Stimulation of Biological Structures on the Nanoscale Using Interfaces with Large Built-In Spontaneous Polarizations.

The electric potential stimulation of biological structures in aqueous environments is well-known to be a result of the gating of voltage-gated ion channels. Such voltage-gated ion channels are ubiquitous in the membranes of a wide variety of cells and they play central roles in a wide variety of sensing mechanisms and neuronal functions in biological systems. Experimental studies of ion-channel gating are frequently conducted using path-clamp techniques by placing a cumbersome external electrode in the vicinity of the extracellular side of the ion channel. Recently, it has been demonstrated that laser-induced polarization of nanoscale quantum dots can produce voltage sufficient to gate voltage-gated ion channels. This study specifically focuses on a new method of gating voltage-gated ion channels using 2D structures made of materials exhibiting large naturally occurring spontaneous polarizations, thereby eliminating the need for an external electrode or an illuminating laser. The work presents the use of self-polarizing semiconductor flakes, namely, 2H-SiC, ZnO, and GaN, to produce electric potential that is sufficient to gate voltage-gated ion channels when existing in proximity to it.

The Use of Semiconductor Quantum Dots with Large, Built-In Spontaneous Polarizations for the Electric Potential Stimulation of Biological Structures on the Nanoscale.

The feasibility of using quantum dots fabricated from materials with built-in spontaneous polarizations for the electric potential stimulation of biological structures in aqueous environments is evaluated by modeling the electric potential produced in the vicinity of such quantum dots. By modeling the external potential created by the spherical nanoscale region of a material with spontaneous polarization, and by considering Debye screening in the vicinity of the quantum dot, it is found that electric potential around these nanostructures is sufficient to cause physiological effects in selected biological systems. These findings suggest that quantum dots may be used in lieu of quantum dots with polarizations produced using an external laser to cause physiological effects. The elimination of the external laser represents a significant benefit of using quantum dots with permanent, built-in spontaneous polarization.

Role of Confined Optical Phonons in Exciton Generation in Spherical Quantum Dot.

Optical control of excitonic states in semiconducting quantum dots has enabled it to be deployed as a qubit for quantum information processing. For self-assembled quantum dots, these excitonic states couple with phonons in the barrier material, for which the previous studies have shown that such exciton-phonon coupling can also lead to the generation of exciton, paving the way for their deployment in qubit-state preparation. Previous studies on self-assembled quantum dots comprising polar materials have considered exciton-phonon coupling by treating phonon modes as bulk acoustic modes only, owing to nearly the same acoustic property of the dot and barrier material. However, the dimensional confinement leads to significant modification phonon modes, even though acoustic confinement is weak but optical confinement cannot be overlooked. In this paper, we investigate for the first time the exciton-optical phonon coupling using dielectric continuum model duly accounting for the dimensional confinement leading to exciton generation. We report that at low temperatures (below 10 K), the exciton creation rate attributed to confined optical phonon is approximately 5.7 times (~6) slower than bulk acoustic phonons, which cannot be ignored, and it should be accounted for in determining the effective phonon assisted exciton creation rate.

Spontaneous Polarization Calculations in Wurtzite II-Oxides, III-Nitrides, and SiC Polytypes through Net Dipole Moments and the Effects of Nanoscale Layering.

Herein, the spontaneous polarization in crystals with hexagonal symmetry are calculated as a function of the number of monolayers composing a nanostructure by adding the dipole moments for consecutive units of the nanostructure. It is shown that in the limit of a large numbers of monolayers that the spontaneous polarization saturates to the expected bulk value of the spontaneous polarization. These results are relevant to understanding the role of the built-in spontaneous polarizations in a variety of nanostructures since these built-in polarizations are generally quite large, on the order of 1 × 108 to 1 × 1010 V/m. Using these formulations, we come to the prediction that small nanolayered structures are theoretically capable of having larger spontaneous polarizations than their bulk counterparts due to how the dipole moments of the anions and cations within a wurtzite lattice cancel out with one another more in larger structures.

Thornber-Feynman carrier-optical-phonon scattering rates in wurtzite crystals.

