plane stiffness and out-of-plane bending stiffness, with high numbers corresponding to membranes that more easily bend and crumple than they stretch and shear. To determine γ, we measure the bending stiffness of graphene monolayers that are 10-100 micrometres in size and obtain a value that is thousands of times higher than the predicted atomic-scale bending stiffness. Interferometric imaging attributes this finding to ripples in the membrane that stiffen the graphene sheets considerably, to the extent that γ is comparable to that of a standard piece of paper. We may therefore apply ideas from kirigami to graphene sheets to build mechanical metamaterials such as stretchable electrodes, springs, and hinges. These results establish graphene kirigami as a simple yet powerful and customizable approach for fashioning one-atom-thick graphene sheets into resilient and movable parts with microscale dimensions.

Graphene-based bimorphs for micron-sized, autonomous origami machines.

Origami-inspired fabrication presents an attractive platform for miniaturizing machines: thinner layers of folding material lead to smaller devices, provided that key functional aspects, such as conductivity, stiffness, and flexibility, are persevered. Here, we show origami fabrication at its ultimate limit by using 2D atomic membranes as a folding material. As a prototype, we bond graphene sheets to nanometer-thick layers of glass to make ultrathin bimorph actuators that bend to micrometer radii of curvature in response to small strain differentials. These strains are two orders of magnitude lower than the fracture threshold for the device, thus maintaining conductivity across the structure. By patterning 2-[Formula: see text]m-thick rigid panels on top of bimorphs, we localize bending to the unpatterned regions to produce folds. Although the graphene bimorphs are only nanometers thick, they can lift these panels, the weight equivalent of a 500-nm-thick silicon chip. Using panels and bimorphs, we can scale down existing origami patterns to produce a wide range of machines. These machines change shape in fractions of a second when crossing a tunable pH threshold, showing that they sense their environments, respond, and perform useful functions on time and length scales comparable with microscale biological organisms. With the incorporation of electronic, photonic, and chemical payloads, these basic elements will become a powerful platform for robotics at the micrometer scale.

Bidirectional Self-Folding with Atomic Layer Deposition Nanofilms for Microscale Origami.

Origami design principles are scale invariant and enable direct miniaturization of origami structures provided the sheets used for folding have equal thickness to length ratios. Recently, seminal steps have been taken to fabricate microscale origami using unidirectionally actuated sheets with nanoscale thickness. Here, we extend the full power of origami-inspired fabrication to nanoscale sheets by engineering bidirectional folding with 4 nm thick atomic layer deposition (ALD) SiNx-SiO2 bilayer films. Strain differentials within these bilayers result in bending, producing microscopic radii of curvature. We lithographically pattern these bilayers and localize the bending using rigid panels to fabricate a variety of complex micro-origami devices. Upon release, these devices self-fold according to prescribed patterns. Our approach combines planar semiconductor microfabrication methods with computerized origami design, making it easy to fabricate and deploy such microstructures en masse. These devices represent an important step forward in the fabrication and assembly of deployable micromechanical systems that can interact with and manipulate micro- and nanoscale environments.

Fabrication of Injectable Micro-Scale Opto-Electronically Transduced Electrodes (MOTEs) for Physiological Monitoring.

In vivo, chronic neural recording is critical to understand the nervous system, while a tetherless, miniaturized recording unit can render such recording minimally invasive. We present a tetherless, injectable micro-scale opto-electronically transduced electrode (MOTE) that is ~60µm × 30µm × 330µm, the smallest neural recording unit to date. The MOTE consists of an AlGaAs micro-scale light emitting diode (µLED) heterogeneously integrated on top of conventional 180nm complementary metal-oxide-semiconductor (CMOS) circuit. The MOTE combines the merits of optics (AlGaAs µLED for power and data uplink), and of electronics (CMOS for signal amplification and encoding). The optical powering and communication enable the extreme scaling while the electrical circuits provide a high temporal resolution (<100µs). This paper elaborates on the heterogeneous integration in MOTEs, a topic that has been touted without much demonstration on feasibility or scalability. Based on photolithography, we demonstrate how to build heterogenous systems that are scalable as well as biologically stable - the MOTEs can function in saline water for more than six months, and in a mouse brain for two months (and counting). We also present handling/insertion techniques for users (i.e. biologists) to deploy MOTEs with little or no extra training.

Capillary Origami with Atomically Thin Membranes.

Small-scale optical and mechanical components and machines require control over three-dimensional structure at the microscale. Inspired by the analogy between paper and two-dimensional materials, origami-style folding of atomically thin materials offers a promising approach for making microscale structures from the thinnest possible sheets. In this Letter, we show that a monolayer of molybdenum disulfide (MoS2) can be folded into three-dimensional shapes by a technique called capillary origami, in which the surface tension of a droplet drives the folding of a thin sheet. We define shape nets by patterning rigid metal panels connected by MoS2 hinges, allowing us to fold micron-scale polyhedrons. Finally, we demonstrate that these shapes can be folded in parallel without the use of micropipettes or microfluidics by means of a microemulsion of droplets that dissolves into the bulk solution to drive folding. These results demonstrate controllable folding of the thinnest possible materials using capillary origami and indicate a route forward for design and parallel fabrication of more complex three-dimensional micron-scale structures and machines.

