Predicting Finite-Bias Tunneling Current Properties from Zero-Bias Features: The Frontier Orbital Bias Dependence at an Exemplar Case of DNA Nucleotides in a Nanogap

The electrical current properties of single-molecule sensing devices based on electronic (tunneling) transport strongly depend on molecule frontier orbital energy, spatial distribution, and position with respect to the electrodes. Here, we present an analysis of the bias dependence of molecule frontier orbital properties at an exemplar case of DNA nucleotides in the gap between H-terminated (3, 3) carbon nanotube (CNT) electrodes and its relation to transversal current rectification. The electronic transport properties of this simple single-molecule device, whose characteristic is the absence of covalent bonding between electrodes and a molecule between them, were obtained using density functional theory and non-equilibrium Green's functions. As in our previous studies, we could observe two distinct bias dependences of frontier orbital energies: the so-called strong and the weak pinning regimes. We established a procedure, from zero-bias and empty-gap characteristics, to estimate finite-bias electronic tunneling transport properties, i.e., whether the molecular junction would operate in the weak or strong pinning regime. We also discuss the use of the zero-bias approximation to calculate electric current properties at finite bias. The results from this work could have an impact on the design of new single-molecule applications that use tunneling current or rectification applicable in high-sensitivity sensors, protein, or DNA sequencing

Tunnel Junction Sensing of TATP Explosive at the Single-Molecule Level

Triacetone triperoxide (TATP) is a homemade, potent explosive and, unfortunately, is used in many terrorist attacks. It is hard to detect, and present techniques for its sensing do not offer portability. Fortunately, TATP is volatile, and gas-sensing-based devices for TATP detection would provide a higher level of safety. Here, we explore the possibility of single molecule TATP detection in the air by tunneling current measurement in the N-terminated carbon-based nanogaps, at the DFT+NEGF level of theory. We found TATP averaged current amplitude of tens nano amperes, with a discrimination ratio with respect to prevalent indoor volatile organic compounds (VOC) of a few orders of magnitude. That high tunneling current is due to specific TATP HOMO contributions to electronic transport. The transport facilitates the strong, in-gap electrical field generated by N-C polar bonds from electrode ends and TATP electrode hybridization, spurred by oxygen atoms from a probed molecule

Single-Molecule Probing By Rectification in a Nanogap

Here in this talk, we propose the simultaneous measurement of rectification and amplitude of tunneling current during electrical probing of a molecule in a nanogap for efficient single-molecule detection. Also, we suggest the application of nitrogen-terminated graphene or CNT nanogaps due to their inherent outstanding features. With DFT and Non-Equilibrium Green's Function formalism, we show that tunneling current through various molecules, including ssDNA, TATP, or small organics placed in those nanogaps, exhibits unique rectification behavior under square pulses of alternating bias. The rectification arises by on-off switching of electronic transport through the molecular HOMO or LUMO levels, sustained by partial charging of the probed molecule, generated by asymmetric hybridization of that level with Bloch states from one of the electrodes. An effect that mimics local gating, i. e. an interaction between the molecule and the nitrogen-induced dipole moment located at the N-C interface of the electrode ends, strongly influences the rectification. The simultaneous measurement of rectification and amplitude of tunneling current could be applied to gas-phase single-molecule detection, as shown in the example case of the TATP. The TATP (triacetone triperoxide) is a volatile, potent, and hard-to-detect explosive made from commonly available chemicals, a terrorist weapon of choice in the last two decades. The rectification could also be applied in the liquid phase, offering the possibility of high-throughput and precise DNA sequencing. We found that the environment (neighboring nucleotides, water molecules, and counterions) does not mask ssDNA rectification while ssDNA traverses the nanogap

Analysis of 4,4′-bis(2,2′diphenyl vinyl)-1,1′- biphenyl using the atmospheric-pressure solids analysis probe for ionization