It is well known that the carrier-optical-phonon scattering rates dominate the carrier-acoustic-phonon scattering rates in many polar materials of interest in electronic and optoelectronic applications. Furthermore, it is known that the Fröhlich coupling constants for carrier-optical-phonon in many materials is close to or great than unity, calling into question the validity of scattering rates based on the Fermi golden rule. In a celebrated paper by Thornber and Feynman it was shown that that the large Fröhlich coupling constant in polar materials does indeed lead to substantial corrections to the Fermi golden rule scattering rates. These large corrections are due to the fact that for strong coupling constants, the first-order perturbative approach underlying the Fermi golden rule does not take into account the presence of many phonons interacting simultaneous with the carrier. In this paper, the Thornber-Feymnan scattering rates for carrier-optical-phonon interactions are derived for several technologically important wurtzite semiconductors-BN, ZnO, CdS, CdSe, ZnS, InN, and SiC- and it is shown that the commonly used Fermi golden rule scattering rates must be corrected by factors ranging up to an order-of-magnitude. The corrections to the Fermi golden rule reported herein have widespread impact on carrier transport for materials with large Fröhlich coupling constants.

High performance ionic-liquid-gated air doped diamond field-effect transistors.

We report successful fabrication of high performance ion-gated field-effect transistors (FETs) on hydrogenated diamond surface. Investigations on the hydrogen (H)-terminated diamond by Hall effect measurements shows Hall mobility as high as ∼200 cm2 V-1 s-1. In addition we demonstrate a rapid fabrication scheme for achieving stable high performance devices useful for determining optimal growth and fabrication conditions. We achieved H-termination using hydrogen plasma treatment with a sheet resistivity as low as ∼1.3 kΩ/sq. Conductivity through the FET channel is studied as a function of bias voltage on the liquid ion-gated electrode from -3.0 to 1.5 V. Stability of the H-terminated diamond surface was studied by varying the substrate temperature up to 350 °C. It was demonstrated that the sheet resistance and carrier densities remain stable over 3 weeks in ambient air atmosphere even at substrate temperatures up to 350 °C, whereas increasing temperature beyond this limit has effected hydrogenation. This study opens new avenues for carrying out fundamental research on diamond FET devices with ease of fabrication and high throughput.

Anharmonic decay of high-frequency LA modes in quasi-isotropic III-nitrides.

We report for the first time an estimation of the spontaneous decay rates at room temperature in a selection of nitride-based nanostructures that are quasi-isotropic. We numerically calculate the phonon distribution functions and the decay rates and find that the decay channel LA → TA + TA dominates over the decay channel LA → LA + TA, which confirms Klemens' prediction [1] that LA phonon will primarily split into two doubly degenerate TA phonons through a greater variety of decay channels compared to the decay of LA into two modes, one belonging to the longitudinal acoustic and the other to the transverse acoustic branch.

Fluorescence Resonant Energy Transfer-Based Quantum Dot Sensor for the Detection of Calcium Ions.

A simple optical aptasensor has been synthesized for the detection of calcium ions. This sensing approach employs a semiconductor quantum dot (QD)-gold nanoparticle as the donor-quencher pair and operates on the principle of fluorescence resonant energy transfer (FRET). On binding with calcium ions, the DNA aptamer undergoes a conformational change, which changes the distance between the quantum dot and the gold nanoparticle, conjugated on the 5' terminal and 3' terminal of the aptamer, respectively. This phenomenon results in the quenching of the quantum dot emission. In this sensor, a maximum quenching of 22.42 ± 0.71% has been achieved at 35 nM calcium ion concentration while the limit of detection has been determined to be 3.77 pM. The sensor has been found to have high specificity for calcium ions in comparison to other metal ions like sodium, magnesium, and potassium. The molecular apta-beacons also demonstrated successful endocytosis and FRET-based calcium ion detection in osteocyte cells when conjugated with a cell-penetrating peptide (DSS).

A study on the response of FRET based DNA aptasensors in intracellular environment.

