AB INITIO calculation of the electromigration wind valence of interstitial hydrogen in f.c.c metals

NASA Astrophysics Data System (ADS)

van Ek, J.; Lodder, A.

1990-02-01

Calculated electromigration wind valences, obtained within a KKR-Green function description, are presented. It is shown that the electromigration wind valence of hydrogen along different migration paths in Cu, Ag and Pd can be calculated including charge transfer effects in the impurity cluster. A nice procedure for retrieving the scalar character of the wind valence in an f.c.c metal introduces an explanation for the isotope effect in the wind valence.

Electromigration induced high fraction of compound formation in SnAgCu flip chip solder joints with copper column

NASA Astrophysics Data System (ADS)

Xu, Luhua; Han, Jung-Kyu; Liang, Jarrett Jun; Tu, K. N.; Lai, Yi-Shao

2008-06-01

To overcome the effect of current crowding on electromigration-induced pancake-type void formation in flip chip solder joints, two types of Cu column in 90μm flip chip SnAgCu solder joints have been studied. They were (1) the solder contacts the Cu column at bottom and side walls and (2) the solder wets only the bottom surface of the copper column. With a current density of 1.6×104A/cm2 at 135°C, no failure was detected after 1290h. However, the resistance increased by about 10% due to the formation of a large fraction of intermetallic compounds. We found that electromigration has accelerated the consumption rate of copper column and converted almost the entire solder joint into intermetallic compound. Mechanically, drop impact test indicates a brittle fracture failure in the intermetallic. The electromigration critical product for the intermetallic is discussed.

Crystal plasticity in Cu damascene interconnect lines undergoing electromigration as revealed by synchrotron x-ray microdiffraction

NASA Astrophysics Data System (ADS)

Budiman, A. S.; Nix, W. D.; Tamura, N.; Valek, B. C.; Gadre, K.; Maiz, J.; Spolenak, R.; Patel, J. R.

2006-06-01

Plastic deformation was observed in damascene Cu interconnect test structures during an in situ electromigration experiment and before the onset of visible microstructural damage (voiding, hillock formation). We show here, using a synchrotron technique of white beam x-ray microdiffraction, that the extent of this electromigration-induced plasticity is dependent on the linewidth. In wide lines, plastic deformation manifests itself as grain bending and the formation of subgrain structures, while only grain rotation is observed in the narrower lines. The deformation geometry leads us to conclude that dislocations introduced by plastic flow lie predominantly in the direction of electron flow and may provide additional easy paths for the transport of point defects. Since these findings occur long before any observable voids or hillocks are formed, they may have direct bearing on the final failure stages of electromigration.

Separation of the Isotopes of Calcium by Countercurrent Electromigration in Fused Salts. Final Report; SEPARATION DES ISOTOPES DU CALCIUM PAR ELECTROMIGRATION A CONTRE COURANT EN SELS FONDUS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Menes, F.; Dirian, G.

1962-12-14

The results obtained up to June 25, 1962, on the separation of Ca isotopes by electromigration in fused salts have been reported in seven progress reports. The data given in these reports are summarized. Later study investigated the improvement of the diaphragm performance using nonclassical methods, preparation of an experiment confirming the performances of the high capacity U tube'' apparatus, and preparation of an installation designed for perfecting the dropping tube'' device. Only preliminary results on these studes are available. (J.S.R.)

Effect of electromigration-induced back stress gradient on nanoindentation marker movement in SnAgCu solder joints

NASA Astrophysics Data System (ADS)

Xu, Luhua; Pang, John H. L.; Tu, K. N.

2006-11-01

The electromigration-induced back stress in Pb-free SnAgCu solder was studied by an area array of nanoindentation markers on the cross section of a solder joint. The marker movements driven by combined electron wind force and electromigration-induced back stress gradient were measured at different locations. The back stress gradient was determined from the observation of marker motion using the proposed model. With the applied current density of 104A/cm2 at 125°C, the stress gradient near the anode is 97kPa/μm.

Electromigration-induced plastic deformation in passivated metal lines

NASA Astrophysics Data System (ADS)

Valek, B. C.; Bravman, J. C.; Tamura, N.; MacDowell, A. A.; Celestre, R. S.; Padmore, H. A.; Spolenak, R.; Brown, W. L.; Batterman, B. W.; Patel, J. R.

2002-11-01

We have used scanning white beam x-ray microdiffraction to study microstructural evolution during an in situ electromigration experiment on a passivated Al(Cu) test line. The data show plastic deformation and grain rotations occurring under the influence of electromigration, seen as broadening, movement, and splitting of reflections diffracted from individual metal grains. We believe this deformation is due to localized shear stresses that arise due to the inhomogeneous transfer of metal along the line. Deviatoric stress measurements show changes in the components of stress within the line, including relaxation of stress when current is removed.

Electromigration failures under bidirectional current stress

NASA Astrophysics Data System (ADS)

Tao, Jiang; Cheung, Nathan W.; Hu, Chenming

1998-01-01

Electromigration failure under DC stress has been studied for more than 30 years, and the methodologies for accelerated DC testing and design rules have been well established in the IC industry. However, the electromigration behavior and design rules under time-varying current stress are still unclear. In CMOS circuits, as many interconnects carry pulsed-DC (local VCC and VSS lines) and bidirectional AC current (clock and signal lines), it is essential to assess the reliability of metallization systems under these conditions. Failure mechanisms of different metallization systems (Al-Si, Al-Cu, Cu, TiN/Al-alloy/TiN, etc.) and different metallization structures (via, plug and interconnect) under AC current stress in a wide frequency range (from mHz to 500 MHz) has been study in this paper. Based on these experimental results, a damage healing model is developed, and electromigration design rules are proposed. It shows that in the circuit operating frequency range, the "design-rule current" is the time-average current. The pure AC component of the current only contributes to self-heating, while the average (DC component) current contributes to electromigration. To ensure longer thermal-migration lifetime under high frequency AC stress, an additional design rule is proposed to limit the temperature rise due to self-joule heating.

Texture-enhanced Al-Cu electrodes on ultrathin Ti buffer layers for high-power durable 2.6 GHz SAW filters

NASA Astrophysics Data System (ADS)

Fu, Sulei; Wang, Weibiao; Xiao, Li; Lu, Zengtian; Li, Qi; Song, Cheng; Zeng, Fei; Pan, Feng

2018-04-01

Achieving high resistance to acoustomigration and electromigration in the electrodes used in high-power and high-frequency surface acoustic wave (SAW) filters is important to mobile communications development. In this study, the effects of the Ti buffer layers on the textures and acoustomigration and electromigration resistances of the Al-Cu electrodes were studied comprehensively. The results demonstrate that both power durability and electromigration lifetime are positively correlated with the Al-Cu electrode texture quality. Ultrathin (˜2 nm) Ti can lead to the strongest Al-Cu (111) textured electrodes, with a full width at half maximum of the rocking curve of 2.09°. This represents a remarkable enhancement of the power durability of high-frequency 2.6 GHz SAW filters from 29 dBm to 35 dBm. It also produces lifetime almost 7 times longer than those of electrodes without Ti buffer layers in electromigration tests. X-ray diffraction and transmission electron microscopy analyses revealed that these improved acoustomigration and electromigration resistances can be attributed primarily to the reductions in overall and large-angle grain boundaries in the highly Al-Cu (111) textured electrodes. Furthermore, the growth mechanism of highly Al-Cu texture films is discussed in terms of surface-interface energy balance.

Electro-migration of heavy metals in an aged electroplating contaminated soil affected by the coexisting hexavalent chromium.

PubMed

Zhang, Weihua; Zhuang, Luwen; Tong, Lizhi; Lo, Irene M C; Qiu, Rongliang

2012-02-01

Cr(VI) was often reported to oxidize soil organic matter at acidic environments due to its high ORP, probably thus changing cationic metal species bound to soil organic matter, and influencing their electro-migration patterns. However, such an effect on the electro-migration was not confirmed in most previous studies. Therefore, this study applied a fixed voltage direct current field on an aged electroplating contaminated clayed soil, with a special interest in the direct or indirect influence of Cr(VI) on the electro-migration of other coexisting metals. After 353 h electrokinetic process, 81% of Zn, 53% of Ni and 22% of Cu in the original soil were electro-migrated into the electrolyte, and most of the remaining concentrated near the cathode. The Cr(VI) oxidized some soil organic matter along its migration pathway, with a pronounced reaction occurred near the anode at low pHs. The resulting Cr(III) reversed its original movement, and migrated towards the cathode, leading to the occurrence of a second Cr concentration peak in the soil. Metal species analyses showed that the amount of metals bound to soil organic matter significantly decreased, while a substantial increase in the Cr species bound to Fe/Mn (hydro-)oxides was observed, suggesting an enhancement of cationic metal electro-migration by the reduction of Cr(VI) into Cr(III). However, the Cr(VI) may form some stable lead chromate precipitates, and in turn demobilize Pb in the soil, as the results showed a low Pb removal and an increase in its acid-extractable and residual fractions after electrokinetic remediation. Copyright © 2011 Elsevier Ltd. All rights reserved.

Effect Of Impurity On Cu Electromigration

NASA Astrophysics Data System (ADS)

Hu, C.-K.; Angyal, M.; Baker, B. C.; Bonilla, G.; Cabral, C.; Canaperi, D. F.; Choi, S.; Clevenger, L.; Edelstein, D.; Gignac, L.; Huang, E.; Kelly, J.; Kim, B. Y.; Kyei-Fordjour, V.; Manikonda, S. L.; Maniscalco, J.; Mittal, S.; Nogami, T.; Parks, C.; Rosenberg, R.; Simon, A.; Xu, Y.; Vo, T. A.; Witt, C.

2010-11-01

The impact of the existence of Cu grain boundaries on the degradation of Cu interconnect lifetime at the 45 nm technology node and beyond has suggested that improved electromigra-tion in Cu grain boundaries has become increasingly important. In this paper, solute effects of non-metallic (C, Cl, O and S) and metallic (Al, Co, In, Mg, Sn, and Ti) impurities on Cu elec-tromigration were investigated. The Cu alloy interconnects were fabricated by adjusting Cu electroplating solutions or by depositing a Cu alloy seed, a thin film layer of impurity, an alloy liner, or a metal cap. A large variation of Cu grain structure in the samples was achieved by adjusting the wafer fabrication process steps. The non-metallic impurities were found to be less than 0.1% in the electroplated Cu with no effect on Cu electromigration lifetimes. Most of the metallic impurities reduced Cu interface and grain boundary mass flows and enhanced Cu lifetime, but Al, Co, and Mg impurities did not mitigate Cu grain boundary diffusion.

Microstructure control of Al-Cu films for improved electromigration resistance

DOEpatents

Frear, D.R.; Michael, J.R.; Romig, A.D. Jr.

1994-04-05

A process for the forming of Al-Cu conductive thin films with reduced electromigration failures is useful, for example, in the metallization of integrated circuits. An improved formation process includes the heat treatment or annealing of the thin film conductor at a temperature within the range of from 200 C to 300 C for a time period between 10 minutes and 24 hours under a reducing atmosphere such as 15% H[sub 2] in N[sub 2] by volume. Al-Cu thin films annealed in the single phase region of a phase diagram, to temperatures between 200 C and 300 C have [theta]-phase Al[sub 2] Cu precipitates at the grain boundaries continuously become enriched in copper, due, it is theorized, to the formation of a thin coating of [theta]-phase precipitate at the grain boundary. Electromigration behavior of the aluminum is, thus, improved because the [theta]-phase precipitates with copper hinder aluminum diffusion along the grain boundaries. Electromigration, then, occurs mainly within the aluminum grains, a much slower process. 5 figures.

Electromigration Reliability of Advanced Interconnects

NASA Astrophysics Data System (ADS)

Hu, C.-K.; Gignac, L. M.; Baker-O'Neal, B.; Liniger, E.; Yu, R.; Flaitz, P.; Stamper, A. K.

2007-10-01

Electromigration behavior in Cu damascene wires was studied for various metal line widths, thicknesses and grain sizes where the grain size was modulated by Cu linewidth and thickness, and by adjusting the wafer annealing process step after Cu electroplating and before Cu chemical mechanical polishing. Significantly different results were found between 0.2 μm and 65 nm CMOS node technologies. A larger variation of Cu grain size between the samples was achieved on 65 nm node which was due to the finer line width and thinner metal thickness. The Cu lifetime and mass flow in samples with bamboo, near bamboo, bamboo-polycrystalline mixture, and polycrystalline grain structures were measured. These factors allow one to accurately resolve the relative contribution between grain boundary and interface diffusions in the Cu nanowires. The electromigration mass flow estimated from the lifetime on the test line on a W via and physically stable liner was found to be linearly proportional to current density. The effects of Cu(Ti) alloy seeds and Cu surface pre-clean techniques before the dielectric cap depositions on Cu electromigration were also observed. A significantly improved Cu lifetime, at the expense of the Cu conductivity, was found. The electromigration activation energies for Cu in Cu(Ti) alloy, along Cu/amorphous a-SiCxNyHz interface and in Cu grain boundaries were found to be 1.3, 0.95 and 0.79+0.05 eV, respectively.

White beam analysis of coupling between precipitation and plasticdeformation during electromigration in a passivated Al(0.5wt. percent Cu)interconnect

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barabash, R.I.; Ice, G.E.; Tamura, N.

2005-09-01

The scaling of device dimensions with a simultaneous increase in functional density imposes a challenge to materials technology and reliability of interconnects. White beam X-ray microdiffraction is particularly well suited for the in situ study of electromigration. M.A. Krivoglaz theory was applied for the interpretation of white beam diffraction. The technique was used to probe microstructure in interconnects and has recently been able to monitor the onset of plastic deformation induced by mass transport during electromigration in Al(Cu) lines even before any macroscopic damage became visible. In the present paper, we demonstrate that the evolution of the dislocation structure duringmore » electromigration is highly inhomogeneous and results in the formation of unpaired randomly distributed geometrically necessary dislocations as well as geometrically necessary dislocation boundaries. When almost all unpaired dislocations and dislocation walls with the density n+ are parallel (as in the case of Al-based interconnects), the anisotropy in the scattering properties of the material becomes important, and the electrical properties of the interconnect depend strongly on the direction of the electric current relative to the orientation of the dislocation network. A coupling between the dissolution, growth and reprecipitation of Al2Cu precipitates and the electromigration-induced plastic deformation of grains in interconnects is observed.« less

Electromigration process for the purification of molten silicon during crystal growth

DOEpatents

Lovelace, Alan M. Administrator of the National Aeronautics and Space; Shlichta, Paul J.

1982-01-01

A process for the purification of molten materials during crystal growth by electromigration of impurities to localized dirty zones. The process has particular applications for silicon crystal growth according to Czochralski techniques and edge-defined film-fed growth (EFG) conditions. In the Czochralski crystal growing process, the impurities are electromigrated away from the crystallization interface by applying a direct electrical current to the molten silicon for electromigrating the charged impurities away from the crystal growth interface. In the EFG crystal growth process, a direct electrical current is applied between the two faces which are used in forming the molten silicon into a ribbon. The impurities are thereby migrated to one side only of the crystal ribbon. The impurities may be removed or left in place. If left in place, they will not adversely affect the ribbon when used in solar collectors. The migration of the impurity to one side only of the silicon ribbon is especially suitable for use with asymmetric dies which preferentially crystallize uncharged impurities along one side or face of the ribbon.

Crystallographic Orientation Effect on Electromigration in Ni-Sn Microbump

NASA Astrophysics Data System (ADS)

Huang, Yi-Ting; Chen, Chih-Hao; Chakroborty, Subhendu; Wu, Albert T.

2017-09-01

This article addresses the reliability challenges regarding electromigration in developing three-dimensional integrated circuits (3D-ICs). The line-type sandwich structure of Ni/Sn3.5Ag(15 μm)/Ni was used to simulate microbumps to examine the reliability of electromigration in 3D-IC technology. The solder strip of Ni/Sn3.5Ag(15 μm)/Ni was stressed with a current density of 1.0 × 104 A/cm2 at 150°C. The current stressing enhanced the reaction between the solder and Ni to form Ni3Sn4, which occupied the entire joint and transformed into a Ni/Ni3Sn4/Ni structure when the solder was completely consumed. Electron backscatter diffraction was used to analyze the crystallographic characteristics of Sn and Ni3Sn4 as related to the electromigration effect. The results indicated that the crystallographic orientation of Sn plays a significant role in the Ni/Sn3.5Ag/Ni, whereas the orientation of Ni3Sn4 is the dominant factor of diffusion behavior in the Ni/Ni3Sn4/Ni.

Microstructure control of Al-Cu films for improved electromigration resistance

DOEpatents

Frear, Darrel R.; Michael, Joseph R.; Romig, Jr., Alton D.

1994-01-01

A process for the forming of Al-Cu conductive thin films with reduced electromigration failures is useful, for example, in the metallization of integrated circuits. An improved formation process includes the heat treatment or annealing of the thin film conductor at a temperature within the range of from 200.degree. C. to 300.degree. C. for a time period between 10 minutes and 24 hours under a reducing atmosphere such as 15% H.sub.2 in N.sub.2 by volume. Al-Cu thin films annealed in the single phase region of a phase diagram, to temperatures between 200.degree. C. and 300.degree. C. have .theta.-phase Al.sub.2 Cu precipitates at the grain boundaries continuously become enriched in copper, due, it is theorized, to the formation of a thin coating of .theta.-phase precipitate at the grain boundary. Electromigration behavior of the aluminum is, thus, improved because the .theta.-phase precipitates with copper hinder aluminum diffusion along the grain boundaries. Electromigration, then, occurs mainly within the aluminum grains, a much slower process.

Liquid-phase electroepitaxy - Dopant segregation

NASA Technical Reports Server (NTRS)

Lagowski, J.; Jastrzebski, L.; Gatos, H. C.

1980-01-01

A theoretical model is presented which accounts for the dopant segregation in liquid-phase electroepitaxy in terms of dopant transport in the liquid phase (by electromigration and diffusion), the growth velocity, and the Peltier effect at the substrate-solution interface. The contribution of dopant electromigration to the magnitude of the effective segregation coefficient is dominant in the absence of convection; the contribution of the Peltier effect becomes significant only in the presence of pronounced convection. Quantitative expressions which relate the segregation coefficient to the growth parameters also permit the determination of the diffusion constant and electromigration mobility of the dopant in the liquid phase. The model was found to be in good agreement with the measured segregation characteristics of Sn in the electroepitaxial growth of GaAs from Ga-As solutions. For Sn in Ga-As solution at 900 C the diffusion constant was found to be 4 x 10 to the -5 sq cm/s and the electromigration velocity (toward the substrate with a positive polarity 2 x 10 to the -5 cm/s current density of 10 A/sq cm.

Quantifying Electromigration Processes in Sn-0.7Cu Solder with Lab-Scale X-Ray Computed Micro-Tomography

NASA Astrophysics Data System (ADS)

Mertens, James Charles Edwin

For decades, microelectronics manufacturing has been concerned with failures related to electromigration phenomena in conductors experiencing high current densities. The influence of interconnect microstructure on device failures related to electromigration in BGA and flip chip solder interconnects has become a significant interest with reduced individual solder interconnect volumes. A survey indicates that x-ray computed micro-tomography (muXCT) is an emerging, novel means for characterizing the microstructures' role in governing electromigration failures. This work details the design and construction of a lab-scale muXCT system to characterize electromigration in the Sn-0.7Cu lead-free solder system by leveraging in situ imaging. In order to enhance the attenuation contrast observed in multi-phase material systems, a modeling approach has been developed to predict settings for the controllable imaging parameters which yield relatively high detection rates over the range of x-ray energies for which maximum attenuation contrast is expected in the polychromatic x-ray imaging system. In order to develop this predictive tool, a model has been constructed for the Bremsstrahlung spectrum of an x-ray tube, and calculations for the detector's efficiency over the relevant range of x-ray energies have been made, and the product of emitted and detected spectra has been used to calculate the effective x-ray imaging spectrum. An approach has also been established for filtering 'zinger' noise in x-ray radiographs, which has proven problematic at high x-ray energies used for solder imaging. The performance of this filter has been compared with a known existing method and the results indicate a significant increase in the accuracy of zinger filtered radiographs. The obtained results indicate the conception of a powerful means for the study of failure causing processes in solder systems used as interconnects in microelectronic packaging devices. These results include the volumetric quantification of parameters which are indicative of both electromigration tolerance of solders and the dominant mechanisms for atomic migration in response to current stressing. This work is aimed to further the community's understanding of failure-causing electromigration processes in industrially relevant material systems for microelectronic interconnect applications and to advance the capability of available characterization techniques for their interrogation.

Separation of Isotopes by Electromigration in Fused Salts; SEPARATION DES ISOTOPES PAR ELECTROMIGRATION EN SELS FONDUS (in French)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Menes, F.

1961-12-01

A process is given for the separation of isotopes by reflux electromigration of fused salts. The process is carried out in a countercurrent manner on a fused mixture of a salt containing the isotopic cations with a salt having the same anion and a cation with a mobility as near as possible to that of the isotopic cations. An electrolytic cell for carrying out the process is described. Examples are presented of the process in which lithium-6 and lithium-7 are separated in a LiBr-KBr mixture, and calcium isotopes are separated in CaBr/sub 2/-KBr and CaBr/sub 2/- LiBr systems. (N.W.R.)

Photovoltaic switching mechanism in lateral structure hybrid perovskite solar cells

DOE PAGES

Yuan, Yongbo; Chae, Jungseok; Shao, Yuchuan; ...

2015-06-05

In this study, long range electromigration of methylammonium ions (MA +) in methyl ammonium lead tri-iodide (MAPbI 3) film is observed directly using the photo­thermal induced resonance technique. The electromigration of MA + leads to the formation of a lateral p-i-n structure, which is the origin of the switchable photovoltaic effect in MAPbI 3 perovskite devices.

Investigation of electromigration behavior in lead-free flip chip solder bumps

NASA Astrophysics Data System (ADS)

Kalkundri, Kaustubh Jayant

Packaging technology has also evolved over time in an effort to keep pace with the demanding requirements. Wirebond and flip chip packaging technologies have become extremely versatile and ubiquitous in catering to myriad applications due to their inherent potential. This research is restricted strictly to flip chip technology. This technology incorporates a process in which the bare chip is turned upside down, i.e., active face down, and is bonded through the I/O to the substrate, hence called flip chip. A solder interconnect that provides electrical connection between the chip and substrate is bumped on a processed silicon wafer prior to dicing for die-attach. The assembly is then reflow-soldered followed by the underfill process to provide the required encapsulation. The demand for smaller and lighter products has increased the number of I/Os without increasing the package sizes, thereby drastically reducing the size of the flip chip solder bumps and their pitch. Reliability assessment and verification of these devices has gained tremendous importance due to their shrinking size. To add to the complexity, changing material sets that are results of recently enacted lead-free solder legislations have raised some compatibility issues that are already being researched. In addition to materials and process related flip chip challenges such as solder-flux compatibility, Coefficient of Thermal Expansion (CTE) mismatch, underfill-flux compatibility and thermal management, flip chip packages are vulnerable to a comparatively newer challenge, namely electromigration observed in solder bumps. It is interesting to note that electromigration has come to the forefront of challenges only recently. It has been exacerbated by the reduction in bump cross-section due to the seemingly continuous shrinking in package size over time. The focus of this research was to understand the overall electromigration behavior in lead-free (SnAg) flip chip solder bumps. The objectives of the research were to comprehend the physics of failure mechanism in electromigration for lead-free solder bumps assembled in a flip chip ceramic package having thick copper under bump metallization and to estimate the unknown critical material parameters from Black's equation that describe failure due to electromigration. In addition, the intent was to verify the 'use condition reliability' by extrapolation from experimental conditions. The methodology adopted for this research was comprised of accelerated electromigration tests on SnAg flip chip solder bumps assembled on ceramic substrate with a thick copper under bump metallization. The experimental approach was comprised of elaborate measurement of the temperature of each sample by separate metallization resistance exhibiting positive resistance characteristics to overcome the variation in Joule heating. After conducting the constant current experiments and analyzing the failed samples, it was found that the primary electromigration failure mode observed was the dissolution of the thick copper under bump metallization in the solder, leading to a change in resistance. The lifetime data obtained from different experiments was solved simultaneously using a multiple regression approach to yield the unknown Black's equation parameters of current density exponent and activation energy. In addition to the implementation of a systematic failure analysis and data analysis procedure, it was also deduced that thermomigration due to the temperature gradient across the chip does impact the overall electromigration behavior. This research and the obtained results were significant in bridging the gap for an overall understanding of this critical failure mode observed in flip chip solder bumps. The measurement of each individual sample temperature instead of an average temperature enabled an accurate analysis for predicting the 'use condition reliability' of a comparable product. The obtained results and the conclusions can be used as potential inputs in future designs and newer generations of flip chip devices that might undergo aggressive scaling. This will enable these devices to retain their functionality during their intended useful life with minimal threat of failure due to the potent issue of electromigration. (Abstract shortened by UMI.)

Feasibilty analyses of electroepitaxial research and development accommodations. Volume 2: Electroepitaxial growth of GaAs

NASA Technical Reports Server (NTRS)

1982-01-01

The technique of electromigration, i.e., electric field induced forced convection, can be used to grow semiconductor material and other compounds from solution by passing electric current through the growth interface while the temperature of the system is maintained constant. Current controlled electromigration, referred to as electroepitaxy, was successfully applied to grow epitaxial layers of various semiconductors and garnets.

Biased resistor network model for electromigration failure and related phenomena in metallic lines

NASA Astrophysics Data System (ADS)

Pennetta, C.; Alfinito, E.; Reggiani, L.; Fantini, F.; Demunari, I.; Scorzoni, A.

2004-11-01

Electromigration phenomena in metallic lines are studied by using a biased resistor network model. The void formation induced by the electron wind is simulated by a stochastic process of resistor breaking, while the growth of mechanical stress inside the line is described by an antagonist process of recovery of the broken resistors. The model accounts for the existence of temperature gradients due to current crowding and Joule heating. Alloying effects are also accounted for. Monte Carlo simulations allow the study within a unified theoretical framework of a variety of relevant features related to the electromigration. The predictions of the model are in excellent agreement with the experiments and in particular with the degradation towards electrical breakdown of stressed Al-Cu thin metallic lines. Detailed investigations refer to the damage pattern, the distribution of the times to failure (TTFs), the generalized Black’s law, the time evolution of the resistance, including the early-stage change due to alloying effects and the electromigration saturation appearing at low current densities or for short line lengths. The dependence of the TTFs on the length and width of the metallic line is also well reproduced. Finally, the model successfully describes the resistance noise properties under steady state conditions.

Simulation of Electromigration Based on Resistor Networks

NASA Astrophysics Data System (ADS)

Patrinos, Anthony John

A two dimensional computer simulation of electromigration based on resistor networks was designed and implemented. The model utilizes a realistic grain structure generated by the Monte Carlo method and takes specific account of the local effects through which electromigration damage progresses. The dynamic evolution of the simulated thin film is governed by the local current and temperature distributions. The current distribution is calculated by superimposing a two dimensional electrical network on the lattice whose nodes correspond to the particles in the lattice and the branches to interparticle bonds. Current is assumed to flow from site to site via nearest neighbor bonds. The current distribution problem is solved by applying Kirchhoff's rules on the resulting electrical network. The calculation of the temperature distribution in the lattice proceeds by discretizing the partial differential equation for heat conduction, with appropriate material parameters chosen for the lattice and its defects. SEReNe (for Simulation of Electromigration using Resistor Networks) was tested by applying it to common situations arising in experiments with real films with satisfactory results. Specifically, the model successfully reproduces the expected grain size, line width and bamboo effects, the lognormal failure time distribution and the relationship between current density exponent and current density. It has also been modified to simulate temperature ramp experiments but with mixed, in this case, results.

Effect of current crowding on whisker growth at the anode in flip chip solder joints

NASA Astrophysics Data System (ADS)

Ouyang, Fan-Yi; Chen, Kai; Tu, K. N.; Lai, Yi-Shao

2007-12-01

Owing to the line-to-bump configuration in flip chip solder joints, current crowding occurs when electrons enter into or exit from the solder bump. At the cathode contact, where electrons enter into the bump, current crowding induced pancake-type void formation has now been observed widely. At the anode contact, where electrons exit from the bump, we report here that whisker is formed. Results of both eutectic SnPb and SnAgCu solder joints are presented and compared. The cross-sectioned surface in SnPb showed dimple and bulge after electromigration, while that of SnAgCu remained flat. The difference is due to a larger back stress in the SnAgCu, consequently, electromigration in SnAgCu is slower than that in SnPb. Nanoindentation markers were used to measure the combined atomic fluxes of back stress and electromigration.

Electromigration model for the prediction of lifetime based on the failure unit statistics in aluminum metallization

NASA Astrophysics Data System (ADS)

Park, Jong Ho; Ahn, Byung Tae

2003-01-01

A failure model for electromigration based on the "failure unit model" was presented for the prediction of lifetime in metal lines.The failure unit model, which consists of failure units in parallel and series, can predict both the median time to failure (MTTF) and the deviation in the time to failure (DTTF) in Al metal lines. The model can describe them only qualitatively. In our model, both the probability function of the failure unit in single grain segments and polygrain segments are considered instead of in polygrain segments alone. Based on our model, we calculated MTTF, DTTF, and activation energy for different median grain sizes, grain size distributions, linewidths, line lengths, current densities, and temperatures. Comparisons between our results and published experimental data showed good agreements and our model could explain the previously unexplained phenomena. Our advanced failure unit model might be further applied to other electromigration characteristics of metal lines.

The electromigration force in metallic bulk

NASA Astrophysics Data System (ADS)

Lodder, A.; Dekker, J. P.

1998-01-01

The voltage induced driving force on a migrating atom in a metallic system is discussed in the perspective of the Hellmann-Feynman force concept, local screening concepts and the linear-response approach. Since the force operator is well defined in quantum mechanics it appears to be only confusing to refer to the Hellmann-Feynman theorem in the context of electromigration. Local screening concepts are shown to be mainly of historical value. The physics involved is completely represented in ab initio local density treatments of dilute alloys and the implementation does not require additional precautions about screening, being typical for jellium treatments. The linear-response approach is shown to be a reliable guide in deciding about the two contributions to the driving force, the direct force and the wind force. Results are given for the wind valence for electromigration in a number of FCC and BCC metals, calculated using an ab initio KKR-Green's function description of a dilute alloy.