An Atmospheric pressure Solids Analysis Probe (ASAP) mass spectrometer are used for investigation the ionization mechanism and fragmentation pathways of 4,4′-bis(2,2′diphenyl vinyl)-1,1′-biphenyl (DPVBi). DPVBi is material used in OLEDs (organic light-emitting diode). Results obtained indicate that by controlling ion source conditions it is possible to optimize forming of desired precursor ion, primarily radical cation and in less content protonated ion of DPVBi. The results presented illustrate the usefulness of ASAP MS in the characterization of DPVBi compounds

Altering Glass Transition of TPD thin Films with UV Light

N,N´-Bis(3-methylphenyl)-N,N’dyphenilbenzidine (TPD) is a hole-transport material used in electroluminescent devices whose glass transition temperature, Tg, depends on the film thickness.[1] For sufficiently thin films (d<30 nm), dewetting of amorphous TPD films deposited on a on fused silica or an ITO substrate occurs even at room temperature.[2] Following a brief report on increased thermal stability of UV irradiated TPD films,[3] we investigated the underlying mechanism responsible for it. From proton NMR and mass spectrometry measurements, coupled with morphology (AFM) and spectroscopy (UV-VIS) studies, we find that photo-excited TPD species react with oxygen in air. This leads to partially oxidized TPD films whose increased thermal stability we ascribe to stronger hydrogen bonding of photo-oxidized TPD species with hydrophilic substrates

Interdimensional radial discrete diffraction in Mathieu photonic lattices

We demonstrate transitional dimensionality of discrete diffraction in radial-elliptical photonic lattices. Varying the order, characteristic structure size, and ellipticity of the Mathieu beams used for the photonic lattices generation, we control the shape of discrete diffraction distribution over the combination of the radial direction with the circular, elliptic, or hyperbolic. We also investigate the transition from one-dimensional to two-dimensional discrete diffraction by varying the input probe beam position. The most pronounced discrete diffraction is observed along the crystal anisotropy direction

Towards the mechanisam of stabilization of TPD thin films with UV light

Triphenyldiamine (TPD) or N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)benzdine is a well known hole-transporting material often used in electroluminescent devices. In bulk material glass transition temperature TTPDg ~ 60°C [1] is rather low and for sufficiently thin films (thickness d ~ 30 nm) deposited on a fused-silica substrate, dewetting occurs even at room temperature [2]. Morphological changes, which are often related to low Tg, lead to degradation of device performance in which thin film s are incorporated. That is why it is interesting to find a way to stabilize thin films. Following a brief report [3] on increased stability of UV irradiated TPD films, we focused on elucidating the underlying mechanism, since an explanation of chemical changes on molecular level has not yet been given. Thin amorphous TPD films were produced in physical vapor deposition (PVO) process on a fused silica or glass substrates. Immediately after evaporation one half of each sample was exposed to UV light under ambient conditions in order to compare effects of irradiation on a single film. Illuminated and non-illuminated areas of films are characterized using UV-visible spectroscopy and atomic force microscopy (AFM). Decrease in absorption bands intensity was observed after irradiation, indicating a chemical change in the sample. AFM study clearly shows that dewetting process at room temperature is stopped for irradiated samples thinner than 30nm. Illuminated samples remained stable even after few weeks of storage under ambient conditions and after 24h exposure to temperatures T > TTPDg. From proton nuclear magnetic resonance and mass spectrometry measurements, we find that photo-excited TPD reacts with oxygen from air, which leads to oxidation and hydroxylation of small amount of TPD molecules. W e conclude that increased thermal stability of irradiated films is due to hydrogen bonding among TPD molecules and molecules formed in hydroxylation process

Mehanizam gašenja fotoluminescencije u tankim filmovima N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)benzidine osvetljenih UV svetlošću u vazduhu