This paper presents a study of the response of FRET based DNA aptasensors in the intracellular environment. Herein, we extend previous studies of aptasensors functioning in the extracellular environment to detection of antigens in the intracellular environment. An essential step in this research is the use of a novel means of achieving the endocytosis of aptasensors. Specifically, it is demonstrated that functioning aptasensors are successfully endocytosed by functionalizing the aptasensors with endocytosis-inducing DSS peptides.

Optimized oxygen deprived low temperature sputtered WO3 thin films for crystalline structures.

We report a detailed analysis on the effects of processing parameters for sputtered tungsten trioxide (WO3) thin nanoscale films on their structural, vibrational and electrical properties. The research aims to understand the fundamental aspects of WO3 sputtering at relatively low temperatures and in an oxygen deprived environment targeting applications of temperature and oxygen sensitive substrates. Structural analysis indicates that films deposited at room temperature, or substrate temperatures at or below 400 °C with low oxygen partial pressure are amorphous. Crystallization of the films was observed with distinct Raman peaks when the films were annealed at 300 °C or above using rapid thermal annealing for 10 min. Films revealed monoclinic phases of WO3 with the presence of W-O-W stretching, bending and lattice vibrational modes in the Raman spectra. Interestingly, a change of transport behavior from insulating to semiconducting was observed for as deposited films on post annealing. Annealed films revealed stoichiometric WO3 phases with no external defects detected. The present study adopts a route to intercalate WO3 in a variety of applications from electrochromic coloration to a nanocrystalline thin film for electronic devices sensitive to higher temperatures and gas flow in the sputtering system.

Indium Dopant Concentration Effects on Zinc Oxide Nanowires.

We report in detail the effects of varying the concentration of indium as a dopant in ZnO on the structural, vibrational, and optical properties of ZnO nanowires. A highly versatile route to dope zinc oxide nanowires by using vapor-liquid-solid growth is employed. It is observed that the ratio of indium in ZnO reactant has a large impact on properties of indium-doped ZnO nanowires. Lower indium concentration reveals better transparency while higher concentrations of indium shows segregation of indium-rich domains within the doped nanocrystals. Photoluminescence measurements demonstrated band gap tuning and a smaller UV to deep emission ratio for doped nanowires. Phonon vibrational modes along with origin of observed anomalous vibrational modes induced due to indium incorporation in ZnO are discussed. An average transmittance of more than 90% is observed for a wide range of spectra in both visible and near-IR regions as compared with indium tin oxide. The lowest resistivity of 1.2 × 10-3 Ω·cm was achieved for ZnO films doped with 7% indium oxide. These dramatically superior optical and electrical properties make it a superior candidate for various technological applications.

Confined and interface optical phonon emission in GaN/InGaN double barrier quantum well heterostructures.

In GaN-based high electron mobility transistors (HEMTs), the fast emission of longitudinal optical (LO) phonons can result in the formation of hot spots near the gate region where high electric fields produce hot electrons. In this work, we investigate the probability of phonon emission as a function of electron energy for confined and interface (IF) phonon modes for wurtzite GaN/InGaN/GaN heterostructures. Hot electrons radiate optical phonons which decay, anharmonically, into acoustic phonons that are essentially heat carriers. Herein, phonon engineering concepts are introduced which facilitate thermal management through the production of polar optical phonons. Some of the electrons near a semiconductor gate which manifests a strong electric field, are accelerated and the resulting hot electrons will produce confined and interface modes when the electrons are incident on a suitably-placed quantum well. This paper focuses on the production of confined and interface phonons. It is shown that interface modes may be preferentially produced which lead to elongated, lower-temperature hot spots.

Electron Scattering via Interface Optical Phonons with High Group Velocity in Wurtzite GaN-based Quantum Well Heterostructure.