Measuring and Manipulating the Adhesion of Graphene.

We present a technique to precisely measure the surface energies between two-dimensional materials and substrates that is simple to implement and allows exploration of spatial and chemical control of adhesion at the nanoscale. As an example, we characterize the delamination of single-layer graphene from monolayers of pyrene tethered to glass in water and maximize the work of separation between these surfaces by varying the density of pyrene groups in the monolayer. Control of this energy scale enables high-fidelity graphene-transfer protocols that can resist failure under sonication. Additionally, we find that the work required for graphene peeling and readhesion exhibits a dramatic rate-independent hysteresis, differing by a factor of 100. This work establishes a rational means to control the adhesion of 2D materials and enables a systematic approach to engineer stimuli-responsive adhesives and mechanical technologies at the nanoscale.

Grains and grain boundaries in single-layer graphene atomic patchwork quilts.

The properties of polycrystalline materials are often dominated by the size of their grains and by the atomic structure of their grain boundaries. These effects should be especially pronounced in two-dimensional materials, where even a line defect can divide and disrupt a crystal. These issues take on practical significance in graphene, which is a hexagonal, two-dimensional crystal of carbon atoms. Single-atom-thick graphene sheets can now be produced by chemical vapour deposition on scales of up to metres, making their polycrystallinity almost unavoidable. Theoretically, graphene grain boundaries are predicted to have distinct electronic, magnetic, chemical and mechanical properties that strongly depend on their atomic arrangement. Yet because of the five-order-of-magnitude size difference between grains and the atoms at grain boundaries, few experiments have fully explored the graphene grain structure. Here we use a combination of old and new transmission electron microscopy techniques to bridge these length scales. Using atomic-resolution imaging, we determine the location and identity of every atom at a grain boundary and find that different grains stitch together predominantly through pentagon-heptagon pairs. Rather than individually imaging the several billion atoms in each grain, we use diffraction-filtered imaging to rapidly map the location, orientation and shape of several hundred grains and boundaries, where only a handful have been previously reported. The resulting images reveal an unexpectedly small and intricate patchwork of grains connected by tilt boundaries. By correlating grain imaging with scanning probe and transport measurements, we show that these grain boundaries severely weaken the mechanical strength of graphene membranes but do not as drastically alter their electrical properties. These techniques open a new window for studies on the structure, properties and control of grains and grain boundaries in graphene and other two-dimensional materials.

Strain solitons and topological defects in bilayer graphene.

Bilayer graphene has been a subject of intense study in recent years. The interlayer registry between the layers can have dramatic effects on the electronic properties: for example, in the presence of a perpendicular electric field, a band gap appears in the electronic spectrum of so-called Bernal-stacked graphene [Oostinga JB, et al. (2007) Nature Materials 7:151-157]. This band gap is intimately tied to a structural spontaneous symmetry breaking in bilayer graphene, where one of the graphene layers shifts by an atomic spacing with respect to the other. This shift can happen in multiple directions, resulting in multiple stacking domains with soliton-like structural boundaries between them. Theorists have recently proposed that novel electronic states exist at these boundaries [Vaezi A, et al. (2013) arXiv:1301.1690; Zhang F, et al. (2013) arXiv:1301.4205], but very little is known about their structural properties. Here we use electron microscopy to measure with nanoscale and atomic resolution the widths, motion, and topological structure of soliton boundaries and related topological defects in bilayer graphene. We find that each soliton consists of an atomic-scale registry shift between the two graphene layers occurring over 6-11 nm. We infer the minimal energy barrier to interlayer translation and observe soliton motion during in situ heating above 1,000 °C. The abundance of these structures across a variety of samples, as well as their unusual properties, suggests that they will have substantial effects on the electronic and mechanical properties of bilayer graphene.

Determination of the Thermal Noise Limit of Graphene Biotransistors.

To determine the thermal noise limit of graphene biotransistors, we have measured the complex impedance between the basal plane of single-layer graphene and an aqueous electrolyte. The impedance is dominated by an imaginary component but has a finite real component. Invoking the fluctuation-dissipation theorem, we determine the power spectral density of thermally driven voltage fluctuations at the graphene/electrolyte interface. The fluctuations have 1/f(p) dependence, with p = 0.75-0.85, and the magnitude of fluctuations scales inversely with area. Our results explain noise spectra previously measured in liquid-gated suspended graphene devices and provide realistic targets for future device performance.

Magnetically Actuated Single-Walled Carbon Nanotubes.

We couple magnetic tweezer techniques with standard lithography methods to make magnetically actuated single-walled carbon nanotube (SWNT) devices. Parallel arrays of 4-10 µm-long SWNT cantilevers are patterned with one end anchored to the substrate and the other end attached to a micron-scale iron magnetic tag that is free to move in solution. Thermal fluctuations of this tag provide a direct measurement of the spring constant of the SWNT cantilevers, yielding values of 10(-7)-10(-8) N/m. This tag is also a handle for applying forces and torques using externally applied magnetic field gradients. These techniques provide a platform on which interaction forces between SWNTs and other objects such as biomolecules and cells can be measured in situ.