Mechanism of electromigration failure in Damascene processed copper interconnects

NASA Astrophysics Data System (ADS)

Michael, Nancy Lyn

2002-11-01

A major unresolved issue in Cu interconnect reliability is the interface role in the failure mechanism of real structures. The present study investigates failure in single-level damascene Cu interconnects with variations in interface condition, passivation and barrier, and linewidth. In the first phase, accelerated electromigration testing of 0.25mum Cu interconnects capped with SiN or SiCN, shows that lifetime and failure mode vary with capping layer. The first mode, seen primarily in SiN samples, is characterized by gradual resistance increase and extensive interface damage, believed to result from failure led by interface electromigration. The competing failure mode, found in SiCN capped samples, is characterized by abrupt resistance increase and localized voiding. The second phase fixes SiCN as the capping material and varies barrier material and line width. The three barrier materials, Ta, TaN, and Ta/TaN, produce similar lifetime statistics and failure is abrupt. Line width, however, does have a strong influence on failure time. The line width/grain size ratio ranged from 0.53 to 2.2 but does not correlate with mean time to failure (MTF). The strong dependence on interface fraction, combined with the conclusion from phase one that interface electromigration is not rate controlling, suggests another mechanism related to the interface is a controlling factor. The possibility that contamination and defects at the interface are key to this failure mode was investigated using electro-thermal fatigue (ETF). In ETF, where lines are simultaneously subjected to thermal cycling and constant current, damage caused by thermal stress is accelerated. Tests reveal that in 80 nm lines, transient failure occurs at times far below MTF in electromigration tests at higher temperatures. Failure found in ETF is clearly a result of damage growth due to thermal/mechanical stress rather than electromigration. At the stress levels created by the moderate ETF test conditions, the only place voids are likely to nucleate and grow is at pre-existing defects and impurities. In narrower lines, where smaller voids can cause catastrophic damage, defects have a greater effect on MTF. Results from this investigation suggest that impurities and defects in the Cu and at the interface, must be carefully controlled to make reliable narrow Cu interconnects.

Electromigration and thermomigration in lead-free tin-silver-copper and eutectic tin-lead flip chip solder joints

NASA Astrophysics Data System (ADS)

Ou Yang, Fan-Yi

Phase separation and microstructure change of eutectic SnPb and SnAgCu flip chip solder joint were investigated under thermomigration, electromigration, stressmigration and the combination of these effects. Different morphological behaviors under DC and AC electromigration were seen. Phase separation with Pb rich phase migration to the anode was observed when current density is below 1.6 x 104 A/cm2 at 100°C. For some cases, phase separation of Pb-rich phase and Su-rich phase as well as refinement of lamellar microstructure has also been observed. We propose that the refinement is due to recrystallization. On the other hand, time-dependent melting of eutectic SnPb flip chip solder joints has been observed to occur frequently with current density above 1.6 x 104 A/cm 2at 100°C. It has been found that it is due to joule heating of the on-chip Al interconnects. We found that electromigration has especially generated voids at the anode of the Al. This damage has greatly increased the resistance of the Al, which produces the heat needed to melt the solder joint. Owing to the line-to-bump configuration in flip chip solder joints, current crowding occurs when electrons enters into or exits from the solder bump. At the cathode contact, current crowding induced pancake-type void formation was observed widely. Furthermore, at the anode contact, we note that hillock or whisker forms. The cross-sectioned surface in SnPb showed dimple and bulge after electromigration, while that of SnAgCu remained flat. The difference is due to a larger back stress in the SnAgCu, consequently electromigration in SnAgCu is slower than that in SnPb. For thermomigration in eutectic SnPb flip chip solder joints, phase separation of Sn and Pb occurred, with Pb moving to the cold end. Both Sn and Pb have a stepwise concentration profile across solder bump. Refinement of lamellar microstructure was observed, indicating recrystallization. Also, thermomigration in eutectic SnAgCu flip chip solder joint were presented. It seems that vacancy flux plays a dominant role in thermomigration in Pb-free solder bumps; voids formed on the cold end and Sn moved to the hot end.

Effect of the Angle Between Sn Grain c-Axis and Electron Flow Direction on Cu-Reinforced Composite Solder Joints Under Current Stressing

NASA Astrophysics Data System (ADS)

Wang, Yan; Han, Jing; Wang, Yishu; Ma, Limin; Guo, Fu

2018-01-01

With a body-centered tetragonal crystal structure, Sn grains were demonstrated to have highly anisotropic behaviors in various properties. The electromigration behavior of lead-free solder was impacted by the grain orientations. In this paper, the angle between the c-axis and the electron flow direction in composite solder joints (angle θ) was proven to be an important factor during electromigration. The effects of angle θ on the electromigration of composite solder joints were investigated in this paper. Cu particle-reinforced Sn3.5Ag solder joints were stressed under a current density of 104 A/cm2 at room temperature. After 336 h current stressing time, different electromigration phenomena occurred at the two sides of the grain boundary in the composite solder joint which contained two Sn grains with different angle θ. The Sn grains with the larger angle θ had a smaller growth rate of Cu6Sn5. In addition, a composite solder joint with a single Sn grain was set as the contrast and its angle θ was smaller than that of the composite solder joint with two Sn grains. The growth rate of Cu6Sn5 in the composite solder joint with a single grain was faster than that of the composite solder joint with two Sn grains.

A quick method for AlCu interconnect electromigration performance predicting and monitoring

NASA Astrophysics Data System (ADS)

Zhang, Wenjie; Yi, Leeward; Tao, Kai; Ma, Yue; Chang, Pingyi; Mao, Duli; Wu, Jin; Zou, S. C.

2006-05-01

The film properties and microstructures of (bottom)Si/SiO2/Ti(top) and (bottom)Si/SiO2/Ti/TiN/AlCu(top) stacks deposited by different processes were characterized. The resistivities of thin Ti films and the reflectivities of AlCu alloy films were found to correlate with the microstructure as well as the mean time to failure (MTTF) in the electromigration (EM) test. A quick-turn monitor for AlCu interconnect reliability in the semiconductor manufacturing industry was established.

Comparison of electrokinetic soil remediation methods using one fixed anode and approaching anodes.

PubMed

Shen, Zhemin; Chen, Xuejun; Jia, Jinping; Qu, Liya; Wang, Wenhua

2007-11-01

During the cation exchange membrane (CEM) enhanced electrokinetic (EK) soil remediation, the nearer to the anode, the higher are the H+ concentrations and the redox potentials. As both low pH and high redox potential are helpful to speed-up Cd electro-migration, soils near the anode can be quickly remedied. Usually EK process is operated with one fixed anode (FA). A novel CEM enhanced EK method with approaching anodes (AAs) is proposed to accelerate electro-migration effect. Several mesh Ti/Ru anodes were inserted as AAs in the treated soil. They were switched in turn from the anode towards the cathode. Thus high H+ ions concentrations and high redox potentials quickly migrate to the cathode. Consequently, soil remediation is accelerated and nearly 44% of energy and 40% of time can be saved. The mechanism of Cd electro-migration behavior in soils during CEM enhanced EK is described as the elution in an electrokinetically driven chromatogram.

A new electrophoretic focusing principle: focusing of nonamphoteric weak ionogenic analytes using inverse electromigration dispersion profiles.

PubMed

Gebauer, Petr; Malá, Zdena; Bocek, Petr

2010-03-01

This contribution introduces a new separation principle in CE which offers focusing of weak nonamphoteric ionogenic species and their inherent transport to the detector. The prerequisite condition for application of this principle is the existence of an inverse electromigration dispersion profile, i.e. a profile where pH is decreasing toward the anode or cathode for focusing of anionic or cationic weak analytes, respectively. The theory presented defines the principal conditions under which an analyte is focused on a profile of this type. Since electromigration dispersion profiles are migrating ones, the new principle offers inherent transport of focused analytes into the detection cell. The focusing principle described utilizes a mechanism different from both CZE (where separation is based on the difference in mobilities) and IEF (where separation is based on difference in pI), and hence, offers another separation dimension in CE. The new principle and its theory presented here are supplemented by convincing experiments as their proof.

Dielectric cracking produced by electromigration in microelectronic interconnects

NASA Astrophysics Data System (ADS)

Chiras, S.; Clarke, D. R.

2000-12-01

The development of stress during electromigration along Al lines, constrained within a dielectric in a coplanar test configuration, is measured. It is shown that, above a certain threshold current density, cracking of the dielectric is induced in the vicinity of the anode. Cracking of the dielectric leads to loss of mechanical constraint on the aluminum conductor which, in turn, leads to increases in electrical resistance with continued current flow. The electromigration-induced stresses are determined from the measured frequency shifts induced in a novel ruby strain sensor embedded immediately beneath the interconnect line on a sapphire substrate. The transparency of the sapphire substrate also facilitated the observation of a hitherto unreported form of dielectric cracking, namely cracking from the interconnect along internal interfaces. The observations of dielectric cracking are in agreement with a recent fracture mechanics model. Analysis of the stress data, together with the results of finite element calculations of the strain energy release rate for crack extension, gives a quantitative estimate of the effective valence Z*(=1.3±0.2) for aluminum.

Thermoreflectance imaging of electromigration evolution in asymmetric aluminum constrictions

NASA Astrophysics Data System (ADS)

Tian, Hao; Ahn, Woojin; Maize, Kerry; Si, Mengwei; Ye, Peide; Alam, Muhammad Ashraful; Shakouri, Ali; Bermel, Peter

2018-01-01

Electromigration (EM) is a phenomenon whereby the flow of current in metal wires moves the underlying atoms, potentially inducing electronic interconnect failures. The continued decrease in commercial lithographically defined feature sizes means that EM presents an increasing risk to the reliability of modern electronics. To mitigate these risks, it is important to look for novel mechanisms to extend lifetime without forfeiting miniaturization. Typically, only the overall increase in the interconnect resistance and failure voltage are characterized. However, if the current flows non-uniformly, spatially resolving the resulting hot spots during electromigration aging experiments may provide better insights into the fundamental mechanisms of this process. In this study, we focus on aluminum interconnects containing asymmetric reservoir and void pairs with contact pads on each end. Such reservoirs are potential candidates for self-healing. Thermoreflectance imaging was used to detect hot spots in electrical interconnects at risk of failure as the voltage was gradually increased. It reveals differential heating with increasing voltage for each polarity. We find that while current flow going from a constriction to a reservoir causes a break at the void, the identical structure with the opposite polarity can sustain higher current (J = 21 × 106 A/cm2) and more localized joule heating and yet is more stable. Ultimately, a break takes place at the contact pad where the current flows from narrow interconnect to larger pads. In summary, thermoreflectance imaging with submicron spatial resolution provides valuable information about localized electromigration evolution and the potential role of reservoirs to create more robust interconnects.

Grain boundary grooving induced by the anisotropic surface drift diffusion driven by the capillary and electromigration forces: Simulations

NASA Astrophysics Data System (ADS)

Akyildiz, Oncu; Omer Ogurtani, Tarik

2011-08-01

The morphological evolution kinetics of a bicrystal thin film induced by anisotropic surface drift diffusion and driven by the applied electrostatic field is investigated via self consistent dynamical computer simulations. The physico-mathematical model, which is based upon the irreversible thermodynamic treatment of surfaces and interfaces with singularities [T. O. Ogurtani, J. Chem. Phys. 124, 144706 (2006)], provided us with auto-control on the otherwise free-motion of the triple junction at the intersection of the grooving surface and the grain boundary, without having any a priori assumption on the equilibrium dihedral angles. The destruction of the symmetry of the freshly formed grain boundary grooves under the anisotropic surface diffusion driven by the concurrent action of the capillarity and electromigration is observed. After prolonged exposure times the applied electric field above the well defined threshold level modifies Mullins' familiar stationary state time law as, t¯1/4, and causes the premature termination of the groove penetration because of the current crowding at the tips of counteracting grain boundary-grooves initiated on both sides of the test modulus. That finding indicates that the electromigration plays the same role as a healing agent [T. O. Ogurtani, J. Appl. Phys. 106, 053503 (2009)] in arresting the thermal grooving, thereby avoiding the premature interconnect failure as in the case of surface roughening and crack initiation caused by compressive stress gradients. The role of the electromigration and wetting parameter on the ridge/slit formations are thoroughly investigated in this study and the prerequisite conditions are also identified.

Remediation of Pb/Cr co-contaminated soil using electrokinetic process and approaching electrode technique.

PubMed

Ng, Yee-Sern; Sen Gupta, Bhaskar; Hashim, Mohd Ali

2016-01-01

Electrokinetic process has emerged as an important tool for remediating heavy metal-contaminated soil. The process can concentrate heavy metals into smaller soil volume even in the absence of hydraulic flow. This makes it an attractive soil pre-treatment method before other remediation techniques are applied such that the chemical consumption in the latter stage can be reduced. The present study evaluates the feasibility of electrokinetic process in concentrating lead (Pb) and chromium (Cr) in a co-contaminated soil using different types of wetting agents, namely 0.01 M NaNO3, 0.1 M citric acid and 0.1 M EDTA. The data obtained showed that NaNO3 and citric acid resulted in poor Pb electromigration in this study. As for Cr migration, these agents were also found to give lower electromigration rate especially at low pH region as a result of Cr(VI) adsorption and possible reduction into Cr(III). In contrast, EDTA emerged as the best wetting agent in this study as it formed water-soluble anionic complexes with both Pb and Cr. This provided effective one-way electromigration towards the anode for both ions, and they were accumulated into smaller soil volume with an enrichment ratio of 1.55-1.82. A further study on the application of approaching cathode in EDTA test showed that soil alkalisation was achieved, but this did not provide significant enhancement on electromigration for Pb and Cr. Nevertheless, the power consumption for electrokinetic process was decreased by 22.5%.

Applications of Electromigration Techniques: Applications of Electromigration Techniques in Food Analysis

NASA Astrophysics Data System (ADS)

Wieczorek, Piotr; Ligor, Magdalena; Buszewski, Bogusław

Electromigration techniques, including capillary electrophoresis (CE), are widely used for separation and identification of compounds present in food products. These techniques may also be considered as alternate and complementary with respect to commonly used analytical techniques, such as high-performance liquid chromatography (HPLC), or gas chromatography (GC). Applications of CE concern the determination of high-molecular compounds, like polyphenols, including flavonoids, pigments, vitamins, food additives (preservatives, antioxidants, sweeteners, artificial pigments) are presented. Also, the method developed for the determination of proteins and peptides composed of amino acids, which are basic components of food products, are studied. Other substances such as carbohydrates, nucleic acids, biogenic amines, natural toxins, and other contaminations including pesticides and antibiotics are discussed. The possibility of CE application in food control laboratories, where analysis of the composition of food and food products are conducted, is of great importance. CE technique may be used during the control of technological processes in the food industry and for the identification of numerous compounds present in food. Due to the numerous advantages of the CE technique it is successfully used in routine food analysis.

High-resolution determination of the stress in individual interconnect lines and the variation due to electromigration

NASA Astrophysics Data System (ADS)

Ma, Qing; Chiras, S.; Clarke, D. R.; Suo, Z.

1995-08-01

Large tensile stresses usually exist in metallic interconnect lines on silicon substrates as a result of thermal mismatch. When a current is subsequently passed any divergence of atomic flux can create superimposed stress variations along the line. Together, these stresses can significantly influence the growth of voids and therefore affect interconnect reliability. In this work, a high-resolution (˜2 μm) optical spectroscopy method has been used to measure the localized stresses around passivated aluminum lines on a silicon wafer, both as-fabricated and after electromigration testing. The method is based on the piezospectroscopic properties of silicon, specifically the frequency shift of the Raman line at 520 R cm-1. By focusing a laser beam at points adjacent to the aluminum lines, the Raman signal was excited and collected. The stresses in the aluminum lines can then be derived from the stresses in the silicon using finite element methods. Large variations of stress along an electromigration-tested line were observed and compared to a theoretical model based on differences in effective diffusivities from grain to grain in a polycrystalline interconnect line.

Effect of Joule heating and current crowding on electromigration in mobile technology

NASA Astrophysics Data System (ADS)

Tu, K. N.; Liu, Yingxia; Li, Menglu

2017-03-01

In the present era of big data and internet of things, the use of microelectronic products in all aspects of our life is manifested by the ubiquitous presence of mobile devices as i-phones and wearable i-products. These devices are facing the need for higher power and greater functionality applications such as in i-health, yet they are limited by physical size. At the moment, software (Apps) is much ahead of hardware in mobile technology. To advance hardware, the end of Moore's law in two-dimensional integrated circuits can be extended by three-dimensional integrated circuits (3D ICs). The concept of 3D ICs has been with us for more than ten years. The challenge in 3D IC technology is dense packing by using both vertical and horizontal interconnections. Mass production of 3D IC devices is behind schedule due to cost because of low yield and uncertain reliability. Joule heating is serious in a dense structure because of heat generation and dissipation. A change of reliability paradigm has advanced from failure at a specific circuit component to failure at a system level weak-link. Currently, the electronic industry is introducing 3D IC devices in mainframe computers, where cost is not an issue, for the purpose of collecting field data of failure, especially the effect of Joule heating and current crowding on electromigration. This review will concentrate on the positive feedback between Joule heating and electromigration, resulting in an accelerated system level weak-link failure. A new driving force of electromigration, the electric potential gradient force due to current crowding, will be reviewed critically. The induced failure tends to occur in the low current density region.

A Field Test of Electromigration as a Method for Remediating Sulfate from Shallow Ground Water

USGS Publications Warehouse

Patterson, C.G.; Runnells, D.D.

1996-01-01

Electromigration offers a potential tool for remediating ground water contaminated with highly soluble components, such as Na+, Cl-, NO3-, and SO4-. A field experiment was designed to test the efficacy of electromigration for preconcentrating dissolved SO42- in ground water associated with a fossil-fuel power plant. Two shallow wells, 25 feet apart (one 25 feet deep, the other 47 feet deep), were constructed in the upper portion of an unconfined alluvial aquifer. The wells were constructed with a double-wall design, with an outer casing of 4-inch PVC and an inner tube of 2-inch PVC; both were fully slotted (0.01 inch). Electrodes were constructed by wrapping the inner tubing with a 100-foot length of rare-earth metal oxide/copper wire. An electrical potential of 10.65 volts DC was applied, and tests were run for periods of 12, 44, and 216 hours. Results showed large changes in the pH from the initial pH of ground water of about 7.5 to values of approximately 2 and 12 at the anode and cathode, respectively. Despite the fact that the test conditions were far from ideal, dissolved SO42- was significantly concentrated at the anode. Over a period of approximately nine days, the concentration of SO42- at the anode reached what appeared to be a steady-state value of 2200 mg/L, compared to the initial value in ground water of approximately 1150 mg/L. The results of this field test should encourage further investigation of electromigration as a tool in the remediation of contaminated ground water.

New methodology for capillary electrophoresis with ESI-MS detection: Electrophoretic focusing on inverse electromigration dispersion gradient. High-sensitivity analysis of sulfonamides in waters.

PubMed

Malá, Zdena; Gebauer, Petr; Boček, Petr

2016-09-07

This article describes for the first time the combination of electrophoretic focusing on inverse electromigration dispersion (EMD) gradient, a new separation principle described in 2010, with electrospray-ionization (ESI) mass spectrometric detection. The separation of analytes along the electromigrating EMD profile proceeds so that each analyte is focused and concentrated within the profile at a particular position given by its pKa and ionic mobility. The proposed methodology combines this principle with the transport of the focused zones to the capillary end by superimposed electromigration, electroosmotic flow and ESI suction, and their detection by the MS detector. The designed electrolyte system based on maleic acid and 2,6-lutidine is suitable to create an inverse EMD gradient of required properties and its components are volatile enough to be compatible with the ESI interface. The characteristic properties of the proposed electrolyte system and of the formed inverse gradient are discussed in detail using calculated diagrams and computer simulations. It is shown that the system is surprisingly robust and allows sensitive analyses of trace amounts of weak acids in the pKa range between approx. 6 and 9. As a first practical application of electrophoretic focusing on inverse EMD gradient, the analysis of several sulfonamides in waters is reported. It demonstrates the potential of the developed methodology for fast and high-sensitivity analyses of ionic trace analytes, with reached LODs around 3 × 10(-9) M (0.8 ng mL(-1)) of sulfonamides in spiked drinking water without any sample pretreatment. Copyright © 2016 Elsevier B.V. All rights reserved.

Electromigration kinetics and critical current of Pb-free interconnects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Minhua; Rosenberg, Robert

2014-04-07

Electromigration kinetics of Pb-free solder bump interconnects have been studied using a single bump parameter sweep technique. By removing bump to bump variations in structure, texture, and composition, the single bump sweep technique has provided both activation energy and power exponents that reflect atomic migration and interface reactions with fewer samples, shorter stress time, and better statistics than standard failure testing procedures. Contact metallurgies based on Cu and Ni have been studied. Critical current, which corresponds to the Blech limit, was found to exist in the Ni metallurgy, but not in the Cu metallurgy. A temperature dependence of critical currentmore » was also observed.« less

Structure control of tungsten nanocontacts through pulsed-voltage application

NASA Astrophysics Data System (ADS)

Suzuki, Yasuchika; Kizuka, Tokushi

2018-05-01

The structural variation in tungsten nanocontacts (NCs) during a pulsed-voltage application was observed in situ by high-resolution transmission electron microscopy. The direction of electromigration in the NCs changed from the well-known direction to the opposite direction at a critical voltage of 0.9 V. Upon applying a higher pulsed voltage of 2.5 V, the NC structure changed to amorphous, with an average conductance density decreased to 82% of that of the crystalline NCs. We demonstrated that the external shape and texture of tungsten NCs can be controlled with an atomic precision through electromigration and amorphization by a pulsed-voltage application.

Electromigrative separation techniques in forensic science: combining selectivity, sensitivity, and robustness.

PubMed

Posch, Tjorben Nils; Pütz, Michael; Martin, Nathalie; Huhn, Carolin

2015-01-01

In this review we introduce the advantages and limitations of electromigrative separation techniques in forensic toxicology. We thus present a summary of illustrative studies and our own experience in the field together with established methods from the German Federal Criminal Police Office rather than a complete survey. We focus on the analytical aspects of analytes' physicochemical characteristics (e.g. polarity, stereoisomers) and analytical challenges including matrix tolerance, separation from compounds present in large excess, sample volumes, and orthogonality. For these aspects we want to reveal the specific advantages over more traditional methods. Both detailed studies and profiling and screening studies are taken into account. Care was taken to nearly exclusively document well-validated methods outstanding for the analytical challenge discussed. Special attention was paid to aspects exclusive to electromigrative separation techniques, including the use of the mobility axis, the potential for on-site instrumentation, and the capillary format for immunoassays. The review concludes with an introductory guide to method development for different separation modes, presenting typical buffer systems as starting points for different analyte classes. The objective of this review is to provide an orientation for users in separation science considering using capillary electrophoresis in their laboratory in the future.

A nonviral transfection approach in vitro: the design of a gold nanoparticle vector joint with microelectromechanical systems.

PubMed

Jen, Chun-Ping; Chen, Yu-Hung; Fan, Chun-sheng; Yeh, Chen-Sheng; Lin, Yu-Cheng; Shieh, Dar-Bin; Wu, Chao-Ling; Chen, Dong-Hwang; Chou, Chen-Hsi

2004-02-17

Au nanoparticles modified with 21-base thiolated-oligonucleotides have been evaluated as delivery vehicles for the development of a nonviral transfection platform. The electromigration combined with electroporation for DNA delivery in an osteoblast like cell was employed to test on microchips. Electroporation introduces foreign materials into cells by applying impulses of electric field to induce multiple transient pores on the cell membrane through dielectric breakdown of the cell membrane. On the basis of the characteristic surface plasmon of the Au particles, UV-vis absorption was utilized to qualitatively judge the efficiency of delivery. Transmission electron microscopy images and atomic absorption measurements (quantitative analysis) provided evidence of the bare Au and Au/oligonucleotide nanoparticles before and after electroporation and electromigration function. The experiments demonstrated that electrophoretic migration followed by electroporation significantly enhanced the transportation efficiency of the nanoparticle-oligonucleotide complexes as compared with electroporation alone. Most interestingly, Au capped with oligonucleotides led to optimal performance. On the other hand, the bare Au colloidal suspensions resulted in aggregation, which might be an obstacle to the internalization process. In addition, analytical results demonstrated an increase in the local particle concentrations on the cell surface that provided additional support for the mechanism underlying the improved Au nanoparticle transportation into cells in the presence of electromigration function.

Can amorphization take place in nanoscale interconnects?

PubMed

Kumar, S; Joshi, K L; van Duin, A C T; Haque, M A

2012-03-09

The trend of miniaturization has highlighted the problems of heat dissipation and electromigration in nanoelectronic device interconnects, but not amorphization. While amorphization is known to be a high pressure and/or temperature phenomenon, we argue that defect density is the key factor, while temperature and pressure are only the means. For nanoscale interconnects carrying modest current density, large vacancy concentrations may be generated without the necessity of high temperature or pressure due to the large fraction of grain boundaries and triple points. To investigate this hypothesis, we performed in situ transmission electron microscope (TEM) experiments on 200 nm thick (80 nm average grain size) aluminum specimens. Electron diffraction patterns indicate partial amorphization at modest current density of about 10(5) A cm(-2), which is too low to trigger electromigration. Since amorphization results in drastic decrease in mechanical ductility as well as electrical and thermal conductivity, further increase in current density to about 7 × 10(5) A cm(-2) resulted in brittle fracture failure. Our molecular dynamics (MD) simulations predict the formation of amorphous regions in response to large mechanical stresses (due to nanoscale grain size) and excess vacancies at the cathode side of the thin films. The findings of this study suggest that amorphization can precede electromigration and thereby play a vital role in the reliability of micro/nanoelectronic devices.

Electromigration-induced Plasticity and Texture in Cu Interconnects

NASA Astrophysics Data System (ADS)

Budiman, A. S.; Hau-Riege, C. S.; Besser, P. R.; Marathe, A.; Joo, Y.-C.; Tamura, N.; Patel, J. R.; Nix, W. D.

2007-10-01

Plastic deformation has been observed in damascene Cu interconnect test structures during an in-situ electromigration experiment and before the onset of visible microstructural damage (ie. voiding) using a synchrotron technique of white beam X-ray microdiffraction. We show here that the extent of this electromigration-induced plasticity is dependent on the texture of the Cu grains in the line. In lines with strong <111> textures, the extent of plastic deformation is found to be relatively large compared to our plasticity results in the previous study[1] using another set of Cu lines with weaker textures. This is consistent with our earlier observation that the occurrence of plastic deformation in a given grain can be strongly correlated with the availability of a <112> direction of the crystal in the proximity of the direction of the electron flow in the line (within an angle of 10°). In <111> out-of-plane oriented grains in a damascene interconnect scheme, the crystal plane facing the sidewall tends to be a {110} plane,[2-4] so as to minimize interfacial energy. Therefore, it is deterministic rather than probabilistic that the <111> grains will have a <112> direction nearly parallel to the direction of electron flow. Thus, strong <111> textures lead to more plasticity, as we observe.

Electromigration failure mode concerning negative resistance shift of Cu interconnects buried in porous low-k dielectric

NASA Astrophysics Data System (ADS)

Zheng, Hui; Yin, Binfeng; Yu, Hewei; Chen, Leigang; Gao, Lin; Zhou, Ke; Kuo, Chinte

2017-02-01

Electromigration failure mode concerning a negative resistance shift of 4%-11% and cathode burnout was reported for Cu interconnects buried in porous low-k in this paper. Evidence for oxidation and debonding of Ta/TaN liner at high temperature was revealed, which was demonstrated to have been enabled by the unsealed porous low-k due to moisture uptake. The cathode burnout was thus attributed to severe Joule heating induced in the insulated liner after oxidation. The resistance decay of Cu also exhibited to be mainly consistent with the calculation from specularity recovery of electron scattering at the Cu/Ta interface after oxidation and debonding of the liner, although other factors like strain relaxation may also have some contribution.

Observation of electromigration in a Cu thin line by in situ coherent x-ray diffraction microscopy

NASA Astrophysics Data System (ADS)

Takahashi, Yukio; Nishino, Yoshinori; Furukawa, Hayato; Kubo, Hideto; Yamauchi, Kazuto; Ishikawa, Tetsuya; Matsubara, Eiichiro

2009-06-01

Electromigration (EM) in a 1-μm-thick Cu thin line was investigated by in situ coherent x-ray diffraction microscopy (CXDM). Characteristic x-ray speckle patterns due to both EM-induced voids and thermal deformation in the thin line were observed in the coherent x-ray diffraction patterns. Both parts of the voids and the deformation were successfully visualized in the images reconstructed from the diffraction patterns. This result not only represents the first demonstration of the visualization of structural changes in metallic materials by in situ CXDM but is also an important step toward studying the structural dynamics of nanomaterials using x-ray free-electron lasers in the near future.

X-Ray Microdiffraction as a Probe to Reveal Flux Divergences in Interconnects

NASA Astrophysics Data System (ADS)

Spolenak, R.; Tamura, N.; Patel, J. R.

2006-02-01

Most reliability issues in interconnect systems occur at a local scale and many of them include the local build-up of stresses. Typical failure mechanisms are electromigration and stress voiding in interconnect lines and fatigue in surface acoustic wave devices. Thus a local probe is required for the investigation of these phenomena. In this paper the application of the Laue microdiffraction technique to investigate flux divergences in interconnect systems will be described. The deviatoric strain tensor of single grains can be correlated with the local microstructure, orientation and defect density. Especially the latter led to recent results about the correlation of stress build-up and orientation in Cu lines and electromigration-induced grain rotation in Cu and Al lines.

1/f noise measurements for faster evaluation of electromigration in advanced microelectronics interconnections

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beyne, Sofie, E-mail: sofie.beyne@imec.be; De Wolf, Ingrid; imec, Kapeldreef 75, B-3001 Leuven

The use of 1/f noise measurements is explored for the purpose of finding faster techniques for electromigration (EM) characterization in advanced microelectronic interconnects, which also enable a better understanding of its underlying physical mechanisms. Three different applications of 1/f noise for EM characterization are explored. First, whether 1/f noise measurements during EM stress can serve as an early indicator of EM damage. Second, whether the current dependence of the noise power spectral density (PSD) can be used for a qualitative comparison of the defect concentration of different interconnects and consequently also their EM lifetime t50. Third, whether the activation energiesmore » obtained from the temperature dependence of the 1/f noise PSD correspond to the activation energies found by means of classic EM tests. In this paper, the 1/f noise technique has been used to assess and compare the EM properties of various advanced integration schemes and different materials, as they are being explored by the industry to enable advanced interconnect scaling. More concrete, different types of copper interconnects and one type of tungsten interconnect are compared. The 1/f noise measurements confirm the excellent electromigration properties of tungsten and demonstrate a dependence of the EM failure mechanism on copper grain size and distribution, where grain boundary diffusion is found to be a dominant failure mechanism.« less

Treatment Prevents Corrosion in Steel and Concrete Structures

NASA Technical Reports Server (NTRS)

2007-01-01

In the mid-1990s, to protect rebar from corrosion, NASA developed an electromigration technique that sends corrosion-inhibiting ions into rebar to prevent rust, corrosion, and separation from the surrounding concrete. Kennedy Space Center worked with Surtreat Holding LLC, of Pittsburgh, Pennsylvania, a company that had developed a chemical option to fight structural corrosion, combining Surtreat's TPS-II anti-corrosive solution and electromigration. Kennedy's materials scientists reviewed the applicability of the chemical treatment to the electromigration process and determined that it was an effective and environmentally friendly match. Ten years later, NASA is still using this approach to fight concrete corrosion, and it has also developed a new technology that will further advance these efforts-a liquid galvanic coating applied to the outer surface of reinforced concrete to protect the embedded rebar from corrosion. Surtreat licensed this new coating technology and put it to use at the U.S. Army Naha Port, in Okinawa, Japan. The new coating prevents corrosion of steel in concrete in several applications, including highway and bridge infrastructures, piers and docks, concrete balconies and ceilings, parking garages, cooling towers, and pipelines. A natural compliment to the new coating, Surtreat's Total Performance System provides diagnostic testing and site analysis to identify the scope of problems for each project, manufactures and prescribes site-specific solutions, controls material application, and verifies performance through follow-up testing and analysis.