Here we present a detailed theoretical analysis of the interaction between electrons and optical phonons of interface and confined modes in a wurtzite AlN/GaN/AlN quantum well heterostructure based on the uniaxial dielectric continuum model. The formalism describing the interface and confined mode optical phonon dispersion relation, electron-phonon scattering rates, and average group velocity of emitted optical phonons are developed and numerically calculated. The dispersion relation of the interface phonons shows a convergence to the resonant phonon frequencies 577.8 and 832.3 cm-1 with a steep slope around the zone center indicating a large group velocity. At the onset of interface phonon emission, the average group velocity is small due to the large contribution of interface and confined mode phonons with close-to-zero group velocity, but eventually increases up to larger values than the bulk GaN acoustic phonon velocity along the wurtzite crystal c-axis (8 nm/ps). By adjusting the GaN thickness in the double heterostructure, the average group velocity can be engineered to become larger than the velocity of acoustic phonons at a specific electron energy. This suggests that the high group velocity interface mode optical phonons can be exploited to remove heat more effectively and reduce junction temperatures in GaN-based heterostructures.

Rapid Detection of Tumor Necrosis Factor-Alpha Using Quantum Dot-Based Optical Aptasensor.

This paper reports an optical "TURN OFF" aptasensor, which is comprised of a deoxyribonucleic acid aptamer attached to a quantum dot on the terminus and gold nanoparticle on the terminus. The photoluminescence intensity is observed to decrease upon progressive addition of the target protein tumor necrosis factor-alpha (TNF- ) to the sensor. For PBS-based TNF- samples, the beacon exhibited 19%-20% quenching at around 22 nM concentration. The photoluminescence intensity and the quenching efficiency showed a linear decrease and a linear increase, respectively, between 0 to 22.3 nM TNF- . The detection limit of the sensor was found to be 97.2 pM. Specificity test results determined that the sensor has higher selectivity toward TNF- than other control proteins such as C-reactive protein, albumin, and transferrin. The beacon successfully detected different concentrations of TNF- in human serum-based samples exhibiting around 10% quenching efficiency at 12.5 nM of the protein.

Terahertz vibrational signature of bacterial spores arising from nanostructure decorated endospore surface.

This theoretical effort is the first to explore the possible hypothesis that terahertz optical activity of Bacillus spores arises from normal vibrational modes of spore coat subcomponents in the terahertz frequency range. Bacterial strains like Bacillus and Clostridium form spores with a hardened coating made of peptidoglycan to protect its genetic material in harsh conditions. In recent years, electron microscopy and atomic force microscopy has revealed that bacterial spore surfaces are decorated with nanocylinders and honeycomb nanostructures. In this article, a simple elastic continuum model is used to describe the vibration of these nanocylinders mainly in Bacillus subtilis, which also leads to the conclusion that the terahertz signature of these spores arises from the vibration of these nanostructures. Three vibrating modes: radial/longitudinal, torsional and flexural, have been identified and discussed for the nanocylinders. The effect of bound water, which shifts the vibration frequency, is also discussed. The peptidoglycan molecule consists of polar and charged amino acids; hence, the sporal surface local vibrations interact strongly with the terahertz radiation.

Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires.

We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In2O3) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In2O3 nanostructure based device characteristics for potential optoelectronic applications. In2O3 nanowires with cubic crystal structure (c-In2O3) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor-liquid-solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy [Formula: see text] defects as confirmed using Raman spectroscopy. A combination of high resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of [Formula: see text] defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.

Ultrafast carrier dynamics and optical pumping of lasing from Ar-plasma treated ZnO nanoribbons.

It is a well-known fact that ZnO has been one of the most studied wide bandgap II-VI materials by the scientific community specifically due to its potential for being used as exciton-related optical devices. Hence, realizing ways to increase the efficiency of these devices is important. We discuss a plasma treatment technique to enhance the near-band-edge (NBE) excitonic emission from ZnO based nanoribbons. We observed an enhancement of the NBE peak and simultaneous quenching of the visible emission peak resulting from the removal of surface traps on these ZnO nanoribbons. More importantly, we report here the associated ultrafast carrier dynamics resulting from this surface treatment. Femtosecond transient absorption spectroscopy was performed using pump-probe differential transmission measurements shedding new light on these improved dynamics with faster relaxation times. The knowledge obtained is important for improving the application of ZnO based optoelectronic devices. We also observed how these improved carrier dynamics have a direct effect on the threshold and efficiency of random lasing from the material.

