Tunable phonon-cavity coupling in graphene membranes.

A major achievement of the past decade has been the realization of macroscopic quantum systems by exploiting the interactions between optical cavities and mechanical resonators. In these systems, phonons are coherently annihilated or created in exchange for photons. Similar phenomena have recently been observed through phonon-cavity coupling-energy exchange between the modes of a single system mediated by intrinsic material nonlinearity. This has so far been demonstrated primarily for bulk crystalline, high-quality-factor (Q > 10(5)) mechanical systems operated at cryogenic temperatures. Here, we propose graphene as an ideal candidate for the study of such nonlinear mechanics. The large elastic modulus of this material and capability for spatial symmetry breaking via electrostatic forces is expected to generate a wealth of nonlinear phenomena, including tunable intermodal coupling. We have fabricated circular graphene membranes and report strong phonon-cavity effects at room temperature, despite the modest Q factor (∼100) of this system. We observe both amplification into parametric instability (mechanical lasing) and the cooling of Brownian motion in the fundamental mode through excitation of cavity sidebands. Furthermore, we characterize the quenching of these parametric effects at large vibrational amplitudes, offering a window on the all-mechanical analogue of cavity optomechanics, where the observation of such effects has proven elusive.

Transfer printing of CVD graphene FETs on patterned substrates.

We describe a simple and scalable method for the transfer of CVD graphene for the fabrication of field effect transistors. This is a dry process that uses a modified RCA-cleaning step to improve the surface quality. In contrast to conventional fabrication routes where lithographic steps are performed after the transfer, here graphene is transferred to a pre-patterned substrate. The resulting FET devices display nearly zero Dirac voltage, and the contact resistance between the graphene and metal contacts is on the order of 910 ± 340 Ω µm. This approach enables formation of conducting graphene channel lengths up to one millimeter. The resist-free transfer process provides a clean graphene surface that is promising for use in high sensitivity graphene FET biosensors.

Detection of DNA and poly-l-lysine using CVD graphene-channel FET biosensors.

A graphene channel field-effect biosensor is demonstrated for detecting the binding of double-stranded DNA and poly-l-lysine. Sensors consist of chemical vapor deposition graphene transferred using a clean, etchant-free transfer method. The presence of DNA and poly-l-lysine are detected by the conductance change of the graphene transistor. A readily measured shift in the Dirac voltage (the voltage at which the graphene's resistance peaks) is observed after the graphene channel is exposed to solutions containing DNA or poly-l-lysine. The 'Dirac voltage shift' is attributed to the binding/unbinding of charged molecules on the graphene surface. The polarity of the response changes to positive direction with poly-l-lysine and negative direction with DNA. This response results in detection limits of 8 pM for 48.5 kbp DNA and 11 pM for poly-l-lysine. The biosensors are easy to fabricate, reusable and are promising as sensors of a wide variety of charged biomolecules.

Stamp transferred suspended graphene mechanical resonators for radio frequency electrical readout.

We present a simple micromanipulation technique to transfer suspended graphene flakes onto any substrate and to assemble them with small localized gates into mechanical resonators. The mechanical motion of the graphene is detected using an electrical, radio frequency (RF) reflection readout scheme where the time-varying graphene capacitor reflects a RF carrier at f = 5-6 GHz producing modulation sidebands at f ± f(m). A mechanical resonance frequency up to f(m) = 178 MHz is demonstrated. We find both hardening/softening Duffing effects on different samples and obtain a critical amplitude of ~40 pm for the onset of nonlinearity in graphene mechanical resonators. Measurements of the quality factor of the mechanical resonance as a function of dc bias voltage V(dc) indicates that dissipation due to motion-induced displacement currents in graphene electrode is important at high frequencies and large V(dc).

High-Q nanomechanics via destructive interference of elastic waves.

Mechanical dissipation poses a ubiquitous challenge to the performance of nanomechanical devices. Here we analyze the support-induced dissipation of high-stress nanomechanical resonators. We develop a model for this loss mechanism and test it on Si(3)N(4) membranes with circular and square geometries. The measured Q values of different harmonics present a nonmonotonic behavior which is successfully explained. For azimuthal harmonics of the circular geometry we predict that destructive interference of the radiated waves leads to an exponential suppression of the clamping loss in the harmonic index. Our model can also be applied to graphene drums under high tension.