ELECTROKINETIC REMEDIATION: BASICS AND TECHNOLOGY STATUS

EPA Science Inventory

Electrokinetic remediation, variably named as electrochemical soil processing, electromigration, electrokinetic decontamination or electroreclamation uses electric currents to extract radionuclides, heavy metals, certain organic compounds, or mixed inorganic species and some orga...

The microstructure, mechanical stress, texture, and electromigration behavior of Al-Pd alloys

NASA Astrophysics Data System (ADS)

Rodbell, K. P.; Knorr, D. B.; Mis, J. D.

1993-06-01

As the minimum feature size of interconnect lines decreases below 0.5 urn, the need to control the line microstructure becomes increasingly important. The alloy content, deposition process, fabrication method, and thermal history all determine the microstructure of an interconnect, which, in turn, affects its performance and reliability. The motivation for this work was to characterize the microstructure of various sputtered Al-Pd alloys (Al-0.3wt.%Pd, Al-2Cu-0.3Pd, and Al-0.3Nb-0.3Pd) vs sputtered Al-Cu control samples (Al-0.5Cu and Al-2Cu) and to assess the role of grain size, mechanical stress, and crystallographic texture on the electromigration behavior of submicrometer wide lines. The grain size, mechanical stress, and texture of blanket films were measured as a function of annealing. The as-deposited film stress was tensile and followed a similar stress history on heating for all of the films; on cooling, however, significant differences were observed between the Al-Pd and Al-Cu films in the shape of their stress-temperature-curves. A strong (111) crystallographic texture was typically found for Al-Cu films deposited on SiO2. A stronger (111) texture resulted when Al-Cu was deposited on 25 nm titanium. Al-0.3Pd films, however, exhibited either a weak (111) or (220) texture when deposited on SiO2, which reverted to a strong (111) texture when deposited on 25 nm titanium. The electromigration lifetimes of passivated, ≈0.7 μm wide lines at 250°C and 2.5 × 106 A/cm2 for both single and multi-level samples (separated with W studs) are reported. The electromigration behavior of Al-0.3Pd was found to be less dependent on film microstructure than on the annealing atmosphere used, i.e. forming gas (90% N2-10%H2) annealed Al-0.3Pd films were superior to all of the alloys investigated, while annealing in only N2 resulted in poor lifetimes.

A general strategy for the ultrafast surface modification of metals.

PubMed

Shen, Mingli; Zhu, Shenglong; Wang, Fuhui

2016-12-07

Surface modification is an essential step in engineering materials that can withstand the increasingly aggressive environments encountered in various modern energy-conversion systems and chemical processing industries. However, most traditional technologies exhibit disadvantages such as slow diffusion kinetics, processing difficulties or compatibility issues. Here, we present a general strategy for the ultrafast surface modification of metals inspired by electromigration, using aluminizing austenitic stainless steel as an example. Our strategy facilitates the rapid formation of a favourable ductile surface layer composed of FeCrAl or β-FeAl within only 10 min compared with several hours in conventional processes. This result indicates that electromigration can be used to achieve the ultrafast surface modification of metals and can overcome the limitations of traditional technologies. This strategy could be used to aluminize ultra-supercritical steam tubing to withstand aggressive oxidizing environments.

Mechanical Stress Effects on Electromigration Voiding in a Meandering Test Stripe

NASA Technical Reports Server (NTRS)

Lowry, L. E.; Tai, B. H.; Mattila, J.; Walsh, L. H.

1993-01-01

Earlier experimental findings concluded that electromigratin voids in these meandering stripe test structures were not randomly distributed and that void nucleation frequenly occurred sub-surface at the metal/thermal oxide interface.

[Diffusion and diffusion-osmosis models of the charged macromolecule transfer in barriers of biosystems].

PubMed

Varakin, A I; Mazur, V V; Arkhipova, N V; Serianov, Iu V

2009-01-01

Mathematical models of the transfer of charged macromolecules have been constructed on the basis of the classical equations of electromigration diffusion of Helmholtz-Smolukhovskii, Goldman, and Goldman-Hodgkin-Katz. It was shown that ion transfer in placental (mimicking lipid-protein barriers) and muscle barriers occurs by different mechanisms. In placental barriers, the electromigration diffusion occurs along lipid-protein channels formed due to the conformational deformation of phospholipid and protein molecules with the coefficients of diffusion D = (2.6-3.6) x 10(-8) cm2/s. The transfer in muscle barriers is due to the migration across charged interfibrillar channels with the negative diffusion activation energy, which is explained by changes in the structure of muscle fibers and expenditures of thermal energy for the extrusion of Cl- from channel walls with the diffusion coefficient D = (6.0-10.0) x 10(-6) cm2/s.

A general strategy for the ultrafast surface modification of metals

PubMed Central

Shen, Mingli; Zhu, Shenglong; Wang, Fuhui

2016-01-01

Surface modification is an essential step in engineering materials that can withstand the increasingly aggressive environments encountered in various modern energy-conversion systems and chemical processing industries. However, most traditional technologies exhibit disadvantages such as slow diffusion kinetics, processing difficulties or compatibility issues. Here, we present a general strategy for the ultrafast surface modification of metals inspired by electromigration, using aluminizing austenitic stainless steel as an example. Our strategy facilitates the rapid formation of a favourable ductile surface layer composed of FeCrAl or β-FeAl within only 10 min compared with several hours in conventional processes. This result indicates that electromigration can be used to achieve the ultrafast surface modification of metals and can overcome the limitations of traditional technologies. This strategy could be used to aluminize ultra-supercritical steam tubing to withstand aggressive oxidizing environments. PMID:27924909

Identification of Microorganisms by Modern Analytical Techniques.

PubMed

Buszewski, Bogusław; Rogowska, Agnieszka; Pomastowski, Paweł; Złoch, Michał; Railean-Plugaru, Viorica

2017-11-01

Rapid detection and identification of microorganisms is a challenging and important aspect in a wide range of fields, from medical to industrial, affecting human lives. Unfortunately, classical methods of microorganism identification are based on time-consuming and labor-intensive approaches. Screening techniques require the rapid and cheap grouping of bacterial isolates; however, modern bioanalytics demand comprehensive bacterial studies at a molecular level. Modern approaches for the rapid identification of bacteria use molecular techniques, such as 16S ribosomal RNA gene sequencing based on polymerase chain reaction or electromigration, especially capillary zone electrophoresis and capillary isoelectric focusing. However, there are still several challenges with the analysis of microbial complexes using electromigration technology, such as uncontrolled aggregation and/or adhesion to the capillary surface. Thus, an approach using capillary electrophoresis of microbial aggregates with UV and matrix-assisted laser desorption ionization time-of-flight MS detection is presented.

Buried structure for increasing fabrication performance of micromaterial by electromigration

NASA Astrophysics Data System (ADS)

Kimura, Yasuhiro; Saka, Masumi

2016-06-01

The electromigration (EM) technique is a physical synthetic growth method for micro/nanomaterials. EM causes atomic diffusion in a metal line by high-density electron flows. The intentional control of accumulation and relaxation of atoms by EM can lead to the fabrication of a micro/nanomaterial. TiN passivation has been utilized as a component of sample in the EM technique. Although TiN passivation can simplify the cumbersome processes for preparing the sample, the leakage of current naturally occurs because of the conductivity of TiN as a side effect and decreases the performance of micro/nanomaterial fabrication. In the present work, we propose a buried structure, which contributes to significantly decreasing the current for fabricating an Al micromaterial by confining the current flow in the EM technique. The fabrication performance was evaluated based on the threshold current for fabricating an Al micromaterial using the buried structure and the previous structure with the leakage of current.

Optimization of the nanotwin-induced zigzag surface of copper by electromigration

NASA Astrophysics Data System (ADS)

Chen, Hsin-Ping; Huang, Chun-Wei; Wang, Chun-Wen; Wu, Wen-Wei; Liao, Chien-Neng; Chen, Lih-Juann; Tu, King-Ning

2016-01-01

By adding nanotwins to Cu, the surface electromigration (EM) slows down. The atomic mobility of the surface step-edges is retarded by the triple points where a twin meets a free surface to form a zigzag-type surface. We observed that EM can alter the zigzag surface structure to optimize the reduction of EM, according to Le Chatelier's principle. Statistically, the optimal alternation is to change an arbitrary (111)/(hkl) zigzag pair to a pair having a very low index (hkl) plane, especially the (200) plane. Using in situ ultrahigh vacuum and high-resolution transmission electron microscopy, we examined the effects of different zigzag surfaces on the rate of EM. The calculated rate of surface EM can be decreased by a factor of ten.By adding nanotwins to Cu, the surface electromigration (EM) slows down. The atomic mobility of the surface step-edges is retarded by the triple points where a twin meets a free surface to form a zigzag-type surface. We observed that EM can alter the zigzag surface structure to optimize the reduction of EM, according to Le Chatelier's principle. Statistically, the optimal alternation is to change an arbitrary (111)/(hkl) zigzag pair to a pair having a very low index (hkl) plane, especially the (200) plane. Using in situ ultrahigh vacuum and high-resolution transmission electron microscopy, we examined the effects of different zigzag surfaces on the rate of EM. The calculated rate of surface EM can be decreased by a factor of ten. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05418d

Utilization of electromigration in civil and environmental engineering--processes, transport rates and matrix changes.

PubMed

Ottosen, Lisbeth M; Christensen, Iben V; Rorig-Dalgård, Inge; Jensen, Pernille E; Hansen, Henrik K

2008-07-01

Electromigration (movement of ions in an applied electric field) is utilized for supply or extraction of ions from various porous materials within both civil and environmental engineering. In civil engineering, most research has been conducted on the removal of chlorides from concrete to hinder reinforcement corrosion while in environmental engineering remediation of heavy metal polluted soil is the issue most studied. Never the less, experiments have been conducted with utilization for several other materials and purposes within both engineering fields. Even though there are many topics of common interest in the use of electromigration for the two fields, there is no tradition for collaboration. The present paper is a review with the aim of pointing out areas of shared interest. Focus is laid on the purposes of the different processes, transport rates of various ions in different materials and on changes in the matrix itself. Desorption and dissolution of the target elements into ionic form is a key issue to most of the processes, and can be the limiting step. The removal rate is generally below 1 cm day(- 1), but it can be much less than 1 mm day(- 1) when desorption is slow and insufficient. Matrix changes occurs under the action of the applied electric field and it includes both physico-chemical and hydrological changes. Some of the solid phases is weathered and new can be formed. Increased fundamental understanding of the effects and side effects, when applying the electric field to a porous material, can lead to improvement of the known technologies and possibly to new applications.

Glyphosate analysis using sensors and electromigration separation techniques as alternatives to gas or liquid chromatography.

PubMed

Gauglitz, Günter; Wimmer, Benedikt; Melzer, Tanja; Huhn, Carolin

2018-01-01

Since its introduction in 1974, the herbicide glyphosate has experienced a tremendous increase in use, with about one million tons used annually today. This review focuses on sensors and electromigration separation techniques as alternatives to chromatographic methods for the analysis of glyphosate and its metabolite aminomethyl phosphonic acid. Even with the large number of studies published, glyphosate analysis remains challenging. With its polar and depending on pH even ionic functional groups lacking a chromophore, it is difficult to analyze with chromatographic techniques. Its analysis is mostly achieved after derivatization. Its purification from food and environmental samples inevitably results incoextraction of ionic matrix components, with a further impact on analysis derivatization. Its purification from food and environmental samples inevitably results in coextraction of ionic matrix components, with a further impact on analysis and also derivatization reactions. Its ability to form chelates with metal cations is another obstacle for precise quantification. Lastly, the low limits of detection required by legislation have to be met. These challenges preclude glyphosate from being analyzed together with many other pesticides in common multiresidue (chromatographic) methods. For better monitoring of glyphosate in environmental and food samples, further fast and robust methods are required. In this review, analytical methods are summarized and discussed from the perspective of biosensors and various formats of electromigration separation techniques, including modes such as capillary electrophoresis and micellar electrokinetic chromatography, combined with various detection techniques. These methods are critically discussed with regard to matrix tolerance, limits of detection reached, and selectivity.

Evidence for oxygen vacancy or ferroelectric polarization induced switchable diode and photovoltaic effects in BiFeO3 based thin films.

PubMed

Guo, Yiping; Guo, Bing; Dong, Wen; Li, Hua; Liu, Hezhou

2013-07-12

The diode and photovoltaic effects of BiFeO3 and Bi0.9Sr0.1FeO(3-δ) polycrystalline thin films were investigated by poling the films with increased magnitude and alternating direction. It was found that both electromigration of oxygen vacancies and polarization flipping are able to induce switchable diode and photovoltaic effects. For the Bi0.9Sr0.1FeO(3-δ) thin films with high oxygen vacancy concentration, reversibly switchable diode and photovoltaic effects can be observed due to the electromigration of oxygen vacancies under an electric field much lower than its coercive field. However, for the pure BiFeO3 thin films with lower oxygen vacancy concentration, the reversibly switchable diode and photovoltaic effect is hard to detect until the occurrence of polarization flipping. The switchable diode and photovoltaic effects can be explained well using the concepts of Schottky-like barrier-to-Ohmic contacts resulting from the combination of oxygen vacancies and polarization. The sign of photocurrent could be independent of the direction of polarization when the modulation of the energy band induced by oxygen vacancies is large enough to offset that induced by polarization. The photovoltaic effect induced by the electromigration of oxygen vacancies is unstable due to the diffusion of oxygen vacancies or the recombination of oxygen vacancies with hopping electrons. Our work provides deep insights into the nature of diode and photovoltaic effects in ferroelectric films, and will facilitate the advanced design of switchable devices combining spintronic, electronic, and optical functionalities.

Electromigration analysis of solder joints under ac load: A mean time to failure model

NASA Astrophysics Data System (ADS)

Yao, Wei; Basaran, Cemal

2012-03-01

In this study, alternating current (ac) electromigration (EM) degradation simulations were carried out for Sn95.5%Ag4.0%Cu0.5 (SAC405- by weight) solder joints. Mass transport analysis was conducted with viscoplastic material properties for quantifying damage mechanism in solder joints. Square, sine, and triangle current wave forms ac were used as input signals. dc and pulsed dc (PDC) electromigration analysis were conducted for comparison purposes. The maximum current density ranged from 2.2×106A/cm2 to 5.0×106A/cm2, frequency ranged from 0.05 Hz to 5 Hz with ambient temperature varying from 350 K to 450 K. Because the room temperature is nearly two-thirds of SAC solder joint's melting point on absolute temperature scale (494.15 K), viscoplastic material model is essential. Entropy based damage evolution model was used to investigate mean time to failure (MTF) behavior of solder joints subjected to ac stressing. It was observed that MTF was inversely proportional to ambient temperature T1.1 in Celsius and also inversely proportional to current density j0.27 in A/cm2. Higher frequency will lead to a shorter lifetime with in the frequency range we studied, and a relationship is proposed as MTF∝f-0.41. Lifetime of a solder joint subjected to ac is longer compared with dc and PDC loading conditions. By introducing frequency, ambient temperature and current density dependency terms, a modified MTTF equation was proposed for solder joints subjected to ac current stressing.

The transport behavior of As, Cu, Pb, and Zn during electrokinetic remediation of a contaminated soil using electrolyte conditioning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Jung-Seok; Kwon, Man Jae; Choi, Jaeyoung

2014-12-01

Electrokinetic remediation (also known as electrokinetics) is a promising technology for removing metals from fine-grained soils. However, few studies have been conducted regarding the transport behavior of multi-metals during electrokinetics. We investigated the transport of As, Cu, Pb, and Zn from soils during electrokinetics, the metal fractionation before and after electrokinetics, the relationships between metal transport and fractionation, and the effects of electrolyte conditioning. The main transport mechanisms of the metals were electroosmosis and electromigration during the first two weeks and electromigration during the following weeks. The direction of electroosmotic flow was from the anode to the cathode, and themore » metals in the dissolved and reducible-oxides fractions were transported to the anode or cathode by electromigration according to the chemical speciation of the metal ions in the pore water. Moreover, a portion of the metals that were initially in the residual fraction transitioned to the reducible and soluble fractions during electrokinetic treatment. However, this alteration was slow and resulted in decreasing metal removal rates as the electrokinetic treatment progressed. In addition, the use of NaOH, H3PO4, and Na2SO4 as electrolytes resulted in conditions that favored the precipitation of metal hydroxides, phosphates, and sulfates in the soil. These results demonstrated that metal removal was affected by the initial metal fractionation, metal speciation in the pore solution, and the physical–chemical parameters of the electrolytes, such as pH and electrolyte composition. Therefore, the treatment time, use of chemicals, and energy consumption could be reduced by optimizing pretreatment and by choosing appropriate electrolytes for the target metals.« less

Removal of organic pollutants and heavy metals in soils by electrokinetic remediation.

PubMed

Ricart, M T; Pazos, M; Gouveia, S; Cameselle, C; Sanroman, M A

2008-07-01

In this work, the feasibility of electrokinetic remediation for the restoration of polluted soil with organic and inorganic compounds had been development and evaluated using a model soil sample. The model soil was prepared with kaolinite clay artificially polluted in the laboratory with chromium and an azo dye: Reactive Black 5 (RB5). The electromigration of Cr in a spiked kaolinite sample was studied in alkaline conditions. Despite of the high pH registered in the kaolinite sample (around pH 9.5), Cr migrated towards the cathode and it was accumulated in the cathode chamber forming a white precipitate. The removal was not complete, and 23% of the initial Cr was retained into the kaolinite sample close to the cathode side. The azo dye RB5 could be effectively removed from kaolinite by electrokinetics and the complete cleanup of the kaolinite could be achieved in alkaline environment. In this condition, RB5 formed an anion that migrated towards the anode where it was accumulated and quickly degraded upon the electrode surface. The electrokinetic treatment of a kaolinite sample polluted with both Cr and RB5 yielded very good results. The removal of Cr was improved compared to the experiment where Cr was the only pollutant, and RB5 reached a removal as high as 95%. RB5 was removed by electromigration towards the anode, where the dye was degraded upon the surface of the electrode by electrochemical oxidation. Cr was transported towards the cathode by electromigration and electroosmosis. It is supposed that the interaction among RB5 and Cr into the kaolinite sample prevented premature precipitation and allow Cr to migrate and concentrate in the cathode chamber.

Statistical analysis of early failures in electromigration

NASA Astrophysics Data System (ADS)

Gall, M.; Capasso, C.; Jawarani, D.; Hernandez, R.; Kawasaki, H.; Ho, P. S.

2001-07-01

The detection of early failures in electromigration (EM) and the complicated statistical nature of this important reliability phenomenon have been difficult issues to treat in the past. A satisfactory experimental approach for the detection and the statistical analysis of early failures has not yet been established. This is mainly due to the rare occurrence of early failures and difficulties in testing of large sample populations. Furthermore, experimental data on the EM behavior as a function of varying number of failure links are scarce. In this study, a technique utilizing large interconnect arrays in conjunction with the well-known Wheatstone Bridge is presented. Three types of structures with a varying number of Ti/TiN/Al(Cu)/TiN-based interconnects were used, starting from a small unit of five lines in parallel. A serial arrangement of this unit enabled testing of interconnect arrays encompassing 480 possible failure links. In addition, a Wheatstone Bridge-type wiring using four large arrays in each device enabled simultaneous testing of 1920 interconnects. In conjunction with a statistical deconvolution to the single interconnect level, the results indicate that the electromigration failure mechanism studied here follows perfect lognormal behavior down to the four sigma level. The statistical deconvolution procedure is described in detail. Over a temperature range from 155 to 200 °C, a total of more than 75 000 interconnects were tested. None of the samples have shown an indication of early, or alternate, failure mechanisms. The activation energy of the EM mechanism studied here, namely the Cu incubation time, was determined to be Q=1.08±0.05 eV. We surmise that interface diffusion of Cu along the Al(Cu) sidewalls and along the top and bottom refractory layers, coupled with grain boundary diffusion within the interconnects, constitutes the Cu incubation mechanism.

The Effect of Sn Orientation on Intermetallic Compound Growth in Idealized Sn-Cu-Ag Interconnects

NASA Astrophysics Data System (ADS)

Kinney, Chris; Linares, Xioranny; Lee, Kyu-Oh; Morris, J. W.

2013-04-01

The work reported here explores the influence of crystal orientation on the growth of the interfacial intermetallic layer during electromigration in Cu||Sn||Cu solder joints. The samples were thin, planar Sn-Ag-Cu (SAC) solder layers between Cu bars subject to a uniaxial current. Electron backscatter diffraction (EBSD) was used to characterize the microstructure before and after testing. The most useful representation of the EBSD data identifies the Sn grain orientation by the angle between the Sn c-axis and the current direction. The tested samples included single-crystal joints with c-axis nearly parallel to the current ("green" samples) and with c-axis perpendicular to the current ("red" samples). At current density of 104 A/cm2 (steady-state temperature of ~150°C), an intermetallic layer grew at an observable rate in the "green" samples, but not in the "red" ones. A current density of 1.15 × 104 A/cm2 (temperature ~160°C) led to measurable intermetallic growth in both samples. The growth fronts were nearly planar and the growth rates constant (after an initial incubation period); the growth rates in the "green" samples were about 10× those in the "red" samples. The Cu concentrations were constant within the joints, showing that the intermetallic growth is dominated by the electromigration flux. The measured growth rates and literature values for the diffusion of Cu in Sn were used to extract values for the effective charge, z *, that governs the electromigration of Cu. The calculated value of z * is significantly larger for current perpendicular to the c-axis than along it.

A study on electromigration-inducing intergranular fracture of fine silver alloy wires

NASA Astrophysics Data System (ADS)

Hsueh, Hao-Wen; Hung, Fei-Yi; Lui, Truan-Sheng

2017-01-01

In this study, Pd-coated Cu, Ag (purity = 4 N), and Ag alloy (Ag-8Au-3Pd) wires were employed to measure the tensile properties during current stressing using the so-called dynamic current tensile (DCT) test. Both the tensile strength and elongation of the wires decreased dramatically in the DCT test, particularly of the Ag-based wires, and the fracture morphology of the Cu-based and Ag-based wires was ductile fracture and intergranular fracture, respectively. Compared to the Cu-based wires, electromigration occurred more easily in the Ag-based wires, and it always generated voids and cracks at the grain boundaries; therefore, the fracture morphology of the Ag-based wires was intergranular fracture owing to the weakened grain boundary. Further, the results indicated that the Ag-based wires could not carry a higher current density than the Cu-based wires, primarily because their extremely low strength and elongation in current stressing might cause serious reliability problems.

In situ synchrotron study of electromigration induced grain rotations in Sn solder joints

NASA Astrophysics Data System (ADS)

Shen, Hao; Zhu, Wenxin; Li, Yao; Tamura, Nobumichi; Chen, Kai

2016-04-01

Here we report an in situ study of the early stage of microstructure evolution induced by electromigration in a Pb-free β-Sn based solder joint by synchrotron polychromatic X-ray microdiffraction. With this technique, crystal orientation evolution is monitored at intragranular levels with high spatial and angular resolution. During the entire experiment, no crystal growth is detected, and rigid grain rotation is observed only in the two grains within the current crowding region, where high density and divergence of electric current occur. Theoretical calculation indicates that the trend of electrical resistance drop still holds under the present conditions in the grain with high electrical resistivity, while the other grain with low resistivity reorients to align its a-axis more parallel with the ones of its neighboring grains. A detailed study of dislocation densities and subgrain boundaries suggests that grain rotation in β-Sn, unlike grain rotation in high melting temperature metals which undergo displacive deformation, is accomplished via diffusional process mainly, due to the high homologous temperature.

Activation energy associated with the electromigration of oligosaccharides through viscosity modifier and polymeric additive containing background electrolytes.

PubMed

Kerékgyártó, Márta; Járvás, Gábor; Novák, Levente; Guttman, András

2016-02-01

The activation energy related to the electromigration of oligosaccharides can be determined from their measured electrophoretic mobilities at different temperatures. The effects of a viscosity modifier (ethylene glycol) and a polymeric additive (linear polyacrylamide) on the electrophoretic mobility of linear sugar oligomers with α1-4 linked glucose units (maltooligosaccharides) were studied in CE using the activation energy concept. The electrophoretic separations of 8-aminopyrene-1,3,6-trisulfonate-labeled maltooligosaccharides were monitored by LIF detection in the temperature range of 20-50°C, using either 0-60% ethylene glycol (viscosity modifier) or 0-3% linear polyacrylamide (polymeric additive) containing BGEs. Activation energy curves were constructed based on the slopes of the Arrhenius plots. With the use of linear polyacrylamide additive, solute size-dependent activation energy variations were found for the maltooligosaccharides with polymerization degrees below and above maltoheptaose (DP 7), probably due to molecular conformation changes and possible matrix interaction effects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electromigration techniques--a fast and economical tool for differentiation of similar strains of microorganisms.

PubMed

Horká, Marie; Horký, Jaroslav; Kubesová, Anna; Mazanec, Karel; Matousková, Hana; Slais, Karel

2010-07-01

The detection and identification of pathogens currently relies upon a very diverse range of techniques and skills, from traditional cultivation and taxonomic procedures to modern rapid and sensitive diagnostic methods. Real-time PCR is now exploited as a front line diagnostic screening tool in human, animal and plant health as well as bio-security. Nevertheless, new techniques for pathogen identification, particularly of unknown samples, are needed. In this study we propose the combination of electrophoresis-based procedures for the fast differentiation of microorganisms. The method feasibility is proved on the model of seven similar strains of Pseudomonas syringae pathovars from 37 sources, identified by gas chromatography of fatty acid methyl esters. The results from the routine laboratory were compared with results of the combination of the developed capillary and gel electrophoresis as well as mass spectrometry. According to our experiments appropriate combination of electromigration techniques appears to be useful for the fast and economical differentiation of unknown microorganisms.

Nanopipettes for Metal Transport

NASA Astrophysics Data System (ADS)

Svensson, K.; Olin, H.; Olsson, E.

2004-09-01

Here we demonstrate, for the first time experimentally, a nanopipette action for metals using multiwalled carbon nanotubes. The process relies on electromigration forces, created at high electron current densities, enabling the transport of material inside the hollow core of carbon nanotubes. In this way nanoparticles of iron were transported to and from electrically conducting substrates.

Nanopipettes for metal transport.

PubMed

Svensson, K; Olin, H; Olsson, E

2004-10-01

Here we demonstrate, for the first time experimentally, a nanopipette action for metals using multiwalled carbon nanotubes. The process relies on electromigration forces, created at high electron current densities, enabling the transport of material inside the hollow core of carbon nanotubes. In this way nanoparticles of iron were transported to and from electrically conducting substrates.

Thermal-Interaction Matrix For Resistive Test Structure

NASA Technical Reports Server (NTRS)

Buehler, Martin G.; Dhiman, Jaipal K.; Zamani, Nasser

1990-01-01

Linear mathematical model predicts increase in temperature in each segment of 15-segment resistive structure used to test electromigration. Assumption of linearity based on fact: equations that govern flow of heat are linear and coefficients in equations (heat conductivities and capacities) depend only weakly on temperature and considered constant over limited range of temperature.

Fabrication of back-contacted silicon solar cells using thermomigration to create conductive vias

DOEpatents

Gee, James M; Schmit, Russell R.

2007-01-30

Methods of manufacturing back-contacted silicon solar cells fabricated using a gradient-driven solute transport process, such as thermomigration or electromigration, to create n-type conductive vias connecting the n-type emitter layer on the front side to n-type ohmic contacts located on the back side.

Microwave evaluation of electromigration susceptibility in advanced interconnects

NASA Astrophysics Data System (ADS)

Sunday, Christopher E.; Veksler, Dmitry; Cheung, Kin C.; Obeng, Yaw S.

2017-11-01

Traditional metrology has been unable to adequately address the needs of the emerging integrated circuits (ICs) at the nano scale; thus, new metrology and techniques are needed. For example, the reliability challenges in fabrication need to be well understood and controlled to facilitate mass production of through-substrate-via (TSV) enabled three-dimensional integrated circuits (3D-ICs). This requires new approaches to the metrology. In this paper, we use the microwave propagation characteristics to study the reliability issues that precede the physical damage caused by electromigration in the Cu-filled TSVs. The pre-failure microwave insertion losses and group delay are dependent on both the device temperature and the amount of current forced through the devices-under-test. The microwave insertion losses increase with the increase in the test temperature, while the group delay increases with the increase in the forced direct current magnitude. The microwave insertion losses are attributed to the defect mobility at the Cu-TiN interface, and the group delay changes are due to resistive heating in the interconnects, which perturbs the dielectric properties of the cladding dielectrics of the copper fill in the TSVs.

Electromigration Failure Mechanism in Sn-Cu Solder Alloys with OSP Cu Surface Finish

NASA Astrophysics Data System (ADS)

Chu, Ming-Hui; Liang, S. W.; Chen, Chih; Huang, Annie T.

2012-09-01

Organic solderable preservative (OSP) has been adopted as the Cu substrate surface finish in flip-chip solder joints for many years. In this study, the electromigration behavior of lead-free Sn-Cu solder alloys with thin-film under bump metallization and OSP surface finish was investigated. The results showed that severe damage occurred on the substrate side (cathode side), whereas the damage on the chip side (cathode side) was not severe. The damage on the substrate side included void formation, copper dissolution, and formation of intermetallic compounds (IMCs). The OSP Cu interface on the substrate side became the weakest point in the solder joint even when thin-film metallization was used on the chip side. Three-dimensional simulations were employed to investigate the current density distribution in the area between the OSP Cu surface finish and the solder. The results indicated that the current density was higher along the periphery of the bonding area between the solder and the Cu pad, consistent with the area of IMC and void formation in our experimental results.