Aptasensor based optical detection of glycated albumin for diabetes mellitus diagnosis.

Glycated albumin (GA) has been reported as an important biomarker for diabetes mellitus. This study investigates an optical sensor comprised of deoxyribonucleic acid (DNA) aptamer, semiconductor quantum dot and gold (Au) nanoparticle for the detection of GA. The system functions as a 'turn on' sensor because an increase in photoluminescence intensity is observed upon the addition of GA to the sensor. This is possibly because of the structure of the DNA aptamer, which folds to form a large hairpin loop before the addition of the analyte and is assumed to open up after the addition of target to the sensor in order to bind to GA. This pushes the quantum dot and the Au nanoparticle away causing an increase in photoluminescence. A linear increase in photoluminescence intensity and quenching efficiency of the sensor is observed as the GA concentration is varied between 0-14 500 nM. Time based photoluminescence studies with the sensor show the decrease in binding rate of the aptamer to the target within a specific time period. The sensor was found to have a higher selectivity towards GA than other control proteins. Further investigation of this simple sensor with greater number of clinical samples can open up avenues for an efficient diagnosis and monitoring of diabetes mellitus when used in conjunction with the traditional method of glucose level monitoring.

Graphene oxide and DNA aptamer based sub-nanomolar potassium detecting optical nanosensor.

Quantum-dot (QD) based nanosensors are frequently used by researchers to detect small molecules, ions and different biomolecules. In this article, we present a sensor complex/system comprised of deoxyribonucleic acid (DNA) aptamer, gold nanoparticle and semiconductor QD, attached to a graphene oxide (GO) flake for detection of potassium. As reported herein, it is demonstrated that QD-aptamer-quencher nanosensor functions even when tethered to GO, opening the way to future applications where sensing can be accomplished simultaneously with other previously demonstrated applications of GO such as serving as a nanocarrier for drug delivery. Herein, it is demonstrated that the DNA based thrombin binding aptamer used in this study undergoes the conformational change needed for sensing even when the nanosensor complex is anchored to the GO. Analysis with the Hill equation indicates the interaction between aptamer and potassium follows sigmoidal Hill kinetics. It is found that the quenching efficiency of the optical sensor is linear with the logarithm of concentration from 1 pM to 100 nM and decreases for higher concentration due to unavailability of aptamer binding sites. Such a simple and sensitive optical aptasensor with minimum detection capability of 1.96 pM for potassium ion can also be employed in-vitro detection of different physiological ions, pathogens and disease detection methods.

Molecular beacon anchored onto a graphene oxide substrate.

In this article, we report a graphene oxide-based nanosensor incorporating semiconductor quantum dots linked to DNA-aptamers that functions as a 'turn-off' fluorescent nanosensor for detection of low concentrations of analytes. A specific demonstration of this turn-off aptasensor is presented for the case of the detection of mercury (II) ions. In this system, ensembles of aptamer-based quantum-dot sensors are anchored onto graphene oxide (GO) flakes which provide a platform for analyte detection in the vicinity of GO. Herein, the operation of this ensemble-based nanosensor is demonstrated for mercury ions, which upon addition of mercury, quenching of the emission intensity from the quantum dots is observed due to resonance energy transfer between quantum dots and the gold nanoparticle connected via a mercury target aptamer. A key result is that the usually dominant effect of quenching of the quantum dot due to close proximity to the GO can be reduced to negligible levels by using a linker molecule in conjunctions with the aptamer-based nanosensor. The effect of ionic concentration of the background matrix on the emission intensity was also investigated. The sensor system is found to be highly selective towards mercury and exhibits a linear behavior (r 2 > 0.99) in the nanomolar concentration range. The detection limit of the sensor towards mercury with no GO present was found to be 16.5 nM. With GO attached to molecular beacon via 14 base, 35 base, and 51 base long linker DNA, the detection limit was found to be 38.4 nM, 9.45 nM, and 11.38 nM; respectively.