Real-time synchronous imaging of electromechanical resonator mode and equilibrium profiles.

Interferometric imaging of normal mode dynamics in electromechanical resonators, oscillating in the rf regime, is demonstrated by synchronous imaging with a pulsed nanosecond laser. Profiles of mechanical modes in suspended thin film structures and their equilibrium profiles are measured through all-optical Fabry-Perot reflectance fits to the temporal traces. As a proof of principle, the mode patterns of a microdrum silicon resonator are visualized, and the extracted vibration modes and equilibrium profile show good agreement with numerical estimations.

Stress and silicon nitride: a crack in the universal dissipation of glasses.

High-stress silicon nitride microresonators exhibit a remarkable room temperature Q factor that even exceeds that of single crystal silicon. A study of the temperature dependent variation of the Q of a 255 micromx255 micromx30 nm thick high-stress Si3N4 membrane reveals that the dissipation Q-1 decreases with lower temperatures and is approximately 3 orders of magnitude smaller than the universal behavior. Stress-relieved cantilevers fabricated from the same material show a Q that is more consistent with typical disordered materials. e-beam and x-ray studies of the nitride film's structure reveal characteristics consistent with a disordered state. Thus, it is shown that stress alters the Q-1, violating the universality of dissipation in disordered materials in a self-supporting structure.

Conformation, length, and speed measurements of electrodynamically stretched DNA in nanochannels.

A method is presented to rapidly and precisely measure the conformation, length, speed, and fluorescence intensity of single DNA molecules constrained by a nanochannel. DNA molecules were driven electrophoretically from a nanoslit into a nanochannel to confine and dynamically elongate them beyond their equilibrium length for repeated detection via laser-induced fluorescence spectroscopy. A single-molecule analysis algorithm was developed to analytically model bursts of fluorescence and determine the folding conformation of each stretched molecule. This technique achieved a molecular length resolution of 114 nm and an analysis time of around 20 ms per molecule, which enabled the sensitive investigation of several aspects of the physical behavior of DNA in a nanochannel. lambda-bacteriophage DNA was used to study the dependence of stretching on the applied device bias, the effect of conformation on speed, and the amount of DNA fragmentation in the device. A mixture of lambda-bacteriophage with the fragments of its own HindIII digest, a standard DNA ladder, was sized by length as well as by fluorescence intensity, which also allowed the characterization of DNA speed in a nanochannel as a function of length over two and a half orders of magnitude.

Selective vibrational detachment of microspheres using optically excited in-plane motion of nanomechanical beams.

Optical excitation plays an important role in the actuation of higher flexural and torsional modes of nanoelectromechanical oscillators. We show that optical fields are efficient for excitation, direct control, and measurement of in-plane motion of cantilever-type nanomechanical oscillators. As a model system, 200- and 250-nm-thick single-crystal silicon cantilevers with dissimilar lengths and widths ranging from 6 to 12 microm and 500 nm to 1 microm, respectively, were fabricated using surface micromachining and dynamically analyzed using optical excitation and interferrometric detection. Three-dimensional finite element analysis incorporating shear, rotational inertia, cross-sectional deplanation, and nonideal boundary conditions due to the structural undercut describe the dynamics of the nanomechanical structures adequately. The quality factor of a particular in-plane harmonic was consistently higher than the transverse mode. The increased dissipation of the out-of-plane mode was attributed to material and acoustic loss mechanisms. The in-plane mode was used to demonstrate vibrational detachment of submicrometer polystyrene spheres on the oscillator surface. In contrast, the out-of-plane motion, even in the strong nonlinear impact regime, was insufficient for the removal of bound polystyrene spheres. Our results suggest that optical excitation of in-plane mechanical modes provide a unique mechanism for controlled removal of particles bound on the surface of nanomechanical oscillators.

Electrospun light-emitting nanofibers.