Electromigration and Thermomechanical Fatigue Behavior of Sn0.3Ag0.7Cu Solder Joints

NASA Astrophysics Data System (ADS)

Zuo, Yong; Bieler, Thomas R.; Zhou, Quan; Ma, Limin; Guo, Fu

2017-12-01

The anisotropy of Sn crystal structures greatly affects the electromigration (EM) and thermomechanical fatigue (TMF) of solder joints. The size of solder joint shrinkage in electronic systems further makes EM and TMF an inseparably coupled issue. To obtain a better understanding of failure under combined moderately high (2000 A/cm2) current density and 10-150°C/1 h thermal cycling, analysis of separate, sequential, and concurrent EM and thermal cycling (TC) was imposed on single shear lap joints, and the microstructure and crystal orientations were incrementally characterized using electron backscatter diffraction (EBSD) mapping. First, it was determined that EM did not significantly change the crystal orientation, but the formation of Cu6Sn5 depended on the crystal orientation, and this degraded subsequent TMF behavior. Secondly, TC causes changes in crystal orientation. Concurrent EM and TC led to significant changes in crystal orientation by discontinuous recrystallization, which is facilitated by Cu6Sn5 particle formation. The newly formed Cu6Sn5 often showed its c-axis close to the direction of electron flow.

In situ synchrotron study of electromigration induced grain rotations in Sn solder joints

DOE PAGES

Shen, Hao; Zhu, Wenxin; Li, Yao; ...

2016-04-18

In this paper we report an in situ study of the early stage of microstructure evolution induced by electromigration in a Pb-free β-Sn based solder joint by synchrotron polychromatic X-ray microdiffraction. With this technique, crystal orientation evolution is monitored at intragranular levels with high spatial and angular resolution. During the entire experiment, no crystal growth is detected, and rigid grain rotation is observed only in the two grains within the current crowding region, where high density and divergence of electric current occur. Theoretical calculation indicates that the trend of electrical resistance drop still holds under the present conditions in themore » grain with high electrical resistivity, while the other grain with low resistivity reorients to align its a-axis more parallel with the ones of its neighboring grains. A detailed study of dislocation densities and subgrain boundaries suggests that grain rotation in β-Sn, unlike grain rotation in high melting temperature metals which undergo displacive deformation, is accomplished via diffusional process mainly, due to the high homologous temperature.« less

Electromigration and morphological changes in Ag nanostructures

NASA Astrophysics Data System (ADS)

Chatterjee, A.; Bai, T.; Edler, F.; Tegenkamp, C.; Weide-Zaage, K.; Pfnür, H.

2018-02-01

Electromigration (EM) as a structuring tool was investigated in Ag nanowires (width 300 nm, thickness 25 nm) and partly in notched and bow-tie Ag structures on a Si(1 0 0) substrate in ultra-high vacuum using a four-tip scanning tunneling microscope in combination with a scanning electron microscope. From simulations of Ag nanowires we got estimates of temperature profiles, current density profiles, EM and thermal migration (TM) mass flux distributions within the nanowire induced by critical current densities of 108 A cm-2. At room temperature, the electron wind force at these current densities by far dominates over thermal diffusion, and is responsible for formation of voids at the cathode and hillocks at the anode side. For current densities that exceed the critical current densities necessary for EM, a new type of wire-like structure formation was found both at room temperature and at 100 K for notched and bow-tie structures. This suggests that the simultaneous action of EM and TM is structure forming, but with a very small influence of TM at low temperature.

Multiscale Microstructures and Microstructural Effects on the Reliability of Microbumps in Three-Dimensional Integration

PubMed Central

Huang, Zhiheng; Xiong, Hua; Wu, Zhiyong; Conway, Paul; Altmann, Frank

2013-01-01

The dimensions of microbumps in three-dimensional integration reach microscopic scales and thus necessitate a study of the multiscale microstructures in microbumps. Here, we present simulated mesoscale and atomic-scale microstructures of microbumps using phase field and phase field crystal models. Coupled microstructure, mechanical stress, and electromigration modeling was performed to highlight the microstructural effects on the reliability of microbumps. The results suggest that the size and geometry of microbumps can influence both the mesoscale and atomic-scale microstructural formation during solidification. An external stress imposed on the microbump can cause ordered phase growth along the boundaries of the microbump. Mesoscale microstructures formed in the microbumps from solidification, solid state phase separation, and coarsening processes suggest that the microstructures in smaller microbumps are more heterogeneous. Due to the differences in microstructures, the von Mises stress distributions in microbumps of different sizes and geometries vary. In addition, a combined effect resulting from the connectivity of the phase morphology and the amount of interface present in the mesoscale microstructure can influence the electromigration reliability of microbumps. PMID:28788356

Electromigration resistance in a short three-contact interconnect tree

NASA Astrophysics Data System (ADS)

Chang, C. W.; Choi, Z.-S.; Thompson, C. V.; Gan, C. L.; Pey, K. L.; Choi, W. K.; Hwang, N.

2006-05-01

Electromigration has been characterized in via-terminated interconnect lines with additional vias in the middle, creating two adjacent segments that can be stressed independently. The mortality of a segment was found to depend on the direction and magnitude of the current in the adjacent segment, confirming that there is not a fixed value of the product of the current density and segment length, jL, that defines immortality in individual segments that are part of a multisegment interconnect tree. Instead, it is found that the probability of failure of a multisegment tree increases with the increasing value of an effective jL product defined in earlier work. However, contrary to expectations, the failures were still observed when (jL)eff was less than the critical jL product for which lines were found to be immortal in single-segment test structures. It is argued that this is due to reservoir effects associated with unstressed segments or due to liner failure at the central via. Multisegment test structures are therefore shown to reveal more types of failure mechanisms and mortality conditions that are not found in tests with single-segment structures.

Non-equilibrium Transport in Carbon based Adsorbate Systems

NASA Astrophysics Data System (ADS)

Fürst, Joachim; Brandbyge, Mads; Stokbro, Kurt; Jauho, Antti-Pekka

2007-03-01

We have used the Atomistix Tool Kit(ATK) and TranSIESTA[1] packages to investigate adsorption of iron atoms on a graphene sheet. The technique of both codes is based on density functional theory using local basis sets[2], and non-equilibrium Green's functions (NEGF) to calculate the charge distribution under external bias. Spin dependent electronic structure calculations are performed for different iron coverages. These reveal adsorption site dependent charge transfer from iron to graphene leading to screening effects. Transport calculations show spin dependent scattering of the transmission which is analysed obtaining the transmission eigenchannels for each spin type. The phenomena of electromigration of iron in these systems at finite bias will be discussed, estimating the so-called wind force from the reflection[3]. [1] M. Brandbyge, J.-L. Mozos, P. Ordejon, J. Taylor, and K. Stokbro. Physical Review B (Condensed Matter and Materials Physics), 65(16):165401/11-7, 2002. [2] Jose M. Soler, Emilio Artacho, Julian D. Gale, Alberto Garcia, Javier Junquera, Pablo Ordejon, and Daniel Sanchez-Portal. Journal of Physics Condensed Matter, 14(11):2745-2779, 2002. [3] Sorbello. Theory of electromigration. Solid State Physics, 1997.

Electromigration and Thermomechanical Fatigue Behavior of Sn0.3Ag0.7Cu Solder Joints

NASA Astrophysics Data System (ADS)

Zuo, Yong; Bieler, Thomas R.; Zhou, Quan; Ma, Limin; Guo, Fu

2018-03-01

The anisotropy of Sn crystal structures greatly affects the electromigration (EM) and thermomechanical fatigue (TMF) of solder joints. The size of solder joint shrinkage in electronic systems further makes EM and TMF an inseparably coupled issue. To obtain a better understanding of failure under combined moderately high (2000 A/cm2) current density and 10-150°C/1 h thermal cycling, analysis of separate, sequential, and concurrent EM and thermal cycling (TC) was imposed on single shear lap joints, and the microstructure and crystal orientations were incrementally characterized using electron backscatter diffraction (EBSD) mapping. First, it was determined that EM did not significantly change the crystal orientation, but the formation of Cu6Sn5 depended on the crystal orientation, and this degraded subsequent TMF behavior. Secondly, TC causes changes in crystal orientation. Concurrent EM and TC led to significant changes in crystal orientation by discontinuous recrystallization, which is facilitated by Cu6Sn5 particle formation. The newly formed Cu6Sn5 often showed its c-axis close to the direction of electron flow.

Electromigration effect upon the Sn-0.7 wt% Cu/Ni and Sn-3.5 wt% Ag/Ni interfacial reactions

NASA Astrophysics Data System (ADS)

Chen, Chih-ming; Chen, Sinn-wen

2001-08-01

This study investigates the effect of electromigration upon the interfacial reactions between the promising lead-free solders, Sn-Cu and Sn-Ag, with Ni substrate. Sandwich-type reaction couples, Sn-0.7 wt% Cu/Ni/Sn-0.7 wt% Cu and Sn-3.5 wt% Ag/Ni/Sn-3.5 wt% Ag, were reacted at 160, 180, and 200 °C for various lengths of time with and without the passage of electric currents. Without passage of electric currents through the couples, only one intermetallic compound Ni3Sn4 with ˜7 at. % Cu solubility was found at both interfaces of the Sn-0.7 wt% Cu/Ni couples. With the passage of an electric current of 500 A/cm2 density, the Cu6Sn5 phase was formed at the solder/Ni interface besides the Ni3Sn4 phase. Similar to those without the passage of electric currents, only the Ni3Sn4 phase was found at the Ni/solder interface. Directions of movement of electrons, Sn, and Cu atoms are the same at the solder/Ni interface, and the growth rates of the intermetallic layers were enhanced. At the Ni/solder interface, the electrons flow in the opposite direction of the Sn and Cu movement, and the growth rates of the intermetallic layers were retarded. Only the Ni3Sn4 phase was formed from the Sn-3.5 wt% Ag/Ni interfacial reaction with and without the passage of electric currents. Similar to the Sn-0.7 wt% Cu/Ni system, the movement of electrons enhances or retards the growth rates of the intermetallic layers at the solder/Ni and Ni/solder interfaces, respectively. Calculation results show the apparent effective charge za* decreases in magnitude with raising temperatures, which indicates the electromigration effect becomes insignificant at higher temperatures.

Electromigration-induced drift in damascene and plasma-etched Al(Cu). II. Mass transport mechanisms in bamboo interconnects

NASA Astrophysics Data System (ADS)

Proost, Joris; Maex, Karen; Delacy, Luc

2000-01-01

We have discussed electromigration (EM)-induced drift in polycrystalline damascene versus reactive ion etched (RIE) Al(Cu) in part I. For polycrystalline Al(Cu), mass transport is well documented to occur through sequential stages : an incubation period (attributed to Cu depletion beyond a critical length) followed by the Al drift stage. In this work, the drift behavior of bamboo RIE and damascene Al(Cu) is analyzed. Using Blech-type test structures, mass transport in RIE lines was shown to proceed both by lattice and interfacial diffusion. The dominating mechanism depends on the Cu distribution in the line, as was evidenced by comparing as-patterned (lattice EM) and RTP-annealed (interface EM) samples. The interfacial EM only occurs at metallic interfaces. In that case, Cu alloying was observed to retard Al interfacial mass transport, giving rise to an incubation time. Although the activation energy for the incubation time was found similar to the one controlling Al lattice drift, for which no incubation time was observed, lattice EM is preferred over interfacial EM because it is insensitive to enhancing geometrical effects upon scaling. When comparing interfacial electromigration in RIE with bamboo damascene Al(Cu), with the incubation time rate controlling for both, the higher EM threshold observed for damascene was shown to be insufficient to compensate for its significantly increased Cu depletion rate, contrary to the case of polycrystalline Al(Cu) interconnects. Two factors were demonstrated to contribute. First, there are more metallic interfaces, intrinsically related to the use of wetting or barrier layers in recessed features. Second, specific to this study, the additional formation of TiAl3 at the trench sidewalls further enhanced the Cu depletion rate, and reduced the rate-controlling incubation time. A separate drift study on RIE via-type test structures indicated that it is very difficult to suppress interfacial mass transport in favor of lattice EM upon TiAl3 formation.

Electromigration and solid state aging of flip chip solder joints and analysis of tin whisker on lead-frame

NASA Astrophysics Data System (ADS)

Lee, Taekyeong

Electromigration and solid state aging in flip chip joint, and whisker on lead frame of Pb-containing (eutectic SnPb) and Pb-free solders (SnAg 3.5, SnAg3.8Cu0.7, and SnCu0.7), have been studied systematically, using Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX), and synchrotron radiation. The high current density in flip chip joint drives the diffusion of atoms of eutectic SnPb and SnAgCu. A marker is used to measure the diffusion flux in a half cross-sectioned solder joint. SnAgCu shows higher resistance against electromigration than eutectic SnPb. In the half cross-sectioned solder joint, void growth is the dominant failure mechanism. However, the whole solder balls in the underfill show that the failure mechanism is a result from the dissolution of electroless Ni under bump metallization (UBM) of about 10 mum thickness. The growth rate between intermetallic compounds in molten and solid solders differed by four orders of magnitude. In liquid solder, the growth rate is about 1 mum/min; the growth rate in solid solder is only about 10 -4 mum/min. The difference is not resulting from factors of thermodynamics, which is the change of Gibbs free energy before and after intermetallic compound formation, but from kinetic factors, which is the rate of change of Gibbs free energy. Even though the difference in growth rate between eutectic SnPb and Pb-free solders during solid state aging was found, the reason behind such difference shown is unclear. The orientation and stress levels of whiskers are measured by white X-ray of synchrotron radiation. The growth direction is nearly parallel to one of the principal axes of tin. The compressive stress level is quite low because the residual stress is relaxed by the whisker growth.

Electromigration-induced void grain-boundary interactions: The mean time to failure for copper interconnects with bamboo and near-bamboo structures

NASA Astrophysics Data System (ADS)

Ogurtani, Tarik Omer; Oren, Ersin Emre

2004-12-01

A well-posed moving boundary-value problem, describing the dynamics of curved interfaces and surfaces associated with voids and/or cracks that are interacting with grain boundaries, is obtained. Extensive computer simulations are performed for void configuration evolution during intergranular motion, under the actions of capillary and electromigration forces in thin-film metallic interconnects with bamboo structures. The analysis of experimental data, utilizing the mean time to failure formulas derived in this paper, gives consistent values for the interface diffusion coefficients and enthalpies of voids. 5.85×10-5exp(-0.95eV/kT)m2s-1 is the value obtained for voids that form in the interior of the copper interconnects avoiding any surface contamination. 1.80×10-4exp(-1.20eV/kT)m2s-1 is obtained for those voids that nucleate either at triple junctions or at the grain-boundary technical surface intersections (grain-boundary groove), where the chemical impurities such as Si, O, S, and even C are segregated during the metallization and annealing processes and may act as trap centers for hopping vacancies.

Electromigration-Induced Surface Drift and Slit Propagation in Polycrystalline Interconnects: Insights from Phase-Field Simulations

NASA Astrophysics Data System (ADS)

Mukherjee, Arnab; Ankit, Kumar; Selzer, Michael; Nestler, Britta

2018-04-01

We employ the phase-field method to assess electromigration (EM) damage in wide polycrystalline interconnects due to grain-boundary grooving. An interplay of surface and grain-boundary diffusion is shown to drastically influence the mode of progressive EM damage. Rapid atomic transport along the surface leads to shape-preserving surface drift reminiscent of Blech drift-velocity experiments. On the other hand, a comparatively faster grain-boundary transport localizes the damage, resulting in the proliferation of intergranular slits with a shape-preserving tip. At steady state, the two regimes exhibit exponents of 1 and 3 /2 , respectively, in Black's law. While surface drift obeys an inverse scaling with grain size, slits exhibit a direct relationship at small sizes, with the dependence becoming weaker at larger ones. Furthermore, we explain the influence of curvature- or EM-mediated healing fluxes running along the surface on groove replenishment. Insights derived from phase-field simulations of EM in bicrystals are extended to investigate the multiphysics of mixed-mode damage of a polycrystalline interconnect line that is characterized by a drift of small grain surfaces, slit propagation, and coarsening. The triple and quadruple junctions are identified as prominent sites of failure.

Electromigration Mechanism of Failure in Flip-Chip Solder Joints Based on Discrete Void Formation.

PubMed

Chang, Yuan-Wei; Cheng, Yin; Helfen, Lukas; Xu, Feng; Tian, Tian; Scheel, Mario; Di Michiel, Marco; Chen, Chih; Tu, King-Ning; Baumbach, Tilo

2017-12-20

In this investigation, SnAgCu and SN100C solders were electromigration (EM) tested, and the 3D laminography imaging technique was employed for in-situ observation of the microstructure evolution during testing. We found that discrete voids nucleate, grow and coalesce along the intermetallic compound/solder interface during EM testing. A systematic analysis yields quantitative information on the number, volume, and growth rate of voids, and the EM parameter of DZ*. We observe that fast intrinsic diffusion in SnAgCu solder causes void growth and coalescence, while in the SN100C solder this coalescence was not significant. To deduce the current density distribution, finite-element models were constructed on the basis of the laminography images. The discrete voids do not change the global current density distribution, but they induce the local current crowding around the voids: this local current crowding enhances the lateral void growth and coalescence. The correlation between the current density and the probability of void formation indicates that a threshold current density exists for the activation of void formation. There is a significant increase in the probability of void formation when the current density exceeds half of the maximum value.

Electromigration in epitaxial Cu(001) lines

NASA Astrophysics Data System (ADS)

Ramanath, G.; Kim, H.; Goindi, H. S.; Frederick, M. J.; Shin, C.-S.; Goswami, R.; Petrov, I.; Greene, J. E.

2002-04-01

We report the electromigration (EM) response of single-domain epitaxial Cu(001) lines on layers of Ta, TaN, and TiN. Epitaxial Cu(001) lines on nitride layers exhibit nearly two orders of magnitude higher mean-time-to-failure (MTTF) values than those on Ta, indicating the strong influence of the underlayer. The activation energy of EM for Cu on the nitrides is ˜0.8-1.2 eV, and that of Cu on Ta is ˜0.2 eV, for 200-300 °C. Our results also indicate that the MTTF values correlate inversely to the crystal quality of the Cu layers measured by X-ray diffraction. The EM resistance of epitaxial Cu lines with different crystal quality on TaN were measured to separate the effects of interface chemistry and crystal quality. While higher quality epitaxial films reveal a higher EM resistance, the magnitude of the change is smaller than that obtained by changing the interface chemistry. Epitaxial lines exhibit more than 3-4 orders of magnitude higher MTTF than polycrystalline lines on the same underlayer. Based upon our results, we propose that the Cu/underlayer interface chemistry and presence of grain boundary diffusion play important roles in unpassivated Cu films.

Microwave evaluation of electromigration susceptibility in advanced interconnects.

PubMed

Sunday, Christopher E; Veksler, Dmitry; Cheung, Kin C; Obeng, Yaw S

2017-11-07

Traditional metrology has been unable to adequately address the needs of the emerging integrated circuits (ICs) at the nano scale; thus, new metrology and techniques are needed. For example, the reliability challenges in fabrication need to be well understood and controlled to facilitate mass production of through-substrate-via (TSV) enabled three-dimensional integrated circuits (3D-ICs). This requires new approaches to the metrology. In this paper, we use the microwave propagation characteristics to study the reliability issues that precede the physical damage caused by electromigration in the Cu-filled TSVs. The pre-failure microwave insertion losses and group delay are dependent on both the device temperature and the amount of current forced through the devices-under-test. The microwave insertion losses increase with the increase in the test temperature, while the group delay increases with the increase in the forced direct current magnitude. The microwave insertion losses are attributed to the defect mobility at the Cu-TiN interface, and the group delay changes are due to resistive heating in the interconnects, which perturbs the dielectric properties of the cladding dielectrics of the copper fill in the TSVs. https://doi.org/10.1063/1.4992135.

Phase nucleation and evolution mechanisms in heterogeneous solids

NASA Astrophysics Data System (ADS)

Udupa, Anirudh

Phase nucleation and evolution is a problem of critical importance in many applications. As the length scales are reduced, it becomes increasingly important to consider interfacial and micro-structural effects that can be safely ignored at larger length scales owing to randomness. The theory of phase nucleation has been addressed usually by the classical nucleation theory, which was originally derived for single component fluid systems, after making an assumption of equilibrium. The criterion has not been rigorously derived for solids, which are far from equilibrium due to dissipation by multiple physical drivers. In this thesis, a thermodynamically sound nucleation criterion is derived for systems with multiple interacting physical phenomena and multiple dissipating mechanisms. This is done, using the tools of continuum mechanics, by determining the change in free energy upon the introduction of a new nucleus into the system. The developed theory is demonstrated to be a generalization of the classical nucleation theory (CNT). The developed theory is then applied to the problem of electromigration driven void nucleation, a serious reliability concern for the microelectronics industry. The void grows and eventually severs the line making the chip nonfunctional. There are two classes of theories at present in the electromigration literature to address the problem of void nucleation, the vacancy supersaturation theory and the entropic dissipation theory, both of which are empirical and based on intuition developed from experimental observations. When the developed theory was applied to the problem of electromigration, it was found to be consistent with the vacancy supersaturation theory, but provided the correct energetic quantity, the chemical potential, which has contribution from both the vacancy concentration as well as the hydrostatic stress. An experiment, consisting of electromigration tests on serpentine lines, was developed to validate the developed nucleation theory. The experimental results are consistent with the developed theory and show that the theory of entropic dissipation is incorrect. A diffuse-interface computational technique was then developed to simulate the problem of electromigration driven void nucleation and growth in arbitrary geometries. Experimentally known results such as Black's law, existence of the Blech length, effect of interface adhesion energy were reproduced. The simulations were also used to infer the numerical value of the nucleation criterion, based on experimental results in the literature. The problem of electromigration is the result of species diffusion due to imparted momentum from the electrons, and the resulting motion of interface is influenced by surface diffusion along the interface, bulk diffusion, and the current density. Similarly, the formation of intermetallic compounds (IMC) and the resulting interface shape in many systems is the result of limiting effects of bulk diffusion, interfacial reaction, surface energy, and surface diffusion. Thus, the dynamics and stability of the interface formed when Cu and Sn react to form the IMC compound Cu6Sn5 is explored next. This system is of significant relevance to modern microelectronic chip assemblies, where solder joints with significant Cu6Sn5 volume fraction are known to be prone to brittle fracture and shorter useful life. Prior experimental observations have shown the interface to possess either a scalloped, flat or needle shaped morphology. The governing mechanism leading to the observed shape of the interface is not clearly known, and is the focus of the present study. In research unrelated to diffusion driven phase evolution, but involving interfaces nevertheless, in the appendix, the problem of interfacial delamination in Through Silicon Vias (TSV) is studied analytically. Three-dimensional (3D) packages utilizing TSVs are seen as enablers of increased performance and "More than Moore" functionality at the present time. However, the use of TSVs introduce a set of reliability concerns, one of which is the thermo-mechanical stress caused by the mismatch in coefficient of thermal expansion (CTE) between the copper via and the surround- ing silicon. The CTE mismatch, causes high stress zones in and around the copper TSVs, which in turn impede the mobility of electrons in the regions surrounding the TSVs. Further, proximal placing of TSVs for improved electrical performance may be restricted by additional stress induced by TSV-TSV interaction. The increased stress of the region surrounding the TSV also increases the risk of interfacial delamination. In order to ensure reliable functioning of 3D chip stacks, design guidelines are necessary on the excluded "keep-out" zone where stress induced by TSVs will impede transistor functionality. Towards this end, we analytically derive, using elasticity theory, the stress field in and around a doubly periodic arrangement of TSVs subjected to a uniform thermal excursion. The model for stress is used to analytically estimate the conditions for interfacial cracks to propagate, as a function of the system geometry and material properties. (Abstract shortened by ProQuest.).

Means and method for capillary zone electrophoresis with laser-induced indirect fluorescence detection

DOEpatents

Yeung, Edward S.; Kuhr, Werner G.

1996-02-20

A means and method for capillary zone electrphoresis with laser-induced indirect fluorescence detection. A detector is positioned on the capillary tube of a capillary zone electrophoresis system. The detector includes a laser which generates a laser beam which is imposed upon a small portion of the capillary tube. Fluorescence of the elutant electromigrating through the capillary tube is indirectly detected and recorded.

Means and method for capillary zone electrophoresis with laser-induced indirect fluorescence detection

DOEpatents

Yeung, Edwards; Kuhr, Werner G.

1991-04-09

A means and method for capillary zone electrphoresis with laser-induced indirect fluorescence detection. A detector is positioned on the capillary tube of a capillary zone electrophoresis system. The detector includes a laser which generates a laser beam which is imposed upon a small portion of the capillary tube. Fluorescence of the elutant electromigrating through the capillary tube is indirectly detected and recorded.

Electromigration and Deposition of Micro-Scale Calcium Carbonate Structures with Controlled Morphology and Polymorphism

DTIC Science & Technology

2013-04-01

precipitation of calcium carbonate in structured templates including microporous polycarbonate membranes and polyethylene foams. Para- meters...polyethylene foam). Microporous polycarbonate membranes and Medium-Density PolyEthylene (MDPE) foam specimens were used as the porous organic...voids in hardened concrete. DOI:10.1520/C624-06. West Conshohocken, PA: ASTM International . www.astm.org. Bersa, L., and M. Liu. 2007. A review on

Reliability of Next Generation Power Electronics Packaging Under Concurrent Vibration, Thermal and High Power Loads

DTIC Science & Technology

2008-02-01

combined thermal g effect and initial current field. The model is implemented using Abaqus user element subroutine and verified against the experimental...Finite Element Formulation The proposed model is implemented with ABAQUS general purpose finite element program using thermal -displacement analysis...option. ABAQUS and other commercially available finite element codes do not have the capability to solve general electromigration problem directly. Thermal

Study of Electromigration-Induced Failures on Cu Pillar Bumps Joined to OSP and ENEPIG Substrates

NASA Astrophysics Data System (ADS)

Hsiao, Yu-Hsiang; Lin, Kwang-Lung; Lee, Chiu-Wen; Shao, Yu-Hsiu; Lai, Yi-Shao

2012-12-01

This work studies electromigration (EM)-induced failures on Cu pillar bumps joined to organic solderability preservative (OSP) on Cu substrates (OSP-bumps) and electroless Ni(P)/electroless Pd/immersion Au (ENEPIG) under bump metallurgy (UBM) on Cu substrates (ENEPIG-bumps). Two failure modes (Cu pad consumption and gap formation) were found with OSP-bumps, but only one failure mode (gap formation) was found with ENEPIG-bumps. The main interfacial compound layer was the Cu6Sn5 compound, which suffered significant EM-induced dissolution, eventually resulting in severe Cu pad consumption at the cathode side for OSP-bumps. A (Cu,Ni)6Sn5 layer with strong resistance to EM-induced dissolution exists at the joint interface when a nickel barrier layer is incorporated at the cathode side (Ni or ENEPIG), and these imbalanced atomic fluxes result in the voids and gap formation. OSP-bumps showed better lifetime results than ENEPIG-bumps for several current stressing conditions. The inverse Cu atomic flux ( J Cu,chem) which diffuses from the Cu pad to cathode side retards the formation of voids. The driving force for J Cu,chem comes from the difference in chemical potential between the (Cu,Ni)6Sn5 and Cu6Sn5 phases.

Generalized model of electromigration with 1:1 (analyte:selector) complexation stoichiometry: part I. Theory.

PubMed

Dubský, Pavel; Müllerová, Ludmila; Dvořák, Martin; Gaš, Bohuslav

2015-03-06

The model of electromigration of a multivalent weak acidic/basic/amphoteric analyte that undergoes complexation with a mixture of selectors is introduced. The model provides an extension of the series of models starting with the single-selector model without dissociation by Wren and Rowe in 1992, continuing with the monovalent weak analyte/single-selector model by Rawjee, Williams and Vigh in 1993 and that by Lelièvre in 1994, and ending with the multi-selector overall model without dissociation developed by our group in 2008. The new multivalent analyte multi-selector model shows that the effective mobility of the analyte obeys the original Wren and Row's formula. The overall complexation constant, mobility of the free analyte and mobility of complex can be measured and used in a standard way. The mathematical expressions for the overall parameters are provided. We further demonstrate mathematically that the pH dependent parameters for weak analytes can be simply used as an input into the multi-selector overall model and, in reverse, the multi-selector overall parameters can serve as an input into the pH-dependent models for the weak analytes. These findings can greatly simplify the rationale method development in analytical electrophoresis, specifically enantioseparations. Copyright © 2015 Elsevier B.V. All rights reserved.

Two-Dimensional Porous Electrode Model for Capacitive Deionization

DOE PAGES

Hemmatifar, Ali; Stadermann, Michael; Santiago, Juan G.

2015-10-28

Here, ion transport in porous conductive materials is of great importance in a variety of electrochemical systems including batteries and supercapacitors. We here analyze the coupling of flow and charge transport and charge capacitance in capacitive deionization (CDI). In CDI, a pair of porous carbon electrodes is employed to electrostatically retain and remove ionic species from aqueous solutions. We here develop and solve a novel unsteady two-dimensional model for capturing the ion adsorption/desorption dynamics in a flow-between CDI system. We use this model to study the complex, nonlinear coupling between electromigration, diffusion, and advection of ions. We also fabricated amore » laboratory-scale CDI cell which we use to measure the near-equilibrium, cumulative adsorbed salt, and electric charge as a function of applied external voltage. We use these integral measures to validate and calibrate this model. We further present a detailed computational study of the spatiotemporal adsorption/desorption dynamics under constant voltage and constant flow conditions. We show results for low (20 mM KCl) and relatively high (200 mM KCl) inlet ion concentrations and identify effects of ion starvation on desalination. We show that in both cases electromigrative transport eventually becomes negligible and diffusive ion transport reduces the desalination rate.« less

Effects of Grain Orientation on Cu6Sn5 Growth Behavior in Cu6Sn5-Reinforced Composite Solder Joints During Electromigration

NASA Astrophysics Data System (ADS)

Han, Jing; Wang, Yan; Tan, Shihai; Guo, Fu

2018-02-01

Electromigration is a major reliability problem in composite solder joints. Due to the anisotropy of the β-Sn crystal structure, the Sn grain orientations present in the solder matrix dominate the principal failure mechanism in solder joints under electric current stressing. In this work, the Cu6Sn5 growth behavior in Cu6Sn5-reinforced composite solder joints with three different Sn grain orientations was investigated at current density of 104 A/cm2 at room temperature. Micron-sized Cu particles were added to Sn-3.5Ag solder at 2% volume fraction using an in situ method. After current stressing for 528 h, the polarity effect in the composite solder joint was greatest for an angle ( θ) between the c-axis and electron flow direction of 30°, resulting in higher growth rate of Cu6Sn5 in the solder matrix compared with composite solder joints with θ of 60° or 90°. There were no noticeable changes in the composite solder joint with θ of 90°. The growth behavior of Cu6Sn5, Cu atomic motion, and Cu diffusivity in the composite solder joints with different Sn grain orientations were analyzed in detail.