The mechanism of photoluminescence (PL) quenching of thin amorphous N,N'-bis(3-methylphenyl)- N,N'-bis(phenyl)benzidine (TPD) films exposed to UV light in air is studied. TPD is small organic molecule widely used in production of organic light emmiting devices (OLEDs). Photoluminescence of TPD films decays exponentially with time of irradiation, i.e. with the increase of concentration of impurities (photo-oxidized TPD molecules) generated by UV irradiation in air. Intensity of PL decreases to half of its original value when the concentration of impurities reaches 0.4%. Average distance between impurities (acceptors) is almost an order of magnitude larger than average distance between host TPD molecules (donors). Direct long range Forster energy transfer is ruled out as the mechanism of PL quenching, as the overlap between donor and acceptor is lacking, and exciton self-diffusion in TPD films is postulated for the mechanism. The presence of oxidation products is confirmed by infrared (IR) spectroscopy. Vibrational spectra of TPD molecule and few other possible products of photo-oxidation of TPD molecule, obtained by density functional theory, are compared to experimental IR spectra.U ovom radu je prikazana studija mehanizma gašenja fotoluminescencije (FL) tankih amorfnih filmova N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)benzidine (TPD) izloženih UV zračenju u vazduhu. TPD je organski molekul koji se često koristi u izradi organskih svetlećih dioda (OLED). Prilikom izlaganja TPD filmova UV zračenju u vazduhu, dolazi do fotooksidacije TPD molekula, te iz tog razloga fotoluminescencija TPD filmova opada eksponencijalno sa vremenom osvetljavanja filmova, odnosno sa povećanjem koncentracije nečistoća nastalih usled fotooksidacije. Intenzitet fotoluminescencije opadne na polovinu svoje početne vrednosti u slučaju kada je 0.4 % nečistoća prisutno u filmu. U tom slučaju je srednje rastojanje između nečistoća (akceptora) šest puta veće od srednjeg rastojanja između TPD molekula (donora). Direktan dugodometni Forsterov transfer energije je odbačen kao mehanizam gašenja fotoluminescencije jer je spektralno preklapanje emisije donora i apsorpcije akceptora zanemarljivo. Iz ovog razloga je postulirana ekscitonska difuzija u TPD filmovima, analogno nalazima u postojećoj literaturi. Prisustvo produkata oksidacije je potvrđeno uz pomoć infracrvene (IR) spektroskopije. Takodje, izračunat je IR spektar koristeći teoriju funkcionala gustine (DFT) i dobijeno je dobro slaganje sa eksperimentalnim rezultatima

Pairing in planar organic superconductors

The nature of superconductivity in planar organics is still a controversial problem. We investigate two types of d-wave and extended s-wave pairing proposed theoretically in a model of kappa-(BEDT-TTF)(2)X organic superconductors. As probes of the pairing symmetry, we calculate the density of states, the tunnelling conductance, the specific heat, and the spin susceptibility. The sensibility of superconductivity to the sample preparation suggests that beside the symmetric d(x2-y2) gap, which appears to be consistent with some experiments (for the specific heat, see Nakazawa and Kanoda, Phys. Rev. B 55 (1995) R8670, for STM, Arai et al., Phys. Rev. B 63 (2001) 194518, and for NMR, Mayaffre et al., Phys. Rev. Lett. 75 (1995) 4122) the asymmetric d(xy)-like or extended s-wave gaps could occur. We show that in comparison with the d(x2-y2) case this should be manifested by a more rapid increase of the specific heat at low temperature, by the presence of inner peaks on the density of states and conductance curves at low temperature, and by a different curvature of the spin susceptibility temperature dependence

Superfluid density and pairing in planar organic superconductors

We calculate self-consistently in-plane superfluid density rho(parallel to)(s) in planar organic superconductors to]for three types of pairing symmetry: d(x2-y2), d(xy)-like and extended s-wave pairing. Assuming strong dimerization, we consider a single band model with elliptical Fermi surface to evaluate: the temperature dependence rho(parallel to)(s) (T) in K-(BEDT-TTF)(2)X compounds for those types of pairing. The obtained results, compared with measurements of the superfluid density in k-(BEDT-TTF)(2)Cu[N(CN)(2)]Br, strongly suggest that in these compounds the gap symmetry, influenced by cooling history, in the "ground state" with the least disorder is of the extended s-wave type. Possible physical reasons for agreement of d(x2-y2), and/or isotropic s-wave pairing with experirncntal results in more disordered "interniediate state" are discussed