We have electrospun light-emitting nanofibers from ruthenium(II) tris(bipyridine)/polyethylene oxide mixtures. The electroluminescent fibers were deposited on gold interdigitated electrodes and lit in a nitrogen atmosphere. The fibers showed light emission at low operating voltages (3-4 V), with turn-on voltages approaching the band gap limit of the organic semiconductor. Because of the fiber size, emission from electrospun light-emitting nanofibers is confined to nanoscale dimensions, an attractive feature for sensing applications and lab-on-a-chip integration where highly localized excitation of molecules is required.

Nanofluidic structures for single biomolecule fluorescent detection.

Fluid-filled nanofabricated cavities can be used to increase the spatial resolution of single molecule confocal microscopy based techniques by creating smaller and more uniformly illuminated probe volumes. Such structures may also be used to temporarily stretch single macromolecules, permitting the resolution of molecular details that would otherwise be beyond the capabilities of a diffraction limited system.

Individually resolved DNA molecules stretched and embedded in electrospun polymer nanofibers.

We have used the flow characteristics of an electrospinning jet to elongate and fix DNA molecules. We embedded and observed fluorescently labeled lambda bacteriophage DNA molecules in polyethylene oxide nanofibers. The embedded DNA molecules were imaged using fluorescence microscopy and found to be stretched to lengths approaching the full dyed contour length.

Optically driven resonance of nanoscale flexural oscillators in liquid.

We demonstrate the operation of radio frequency nanoscale flexural resonators in air and liquid. Doubly clamped string, as well as singly clamped cantilever resonators, with nanoscale cross-sectional dimensions and resonant frequencies as high as 145 MHz are driven in air as well as liquid with an amplitude modulated laser. We show that this laser drive technique can impart sufficient energy to a nanoscale resonator to overcome the strong viscous damping present in these media, resulting in a mechanical resonance that can be measured by optical interference techniques. Resonance in air, isopropyl alcohol, acetone, water, and phosphate-buffered saline is demonstrated for devices having cross-sectional dimensions close to 100 nm. For operation in air, quality factors as high as 400 at 145 MHz are demonstrated. In liquid, quality factors ranging from 3 to 10 and frequencies ranging from 20 to 100 MHz are observed. These devices, and an all-optical actuation and detection system, may provide insight into the physics of the interaction of nanoscale mechanical structures with their environments, greatly extending the viscosity range over which such small flexural resonant devices can be operated.

Conformational analysis of single DNA molecules undergoing entropically induced motion in nanochannels.

We have used the interface between a nanochannel and a microchannel as a tool for applying controlled forces on a DNA molecule. A molecule, with a radius of gyration larger than the nanochannel width, that straddles such an interface is subject to an essentially constant entropic force, which can be balanced against other forces such as the electrophoretic force from an applied electric field. By controlling the applied field we can position the molecule as desired and observe the conformation of the molecule as it stretches, relaxes, and recoils from the nanochannel. We quantify and present models for the molecular motion in response to the entropic, electrophoretic, and frictional forces acting on it. By determining the magnitude of the drag coefficients for DNA molecules in the nanostructure, we are able to estimate the confinement-induced recoil force. Finally, we demonstrate that we can use a controlled applied field and the entropic interfacial forces to unfold molecules, which can then be manipulated and positioned in their simple extended morphology.

Zero mode waveguides for single-molecule spectroscopy on lipid membranes.