The failure models of Sn-based solder joints under coupling effects of electromigration and thermal cycling

NASA Astrophysics Data System (ADS)

Ma, Limin; Zuo, Yong; Liu, Sihan; Guo, Fu; Wang, Xitao

2013-01-01

Currently, the main concerns of Pb-free solder joints are focusing on electromigration (EM) and thermomechanical fatigue (TMF) problems. Many models have been established to understand the failure mechanisms of the joint under such single test conditions. Based on the fact that almost all microelectronic devices serve in combination conditions of fluctuated temperature and electric current stressing, the coupling effects of EM and TMF on evolution of microstructure and resistance of solder joint had been investigated. The failure models of binary SnBi alloy and ternary SnAgCu (SAC) solder under the coupling stressing were divided into four and three different stages, respectively. The failure mechanisms were dominant by the relationship of phase segregation, polarity effect, phase coarsening, and the coefficient of thermal expansion mismatch. Cracks tend to form and propagate along the interface between intermetallic compound layers and solder matrix in SAC solder. However, grain boundary was considered as the nucleation sites for microcracks in SnBi solder. High current density alleviates the deterioration of solder at the beginning stage of coupling stressing through Joule heating effect. An abrupt jump of resistance could be observed before the failure of the joint. The failure molds were determined by interactions of EM behaviors and TMF damages.

A study of electromigration behaviors of Ge2Sb2Te5 chalcogenide nano-strips subjected to pulse bias

NASA Astrophysics Data System (ADS)

Huang, Yin-Hsien; Hsieh, Tsung-Eong

2017-07-01

Electromigration (EM) behaviors of pristine Ge2Sb2Te5 (GST) and cerium-doped GST (Ce-GST) nano-strips were investigated by the mean-time-to-failure (MTTF) tests under the pulse bias at the conditions of pulse frequency (f) ranging from 1 to 25 MHz and duty cycle ranging from 50% to 80%. Analytical results indicated that, at f greater than 10 MHz, the EM failure of GST nano-strips in pulse bias environment could be depicted by the ‘average current model’. With the aid of Black’s theory, the activation energies (E a) of EM process under pulse bias were found to be 0.63 and 0.56 eV for GST and Ce-GST nano-strips, respectively. The E a values were comparatively smaller than those observed in direct-current MTTF test of GST thin-film samples, implying the enhancement of surface diffusion and skin effect in GST nano-strips. The morphology and composition analyses indicated that the electrostatic and the electron-wind forces might simultaneously involve in the mass transport in GST nano-strips under the test conditions of this study. The composition analysis also revealed that doping could not effectively alleviate the element segregation in GST subjected to electrical bias.

Innovative Multiphase Nanoparticle Composites Developed Using Electrophoresis And Electromigration

DTIC Science & Technology

2008-12-01

Fig. 2. Surface of enamel steel sheet showing the array of fine cracks in the enamel . Copper metal was deposited on the...suspensions of enameling frit are used, a layer of glass particles can be built up that can be fused into a tightly bonded vitreous coating. 1...Prescribed by ANSI Std Z39-18 Electrophoresis has been particularly important in enameling because it can deposit a glassy frit layer uniformly

Reliability Analysis/Assessment of Advanced Technologies

DTIC Science & Technology

1990-05-01

34, Reliability Physics 1980 , IEEE, p. 165. 25. RADC-TR-83-244. 26. Towner, Janet M., et. al., "Aluminum Electromigration Under Pulsed D.C. Conditions...Duvvury, Redwine, Kitagawa, Haas, Chuang, Beydler, Hyslop , "Impact of Hot Carriers On DRAM circuits", 1987 IEEE/IRPS. 58. Cahoon, Thornewell, Tsai...et. a]., "Substrate for Large Silicon Chip and Full Wafer Packaging", Semiconductor International, pp. 149-156, April 1980 . 5. T.E. Lewis and D.L

Electromigration Related Effects At Metal-Metal Interfaces: Application To Railguns

DTIC Science & Technology

2007-03-01

found at the armature-rail contact due to local melting, to determine the kinetics of liquid flow Ga under electric current conditions. For this, a...model system comprising a bead of Ga on a Cu thin film track was devised in order to enable liquefaction and current induced movement of Ga to occur...along the Cu track. Upon application of current, Ga underwent liquefaction due to Joule heating and once liquid, it rapidly migrated along the Cu

On-clip high frequency reliability and failure test structures

DOEpatents

Snyder, Eric S.; Campbell, David V.

1997-01-01

Self-stressing test structures for realistic high frequency reliability characterizations. An on-chip high frequency oscillator, controlled by DC signals from off-chip, provides a range of high frequency pulses to test structures. The test structures provide information with regard to a variety of reliability failure mechanisms, including hot-carriers, electromigration, and oxide breakdown. The system is normally integrated at the wafer level to predict the failure mechanisms of the production integrated circuits on the same wafer.

Failure mechanism of THz GaAs photoconductive antenna

NASA Astrophysics Data System (ADS)

Qadri, Syed B.; Wu, Dong H.; Graber, Benjamin D.; Mahadik, Nadeemullah A.; Garzarella, Anthony

2012-07-01

We investigated the failure mechanism of THz GaAs photoconductive antenna using high resolution x-ray diffraction topography. From these studies, it was found that grain boundaries are formed during the high frequency device operation. This results in the segregation of gold at the boundaries causing electromigration of the metal between the gold micro-strips. This disrupts the photocurrents from being produced by femtosecond laser thus preventing terahertz beam generation from the photoconductive antennae leading to device failure.

Product Reliability Trends, Derating Considerations and Failure Mechanisms with Scaled CMOS

NASA Technical Reports Server (NTRS)

White, Mark; Vu, Duc; Nguyen, Duc; Ruiz, Ron; Chen, Yuan; Bernstein, Joseph B.

2006-01-01

As microelectronics is scaled into the deep sub-micron regime, space and aerospace users of advanced technology CMOS are reassessing how scaling effects impact long-term product reliability. The effects of electromigration (EM), time-dependent-dielectric-breakdown (TDDB) and hot carrier degradation (HCI and NBTI) wearout mechanisms on scaled technologies and product reliability are investigated, accelerated stress testing across several technology nodes is performed, and FA is conducted to confirm the failure mechanism(s).

Electromigration of intergranular voids in metal films for microelectronic interconnects

NASA Astrophysics Data System (ADS)

Averbuch, Amir; Israeli, Moshe; Ravve, Igor

2003-04-01

Voids and cracks often occur in the interconnect lines of microelectronic devices. They increase the resistance of the circuits and may even lead to a fatal failure. Voids may occur inside a single grain, but often they appear on the boundary between two grains. In this work, we model and analyze numerically the migration and evolution of an intergranular void subjected to surface diffusion forces and external voltage applied to the interconnect. The grain-void interface is considered one-dimensional, and the physical formulation of the electromigration and diffusion model results in two coupled fourth-order one-dimensional time-dependent PDEs. The boundary conditions are specified at the triple points, which are common to both neighboring grains and the void. The solution of these equations uses a finite difference scheme in space and a Runge-Kutta integration scheme in time, and is also coupled to the solution of a static Laplace equation describing the voltage distribution throughout the grain. Since the voltage distribution is required only along the interface line, the two-dimensional discretization of the grain interior is not needed, and the static problem is solved by the boundary element method at each time step. The motion of the intergranular void was studied for different ratios between the diffusion and the electric field forces, and for different initial configurations of the void.

Analytical characterization of wine and its precursors by capillary electrophoresis.

PubMed

Gomez, Federico J V; Monasterio, Romina P; Vargas, Verónica Carolina Soto; Silva, María F

2012-08-01

The accurate determination of marker chemical species in grape, musts, and wines presents a unique analytical challenge with high impact on diverse areas of knowledge such as health, plant physiology, and economy. Capillary electromigration techniques have emerged as a powerful tool, allowing the separation and identification of highly polar compounds that cannot be easily separated by traditional HPLC methods, providing complementary information and permitting the simultaneous analysis of analytes with different nature in a single run. The main advantage of CE over traditional methods for wine analysis is that in most cases samples require no treatment other than filtration. The purpose of this article is to present a revision on capillary electromigration methods applied to the analysis of wine and its precursors over the last decade. The current state of the art of the topic is evaluated, with special emphasis on the natural compounds that have allowed wine to be considered as a functional food. The most representative revised compounds are phenolic compounds, amino acids, proteins, elemental species, mycotoxins, and organic acids. Finally, a discussion on future trends of the role of capillary electrophoresis in the field of analytical characterization of wines for routine analysis, wine classification, as well as multidisciplinary aspects of the so-called "from soil to glass" chain is presented. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ removal of copper from sediments by a galvanic cell.

PubMed

Yuan, Songhu; Wu, Chan; Wan, Jinzhong; Lu, Xiaohua

2009-01-01

This study dealt with in situ removal of copper from sediments through an electrokinetic (EK) process driven by a galvanic cell. Iron (Fe) and carbon (C) were placed separately and connected with a conductive wire. Polluted sediments were put between them and water was filled above the sediments. The galvanic cell was thus formed due to the different electrode potentials of Fe and C. The cell could remove the pollutants in the sediments by electromigration and/or electroosmosis. Results showed that a weak voltage less than 1V was formed by the galvanic cell. The voltage decreased with the increase of time. A slight increase of sediment pH from the anode (Fe) to the cathode (C) was observed. The presence of supernatant water inhibited the variation of sediment pH because H(+) and OH(-) could diffuse into the water. The removal of copper was affected by the sediment pH and the distribution of electrolyte in sediment and supernatant water. Lower pH led to higher removal efficiency. More electrolyte in the sediment and/or less electrolyte in the supernatant water favored the removal of copper. The major removal mechanism was proposed on the basis of the desorption of copper from sediment to pore solution and the subsequent electromigration of copper from the anode to the cathode. The diffusion of copper from sediment to supernatant water was negligible.

Modeling pH variation in reverse osmosis.

PubMed

Nir, Oded; Bishop, Noga Fridman; Lahav, Ori; Freger, Viatcheslav

2015-12-15

The transport of hydronium and hydroxide ions through reverse osmosis membranes constitutes a unique case of ionic species characterized by uncommonly high permeabilities. Combined with electromigration, this leads to complex behavior of permeate pH, e.g., negative rejection, as often observed for monovalent ions in nanofiltration of salt mixtures. In this work we employed a rigorous phenomenological approach combined with chemical equilibrium to describe the trans-membrane transport of hydronium and hydroxide ions along with salt transport and calculate the resulting permeate pH. Starting from the Nernst-Planck equation, a full non-linear transport equation was derived, for which an approximate solution was proposed based on the analytical solution previously developed for trace ions in a dominant salt. Using the developed approximate equation, transport coefficients were deduced from experimental results obtained using a spiral wound reverse osmosis module operated under varying permeate flux (2-11 μm/s), NaCl feed concentrations (0.04-0.18 M) and feed pH values (5.5-9.0). The approximate equation agreed well with the experimental results, corroborating the finding that diffusion and electromigration, rather than a priori neglected convection, were the major contributors to the transport of hydronium and hydroxide. The approach presented here has the potential to improve the predictive capacity of reverse osmosis transport models for acid-base species, thereby improving process design/control. Copyright © 2015 Elsevier Ltd. All rights reserved.

The influence of microstructure on the probability of early failure in aluminum-based interconnects

NASA Astrophysics Data System (ADS)

Dwyer, V. M.

2004-09-01

For electromigration in short aluminum interconnects terminated by tungsten vias, the well known "short-line" effect applies. In a similar manner, for longer lines, early failure is determined by a critical value Lcrit for the length of polygranular clusters. Any cluster shorter than Lcrit is "immortal" on the time scale of early failure where the figure of merit is not the standard t50 value (the time to 50% failures), but rather the total probability of early failure, Pcf. Pcf is a complex function of current density, linewidth, line length, and material properties (the median grain size d50 and grain size shape factor σd). It is calculated here using a model based around the theory of runs, which has proved itself to be a useful tool for assessing the probability of extreme events. Our analysis shows that Pcf is strongly dependent on σd, and a change in σd from 0.27 to 0.5 can cause an order of magnitude increase in Pcf under typical test conditions. This has implications for the web-based two-dimensional grain-growth simulator MIT/EmSim, which generates grain patterns with σd=0.27, while typical as-patterned structures are better represented by a σd in the range 0.4 - 0.6. The simulator will consequently overestimate interconnect reliability due to this particular electromigration failure mode.

Mean-time-to-failure study of flip chip solder joints on Cu/Ni(V)/Al thin-film under-bump-metallization

NASA Astrophysics Data System (ADS)

Choi, W. J.; Yeh, E. C. C.; Tu, K. N.

2003-11-01

Electromigration of eutectic SnPb flip chip solder joints and their mean-time-to-failure (MTTF) have been studied in the temperature range of 100 to 140 °C with current densities of 1.9 to 2.75×104 A/cm2. In these joints, the under-bump-metallization (UBM) on the chip side is a multilayer thin film of Al/Ni(V)/Cu, and the metallic bond-pad on the substrate side is a very thick, electroless Ni layer covered with 30 nm of Au. When stressed at the higher current densities, the MTTF was found to decrease much faster than what is expected from the published Black's equation. The failure occurred by interfacial void propagation at the cathode side, and it is due to current crowding near the contact interface between the solder bump and the thin-film UBM. The current crowding is confirmed by a simulation of current distribution in the solder joint. Besides the interfacial void formation, the intermetallic compounds formed on the UBM as well as the Ni(V) film in the UBM have been found to dissolve completely into the solder bump during electromigration. Therefore, the electromigation failure is a combination of the interfacial void formation and the loss of UBM. Similar findings in eutectic SnAgCu flip chip solder joints have also been obtained and compared.

Subnanometer Motion of Cargoes Driven by Thermal Gradients Along Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Barreiro, Amelia; Rurali, Riccardo; Hernández, Eduardo R.; Moser, Joel; Pichler, Thomas; Forró, László; Bachtold, Adrian

2008-05-01

An important issue in nanoelectromechanical systems is developing small electrically driven motors. We report on an artificial nanofabricated motor in which one short carbon nanotube moves relative to another coaxial nanotube. A cargo is attached to an ablated outer wall of a multiwalled carbon nanotube that can rotate and/or translate along the inner nanotube. The motion is actuated by imposing a thermal gradient along the nanotube, which allows for subnanometer displacements, as opposed to an electromigration or random walk effect.

On-clip high frequency reliability and failure test structures

DOEpatents

Snyder, E.S.; Campbell, D.V.

1997-04-29

Self-stressing test structures for realistic high frequency reliability characterizations. An on-chip high frequency oscillator, controlled by DC signals from off-chip, provides a range of high frequency pulses to test structures. The test structures provide information with regard to a variety of reliability failure mechanisms, including hot-carriers, electromigration, and oxide breakdown. The system is normally integrated at the wafer level to predict the failure mechanisms of the production integrated circuits on the same wafer. 22 figs.

ESREF 98 - 9th European Symposium on Reliability of Electron Devices, Failure Physics and Analysis

DTIC Science & Technology

1998-10-19

Gap effects within a nanosecond time scale. Effective Density of States Because of the limited possibility of compact Mobility models to deal with the...brackets) and the dislocation source action mobility M. The force is the balance between the normal stress a,, on the dislocations and the osmotic The...on, the electromigration force acts theration kt. on the atoms and a transport to the anode side of the t It is the mobility term that accounts for

Structural tuning of nanogaps using electromigration induced by field emission current with bipolar biasing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yagi, Mamiko; Ito, Mitsuki; Shirakashi, Jun-ichi, E-mail: shrakash@cc.tuat.ac.jp

We report a new method for fabrication of Ni nanogaps based on electromigration induced by a field emission current. This method is called “activation” and is demonstrated here using a current source with alternately reversing polarities. The activation procedure with alternating current bias, in which the current source polarity alternates between positive and negative bias conditions, is performed with planar Ni nanogaps defined on SiO{sub 2}/Si substrates at room temperature. During negative biasing, a Fowler-Nordheim field emission current flows from the source (cathode) to the drain (anode) electrode. The Ni atoms at the tip of the drain electrode are thusmore » activated and then migrate across the gap from the drain to the source electrode. In contrast, in the positive bias case, the field emission current moves the activated atoms from the source to the drain electrode. These two procedures are repeated until the tunnel resistance of the nanogaps is successively reduced from 100 TΩ to 48 kΩ. Scanning electron microscopy and atomic force microscopy studies showed that the gap separation narrowed from approximately 95 nm to less than 10 nm because of the Ni atoms that accumulated at the tips of both the source and drain electrodes. These results show that the alternately biased activation process, which is a newly proposed atom transfer technique, can successfully control the tunnel resistance of the Ni nanogaps and is a suitable method for formation of ultrasmall nanogap structures.« less

Effect of Electromigration on the Type of Drop Failure of Sn-3.0Ag-0.5Cu Solder Joints in PBGA Packages

NASA Astrophysics Data System (ADS)

Huang, M. L.; Zhao, N.

2015-10-01

Board-level drop tests of plastic ball grid array (PBGA) packages were performed in accordance with the Joint Electron Devices Engineering Council standard to investigate the effect of electromigration (EM) on the drop reliability of Sn-3.0Ag-0.5Cu solder joints with two substrate surface finishes, organic solderability preservative (OSP) and electroless nickel electroless palladium immersion gold (ENEPIG). In the as-soldered state, drop failures occurred at the substrate sides only, with cracks propagating within the interfacial intermetallic compound (IMC) layer for OSP solder joints and along the IMC/Ni-P interface for ENEPIG solder joints. The drop lifetime of OSP solder joints was approximately twice that of ENEPIG joints. EM had an important effect on crack formation and drop lifetime of the PBGA solder joints. ENEPIG solder joints performed better in drop reliability tests after EM, that is, the drop lifetime of ENEPIG joints decreased by 43% whereas that of OSP solder joints decreased by 91%, compared with the as-soldered cases. The more serious polarity effect, i.e., excessive growth of the interfacial IMC at the anode, was responsible for the sharper decrease in drop lifetime. The different types of drop failure of PBGA solder joints before and after EM, including the position of initiation and the propagation path of cracks, are discussed on the basis of the growth behavior of interfacial IMC.

Simulations of stress evolution and the current density scaling of electromigration-induced failure times in pure and alloyed interconnects

NASA Astrophysics Data System (ADS)

Park, Young-Joon; Andleigh, Vaibhav K.; Thompson, Carl V.

1999-04-01

An electromigration model is developed to simulate the reliability of Al and Al-Cu interconnects. A polynomial expression for the free energy of solution by Murray [Int. Met. Rev. 30, 211 (1985)] was used to calculate the chemical potential for Al and Cu while the diffusivities were defined based on a Cu-trapping model by Rosenberg [J. Vac. Sci. Technol. 9, 263 (1972)]. The effects of Cu on stress evolution and lifetime were investigated in all-bamboo and near-bamboo stud-to-stud structures. In addition, the significance of the effect of mechanical stress on the diffusivity of both Al and Cu was determined in all-bamboo and near-bamboo lines. The void nucleation and growth process was simulated in 200 μm, stud-to-stud lines. Current density scaling behavior for void-nucleation-limited failure and void-growth-limited failure modes was simulated in long, stud-to-stud lines. Current density exponents of both n=2 for void nucleation and n=1 for void growth failure modes were found in both pure Al and Al-Cu lines. Limitations of the most widely used current density scaling law (Black's equation) in the analysis of the reliability of stud-to-stud lines are discussed. By modifying the input materials properties used in this model (when they are known), this model can be adapted to predict the reliability of other interconnect materials such as pure Cu and Cu alloys.

Electromigration in Cu(Al) and Cu(Mn) damascene lines

NASA Astrophysics Data System (ADS)

Hu, C.-K.; Ohm, J.; Gignac, L. M.; Breslin, C. M.; Mittal, S.; Bonilla, G.; Edelstein, D.; Rosenberg, R.; Choi, S.; An, J. J.; Simon, A. H.; Angyal, M. S.; Clevenger, L.; Maniscalco, J.; Nogami, T.; Penny, C.; Kim, B. Y.

2012-05-01

The effects of impurities, Mn or Al, on interface and grain boundary electromigration (EM) in Cu damascene lines were investigated. The addition of Mn or Al solute caused a reduction in diffusivity at the Cu/dielectric cap interface and the EM activation energies for both Cu-alloys were found to increase by about 0.2 eV as compared to pure Cu. Mn mitigated and Al enhanced Cu grain boundary diffusion; however, no significant mitigation in Cu grain boundary diffusion was observed in low Mn concentration samples. The activation energies for Cu grain boundary diffusion were found to be 0.74 ± 0.05 eV and 0.77 ± 0.05 eV for 1.5 μm wide polycrystalline lines with pure Cu and Cu (0.5 at. % Mn) seeds, respectively. The effective charge number in Cu grain boundaries Z*GB was estimated from drift velocity and was found to be about -0.4. A significant enhancement in EM lifetimes for Cu(Al) or low Mn concentration bamboo-polycrystalline and near-bamboo grain structures was observed but not for polycrystalline-only alloy lines. These results indicated that the existence of bamboo grains in bamboo-polycrystalline lines played a critical role in slowing down the EM-induced void growth rate. The bamboo grains act as Cu diffusion blocking boundaries for grain boundary mass flow, thus generating a mechanical stress-induced back flow counterbalancing the EM force, which is the equality known as the "Blech short length effect."

High frequency pulsed electromigration

NASA Astrophysics Data System (ADS)

Malone, David Wayne

Electromigration life tests were performed on copper-alloyed aluminum test structures that were representative of modern CMOS metallization schemes, complete with Ti/TiN cladding layers and a tungsten-plug contact at the cathode. A total of 18 electrical stress treatments were applied. One was a DC current of 15 mA. The other 17 were pulsed currents, varied according to duty cycle and frequency. The pulse amplitude was 15 mA (˜2.7 × 10sp6 A/cmsp2) for all treatments. Duty cycles ranged from 33.3% to 80%, and frequencies fell into three rough ranges-100 KHz, 1 MHz, and 100 MHz. The ambient test temperature was 200sp°C in all experiments. Six to 9 samples were subjected to each treatment. Experimental data were gathered in the form of test stripe resistance versus time, R(t). For purposes of lifetime analysis, "failure" was defined by the criterion R(t)/R(0) = 1.10, and the median time to failure, tsb{50}, was used as the primary basis of comparison between test groups. It was found that the dependence of tsb{50} on pulse duty cycle conformed rather well to the so-called "average current density model" for duty cycles of 50% and higher. Lifetimes were less enhanced for a duty cycle of 33.3%, but they were still considerably longer than an "on-time" model would predict. No specific dependence of tsb{50} on pulse frequency was revealed by the data, that is, reasonably good predictions of tsb{50} could be made by recognizing the dominant influence of duty cycle. These findings confirm that IC miniaturization can be more aggressively pursued than an on-time prediction would allow. It is significant that this was found to be true for frequencies on the order of 100 MHz, where many present day digital applications operate. Post-test optical micrographs were obtained for each test subject in order to determine the location of electromigration damage. The pulse duty cycle was found to influence the location. Most damage occurred at the cathode contact, regardless of treatment conditions, but there was an increased incidence of damage farther downwind with decreasing duty cycle. This tendency and the deviation from the average current density model for small duty cycles were explained in terms of the Blech length, its dependence on microstructure and duty cycle, and its impact on the relative rates of damage and recovery.

Changes in electrical and thermal parameters of led packages under different current and heating stresses

NASA Astrophysics Data System (ADS)

Jayawardena, Adikaramge Asiri

The goal of this dissertation is to identify electrical and thermal parameters of an LED package that can be used to predict catastrophic failure real-time in an application. Through an experimental study the series electrical resistance and thermal resistance were identified as good indicators of contact failure of LED packages. This study investigated the long-term changes in series electrical resistance and thermal resistance of LED packages at three different current and junction temperature stress conditions. Experiment results showed that the series electrical resistance went through four phases of change; including periods of latency, rapid increase, saturation, and finally a sharp decline just before failure. Formation of voids in the contact metallization was identified as the underlying mechanism for series resistance increase. The rate of series resistance change was linked to void growth using the theory of electromigration. The rate of increase of series resistance is dependent on temperature and current density. The results indicate that void growth occurred in the cap (Au) layer, was constrained by the contact metal (Ni) layer, preventing open circuit failure of contact metal layer. Short circuit failure occurred due to electromigration induced metal diffusion along dislocations in GaN. The increase in ideality factor, and reverse leakage current with time provided further evidence to presence of metal in the semiconductor. An empirical model was derived for estimation of LED package failure time due to metal diffusion. The model is based on the experimental results and theories of electromigration and diffusion. Furthermore, the experimental results showed that the thermal resistance of LED packages increased with aging time. A relationship between thermal resistance change rate, with case temperature and temperature gradient within the LED package was developed. The results showed that dislocation creep is responsible for creep induced plastic deformation in the die-attach solder. The temperatures inside the LED package reached the melting point of die-attach solder due to delamination just before catastrophic open circuit failure. A combined model that could estimate life of LED packages based on catastrophic failure of thermal and electrical contacts is presented for the first time. This model can be used to make a-priori or real-time estimation of LED package life based on catastrophic failure. Finally, to illustrate the usefulness of the findings from this thesis, two different implementations of real-time life prediction using prognostics and health monitoring techniques are discussed.

Modeling and Studying the Effect of Texture and Elastic Anisotropy of Copper Microstructure in Nanoscale Interconnects on Reliability in Integrated Circuits

NASA Astrophysics Data System (ADS)

Basavalingappa, Adarsh

Copper interconnects are typically polycrystalline and follow a lognormal grain size distribution. Polycrystalline copper interconnect microstructures with a lognormal grain size distribution were obtained with a Voronoi tessellation approach. The interconnect structures thus obtained were used to study grain growth mechanisms, grain boundary scattering, scattering dependent resistance of interconnects, stress evolution, vacancy migration, reliability life times, impact of orientation dependent anisotropy on various mechanisms, etc. In this work, the microstructures were used to study the impact of microstructure and elastic anisotropy of copper on thermal and electromigration induced failure. A test structure with copper and bulk moduli values was modeled to do a comparative study with the test structures with textured microstructure and elastic anisotropy. By subjecting the modeled test structure to a thermal stress by ramping temperature down from 400 °C to 100 °C, a significant variation in normal stresses and pressure were observed at the grain boundaries. This variation in normal stresses and hydrostatic stresses at the grain boundaries was found to be dependent on the orientation, dimensions, surroundings, and location of the grains. This may introduce new weak points within the metal line where normal stresses can be very high depending on the orientation of the grains leading to delamination and accumulation sites for vacancies. Further, the hydrostatic stress gradients act as a driving force for vacancy migration. The normal stresses can exceed certain grain orientation dependent critical threshold values and induce delamination at the copper and cap material interface, thereby leading to void nucleation and growth. Modeled test structures were subjected to a series of copper depositions at 250 °C followed by copper etch at 25 °C to obtain initial stress conditions. Then the modeled test structures were subjected to 100,000 hours ( 11.4 years) of simulated thermal stress at an elevated temperature of 150 °C. Vacancy migration due to concentration gradients, thermal gradients, and mechanical stress gradients were considered under the applied thermal stress. As a result, relatively high concentrations of vacancies were observed in the test structure due to a driving force caused by the pressure gradients resulting from the elastic anisotropy of copper. The grain growth mechanism was not considered in these simulations. Studies with two grain analysis demonstrated that the stress gradients developed will be severe when (100) grains are adjacent to (111) grains, therefore making them the weak points for potentially reliability failures. Ilan Blech discovered that electromigration occurs above a critical product of the current density and metal length, commonly referred as Blech condition. Electromigration stress simulations in this work were carried out by subjecting test structures to scaled current densities to overcome the Blech condition of (jL)crit for small dimensions of test structure and the low temperature stress condition used. Vacancy migration under the electromigration stress conditions was considered along with the vacancy migration induced stress evolution. A simple void growth model was used which assumes voids start to form when vacancies reach a critical level. Increase of vacancies in a localized region increases the resistance of the metal line. Considering a 10% increase in resistance as a failure criterion, the distributions of failure times were obtained for given electromigration stress conditions. Bimodal/multimodal failure distributions were obtained as a result. The sigma values were slightly lower than the ones commonly observed from experiments. The anisotropy of the elastic moduli of copper leads to the development of significantly different stress values which are dependent on the orientation of the grains. This results in some grains having higher normal stress than the others. This grain orientation dependent normal stress can reach a critical stress necessary to induce delamination at the copper and cap interface. Time taken to reach critical stress was considered as time to fail and distributions of failure times were obtained for structures with different grain orientations in the microstructure for different critical stress values. The sigma values of the failure distributions thus obtained for different constant critical stress values had a strong dependence of on the critical stress. It is therefore critical to use the appropriate critical stress value for the delamination of copper and cap interface. The critical stress necessary to overcome the local adhesion of the copper and the cap material interface is dependent on grain orientation of the copper. Simulations were carried out by considering grain orientation dependent critical normal stress values as failure criteria. The sigma value thus obtained with selected critical stress values were comparable to sigma values commonly observed from experiments.

A new configuration of membrane stack for retrieval of nickel absorbed in resins*

PubMed Central

Chen, Xue-fen; Wu, Zu-cheng

2005-01-01

A new configuration integrated ion exchange effect with both electro-migration and electrochemical reaction in a single cell was developed to effectively retrieve metal ions from simulated wastewater using ion exchange resins without additive chemicals. By simply assembling cation exchange resins and anion exchange resins separated by homogeneous membranes, we found that the system will always be acidic in the concentrate compartment so that ion exchange resins could be in-situ regenerated without hydroxide precipitation. Such a realizable design will be really suitable for wastewater purification. PMID:15909341

Enhancing the efficiency of zero valent iron by electrolysis: Performance and reaction mechanism.

PubMed

Xiong, Zhaokun; Lai, Bo; Yang, Ping

2018-03-01

Electrolysis was applied to enhance the efficiency of micron-size zero valent iron (mFe 0 ) and thereby promote p-nitrophenol (PNP) removal. The rate of PNP removal by mFe 0 with electrolysis was determined in cylindrical electrolysis reactor that employed annular aluminum plate cathode as a function of experimental factors, including initial pH, mFe 0 dosage and current density. The rate constants of PNP removal by Ele-mFe 0 were 1.72-144.50-fold greater than those by pristine mFe 0 under various tested conditions. The electrolysis-induced improvement could be primarily ascribed to stimulated mFe 0 corrosion, as evidenced by Fe 2+ release. The application of electrolysis could extend the working pH range of mFe 0 from 3.0 to 6.0 to 3.0-10.0 for PNP removal. Additionally, intermediates analysis and scavengers experiments unraveled the reduction capacity of mFe 0 was accelerated in the presence of electrolysis instead of oxidation. Moreover, the electrolysis effect could also delay passivation of mFe 0 under acidic condition, as evidenced by SEM-EDS, XRD, and XPS analysis after long-term operation. This is mainly due to increased electromigration meaning that iron corrosion products (iron hydroxides and oxides) are not primarily formed in the vicinity of the mFe 0 or at its surface. In the presence of electrolysis, the effect of electric field significantly promoted the efficiency of electromigration, thereby enhanced mFe 0 corrosion and eventually accelerated the PNP removal rates. Copyright © 2017 Elsevier Ltd. All rights reserved.

Determination of thermodynamic values of acidic dissociation constants and complexation constants of profens and their utilization for optimization of separation conditions by Simul 5 Complex.

PubMed

Riesová, Martina; Svobodová, Jana; Ušelová, Kateřina; Tošner, Zdeněk; Zusková, Iva; Gaš, Bohuslav

2014-10-17

In this paper we determine acid dissociation constants, limiting ionic mobilities, complexation constants with β-cyclodextrin or heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin, and mobilities of resulting complexes of profens, using capillary zone electrophoresis and affinity capillary electrophoresis. Complexation parameters are determined for both neutral and fully charged forms of profens and further corrected for actual ionic strength and variable viscosity in order to obtain thermodynamic values of complexation constants. The accuracy of obtained complexation parameters is verified by multidimensional nonlinear regression of affinity capillary electrophoretic data, which provides the acid dissociation and complexation parameters within one set of measurements, and by NMR technique. A good agreement among all discussed methods was obtained. Determined complexation parameters were used as input parameters for simulations of electrophoretic separation of profens by Simul 5 Complex. An excellent agreement of experimental and simulated results was achieved in terms of positions, shapes, and amplitudes of analyte peaks, confirming the applicability of Simul 5 Complex to complex systems, and accuracy of obtained physical-chemical constants. Simultaneously, we were able to demonstrate the influence of electromigration dispersion on the separation efficiency, which is not possible using the common theoretical approaches, and predict the electromigration order reversals of profen peaks. We have shown that determined acid dissociation and complexation parameters in combination with tool Simul 5 Complex software can be used for optimization of separation conditions in capillary electrophoresis. Copyright © 2014 Elsevier B.V. All rights reserved.

Electromigration Critical Product to Measure Effect of Underfill Material in Suppressing Bi Segregation in Sn-58Bi Solder

NASA Astrophysics Data System (ADS)

Zhao, Xu; Takaya, Satoshi; Muraoka, Mikio

2017-08-01

Recently, we detected length-dependent electromigration (EM) behavior in Sn-58Bi (SB) solder and revealed the existence of Bi back-flow, which retards EM-induced Bi segregation and is dependent on solder length. The cause of the back-flow is attributed to an oxide layer formed on the SB solder. At present, underfill (UF) material is commonly used in flip-chip packaging as filler between chip and substrate to surround solder bumps. In this study, we quantitatively investigated the effect of UF material as a passivation layer on EM in SB solder strips. EM tests on SB solder strips with length of 50 μm, 100 μm, and 150 μm were conducted simultaneously. Some samples were coated with commercial thermosetting epoxy UF material, which acted as a passivation layer on the Cu-SB-Cu interconnections. The value of the critical product for SB solder was estimated to be 38 A/cm to 43 A/cm at 353 K to 373 K without UF coating and 59 A/cm at 373 K with UF coating. The UF material acting as a passivation layer suppressed EM-induced Bi segregation and increased the threshold current density by 37% to 55%. However, at very high current density, this effect became very slight. In addition, Bi atoms can diffuse to the anode side through the Sn phase, hence addition of microelements to the Sn phase to form obstacles, such as intermetallic compounds, may retard Bi segregation in SB solder.

Effect of surface finish on the failure mechanisms of flip-chip solder joints under electromigration

NASA Astrophysics Data System (ADS)

Lin, Y. L.; Lai, Y. S.; Tsai, C. M.; Kao, C. R.

2006-12-01

Two substrate surface finishes, Au/Ni and organic solderable preservative (OSP), were used to study the effect of the surface finish on the reliability of flip-chip solder joints under electromigration at 150°C ambient temperature. The solder used was eutectic PbSn, and the applied current density was 5×103 A/cm2 at the contact window of the chip. The under bump metallurgy (UBM) on the chip was sputtered Cu/Ni. It was found that the mean-time-to-failure (MTTF) of the OSP joints was six times better than that of the Au/Ni joints (3080 h vs. 500 h). Microstructure examinations uncovered that the combined effect of current crowding and the accompanying local Joule heating accelerated the local Ni UBM consumption near the point of electron entrance. Once Ni was depleted at a certain region, this region became nonconductive, and the flow of the electrons was diverted to the neighboring region. This neighboring region then became the place where electrons entered the joint, and the local Ni UBM consumption was accelerated. This process repeated itself, and the Ni-depleted region extended further on, creating an ever-larger nonconductive region. The solder joint eventually, failed when the nonconductive region became too large, making the effective current density very high. Accordingly, the key factor determining the MTTF was the Ni consumption rate. The joints with the OSP surface finish had a longer MTTF because Cu released from the substrate was able to reduce the Ni consumption rate.

Effects of media stray field on electromigration characteristics in current-perpendicular-to-plane giant magnetoresistance spin-valve read sensors

NASA Astrophysics Data System (ADS)

Gui Zeng, Ding; Lee, Kyoung-il; Chung, Kyung-Won; Bae, Seongtae

2012-05-01

Effects of magnetic stray field retrieved from both longitudinal and perpendicular magnetic recording media (denoted by "media stray field") on electromigration (EM) characteristics of current-perpendicular-to-plane (CPP) giant magnetoresistance spin-valve (GMR SV) read sensors have been numerically studied to explore the electrical and magnetic stability of the read sensor under real operation. The mean-time-to-failure (MTTF) of the CPP GMR SV read sensors was found to have a strong dependence on the physical parameters of the recording media and recorded information status, such as the pulse width of media stray field, the bit length, and the head moving velocity. According to the numerical calculation results, it was confirmed that in the longitudinal media, the shorter the stray field pulse width (i.e., the sharper the media transition) allows for the longer MTTF of the CPP GMR SV read sensors; while in the perpendicular media, the sharper the media transition gives rise to a shorter MTTF. Interestingly, it was also revealed that the MTTF could be improved by reducing the bit length as well as increasing the head velocity in both longitudinal and perpendicular media. Furthermore, the bit distribution patterns, especially the number of consecutive `0' bits strongly affected the MTTF of GMR SV read sensors. The strong dependences of MTTF on the media stray field during CPP GMR SV sensor operation are thought to be mainly attributed to the thermal cycling (temperature rise and fall) caused by the resistance change due to GMR effects.

Migration and distribution of sodium ions and organic matters during electro-dewatering of waste activated sludge at different dosages of sodium sulfate.

PubMed

Xiao, Jun; Wu, Xu; Yu, Wenbo; Liang, Sha; Yu, Jiangwei; Gu, Yueyuan; Deng, Huali; Hu, Jiukun; Xiao, Keke; Yang, Jiakuan

2017-12-01

In this study, the influence of Na 2 SO 4 on electro-dewatering (EDW) of waste activated sludge (WAS) was investigated. The highest water removal efficiency of 42.5% was achieved at the optimum Na 2 SO 4 dosage of 12.5 g kg -1 DS during EDW process at a constant voltage of 20 V. The migration and distribution of water, organic matters and Na + at different Na 2 SO 4 dosages were investigated through layered experiments. The results indicated the entire EDW process followed the S curve model, and it can be divided into three stages: (1) initial desalination stage: at the initial few min of EDW process, the rate of electroosmosis was extremely slow while electromigration of ions like Na + was intense, and the electromigration was more obvious with increased Na 2 SO 4 dosage; (2) dewatering stage: the dewatering efficiency increased dramatically via electroosmosis; (3) the dewaterability limit stage: the maximum value of dewatering efficiency has been achieved, while the water removal efficiency and dry solids content remained constant. During the EDW process, the possible electrolysis resulted in a pH gradient in the sludge cake. With the addition of Na 2 SO 4 in the EDW, the pH gradient was intensified, and the migration rate of organic matters moving from cathode to anode increased while compared with the raw WAS. This study provided insights into the mechanism of EDW process at different dosages of Na 2 SO 4 . Copyright © 2017 Elsevier Ltd. All rights reserved.

Mathematical modeling and computer simulation of isoelectric focusing with electrochemically defined ampholytes

NASA Technical Reports Server (NTRS)

Palusinski, O. A.; Allgyer, T. T.; Mosher, R. A.; Bier, M.; Saville, D. A.

1981-01-01

A mathematical model of isoelectric focusing at the steady state has been developed for an M-component system of electrochemically defined ampholytes. The model is formulated from fundamental principles describing the components' chemical equilibria, mass transfer resulting from diffusion and electromigration, and electroneutrality. The model consists of ordinary differential equations coupled with a system of algebraic equations. The model is implemented on a digital computer using FORTRAN-based simulation software. Computer simulation data are presented for several two-component systems showing the effects of varying the isoelectric points and dissociation constants of the constituents.

Theoretical studies in isoelectric focusing. [mathematical modeling and computer simulation for biologicals purification process

NASA Technical Reports Server (NTRS)

Mosher, R. A.; Palusinski, O. A.; Bier, M.

1982-01-01

A mathematical model has been developed which describes the steady state in an isoelectric focusing (IEF) system with ampholytes or monovalent buffers. The model is based on the fundamental equations describing the component dissociation equilibria, mass transport due to diffusion and electromigration, electroneutrality, and the conservation of charge. The validity and usefulness of the model has been confirmed by using it to formulate buffer systems in actual laboratory experiments. The model has been recently extended to include the evolution of transient states not only in IEF but also in other modes of electrophoresis.

Nanogap structures for molecular nanoelectronics.

PubMed

Motto, Paolo; Dimonte, Alice; Rattalino, Ismael; Demarchi, Danilo; Piccinini, Gianluca; Civera, Pierluigi

2012-02-09

This study is focused on the realization of nanodevices for nano and molecular electronics, based on molecular interactions in a metal-molecule-metal (M-M-M) structure. In an M-M-M system, the electronic function is a property of the structure and can be characterized through I/V measurements. The contact between the metals and the molecule was obtained by gold nanogaps (with a dimension of less than 10 nm), produced with the electromigration technique. The nanogap fabrication was controlled by a custom hardware and the related software system. The studies were carried out through experiments and simulations of organic molecules, in particular oligothiophenes.

Size effect in Quincke rotation: a numerical study.

PubMed

Peters, F; Lobry, L; Khayari, A; Lemaire, E

2009-05-21

This paper deals with the Quincke rotation of small insulating particles. This dc electrorotation of insulating objects immersed in a slightly conducting liquid is usually explained by looking at the action of the free charges present in the liquid. Under the effect of the dc electric field, the charges accumulate at the surface of the insulating particle which, in turn, acquires a dipole moment in the direction opposite to that of the field and begins to rotate in order to flip its dipole moment. In the classical Quincke model, the charge distribution around the rotor is supposed to be purely superficial. A consequence of this assumption is that the angular velocity does not depend on the rotor size. Nevertheless, this hypothesis holds only if the rotor size is much larger than the characteristic ion layer thickness around the particle. In the opposite case, we show thanks to numerical calculations that the bulk charge distribution has to be accounted for to predict the electromechanical behavior of the rotor. We consider the case of an infinite insulating cylinder whose axis is perpendicular to the dc electric field. We use the finite element method to solve the conservation equations for the positive and the negative ions coupled with Navier-Stokes and Poisson equations. Doing so, we compute the bulk charge distribution and the velocity field in the liquid surrounding the cylinder. For sufficiently small cylinders, we show that the smaller the cylinder is, the smaller its angular velocity is when submitted to a dc electric field. This size effect is shown to originate both in ion diffusion and electromigration in the charge layer. At last, we propose a simple analytical model which allows calculating the angular velocity of the rotor when electromigration is present but weak and diffusion can be neglected.

Size effect in Quincke rotation: A numerical study

NASA Astrophysics Data System (ADS)

Peters, F.; Lobry, L.; Khayari, A.; Lemaire, E.

2009-05-01

This paper deals with the Quincke rotation of small insulating particles. This dc electrorotation of insulating objects immersed in a slightly conducting liquid is usually explained by looking at the action of the free charges present in the liquid. Under the effect of the dc electric field, the charges accumulate at the surface of the insulating particle which, in turn, acquires a dipole moment in the direction opposite to that of the field and begins to rotate in order to flip its dipole moment. In the classical Quincke model, the charge distribution around the rotor is supposed to be purely superficial. A consequence of this assumption is that the angular velocity does not depend on the rotor size. Nevertheless, this hypothesis holds only if the rotor size is much larger than the characteristic ion layer thickness around the particle. In the opposite case, we show thanks to numerical calculations that the bulk charge distribution has to be accounted for to predict the electromechanical behavior of the rotor. We consider the case of an infinite insulating cylinder whose axis is perpendicular to the dc electric field. We use the finite element method to solve the conservation equations for the positive and the negative ions coupled with Navier-Stokes and Poisson equations. Doing so, we compute the bulk charge distribution and the velocity field in the liquid surrounding the cylinder. For sufficiently small cylinders, we show that the smaller the cylinder is, the smaller its angular velocity is when submitted to a dc electric field. This size effect is shown to originate both in ion diffusion and electromigration in the charge layer. At last, we propose a simple analytical model which allows calculating the angular velocity of the rotor when electromigration is present but weak and diffusion can be neglected.

Equivalence-point electromigration acid-base titration via moving neutralization boundary electrophoresis.

PubMed

Yang, Qing; Fan, Liu-Yin; Huang, Shan-Sheng; Zhang, Wei; Cao, Cheng-Xi

2011-04-01

In this paper, we developed a novel method of acid-base titration, viz. the electromigration acid-base titration (EABT), via a moving neutralization boundary (MNR). With HCl and NaOH as the model strong acid and base, respectively, we conducted the experiments on the EABT via the method of moving neutralization boundary for the first time. The experiments revealed that (i) the concentration of agarose gel, the voltage used and the content of background electrolyte (KCl) had evident influence on the boundary movement; (ii) the movement length was a function of the running time under the constant acid and base concentrations; and (iii) there was a good linearity between the length and natural logarithmic concentration of HCl under the optimized conditions, and the linearity could be used to detect the concentration of acid. The experiments further manifested that (i) the RSD values of intra-day and inter-day runs were less than 1.59 and 3.76%, respectively, indicating similar precision and stability in capillary electrophoresis or HPLC; (ii) the indicators with different pK(a) values had no obvious effect on EABT, distinguishing strong influence on the judgment of equivalence-point titration in the classic one; and (iii) the constant equivalence-point titration always existed in the EABT, rather than the classic volumetric analysis. Additionally, the EABT could be put to good use for the determination of actual acid concentrations. The experimental results achieved herein showed a new general guidance for the development of classic volumetric analysis and element (e.g. nitrogen) content analysis in protein chemistry. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Generalized model of electromigration with 1:1 (analyte:selector) complexation stoichiometry: part II. Application to dual systems and experimental verification.

PubMed

Müllerová, Ludmila; Dubský, Pavel; Gaš, Bohuslav

2015-03-06

Interactions among analyte forms that undergo simultaneous dissociation/protonation and complexation with multiple selectors take the shape of a highly interconnected multi-equilibrium scheme. This makes it difficult to express the effective mobility of the analyte in these systems, which are often encountered in electrophoretical separations, unless a generalized model is introduced. In the first part of this series, we presented the theory of electromigration of a multivalent weakly acidic/basic/amphoteric analyte undergoing complexation with a mixture of an arbitrary number of selectors. In this work we demonstrate the validity of this concept experimentally. The theory leads to three useful perspectives, each of which is closely related to the one originally formulated for simpler systems. If pH, IS and the selector mixture composition are all kept constant, the system is treated as if only a single analyte form interacted with a single selector. If the pH changes at constant IS and mixture composition, the already well-established models of a weakly acidic/basic analyte interacting with a single selector can be employed. Varying the mixture composition at constant IS and pH leads to a situation where virtually a single analyte form interacts with a mixture of selectors. We show how to switch between the three perspectives in practice and confirm that they can be employed interchangeably according to the specific needs by measurements performed in single- and dual-selector systems at a pH where the analyte is fully dissociated, partly dissociated or fully protonated. Weak monoprotic analyte (R-flurbiprofen) and two selectors (native β-cyclodextrin and monovalent positively charged 6-monodeoxy-6-monoamino-β-cyclodextrin) serve as a model system. Copyright © 2015 Elsevier B.V. All rights reserved.

Electromigration effect on intermetallic growth and Young's modulus in SAC solder joint

NASA Astrophysics Data System (ADS)

Xu, Luhua; Pang, John H. L.; Ren, Fei; Tu, K. N.

2006-12-01

Solid-state intermetallic compound (IMC) growth behavior plays and important role in solder joint reliability of electronic packaging assemblies. The directional impact of electromigration (EM) on the growth of interfacial IMCs in Ni/SAC/Ni, Cu/SAC/Ni single BGA ball solder joint, and fine pitch ball-grid-array (FPBGA) at the anode and cathode sides is reported in this study. When the solder joint was subjected to a current density of 5,000 A/cm2 at 125°C or 150°C, IMC layer growth on the anode interface was faster than that on the cathode interface, and both were faster than isothermal aging due to the Joule heating effect. The EM affects the IMC growth rate, as well as the composition and mechanical properties. The Young’s modulus and hardness were measured by the nanoindentation continuous stiffness measurement (CSM) from planar IMC surfaces after EM exposure. Different values were observed at the anode and cathode. The energy-dispersive x-ray (EDX) line scan analysis was conducted at the interface from the cathode to anode to study the presence of species; Ni was found in the anode IMC at SAC/Cu in the Ni/SAC/Cu joint, but not detected when the current was reverse. Electron-probe microanalysis (EPMA) measurement on the Ni/SAC/Ni specimen also confirmed the polarized Ni and Cu distributions in cathode and anode IMCs, which were (Ni0.57Cu0.43)3Sn4 and (Cu0.73Ni0.27)6Sn5, respectively. Thus, the Young’s moduli of the IMC are 141 and 175 GPa, respectively.

Effect of Sn-Ag-Cu on the Improvement of Electromigration Behavior in Sn-58Bi Solder Joint

NASA Astrophysics Data System (ADS)

Wang, Fengjiang; Zhou, Lili; Zhang, Zhijie; Wang, Jiheng; Wang, Xiaojing; Wu, Mingfang

2017-10-01

Reliability issues caused by the formation of a Bi-rich layer at the anode interface usually occurs in the Sn-58Bi eutectic solder joint during electromigration (EM). To improve the EM performance of a Sn-58Bi solder joint, Sn-3.0Ag-0.5Cu solder was introduced into it to produce SnBi-SnAgCu structural or compositional composite joints, and their EM behaviors were investigated with the current density of 1.0 × 104 A/cm2 for different stressing times. The structure of the compositional composite solder joint was obtained by the occurrence of partial or full mixing between Sn-Bi and Sn-Ag-Cu solder with a suitable soldering temperature. In the structural composite joint, melted Sn-Bi was partially mixed with Sn-Ag-Cu solder to produce a Cu/Sn-Bi/Sn-Ag-Cu/Sn-Bi/Cu structure. In the compositional composite joint, full melting and mixing between these two solders occurred to produce a Cu/Sn-Ag-Cu-Bi/Cu structure, in which the solder matrix was a homogeneous structure including Sn, Bi phases, Cu6Sn5 and Ag3Sn IMCs. After current stressing, the EM performance of Sn-Bi solder was obviously improved with the structural or the compositional composite joint. In Sn-58Bi joints, a thick Bi-rich layer was easily produced at the anode interface, and obviously increased with stressing time. However, after current stressing on the structural composite joints, the existence of s Sn-3.0Ag-0.5Cu interlayer between the two Sn-58Bi solders effectively acted as a diffusion barrier and significantly slowed the formation of the Bi-rich layer at the anode side and the IMC thicknesses at the interfaces.

Nanogap structures for molecular nanoelectronics

PubMed Central

2012-01-01

This study is focused on the realization of nanodevices for nano and molecular electronics, based on molecular interactions in a metal-molecule-metal (M-M-M) structure. In an M-M-M system, the electronic function is a property of the structure and can be characterized through I/V measurements. The contact between the metals and the molecule was obtained by gold nanogaps (with a dimension of less than 10 nm), produced with the electromigration technique. The nanogap fabrication was controlled by a custom hardware and the related software system. The studies were carried out through experiments and simulations of organic molecules, in particular oligothiophenes. PMID:22321736

An investigation into the feasibility of myoglobin-based single-electron transistors

PubMed Central

Li, Debin; Gannett, Peter M.; Lederman, David

2016-01-01

Myoglobin single-electron transistors were investigated using nanometer-gap platinum electrodes fabricated by electromigration at cryogenic temperatures. Apomyoglobin (myoglobin without heme group) was used as a reference. The results suggest single electron transport is mediated by resonant tunneling with the electronic and vibrational levels of the heme group in a single protein. They also represent a proof-of-principle that proteins with redox centers across nanometer-gap electrodes can be utilized to fabricate single-electron transistors. The protein orientation and conformation may significantly affect the conductance of these devices. Future improvements in device reproducibility and yield will require control of these factors. PMID:22972432

Effect of Sn Grain Orientation on the Cu6Sn5 Formation in a Sn-Based Solder Under Current Stressing

NASA Astrophysics Data System (ADS)

Lin, Chih-Fan; Lee, Shang-Hua; Chen, Chih-Ming

2012-08-01

A SnAgCu-based solder stripe between two Cu electrodes is current stressed with a density of 5 × 104 A/cm2 at 393 K (120 °C). After current stressing for 24 hours, electromigration induces the Cu dissolution from the cathode-side Cu electrode, leading to the Cu6Sn5 formation in the solder stripe. Very interestingly, the Cu6Sn5 phase is selectively formed within a specific Sn grain. Electron backscattering diffraction analysis indicates the crystallographic orientations of Sn grains play an important role in the selective Cu6Sn5 formation.

Growth of <111>-oriented Cu layer on thin TaWN films

NASA Astrophysics Data System (ADS)

Takeyama, Mayumi B.; Sato, Masaru

2017-07-01

In this study, we examine the growth of a <111>-oriented Cu layer on a thin TaWN ternary alloy barrier for good electromigration reliability. The strongly preferentially oriented Cu(111) layer is observed on a thin TaWN barrier even in the as-deposited Cu (100 nm)/TaWN (5 nm)/Si system. Also, this system tolerates annealing at 700 °C for 1 h without silicide reaction. It is revealed that the TaWN film is one of the excellent barriers with thermal stability and low resistivity. Simultaneously, the TaWN film is a candidate for a superior underlying material to achieve the Cu(111) preferential orientation.

Synaptic plasticity and oscillation at zinc tin oxide/silver oxide interfaces

NASA Astrophysics Data System (ADS)

Murdoch, Billy J.; McCulloch, Dougal G.; Partridge, James G.

2017-02-01

Short-term plasticity, long-term potentiation, and pulse interval dependent plasticity learning/memory functions have been observed in junctions between amorphous zinc-tin-oxide and silver-oxide. The same junctions exhibited current-controlled negative differential resistance and when connected in an appropriate circuit, they behaved as relaxation oscillators. These oscillators produced voltage pulses suitable for device programming. Transmission electron microscopy, energy dispersive X-ray spectroscopy, and electrical measurements suggest that the characteristics of these junctions arise from Ag+/O- electromigration across a highly resistive interface layer. With memory/learning functions and programming spikes provided in a single device structure, arrays of similar devices could be used to form transistor-free neuromorphic circuits.

Oxygen adsorption on Cu-9 at. %Al(111) studied by low energy electron diffraction and Auger electron spectroscopy

NASA Astrophysics Data System (ADS)

Yoshitake, Michiko; Bera, Santanu; Yamauchi, Yasuhiro; Song, Weijie

2003-07-01

Cu-based alloys have been used for electric cables for long time. In the field of microelectronics, Al had been used for electrical wiring. However, it became clear that electromigration occurs in Al that causes breaking of wires in minute wirings. Due to this problem, Cu wiring is used in most advanced microprocessors. Cu metal is more corrosive than Al and Cu-based alloys with a small amount of Al is expected to solve problems both on electromigration and corrosion. The initial stage of corrosion is oxygen adsorption. We studied surface segregation of Al on Cu-9% Al(111) and oxygen adsorption on the surface with/without Al segregation in ultrahigh vacuum by low energy electron diffraction (LEED) and Auger electron spectroscopy. It was found that Al segregates on the surface to form (√3×√3)R30° structure and the structure vanishes above 595 K to give (1×1) structure while Al still segregates. The specimen was exposed to oxygen at different temperatures. The amount of oxygen uptake was not structure dependent but temperature dependent. Below 595 K, only a small amount of oxygen adsorbed. Between 595 and 870 K, oxygen adsorbed surface showed amorphous LEED pattern. The specimen was annealed at 1070 K after oxygen exposure. When the specimen was exposed oxygen below 870 K, the oxygen Auger intensity decreased significantly by annealing and the annealed surface showed (√3×√3)R30° structure at room temperature. When the specimen was exposed to oxygen at 870 K, diffused spots developed newly in LEED pattern but the pattern disappeared after 1070 K annealing while oxygen Auger intensity remained almost constant. Exposing the specimen to oxygen at 995 K resulted in clear spots in the LEED pattern, which were attributed to the (7/√3×7√3)R30° structure.

Surface evolution in bare bamboo-type metal lines under diffusion and electric field effects

NASA Astrophysics Data System (ADS)

Averbuch, Amir; Israeli, Moshe; Nathan, Menachem; Ravve, Igor

2003-07-01

Irregularities such as voids and cracks often occur in bamboo-type metal lines of microelectronic interconnects. They increase the resistance of the circuits, and may even lead to a fatal failure. In this work, we analyze numerically the electromigration of an unpassivated bamboo-type line with pre-existing irregularities in its top surface (also called a grain-void interface). The bamboo line is subjected to surface diffusion forces and external electric fields. Under these forces, initial defects may either heal or become worse. The grain-void interface is considered to be one-dimensional, and the physical formulation of an electromigration and diffusion model results in two coupled, fourth order, one-dimensional time-dependent PDEs, with the boundary conditions imposed at the electrode points and at the triple point, which belongs to two neighboring grains and the void. These equations are discretized by finite differences on a regular grid in space, and by a Runge-Kutta integration scheme in time, and solved simultaneously with a static Laplace equation describing the voltage distribution throughout each grain, when the substrate conductivity is neglected. Since the voltage distribution is required only along an interface line, the two-dimensional discretization of the grain interior is not needed, and the static problem is solved by the boundary element method at each time step. The motion of the interface line is studied for different ratios between diffusion and electric field forces, and for different initial configurations of the grain-void interface. We study plain and tilted contour lines, considering positive and negative tilts with respect to the external electric field, a stepped contour with field lines entering or exiting the 'step', and a number of modifications of the classical Mullins problem of thermal grooving. We also consider a two-grain Mullins problem with a normal and tilted boundary between the grains, examining positive and negative tilts.

Computation for Electromigration in Interconnects of Microelectronic Devices

NASA Astrophysics Data System (ADS)

Averbuch, Amir; Israeli, Moshe; Ravve, Igor; Yavneh, Irad

2001-03-01

Reliability and performance of microelectronic devices depend to a large extent on the resistance of interconnect lines. Voids and cracks may occur in the interconnects, causing a severe increase in the total resistance and even open circuits. In this work we analyze void motion and evolution due to surface diffusion effects and applied external voltage. The interconnects under consideration are three-dimensional (sandwich) constructs made of a very thin metal film of possibly variable thickness attached to a substrate of nonvanishing conductance. A two-dimensional level set approach was applied to study the dynamics of the moving (assumed one-dimensional) boundary of a void in the metal film. The level set formulation of an electromigration and diffusion model results in a fourth-order nonlinear (two-dimensional) time-dependent PDE. This equation was discretized by finite differences on a regular grid in space and a Runge-Kutta integration scheme in time, and solved simultaneously with a second-order static elliptic PDE describing the electric potential distribution throughout the interconnect line. The well-posed three-dimensional problem for the potential was approximated via singular perturbations, in the limit of small aspect ratio, by a two-dimensional elliptic equation with variable coefficients describing the combined local conductivity of metal and substrate (which is allowed to vary in time and space). The difference scheme for the elliptic PDE was solved by a multigrid technique at each time step. Motion of voids in both weak and strong electric fields was examined, and different initial void configurations were considered, including circles, ellipses, polygons with rounded corners, a butterfly, and long grooves. Analysis of the void behavior and its influence on the resistance gives the circuit designer a tool for choosing the proper parameters of an interconnect (width-to-length ratio, properties of the line material, conductivity of the underlayer, etc.).

Application of Nano-SiO₂ and Nano-Fe₂O₃ for Protection of Steel Rebar in Chloride Contaminated Concrete: Epoxy Nanocomposite Coatings and Nano-Modified Mortars.

PubMed

Nguyen, Tuan Anh; Nguyen, The Huyen; Pham, Thi Lua; Dinh, Thi Mai Thanh Dinh; Thai, Hoang; Shi, Xianming

2017-01-01

The effect of incorporating nanoparticles on the corrosion resistance of epoxy-coated steel in salt contaminated mortars was investigated using potentiodynamic polarization and electrochemical impedance spectroscopy. Researchers conducted electrochemical monitoring of the coated steel embedded in mortar over 100 days of immersion in 0.1 M NaOH solutions. The chloride permeability and microstructure of Portland cement mortar with admixed nano-materials (at 1% by weight of cement) were examined using an electromigration test and field emission scanning electron microscopy (FESEM). Electrochemical monitoring showed that nano Fe₂O₃ improved the corrosion resistance of the coated rebar. The incorporation of a small amount of nano Fe₂O₃ (1% by total weight of resin and hardener) into the epoxy coating reduced the corrosion current of the epoxy-coated steel in chloride-contaminated mortar (0.3% chloride by weight of cement). After 100 days of immersion, the nanoparticles reduced the corrosion current of epoxy-coated steel by a factor of 6. The FESEM test revealed that admixing of nano-materials not only led to denser cement mortar but also changed the morphology of cement hydration products. The test results of compressive strength showed that nanoparticles increased the strength of cement mortar. The electromigration test showed that the incorporation of nanoparticles improved the chloride penetration resistance of the mortar, as indicated by the reduced apparent diffusion coefficients of the chloride anion. When nano-SiO₂ and nano-Fe₂O₃ were admixed into fresh cement mortar at 1% by weight of cement, the value of D(Cl−) was decreased by 83%, from 7.35×10(−11) m²/s (control specimen) to 1.21×10(−11) m²/s and 1.36×10(−11) m²/s, respectively.

A critical overview of non-aqueous capillary electrophoresis. Part I: mobility and separation selectivity.