Zero mode waveguides (ZMWs), subwavelength optical nanostructures with dimensions ranging from 50 to 200 nm, have been used to study systems involving ligand-receptor interactions. We show that under proper conditions, lipid membranes will invaginate into the nanostructures, which confine optical excitation to subattoliter volumes. Fluorescence correlation spectroscopy (FCS) was used to characterize the diffusion of fluorescently tagged lipids in liquid-disordered phase 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and gel phase 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) membranes incubated on the nanostructured surface. In contrast to the POPC, DSPC membranes did not appear to enter the structures, suggesting that invagination is dependent on membrane rigidity. Although correlation curves obtained from POPC membranes conformed to previously derived models for diffusion in the evanescent field within the nanostructure, the diffusion constants obtained were systematically lower than expected. The validity of the one-dimensional diffusion model for membrane diffusion is discussed and it is concluded that the erroneous diffusion constants are a result of nontrivial membrane conformation within the ZMWs. Additionally, FCS was used to characterize the fraction of fluorescently labeled tetanus toxin C fragment bound to a ganglioside-populated POPC membrane within the ZMWs. This allowed the determination of the toxin's equilibrium binding constant at a concentration of 500 nM; higher than possible with diffraction-limited FCS. To our knowledge, the results presented here are the first reported for supported lipid bilayers in nanostructured devices. Furthermore, they open the possibility of studying membrane imbedded receptors and proteins at physiological concentrations with single-molecule resolution.

A polymeric microchip with integrated tips and in situ polymerized monolith for electrospray mass spectrometry.

We describe the integration of a cyclo-olefin polymer based microchip with a sheathless capillary tip for electrospray ionization-mass spectrometry (ESI-MS). The microchip was fabricated by hot embossing and thermal bonding. Its design includes a side channel for adjusting the composition of the electrospray solution so that analytes in 100% water can be analyzed. The fused silica capillaries, used for sample introduction, and the electrospray tips for MS coupling were directly inserted into the microchannel before thermal bonding of the device. A microfabricated on-chip gold microelectrode was used to apply the electrospray voltage. Annealing the device after thermal bonding increased the pressure resistance of the microchip. The cross section of the microchannel was imaged by scanning electron microscopy to estimate the effects of the annealing step. The relationship between the applied electrospray voltages and MS signal was measured at different flow rates by coupling the device to an ion trap mass spectrometer. The performance of the microchip was evaluated by MS analysis of imipramine in ammonium acetate buffer solution by direct infusion. An alkylacrylate based monolith polymer bed for on-chip sample pretreatment and separation was polymerized in the microchannel and tested for ESI-MS applications.

Enumeration of DNA molecules bound to a nanomechanical oscillator.

Resonant nanoelectromechanical systems (NEMS) are being actively investigated as sensitive mass detectors for applications such as chemical and biological sensing. We demonstrate that highly uniform arrays of nanomechanical resonators can be used to detect the binding of individual DNA molecules through resonant frequency shifts resulting from the added mass of bound analyte. Localized binding sites created with gold nanodots create a calibrated response with sufficient sensitivity and accuracy to count small numbers of bound molecules. The amount of nonspecifically bound material from solution, a fundamental issue in any ultra-sensitive assay, was measured to be less than the mass of one DNA molecule, allowing us to detect a single 1587 bp DNA molecule.

Compression and free expansion of single DNA molecules in nanochannels.

We investigated compression and ensuing expansion of long DNA molecules confined in nanochannels. Transverse confinement of DNA molecules in the nanofluidic channels leads to elongation of their unconstrained equilibrium configuration. The extended molecules were compressed by electrophoretically driving them into porelike constrictions inside the nanochannels. When the electric field was turned off, the DNA strands expanded. This expansion, the dynamics of which has not previously been observable in artificial systems, is explained by a model that is a variation of de Gennes's polymer model.

lambda-Repressor oligomerization kinetics at high concentrations using fluorescence correlation spectroscopy in zero-mode waveguides.

Fluorescence correlation spectroscopy (FCS) has demonstrated its utility for measuring transport properties and kinetics at low fluorophore concentrations. In this article, we demonstrate that simple optical nanostructures, known as zero-mode waveguides, can be used to significantly reduce the FCS observation volume. This, in turn, allows FCS to be applied to solutions with significantly higher fluorophore concentrations. We derive an empirical FCS model accounting for one-dimensional diffusion in a finite tube with a simple exponential observation profile. This technique is used to measure the oligomerization of the bacteriophage lambda repressor protein at micromolar concentrations. The results agree with previous studies utilizing conventional techniques. Additionally, we demonstrate that the zero-mode waveguides can be used to assay biological activity by measuring changes in diffusion constant as a result of ligand binding.