PubMed

Kenndler, Ernst

2014-03-28

This two-part review critically gives an overview on the theoretical and practical advances in non-aqueous capillary electrophoresis (NACE) achieved over the recent five years. Part I starts out by reviewing the aspects relevant to electromigration in organic solvents and evaluates potential advantages of the latter in comparison to aqueous solvent systems. The crucial role of solubility for the species involved in CE - analytes and back ground electrolyte constituents - is discussed both for ionic and neutral compounds. The impact of organic solvents on the electrophoretic and electroosmotic mobility and on the ionization (pKa values) of weak acids and bases is highlighted. Special emphasis is placed on methanol, acetonitrile and mixtures of these solvents, being the most frequent employed media for NACE applications. In addition, also solvents less commonly used in NACE will be covered, including other alcohols, amides (formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide), propylene carbonate, dimethylsulphoxide, and nitromethane. The discussions address the consequences of dramatic pKa shifts frequently seen for weak acids and bases, and the important contributions of medium-specific electroosmotic flow (EOF) to electromigration in nonaqueous media. Important for NACE, the role of the water content on pKa and mobility is analyzed. Finally, association phenomena rather specific to nonaqueous solvents (ion pairing, homo- and heteroconjugation) will be addressed, along with their potential advantages for the development of NACE separation protocols. It is pointed out that this review is not intended as a listing of all papers that have been published on NACE in the period mentioned above. It rather deals with general aspects of migration and selectivity in organic solvent systems, and discusses - critically - examples from the literature with particular interest to the topic. An analog discussion about the role of the solvent on efficiency will be presented in Part II. Copyright © 2014 Elsevier B.V. All rights reserved.

EM calibration based on Post OPC layout analysis

NASA Astrophysics Data System (ADS)

Sreedhar, Aswin; Kundu, Sandip

2010-03-01

Design for Manufacturability (DFM) involves changes to the design and CAD tools to help increase pattern printability and improve process control. Design for Reliability (DFR) performs the same to improve reliability of devices from failures such as Electromigration (EM), gate-oxide break down, hot carrier injection (HCI), Negative Bias Temperature Insatiability (NBTI) and mechanical stress effects. Electromigration (EM) occurs due to migration or displacement of atoms as a result of the movement of electrons through a conducting medium. The rate of migration determines the Mean Time to Failure (MTTF) which is modeled as a function of temperature and current density. The model itself is calibrated through failure analysis (FA) of parts that are deemed to have failed due to EM against design parameters such as linewidth. Reliability Verification (RV) of a design involves verifying that every conducting line in a design meets certain MTTF threshold. In order to perform RV, current density for each wire must be computed. Current itself is a function of the parasitics that are determined through RC extraction. The standard practice is to perform the RC extraction and current density calculation on drawn, pre-OPC layouts. If a wire fails to meet threshold for MTTF, it may be resized. Subsequently, mask preparation steps such as OPC and PSM introduce extra features such as SRAFs, jogs,hammerheads and serifs that change their resistance, capacitance and current density values. Hence, calibrating EM model based on pre-OPC layouts will lead to different results compared to post-OPC layouts. In this work, we compare EM model calibration and reliability check based on drawn layout versus predicted layout, where the drawn layout is pre-OPC layout and predicted layout is based on litho simulation of post-OPC layout. Results show significant divergence between these two approaches, making a case for methodology based on predicted layout.

Dry silver electromigration process for optical glass waveguide fabrication and fluxless bonding technology for photonics and MEMS packaging

NASA Astrophysics Data System (ADS)

Chuang, Ricky Wenkuei

2001-07-01

An effectively simple dry silver electromigration technology without the need of evaporating separate gold or aluminum film electrodes onto both sides of glass is reported to fabricate low-loss deep multimode planar and channel waveguides on BK7 and BF450 glass substrates. A relatively high electrical field ranging from 440 to 545 V/mm was applied to the glass to speed up the migration, while at the same time preventing silver ions that were driven into the glass from reducing into silver atom; a major contributor to waveguide loss. The deep planar and channel waveguides thus fabricated showed no discolors or cracks, of which the attenuation losses of less than 2dB/cm and 0.1dB/cm were later measured from channel waveguides constructed on the BK7 and BF450 glass substrates, respectively, using our 0.6328mum He-Ne laser edge-coupling setup. To complete the waveguide studies, the scanning electron microscope (SEM) equipped with energy-dispersive X-ray (EDX) detector was adopted to obtain the concentration profiles of silver and sodium ions distributed in a waveguiding region after the exchange. The EDX measurements acquired hereafter were then utilized along with the Gladstone-Dale relation altogether to deduce the refractive index profile; of which a nearly step-like profile was consistently deduced from every deep planar and channel waveguides fabricated. Finally, a numerical model utilizing the space charge approach was devised to explain the nonlinear current effect often observed during the actual waveguide fabrication. The simulation results have confirmed that the nonlinear current-versus-time profile obtained is mainly attributed to the inhomogeneous distribution of the electric field in the glass substrate due to a space charge region created by the separation between silver- and sodium-ion migration fronts as a result of their unequal mobilities; a phenomenon which is ultimately responsible for the eventual slow down in the ion exchange rate as monitored during the actual electromigration process. A fluxless oxidation-free bonding technology using multilayer composite solders based on the non eutectic binary alloys of indium-tin (In-Sn), silver-indium (Ag-In), gold-tin (Au-Sn), and bismuth-tin (Bi-Sn) has been established and studied to determine its applicability to photonics and MEMS packaging. The scanning acoustic microscopy (SAM) conducted on these solder samples has consistently shown that a nearly void-free joint fabricated from each non-eutectic binary alloy system can be reliably achieved. In addition, the scanning electron microscopy (SEM) equipped with the energy dispersive X-ray (EDX) detector was also performed on the cross section of each sample to determine its joint composition, especially of any sign of intermetallic compounds. These results will demonstrate that any intermetallic compound or phase present in a joint fabricated with a pre-determined multilayer composition based on a specific binary alloy system can be well understood and fully justified by correlating the experimental outcome with its respective binary phase diagram.

The Reciprocal Principle of Selectand-Selector-Systems in Supramolecular Chromatography †.

PubMed

Schurig, Volker

2016-11-15

In selective chromatography and electromigration methods, supramolecular recognition of selectands and selectors is due to the fast and reversible formation of association complexes governed by thermodynamics. Whereas the selectand molecules to be separated are always present in the mobile phase, the selector employed for the separation of the selectands is either part of the stationary phase or is added to the mobile phase. By the reciprocal principle, the roles of selector and selectand can be reversed. In this contribution in honor of Professor Stig Allenmark, the evolution of the reciprocal principle in chromatography is reviewed and its advantages and limitations are outlined. Various reciprocal scenarios, including library approaches, are discussed in efforts to optimize selectivity in separation science.

Very High Output Thermoelectric Devices Based on ITO Nanocomposites

NASA Technical Reports Server (NTRS)

Fralick, Gustave; Gregory, Otto J.

2009-01-01

A material having useful thermoelectric properties was synthesized by combining indium-tin-oxide (ITO) with a NiCoCrAlY alloy/alumina cermet. This material had a very large Seebeck coefficient with electromotive-force-versustemperature behavior that is considered to be excellent with respect to utility in thermocouples and other thermoelectric devices. When deposited in thin-film form, ceramic thermocouples offer advantages over precious-metal (based, variously, on platinum or rhodium) thermocouples that are typically used in gas turbines. Ceramic thermocouples exhibit high melting temperatures, chemical stability at high temperatures, and little or no electromigration. Oxide ceramics also resist oxidation better than metal thermocouples, cost substantially less than precious-metal thermocouples, and, unlike precious-metal thermocouples, do not exert catalytic effects.

Effect of Al-trace dimension on Joule heating and current crowding in flip-chip solder joints under accelerated electromigration

NASA Astrophysics Data System (ADS)

Liang, S. W.; Chang, Y. W.; Chen, Chih

2006-04-01

Three-dimensional thermoelectrical simulation was conducted to investigate the influence of Al-trace dimension on Joule heating and current crowding in flip-chip solder joints. It is found that the dimension of the Al-trace effects significantly on the Joule heating, and thus directly determines the mean time to failure (MTTF). Simulated at a stressing current of 0.6A at 70°C, we estimate that the MTTF of the joints with Al traces in 100μm width was 6.1 times longer than that of joints with Al traces in 34μm width. Lower current crowding effect and reduced hot-spot temperature are responsible for the improved MTTF.

Recent applications of nanomaterials in capillary electrophoresis.

PubMed

González-Curbelo, Miguel Ángel; Varela-Martínez, Diana Angélica; Socas-Rodríguez, Bárbara; Hernández-Borges, Javier

2017-10-01

Nanomaterials have found an important place in Analytical Chemistry and, in particular, in Separation Science. Among them, metal-organic frameworks, magnetic and non-magnetic nanoparticles, carbon nanotubes and graphene, as well as their combinations, are the most important nanomaterials that have been used up to now. Concerning capillary electromigration techniques, these nanomaterials have also been used as both pseudostationary phases in electrokinetic chromatography (EKC) and as stationary phases in microchip capillary electrophoresis (CE) and capillary electrochromatography (CEC), as a result of their interesting and particular properties. This review article pretends to provide a general and critical revision of the most recent applications of nanomaterials in this field (period 2010-2017). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Holographic investigation of silver electromigration in nano-sized As2S3 films

NASA Astrophysics Data System (ADS)

Sainov, S.; Todorov, R.; Bodurov, I.; Yovcheva, Temenuzhka

2013-10-01

Holographic gratings with a diffraction efficiency (DE) greater than 8% and a spatial resolution of 2237 mm-1 are recorded in very thin As2S3 films with a thickness of 100 nm. Silver photo-diffusion is observed during the holographic recording process while applying a corona discharge. We use the method of holographic grating relaxation spectroscopy (forced Rayleigh scattering) based on the evanescent waves to determine that the silver diffusion coefficient in the thin As2S3 film is in the range of (0.9-10.3) × 10-13 cm2 s-1 depending on the corona charge polarity. This work is dedicated to the 90th anniversary of the birth of Academician Jordan Malinowski.

Chiral drug analysis using mass spectrometric detection relevant to research and practice in clinical and forensic toxicology.

PubMed

Schwaninger, Andrea E; Meyer, Markus R; Maurer, Hans H

2012-12-21

This paper reviews analytical approaches published in 2002-2012 for chiral drug analysis and their relevance in research and practice in the field of clinical and forensic toxicology. Separation systems such as gas chromatography, high performance liquid chromatography, capillary electromigration, and supercritical fluid chromatography, all coupled to mass spectrometry, are discussed. Typical applications are reviewed for relevant chiral analytes such as amphetamines and amphetamine-derived designer drugs, methadone, tramadol, psychotropic and other CNS acting drugs, anticoagulants, cardiovascular drugs, and some other drugs. Usefulness of chiral drug analysis in the interpretation of analytical results in clinical and forensic toxicology is discussed as well. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrotransport and diffusivity of molybdenum, rhenium, tungsten, and zirconium in beta-thorium

NASA Technical Reports Server (NTRS)

Schmidt, F. A.; Beck, M. S.; Rehbein, D. K.; Conzemius, R. J.; Carlson, O. N.

1984-01-01

The electric mobilities, diffusivities, and effective valences were determined for molybdenum, rhenium, tungsten, and zirconium in beta-thorium. All four solutes migrated in the same direction as the electron flow. Rhenium and molybdenum were found to be very mobile, with tungsten somewhat slower. Zirconium was found to move at a rate near that of the self-diffusion of beta-thorium, viz., about 10 to the -11th sq m/s at 1500 C. The electromigration velocities showed a similar trend. A comparison was made between experimental data obtained by scanning laser mass spectrometry and theoretical transport equations for two purification experiments. Good agreement was obtained with both the concentration profile predicted by DeGroot and the purification ratio predicted by Verhoeven.

Study of complete interconnect reliability for a GaAs MMIC power amplifier

NASA Astrophysics Data System (ADS)

Lin, Qian; Wu, Haifeng; Chen, Shan-ji; Jia, Guoqing; Jiang, Wei; Chen, Chao

2018-05-01

By combining the finite element analysis (FEA) and artificial neural network (ANN) technique, the complete prediction of interconnect reliability for a monolithic microwave integrated circuit (MMIC) power amplifier (PA) at the both of direct current (DC) and alternating current (AC) operation conditions is achieved effectively in this article. As a example, a MMIC PA is modelled to study the electromigration failure of interconnect. This is the first time to study the interconnect reliability for an MMIC PA at the conditions of DC and AC operation simultaneously. By training the data from FEA, a high accuracy ANN model for PA reliability is constructed. Then, basing on the reliability database which is obtained from the ANN model, it can give important guidance for improving the reliability design for IC.

Stereoisomers Separation

NASA Astrophysics Data System (ADS)

Wieczorek, Piotr

The use of capillary electrophoresis for enantiomer separation and optical purity determination is presented. The contents start with basic information about the nature of stereoizomers and the mechanism of enantioseparation using capillary electrophoresis techniques. The molecules to be separated show identical chemical structure and electrochemical behavior. Therefore, the chiral recognition of enantiomers is possible only by bonding to chiral selector and the separation based on very small differences in complexation energies of diastereomer complexes formed. This method is useful for this purpose due to the fact that different compounds can be used as chiral selectors. The mostly used chiral selectors like cyclodextrins, crown ethers, chiral surfactants, macrocyclic antibiotics, transition metal complexes, natural, and synthetic polymers and their application for this purpose is also discussed. Finally, examples of practical applications of electromigration techniques for enantiomers separation and determination are presented.

Electrokinetic mixing vortices due to electrolyte depletion at microchannel junctions.

PubMed

Takhistov, Paul; Duginova, Ksenia; Chang, Hsueh-Chia

2003-07-01

Due to electric field leakage across sharp corners, the irrotational character of Ohmic electroosmotic flow is violated. Instead, we demonstrate experimentally and theoretically evidence of electrolyte depletion and vortex separation in electroosmotic flow around a junction between wide and narrow channels. When the penetration length of the electric field exceeds the width of the narrow channel and if the electric field is directed from the narrow to the wide channel, the electromigration of ions diminishes significantly at the junction end of the narrow channel due to this leakage. Concentration depletion then develops at that location to maintain current balance but it also increases the corner zeta potential and the local electroosmotic slip velocity. A back pressure gradient hence appears to maintain flow balance and, at a sufficient magnitude, generates a pair of vortices.

Removal of fluorine from contaminated soil by electrokinetic treatment driven by solar energy.

PubMed

Zhou, Ming; Zhu, Shufa; Liu, Yana; Wang, Xuejian

2013-08-01

Instead of direct current power supply, a series of electrokinetic remediation experiments driven by solar energy on fluorine-contaminated soil were conducted in a self-made electrolyzer, in order to reduce energy expenditure of electrokinetic remediation. After the 12-day electrokinetic remediation driven by solar energy, the removal efficiency of fluorine was 22.3%, and electrokinetic treatment had an impact on changes in partitioning of fluorine in soil. It proved that the combination of electrokinetics and solar energy was feasible and effective to some extent for the remediation of fluorine-contaminated soil. Meanwhile, the experimental results also indicated that the electromigration was a more dominant transport mechanism for the removal of fluorine from contaminated soil than electroosmosis, and the weather condition was the important factor in affecting the removal efficiency.

Measurement of strain in Al-Cu interconnect lines with x-ray microdiffraction

NASA Astrophysics Data System (ADS)

Solak, H. H.; Vladimirsky, Y.; Cerrina, F.; Lai, B.; Yun, W.; Cai, Z.; Ilinski, P.; Legnini, D.; Rodrigues, W.

1999-07-01

We report measurement of strain in patterned Al-Cu interconnect lines with x-ray microdiffraction technique with a ˜1 μm spatial resolution. Monochromatized x rays from an undulator were focused on the sample using a phase fresnel zone plate and diffracted light was collected by an area detector in a symmetric, angle dispersive x-ray diffraction geometry. Measurements were made before and after the line sample was stressed for electromigration. Results show an increase in inter- and intra-grain strain variation after the testing. Differences in strain behavior of grains with (111) and (200) crystallographic planes parallel to the substrate surface were observed. A position dependent variation of strain after the testing was measured whereas no such dependence was found before the testing.

Ion concentration in micro and nanoscale electrospray emitters.

PubMed

Yuill, Elizabeth M; Baker, Lane A

2018-06-01

Solution-phase ion transport during electrospray has been characterized for nanopipettes, or glass capillaries pulled to nanoscale tip dimensions, and micron-sized electrospray ionization emitters. Direct visualization of charged fluorophores during the electrospray process is used to evaluate impacts of emitter size, ionic strength, analyte size, and pressure-driven flow on heterogeneous ion transport during electrospray. Mass spectrometric measurements of positively- and negatively-charged proteins were taken for micron-sized and nanopipette emitters under low ionic strength conditions to further illustrate a discrepancy in solution-driven transport of charged analytes. A fundamental understanding of analyte electromigration during electrospray, which is not always considered, is expected to provide control over selective analyte depletion and enrichment, and can be harnessed for sample cleanup. Graphical abstract Fluorescence micrographs of ion migration in nanoscale pipettes while solution is electrosprayed.

Quantized conductance observed during sintering of silver nanoparticles by intense terahertz pulses

NASA Astrophysics Data System (ADS)

Takano, Keisuke; Harada, Hirofumi; Yoshimura, Masashi; Nakajima, Makoto

2018-04-01

We show that silver nanoparticles, which are deposited on a terahertz-receiving antenna, can be sintered by intense terahertz pulse irradiation. The conductance of the silver nanoparticles between the antenna electrodes is measured under the terahertz pulse irradiation. The dispersant materials surrounding the nanoparticles are peeled off, and conduction paths are created. We reveal that, during sintering, quantum point contacts are formed, leading to quantized conductance between the electrodes with the conductance quantum, which reflects the formation of atomically thin wires. The terahertz electric pulses are sufficiently intense to activate electromigration, i.e., transfer of kinetic energy from the electrons to the silver atoms. The silver atoms move and atomically thin wires form under the intense terahertz pulse irradiation. These findings may inspire nanoscale structural processing by terahertz pulse irradiation.

A review on solder reflow and flux application for flip chip

NASA Astrophysics Data System (ADS)

Suppiah, Sarveshvaran; Ong, Nestor Rubio; Sauli, Zaliman; Sarukunaselan, Karunavani; Alcain, Jesselyn Barro; Visvanathan, Susthitha Menon; Retnasamy, Vithyacharan

2017-09-01

This paper encompassed of the evolution and key findings, critical technical challenges, solutions and bonding equipment of solder reflow in flip chip bonding. Upon scrutinizing researches done by others, it can be deduced that peak temperature, time above liquidus, soak temperature, soak time, cooling rate and reflow environment played a vital role in achieving the desired bonding profile. In addition, flux is also needed with the purpose of removing oxides/contaminations on bump surface as well as to promote wetting of solder balls. Electromigration and warpage are the two main challenges faced by solder reflow process which can be overcome by the advancement in under bump metallization (UBM) and substrate technology. The review is ended with a brief description of the current equipment used in solder reflow process.

Physics-based simulation of EM and SM in TSV-based 3D IC structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kteyan, Armen; Sukharev, Valeriy; Zschech, Ehrenfried

2014-06-19

Evolution of stresses in through-silicon-vias (TSVs) and in the TSV landing pad due to the stress migration (SM) and electromigration (EM) phenomena are considered. It is shown that an initial stress distribution existing in a TSV depends on its architecture and copper fill technology. We demonstrate that in the case of proper copper annealing the SM-induced redistribution of atoms results in uniform distributions of the hydrostatic stress and concentration of vacancies along each segment. In this case, applied EM stressing generates atom migration that is characterized by kinetics depending on the preexisting equilibrium concentration of vacancies. Stress-induced voiding in TSVmore » is considered. EM induced voiding in TSV landing pad is analyzed in details.« less

The Influence of Impurities and Metallic Capping Layers on the Microstructure of Copper Interconnects

NASA Astrophysics Data System (ADS)

Rizzolo, Michael

As copper interconnects have scaled to ever smaller dimensions on semiconductor devices, the microstructure has become increasingly detrimental for performance and reliability. Small grains persist in interconnects despite annealing at high temperatures, leading to higher line resistance and more frequent electromigration-induced failures. Conventionally, it was believed that impurities from the electrodeposition pinned grain growth, but limitations in analytical techniques meant the effect was inferred rather than observed. Recent advances in analytical techniques, however, have enabled this work to quantify impurity content, location, and diffusion in relation to microstructural changes in electroplated copper. Surface segregation of impurities during the initial burst of grain growth was investigated. After no surface segregation was observed, a microfluidic plating cell was constructed to plate multilayer films with regions of intentionally high and low impurity concentrations to determine if grain growth could be pinned by the presence of impurities; it was not. An alternate mechanism for grain boundary pinning based on the texture of the seed layer is proposed, supported by time-resolved transmission electron microscopy and transmission electron backscatter diffraction data. The suggested model posits that the seed in narrow features has no preferred orientation, which results in rapid nucleation of subsurface grains in trench regions prior to recrystallization from the overburden down. These rapidly growing grains are able to block off several trenches from the larger overburden grains, inhibiting grain growth in narrow features. With this knowledge in hand, metallic capping layers were employed to address the problematic microstructure in 70nm lines. The capping layers (chromium, nickel, zinc, and tin) were plated on the copper overburden prior to annealing to manipulate the stress gradient and microstructural development during annealing. It appeared that regardless of as-plated stress, nickel capping altered the recrystallized texture of the copper over patterned features. The nickel capping also caused a 2x increase in the number of advantageous 'bamboo' grains that span the entire trench, which effectively block electromigration pathways. These data provides a more fundamental understanding of manipulating the microstructure in copper interconnects using pre-anneal capping layers, and demonstrates a strategy to improve the microstructure beyond the capabilities of simple annealing.

Reduction of the 3,4,9,10-perylenediimides and the formation of eletrodeposited films based on their radical anions

NASA Astrophysics Data System (ADS)

Zhu, Yuan-Yuan; Gu, Shuang-Xi

2014-09-01

The reduction of the two 3,4,9,10-perylene diimide (PDI) derivatives in the mixture of hydrazine hydrate and N,N-dimethylformamide was investigated by the UV-vis absorption spectra, fluorescence spectra (FL) and electron spin resonance spectroscopy (ESR). The time dependence of the PDI content, as well as the structure of PDI aggregates were also investigated and discussed. Combining the electro-migration behavior of PDI-· with the molecular self-assembly properties, the films of two PDI derivatives (PDI-32 and PDI-123) were successfully fabricated via anode electro-deposition (AED). The difference of aggregation state between the two PDI films was studied by UV-vis absorption spectra, XRD and SEM. Based on these, the formation mechanism of PDI films was also deduced.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bauer, R.; Ebersberger, B.; Kupfer, C.

SnAg solder bump is one bump type which is used to replace eutectic SnPb bumps. In this work tests have been done to characterize the reliability properties of this bump type. Electromigration (EM) tests, which were accelerated by high current and high temperature and high temperature storage (HTS) tests were performed. It was found that the reliability properties are sensitive to the material combinations in the interconnect stack. The interconnect stack includes substrate pad, pad finish, bump, underbump metallization (UBM) and the chip pad. Therefore separate test groups for SnAg bumps on Cu substrate pads with organic solderability preservative (OSP)more » finish and the identical bumps on pads with Ni/Au finish were used. In this paper the reliability test results and the corresponding failure analysis are presented. Some explanations about the differences in formation of intermetallic compounds (IMCs) are given.« less

Corrosion Propagation of Rebar Embedded in High Performance Concrete

NASA Astrophysics Data System (ADS)

Nazim, Manzurul

The FDOT has been using supplementary cementitious materials while constructing steel reinforced concrete marine bridge structures for over 3 decades. Previous findings indicated that such additions in concrete mix make the concrete more durable. To better understand corrosion propagation of rebar in high performance concrete: mature concrete samples that were made (2008/2009) with Portland cement, a binary mix, a ternary mix and recently prepared (April 2016 with 50% OPC + 50% slag and 80% OPC + 20% Fly ash) concrete samples were considered. None of these concretes had any admixed chloride to start with. An accelerated chloride transport process was used to drive chloride ions into the concrete so that chlorides reach and exceed the chloride threshold at the rebar surface and initiate corrosion. Electrochemical measurements were taken at regular intervals (during and after the electro-migration process) to observe the corrosion propagation in each sample.

Auger compositional depth profiling of the metal contact-TlBr interface

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Swanberg, E. L.; Voss, L. F.; Graff, R. T.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Kim, H.; Cirignano, L.; Shah, K.

2015-08-01

Degradation of room temperature operation of TlBr radiation detectors with time is thought to be due to electromigration of Tl and Br vacancies within the crystal as well as the metal contacts migrating into the TlBr crystal itself due to electrochemical reactions at the metal/TlBr interface. Scanning Auger electron spectroscopy (AES) in combination with sputter depth profiling was used to investigate the metal contact surface/interfacial structure on TlBr devices. Device-grade TlBr was polished and subjected to a 32% HCl etch to remove surface damage and create a TlBr1-xClx surface layer prior to metal contact deposition. Auger compositional depth profiling results reveal non-equilibrium interfacial diffusion after device operation in both air and N2 at ambient temperature. These results improve our understanding of contact/device degradation versus operating environment for further enhancing radiation detector performance.

Laterally configured resistive switching device based on transition-metal nano-gap electrode on Gd oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kawakita, Masatoshi; Okabe, Kyota; Kimura, Takashi

2016-01-11

We have developed a fabrication process for a laterally configured resistive switching device based on a Gd oxide. A nano-gap electrode connected by a Gd oxide with the ideal interfaces has been created by adapting the electro-migration method in a metal/GdO{sub x} bilayer system. Bipolar set and reset operations have been clearly observed in the Pt/GdO{sub x} system similarly in the vertical device based on GdO{sub x}. Interestingly, we were able to observe a clear bipolar switching also in a ferromagnetic CoFeB nano-gap electrode with better stability compared to the Pt/GdO{sub x} device. The superior performance of the CoFeB/GdO{sub x}more » device implies the importance of the spin on the resistive switching.« less

A graphene integrated highly transparent resistive switching memory device

NASA Astrophysics Data System (ADS)

Dugu, Sita; Pavunny, Shojan P.; Limbu, Tej B.; Weiner, Brad R.; Morell, Gerardo; Katiyar, Ram S.

2018-05-01

We demonstrate the hybrid fabrication process of a graphene integrated highly transparent resistive random-access memory (TRRAM) device. The indium tin oxide (ITO)/Al2O3/graphene nonvolatile memory device possesses a high transmittance of >82% in the visible region (370-700 nm) and exhibits stable and non-symmetrical bipolar switching characteristics with considerably low set and reset voltages (<±1 V). The vertical two-terminal device shows an excellent resistive switching behavior with a high on-off ratio of ˜5 × 103. We also fabricated a ITO/Al2O3/Pt device and studied its switching characteristics for comparison and a better understanding of the ITO/Al2O3/graphene device characteristics. The conduction mechanisms in high and low resistance states were analyzed, and the observed polarity dependent resistive switching is explained based on electro-migration of oxygen ions.

Electrokinetic remediation of inorganic and organic pollutants in textile effluent contaminated agricultural soil.

PubMed

Annamalai, Sivasankar; Santhanam, Manikandan; Sundaram, Maruthamuthu; Curras, Marta Pazos

2014-12-01

The discharge from the dyeing industries constitutes unfixed dyes, inorganic salts, heavy metal complexes etc., which spoil the surrounding areas of industrial sites. The present article reports the use of direct current electrokinetic technique for the treatment of textile contaminated soil. Impressed direct current voltage of 20 V facilitates the dye/metal ions movement in the naturally available dye contaminated soil towards the opposite electrode by electromigration. IrO2–RuO2–TiO2/Ti was used as anode and Ti used as cathode. UV–Visible spectrum reveals that higher dye intensity was nearer to the anode. Ni, Cr and Pb migration towards the cathode and migration of Cu, SO42− and Cl− towards anode were noticed. Chemical oxygen demand in soil significantly decreased upon employing electrokinetic. This technology may be exploited for faster and eco-friendly removal of dye in soil environment.

Analysis of pilocarpine and its trans epimer, isopilocarpine, by capillary electrophoresis.

PubMed

Baeyens, W; Weiss, G; Van Der Weken, G; Van Den Bossche, W

1993-05-28

Capillary zone electrophoresis was used for the separation of pilocarpine from its epimer, isopilocarpine, using coated fused-silica capillaries of 20 cm x 25 microm I.D., 8 kV running voltage, migration buffer of 0.1 M sodium dihydrogenphosphate pH 8, detection at 217 nm and injection by electromigration. Injections of aqueous, acid and basic solutions were compared. Linearity of the signal for pilocarpine hydrochloride up to 200 microg ml(-1) in 0.05 M hydrochloric acid was obtained, using naphazoline nitrate as internal standard. Optimization of migration buffer pH using coated silica capillaries of 50 cm x 50 microm I.D. showed that at pH 6.9 pilocarpine can be separated from ++isopilocarpine. Inclusion of beta-cyclodextrin in the buffer allows full baseline separation of both epimers. The method was applied to the analysis of a commercial ophthalmic pilocarpine solution.

Accelerated reliability testing of highly aligned single-walled carbon nanotube networks subjected to DC electrical stressing.

PubMed

Strus, Mark C; Chiaramonti, Ann N; Kim, Young Lae; Jung, Yung Joon; Keller, Robert R

2011-07-01

We investigate the electrical reliability of nanoscale lines of highly aligned, networked, metallic/semiconducting single-walled carbon nanotubes (SWCNTs) fabricated through a template-based fluidic assembly process. We find that these SWCNT networks can withstand DC current densities larger than 10 MA cm(-2) for several hours and, in some cases, several days. We develop test methods that show that the degradation rate, failure predictability and total device lifetime can be linked to the initial resistance. Scanning electron and transmission electron microscopy suggest that fabrication variability plays a critical role in the rate of degradation, and we offer an empirical method of quickly determining the long-term performance of a network. We find that well-fabricated lines subject to constant electrical stress show a linear accumulation of damage reminiscent of electromigration in metallic interconnects, and we explore the underlying physical mechanisms that could cause such behavior.

Electroepitaxy of multicomponent systems - Ternary and quarternary compounds

NASA Technical Reports Server (NTRS)

Bryskiewicz, T.; Lagowski, J.; Gatos, H. C.

1980-01-01

A theoretical model is presented which accounts for the electroepitaxial growth kinetics and composition of multicomponent compounds in terms of mass transport in the liquid and phase diagram relationships. The mass transport in the interface is dominated by electromigration in the absence of convection and by diffusion in the presence of convection. The composition of the solid is controlled by the Peltier effect at the growth interface and by the diffusion and mobility constants of the solute components and the growth velocity (current density). Thus, for a given solution composition, the composition of the solid can be varied by varying the current density. For a given current density the composition remains constant even in the case of relatively thick epitaxial layers. All aspects of the model were found to be in good agreement with the growth and composition characteristics of Ga/x-1/Al/x/As layers.

Potential Electrokinetic Remediation Technologies of Laboratory Scale into Field Application- Methodology Overview

NASA Astrophysics Data System (ADS)

Ayuni Suied, Anis; Tajudin, Saiful Azhar Ahmad; Nizam Zakaria, Muhammad; Madun, Aziman

2018-04-01

Heavy metal in soil possesses high contribution towards soil contamination which causes to unbalance ecosystem. There are many ways and procedures to make the electrokinetic remediation (EKR) method to be efficient, effective, and potential as a low cost soil treatment. Electrode compartment for electrolyte is expected to treat the contaminated soil through electromigration and enhance metal ions movement. The electrokinetic is applicable for many approaches such as electrokinetic remediation (EKR), electrokinetic stabilization (EKS), electrokinetic bioremediation and many more. This paper presents a critical review on comparison of laboratory scale between EKR, EKS and EK bioremediation treatment by removing the heavy metal contaminants. It is expected to propose one framework of contaminated soil mapping. Electrical Resistivity Method (ERM) is one of famous indirect geophysical tools for surface mapping and subsurface profiling. Hence, ERM is used to mapping the migration of heavy metal ions by electrokinetic.

Epitaxial nickel disilicide with low resistivity and excellent reliability.

PubMed

Hsin, Cheng-Lun; Deng, Shiu-Sheng

2016-02-12

Ultra-thin epitaxial NiSi2 was formed, and its structure was examined by electron microscopy and x-ray diffraction. Compared with previous reports, the measured resistivity of the epitaxial NiSi2 was unprecedentedly low, reaching 7 μΩ cm in the experimental results and up to 14.93 μΩ cm after modification. The reliability, which was investigated under different temperatures and current densities to understand its electronic characteristics, was 1.5 times better than that of the conventional polycrystalline counterpart. Black's equation and the measured mean-time-to-failure (MTTF) were used to obtain the reliability characteristics of epitaxial and poly-NiSi2. Confidence intervals at 95% for each MTTF confirmed the single failure mode. The electromigration phenomenon was observed to be the failure mechanism. Our results provide evidence that epitaxial NiSi2 is a promising contact material for future electronics.

Epitaxial nickel disilicide with low resistivity and excellent reliability

NASA Astrophysics Data System (ADS)

Hsin, Cheng-Lun; Deng, Shiu-Sheng

2016-02-01

Ultra-thin epitaxial NiSi2 was formed, and its structure was examined by electron microscopy and x-ray diffraction. Compared with previous reports, the measured resistivity of the epitaxial NiSi2 was unprecedentedly low, reaching 7 μΩ cm in the experimental results and up to 14.93 μΩ cm after modification. The reliability, which was investigated under different temperatures and current densities to understand its electronic characteristics, was 1.5 times better than that of the conventional polycrystalline counterpart. Black’s equation and the measured mean-time-to-failure (MTTF) were used to obtain the reliability characteristics of epitaxial and poly-NiSi2. Confidence intervals at 95% for each MTTF confirmed the single failure mode. The electromigration phenomenon was observed to be the failure mechanism. Our results provide evidence that epitaxial NiSi2 is a promising contact material for future electronics.

The effect of an electric field on the morphological stability of the crystal-melt interface of a binary alloy. III - Weakly nonlinear theory

NASA Technical Reports Server (NTRS)

Wheeler, A. A.; Mcfadden, G. B.; Coriell, S. R.; Hurle, D. T. J.

1990-01-01

The effect of a constant electric current on the crystal-melt interface morphology during directional solidification at constant velocity of a binary alloy is considered. A linear temperature field is assumed, and thermoelectric effects and Joule heating are neglected; electromigration and differing electrical conductivities of crystal and melt are taken into account. A two-dimensional weakly nonlinear analysis is carried out to third order in the interface amplitude, resulting in a cubic amplitude equation that describes whether the bifurcation from the planar state is supercritical or subcritical. For wavelengths corresponding to the most dangerous mode of linear theory, the demarcation between supercritical and subcritical behavior is calculated as a function of processing conditions and material parameters. The bifurcation behavior is a sensitive function of the magnitude and direction of the electric current and of the electrical conductivity ratio.

Towards nanoprinting with metals on graphene.

PubMed

Melinte, G; Moldovan, S; Hirlimann, C; Liu, X; Bégin-Colin, S; Bégin, D; Banhart, F; Pham-Huu, C; Ersen, O

2015-08-28

Graphene and carbon nanotubes are envisaged as suitable materials for the fabrication of the new generation of nanoelectronics. The controlled patterning of such nanostructures with metal nanoparticles is conditioned by the transfer between a recipient and the surface to pattern. Electromigration under the impact of an applied voltage stands at the base of printing discrete digits at the nanoscale. Here we report the use of carbon nanotubes as nanoreservoirs for iron nanoparticles transfer on few-layer graphene. An initial Joule-induced annealing is required to ensure the control of the mass transfer with the nanotube acting as a 'pen' for the writing process. By applying a voltage, the tube filled with metal nanoparticles can deposit metal on the surface of the graphene sheet at precise locations. The reverse transfer of nanoparticles from the graphene surface to the nanotube when changing the voltage polarity opens the way for error corrections.

Towards nanoprinting with metals on graphene

NASA Astrophysics Data System (ADS)

Melinte, G.; Moldovan, S.; Hirlimann, C.; Liu, X.; Bégin-Colin, S.; Bégin, D.; Banhart, F.; Pham-Huu, C.; Ersen, O.

2015-08-01

Graphene and carbon nanotubes are envisaged as suitable materials for the fabrication of the new generation of nanoelectronics. The controlled patterning of such nanostructures with metal nanoparticles is conditioned by the transfer between a recipient and the surface to pattern. Electromigration under the impact of an applied voltage stands at the base of printing discrete digits at the nanoscale. Here we report the use of carbon nanotubes as nanoreservoirs for iron nanoparticles transfer on few-layer graphene. An initial Joule-induced annealing is required to ensure the control of the mass transfer with the nanotube acting as a `pen' for the writing process. By applying a voltage, the tube filled with metal nanoparticles can deposit metal on the surface of the graphene sheet at precise locations. The reverse transfer of nanoparticles from the graphene surface to the nanotube when changing the voltage polarity opens the way for error corrections.

Recent advances in combination of capillary electrophoresis with mass spectrometry: methodology and theory.

PubMed

Klepárník, Karel

2015-01-01

This review focuses on the latest development of microseparation electromigration methods in capillaries and microfluidic devices with MS detection and identification. A wide selection of 183 relevant articles covers the literature published from June 2012 till May 2014 as a continuation of the review article on the same topic by Kleparnik [Electrophoresis 2013, 34, 70-86]. Special attention is paid to the new improvements in the theory of instrumentation and methodology of MS interfacing with capillary versions of zone electrophoresis, ITP, and IEF. Ionization methods in MS include ESI, MALDI, and ICP. Although the main attention is paid to the development of instrumentation and methodology, representative examples illustrate also applications in the proteomics, glycomics, metabolomics, biomarker research, forensics, pharmacology, food analysis, and single-cell analysis. The combinations of MS with capillary versions of electrochromatography and micellar electrokinetic chromatography are not included. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrical Characterization of Thin Film Cadmium Telluride Electrodeposited from Tri-N Telluride

NASA Astrophysics Data System (ADS)

von Windheim, Jesko A.

The electrical transport properties of CdTe electrodeposited from tri-n-butylphosphine telluride have been studied by resistivity and Hall effect measurements. Methods have been developed to reproducibly remove large area samples from their conducting substrates, and these samples were prepared for temperature dependent Hall measurements and resistivity measurements. Apparatus was designed and built to routinely measure Hall voltages as low as 250 muV for source impedances up to 10 ^{12} Omega. The central aspect of the measurement system was a low cost, differential electrometer amplifier designed around the AD549L monolithic electrometer operational amplifier. Temperature control was achieved via a Eurotherm 808 temperature controller, and a cooled stream of nitrogen gas. With this system, temperature could be maintained within +/- 0.5^circC at set points between -40^circC and +40^circC. Data collection, temperature ramping, and power to the magnet were all computer controlled, and resistivity measurements were fully automated. As-annealed electrodeposited CdTe was found to be consistently p-type, with resistivity values typically 10^6- 10^{7 } Omega-cm. Various donor and acceptor dopants have been incorporated into polycrystalline CdTe films by three methods: electrochemical codeposition, electromigration and vapour techniques. The dopants were Cd, Te, Cu, Ag, In, and O_2. The activity of the dopant was dependent on the method that was used for incorporation. Oxygen was found to only have a significant effect when it was incorporated in situ, during deposition. For Cd and Te, on the other hand, little effect was seen when their concentration was varied in situ. However, hole concentration increased substantially when Te was incorporated by diffusion, and a p to n conversion was observed when Cd was incorporated by diffusion. The carrier concentration of p-type CdTe could be systematically increased by increasing the current density for the electromigration of copper. The decreasing carrier concentration was accompanied by a decrease in resistivity and a decrease in mobility. The effect of dopant density on the resistivity of the polycrystalline cadmium telluride films, deposited from tri-n-butylphosphine telluride, can consistently be described by a grain boundary model. In this model charging of grain boundary states results in a barrier and can affect the carrier density. According to the model, dopants accumulated at grain boundaries do not generate carriers and do not affect the density of interface states.

Investigation of the acid-base and electromigration properties of 5-azacytosine derivatives using capillary electrophoresis and density functional theory calculations.

PubMed

Geffertová, Denisa; Ali, Syed Tahir; Šolínová, Veronika; Krečmerová, Marcela; Holý, Antonín; Havlas, Zdeněk; Kašička, Václav

2017-01-06

Capillary electrophoresis (CE) and quantum mechanical density functional theory (DFT) were applied to the investigation of the acid-base and electromigration properties of important compounds: newly synthesized derivatives of 5-azacytosine - analogs of efficient antiviral drug cidofovir. These compounds exhibit a strong antiviral activity and they are considered as potential new antiviral agents. For their characterization and application, it is necessary to know their acid-base properties, particularly the acidity constants (pK a ) of their ionogenic groups (the basic N 3 atom of the triazine ring and the acidic phosphonic acid group in the alkyl chain). First, the mixed acidity constants (pK a mix ) of these ionogenic groups and the ionic mobilities of these compounds were determined by nonlinear regression analysis of the pH dependence of their effective electrophoretic mobilities. Effective mobilities were measured by CE in a series of background electrolytes in a wide pH range (2.0-10.5), at constant ionic strength (25mM) and constant temperature (25°C). Subsequently, the pK a mix values were recalculated to thermodynamic pK a values using the Debye-Hückel theory. The thermodynamic pK a value of the NH + moiety at the N 3 atom of the triazine ring was found to be in the range 2.82-3.30, whereas the pK a of the hydrogenphosphonate group reached values from 7.19 to 7.47, depending on the structure of the analyzed compounds. These experimentally determined pK a values were in good agreement with those calculated by quantum mechanical DFT. In addition, DFT calculations revealed that from the four nitrogen atoms in the 5-azacytosine moiety, the N 3 atom of the triazine ring is preferentially protonated. Effective charges of analyzed compounds ranged from zero or close-to-zero values at pH 2 to -2 elementary charges at pH≥9. Ionic mobilities were in the range (-16.7 to -19.1)×10 -9 m 2 V -1 s -1 for univalent anions and in the interval (-26.9 to -30.3)×10 -9 m 2 V -1 s -1 for divalent anions. Copyright © 2016 Elsevier B.V. All rights reserved.

Growth of large-scale nanotwinned Cu nanowire arrays from anodic aluminum oxide membrane by electrochemical deposition process: controllable nanotwin density and growth orientation with enhanced electrical endurance performance

NASA Astrophysics Data System (ADS)

Chan, Tsung-Cheng; Lin, Yen-Miao; Tsai, Hung-Wei; Wang, Zhiming M.; Liao, Chien-Neng; Chueh, Yu-Lun

2014-06-01

Densely nanotwinned Cu nanowire (NW) arrays with an identical diameter of ~55 nm were fabricated by pulse electrochemical deposition at low temperature using anodic aluminum oxide as a template. Different growth orientations of nanotwinned Cu nanowire arrays were investigated. The endurance of the electrical current density before breakdown of the nanotwinned Cu NWs can reach up to 2.4 × 108 A cm-2. The formation of highly dense nanotwins is attributed to relaxation of coalescence induced stress and twin fault stacking when Cu NWs grow by two-dimensional kinetics. A mechanism based on the twinning structure effect on the electromigration was proposed to explain the improved electrical endurance of Cu. The result demonstrates that the formation of nanotwins into Cu NWs can effectively suppress the void growth, leading to extended life time for use in electronic devices.Densely nanotwinned Cu nanowire (NW) arrays with an identical diameter of ~55 nm were fabricated by pulse electrochemical deposition at low temperature using anodic aluminum oxide as a template. Different growth orientations of nanotwinned Cu nanowire arrays were investigated. The endurance of the electrical current density before breakdown of the nanotwinned Cu NWs can reach up to 2.4 × 108 A cm-2. The formation of highly dense nanotwins is attributed to relaxation of coalescence induced stress and twin fault stacking when Cu NWs grow by two-dimensional kinetics. A mechanism based on the twinning structure effect on the electromigration was proposed to explain the improved electrical endurance of Cu. The result demonstrates that the formation of nanotwins into Cu NWs can effectively suppress the void growth, leading to extended life time for use in electronic devices. Electronic supplementary information (ESI) available: X-ray diffraction spectra of Cu NWs grown by electrochemical deposition with a current density of 1.5 A cm-2 at -1 °C and room temperature; bright-field TEM images of Cu NWs deposited at -1 °C with a current density of 0.4, 0.8, 1.8, and 1.5 A cm-2, respectively; illustration of the effect of twin density on the MTTF of Cu NWs. See DOI: 10.1039/c3nr06194a

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strelcov, Evgheni; Cothren, Joshua E.; Leonard, Donovan N.

Progress in rational engineering of Li-ion batteries requires better understanding of the electrochemical processes and accompanying transformations in the electrode materials on multiple length scales. In spite of recent progress in utilizing transmission electron microscopy (TEM) to analyze these materials, in situ scanning electron microscopy (SEM) was mostly overlooked as a powerful tool that allows probing these phenomena on the nano and mesoscale. In this paper, we report on in situ SEM study of lithiation in a V 2O 5-based single-nanobelt battery with ionic liquid electrolyte. Coupled with cyclic voltammetry measurements, in situ SEM revealed the peculiarities of subsurface intercalation,more » formation of solid-electrolyte interface (SEI) and electromigration of liquid. We observed that single-crystalline vanadia nanobelts do not undergo large-scale amorphization or fracture during electrochemical cycling, but rather transform topochemically with only a slight shape distortion. Lastly, the SEI layer seems to have significant influence on the lithium ion diffusion and overall capacity of the single-nanobelt battery.« less

Application of electrokinetic soil flushing to four herbicides: A comparison.

PubMed

dos Santos, E Vieira; Souza, F; Saez, C; Cañizares, P; Lanza, M R V; Martinez-Huitle, C A; Rodrigo, M A

2016-06-01

In this work, four bench-scale plants containing soil spiked with four herbicides (2,4-Dichlorophenoxyacetic acid (2,4-D), oxyfluorfen, chlorsulfuron and atrazine) undergo treatment consisting of an electrokinetic soil flushing (EKSF). Results clearly demonstrate that efficiency of EKSF depends on the chemical characteristic of the pesticide used. The amount of pesticide collected in the anode well is more significant than that collected in the cathode wells, indicating that the electromigration is much more important than drainage by electro-osmotic flux for this application. After 15 d of treatment, the 2,4-D is the pesticide most efficiently removed (95% of removal), while chlorsulfuron is the pesticide more resilient to the treatment. Additionally, volatilization was found to be a process of the major significance in the application of electrokinetic techniques to soil polluted with herbicides and because of that it should always be taken into account in the future design of full-scale processes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cathode Degradation in Thallium Bromide Devices

NASA Astrophysics Data System (ADS)

Datta, Amlan; Motakef, Shariar

2015-06-01

Thallium bromide (TlBr) is a wide bandgap, compound semiconductor with high gamma-ray stopping power and promising physical properties. However, performance degradation and the eventual irreversible failure of TlBr devices can occur rapidly at room temperature, due to “polarization”, caused by the electromigration of Tl+ and Br- ions to the electrical contacts across the device. Using the Accelerated Device Degradation (ADD) experiment, the degradation phenomena in TlBr devices have been visualized and recorded. This paper focuses on “ageing” of the device cathode at various temperatures. ADD is a fast and reliable direct characterization technique that can be used to identify the effects of various growth and post-growth process modifications on device degradation. Using this technique we have identified cathode degradation with the migration of Br- ions and an associated generation and growth of Thallium-rich fractal “ferns” from the cathode. Its effect on the radiation response of the device has also been discussed in this paper. The chemical changes in the cathode were characterized using Energy-dispersive X-ray spectroscopy.

Spectral focusing of broadband silver electroluminescence in nanoscopic FRET-LEDs

NASA Astrophysics Data System (ADS)

Puchert, Robin P.; Steiner, Florian; Plechinger, Gerd; Hofmann, Felix J.; Caspers, Ines; Kirschner, Johanna; Nagler, Philipp; Chernikov, Alexey; Schüller, Christian; Korn, Tobias; Vogelsang, Jan; Bange, Sebastian; Lupton, John M.

2017-07-01

Few inventions have shaped the world like the incandescent bulb. Edison used thermal radiation from ohmically heated conductors, but some noble metals also exhibit 'cold' electroluminescence in percolation films, tunnel diodes, electromigrated nanoparticle aggregates, optical antennas or scanning tunnelling microscopy. The origin of this radiation, which is spectrally broad and depends on applied bias, is controversial given the low radiative yields of electronic transitions. Nanoparticle electroluminescence is particularly intriguing because it involves localized surface-plasmon resonances with large dipole moments. Such plasmons enable very efficient non-radiative fluorescence resonance energy transfer (FRET) coupling to proximal resonant dipole transitions. Here, we demonstrate nanoscopic FRET-light-emitting diodes which exploit the opposite process, energy transfer from silver nanoparticles to exfoliated monolayers of transition-metal dichalcogenides. In diffraction-limited hotspots showing pronounced photon bunching, broadband silver electroluminescence is focused into the narrow excitonic resonance of the atomically thin overlayer. Such devices may offer alternatives to conventional nano-light-emitting diodes in on-chip optical interconnects.

A Sinusoidal Applied Electric Potential can Induce a Long-Range, Steady Electrophoretic Force

NASA Astrophysics Data System (ADS)

Amrei, Seyyed Hashemi; Ristenpart, William D.; Miller, Greg R.

2017-11-01

We use the standard electrokinetic model to numerically investigate the electric field in aqueous solutions between parallel electrodes under AC polarization. In contrast to prior work, we invoke no simplifying assumptions regarding the applied voltage, frequency, or mismatch in ionic mobilities. We find that the nonlinear electromigration terms significantly contribute to the overall shape of the electric potential vs. time, which at sufficiently high applied potentials develops multi-modal peaks. More surprisingly, we find that electrolytes with non-equal mobilities yield an electric field with non-zero time average at large distances from the electrodes. Our calculations indicate this long-range electric field suffices to levitate colloidal particles many microns away from the electrode against the gravitational field, in accord with experimental observations of such behavior (Woehl et al., PRX, 2015). Moreover, the results indicate that particles will aggregate laterally near electrodes in some electrolytes but separate in others, helping explain a longstanding but not well understood phenomenon.

A numerical study on electrochemical transport of ions in calcium fluoride slag

NASA Astrophysics Data System (ADS)

Karimi-Sibaki, E.; Kharicha, A.; Wu, M.; Ludwig, A.

2016-07-01

Electrically resistive CaF 2-based slags are widely used in electroslag remelting (ESR) process to generate Joule heat for the melting of electrode. The electric current is conducted by ions (electrolyte) such as Ca +2 or F -, thus it is necessary to establish electrochemical models to study electrical behavior of slag. This paper presents a numerical model on electrochemical transport of ions in an arbitrary symmetrical (ZZ) and non-symmetrical (CaF2) stagnant electrolytes blocked by two parallel, planar electrodes. The dimensionless Poisson-Nernst-Planck (PNP) equations are solved to model electro-migration and diffusion of ions. The ions are considered to be inert that no Faradic reactions occur. Spatial variations of concentrations of ions, charge density and electric potential across the electrolyte are analyzed. It is shown that the applied potential has significant influence on the system response. At high applied voltage, the anodic potential drop near the electrode is significantly larger than cathodic potential drop in fully dissociated CaF2 electrolyte.

Membrane rejection of nitrogen compounds

NASA Technical Reports Server (NTRS)

Lee, S.; Lueptow, R. M.

2001-01-01

Rejection characteristics of nitrogen compounds were examined for reverse osmosis, nanofiltration, and low-pressure reverse osmosis membranes. The rejection of nitrogen compounds is explained by integrating experimental results with calculations using the extended Nernst-Planck model coupled with a steric hindrance model. The molecular weight and chemical structure of nitrogen compounds appear to be less important in determining rejection than electrostatic properties. The rejection is greatest when the Donnan potential exceeds 0.05 V or when the ratio of the solute radius to the pore radius is greater than 0.8. The transport of solute in the pore is dominated by diffusion, although convective transport is significant for organic nitrogen compounds. Electromigration contributes negligibly to the overall solute transport in the membrane. Urea, a small organic compound, has lower rejection than ionic compounds such as ammonium, nitrate, and nitrite, indicating the critical role of electrostatic interaction in rejection. This suggests that better treatment efficiency for organic nitrogen compounds can be obtained after ammonification of urea.

Purely electronic mechanism of electrolyte gating of indium tin oxide thin films

DOE PAGES

Leng, X.; Bozovic, I.; Bollinger, A. T.

2016-08-10

Epitaxial indium tin oxide films have been grown on both LaAlO 3 and yttria-stabilized zirconia substrates using RF magnetron sputtering. Electrolyte gating causes a large change in the film resistance that occurs immediately after the gate voltage is applied, and shows no hysteresis during the charging/discharging processes. When two devices are patterned next to one another and the first one gated through an electrolyte, the second one shows no changes in conductance, in contrast to what happens in materials (like tungsten oxide) susceptible to ionic electromigration and intercalation. These findings indicate that electrolyte gating in indium tin oxide triggers amore » pure electronic process (electron depletion or accumulation, depending on the polarity of the gate voltage), with no electrochemical reactions involved. Electron accumulation occurs in a very thin layer near the film surface, which becomes highly conductive. These results contribute to our understanding of the electrolyte gating mechanism in complex oxides and may be relevant for applications of electric double layer transistor devices.« less

Spectral focusing of broadband silver electroluminescence in nanoscopic FRET-LEDs.

PubMed

Puchert, Robin P; Steiner, Florian; Plechinger, Gerd; Hofmann, Felix J; Caspers, Ines; Kirschner, Johanna; Nagler, Philipp; Chernikov, Alexey; Schüller, Christian; Korn, Tobias; Vogelsang, Jan; Bange, Sebastian; Lupton, John M

2017-07-01

Few inventions have shaped the world like the incandescent bulb. Edison used thermal radiation from ohmically heated conductors, but some noble metals also exhibit 'cold' electroluminescence in percolation films, tunnel diodes, electromigrated nanoparticle aggregates, optical antennas or scanning tunnelling microscopy. The origin of this radiation, which is spectrally broad and depends on applied bias, is controversial given the low radiative yields of electronic transitions. Nanoparticle electroluminescence is particularly intriguing because it involves localized surface-plasmon resonances with large dipole moments. Such plasmons enable very efficient non-radiative fluorescence resonance energy transfer (FRET) coupling to proximal resonant dipole transitions. Here, we demonstrate nanoscopic FRET-light-emitting diodes which exploit the opposite process, energy transfer from silver nanoparticles to exfoliated monolayers of transition-metal dichalcogenides. In diffraction-limited hotspots showing pronounced photon bunching, broadband silver electroluminescence is focused into the narrow excitonic resonance of the atomically thin overlayer. Such devices may offer alternatives to conventional nano-light-emitting diodes in on-chip optical interconnects.

Magnetic field dependent electronic transport of Mn4 single-molecule magnet.

NASA Astrophysics Data System (ADS)

Haque, F.; Langhirt, M.; Henderson, J. J.; Del Barco, E.; Taguchi, T.; Christou, G.

2010-03-01

We have performed single-electron transport measurements on a Mn4 single-molecule magnet (SMM) in where amino groups were added to electrically protect the magnetic core and to increase the stability of the molecule when deposited on the single-electron transistor (SET) chip. A three-terminal SET with nano-gap electro-migrated gold electrodes and a naturally oxidized Aluminum back gate. Experiments were conducted at temperatures down to 230mK in the presence of high magnetic fields generated by a superconducting vector magnet. Mn4 molecules were deposited from solution to form a mono-layer. The optimum deposition time was determined by AFM analysis on atomically flat gold surfaces. We have observed Coulomb blockade an electronic excitations that curve with the magnetic field and present zero-field splitting, which represents evidence of magnetic anisotropy. Level anticrossings and large excitations slopes are associated with the behavior of molecular states with high spin values (S ˜ 9), as expected from Mn4.

Electrodeposition of Au/Ag bimetallic dendrites assisted by Faradaic AC-electroosmosis flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ji, Jianlong; Li, Pengwei; Sang, Shengbo, E-mail: sbsang@tyut.edu.cn

2014-03-15

Au/Ag bimetallic dendrites were synthesized successfully from the corresponding aqueous solution via the AC electrodeposition method. Both of the morphologies and compositions could be tuned by the electrolyte concentration and AC frequency. The prepared bimetallic dendrites were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and UV–vis spectroscopy. The underlying dendrite growth mechanism was then proposed in the context of the Directed Electrochemical Nanowires Assembly (DENA) models. Owing to the unscreened voltage dropping in the electrolyte bulk, electromigration dominates the species flux process, and cations tend to accumulate in areas with strong electricmore » field intensity, such as electrode edges. Moreover, Faradaic AC-electro-osmosis (ACEO) flow could increase the effective diffusion layer thickness in these areas during the electrochemical reaction, and leads to dendrite growth. Further Micro-Raman observations illustrated that the Au/Ag bimetallic dendrites exhibited pronounced surface-enhanced Raman scattering (SERS) activity, using 4-mercaptopyridine (4-MP) as model molecules.« less

A first-principles analysis of ballistic conductance, grain boundary scattering and vertical resistance in aluminum interconnects

NASA Astrophysics Data System (ADS)

Zhou, Tianji; Lanzillo, Nicholas A.; Bhosale, Prasad; Gall, Daniel; Quon, Roger

2018-05-01

We present an ab initio evaluation of electron scattering mechanisms in Al interconnects from a back-end-of-line (BEOL) perspective. We consider the ballistic conductance as a function of nanowire size, as well as the impact of surface oxidation on electron transport. We also consider several representative twin grain boundaries and calculate the specific resistivity and reflection coefficients for each case. Lastly, we calculate the vertical resistance across the Al/Ta(N)/Al and Cu/Ta(N)/Cu interfaces, which are representative of typical vertical interconnect structures with diffusion barriers. Despite a high ballistic conductance, the calculated specific resistivities at grain boundaries are 70-100% higher in Al than in Cu, and the vertical resistance across Ta(N) diffusion barriers are 60-100% larger for Al than for Cu. These results suggest that in addition to the well-known electromigration limitations in Al interconnects, electron scattering represents a major problem in achieving low interconnect line resistance at fine dimensions.

Apparatus and method for measurement of the mechanical properties and electromigration of thin films

DOEpatents

Maris, Humphrey J.

2001-01-01

A method for characterizing a sample comprising the steps of depositing the sample on a substrate, measuring a first change in optical response of the sample, changing the lateral strain of the sample, measuring a second change in optical response of the sample, comparing the second change in optical response of with the first change in optical response and associating a difference between the second change and the first change in optical response with a property of interest in the sample. The measurement of the first change in optical response is made with the sample having an initial lateral strain. The measurement of the second change in optical response is made after the lateral strain in the sample is changed from the initial lateral strain to a different lateral strain. The second change in optical response is compared to the first change in optical response to find the difference between the second change and the first change.

Apparatus and method for measurement of the mechanical properties and electromigration of thin films

DOEpatents

Maris, Humphrey J.

2000-01-01

A method for characterizing a sample comprising the steps of depositing the sample on a substrate, measuring a first change in optical response of the sample, changing the lateral strain of the sample, measuring a second change in optical response of the sample, comparing the second change in optical response of with the first change in optical response and associating a difference between the second change and the first change in optical response with a property of interest in the sample. The measurement of the first change in optical response is made with the sample having an initial lateral strain. The measurement of the second change in optical response is made after the lateral strain in the sample is changed from the initial lateral strain to a different lateral strain. The second change in optical response is compared to the first change in optical response to find the difference between the second change and the first change.

Recent advances in CE-MS coupling: Instrumentation, methodology, and applications.

PubMed

Týčová, Anna; Ledvina, Vojtěch; Klepárník, Karel

2017-01-01

This review focuses on the latest development of microseparation electromigration methods in capillaries and microfluidic devices coupled with MS for detection and identification of important analytes. It is a continuation of the review article on the same topic by Kleparnik (Electrophoresis 2015, 36, 159-178). A wide selection of 161 relevant articles covers the literature published from June 2014 till May 2016. New improvements in the instrumentation and methodology of MS interfaced with capillary or microfluidic versions of zone electrophoresis, isotachophoresis, and isoelectric focusing are described in detail. The most frequently implemented MS ionization methods include electrospray ionization, matrix-assisted desorption/ionization and inductively coupled plasma ionization. Although the main attention is paid to the development of instrumentation and methodology, representative examples illustrate also applications in the proteomics, glycomics, metabolomics, biomarker research, forensics, pharmacology, food analysis, and single-cell analysis. The combinations of MS with capillary versions of electrochromatography, and micellar electrokinetic chromatography are not included. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Stressing Effect of Electromigration from the Maxwell Stress and a Preliminary Mean-Time-to-Failure Analysis

NASA Astrophysics Data System (ADS)

Zhou, Peng

2013-06-01

As temperature increases, it is suggested that atoms on lattice sites serve as dynamic defects and cause a much more homogeneous distribution of the Maxwell stress throughout the crystal lattice compared with that caused by static defects. Though this stressing effect mostly leads to Joule heating, it also results in distortion of the crystal lattice, which leads to a decrease in the activation energy for atomic diffusion and causes enhancements in the phase growth rates at both interfaces of diffusion couples. Due to this stressing effect, the decrease in the activation energy is proportional to a square term of the current density J. A mean-time-to-failure analysis is performed for failure caused by excessive growth of intermediate phases, and a mean-time-to-failure (MTTF) equation is found. This equation appears similar to Black's equation but with an extra exponential term arising from the stressing effect of the crystal lattice.

A new statistical methodology predicting chip failure probability considering electromigration

NASA Astrophysics Data System (ADS)

Sun, Ted

In this research thesis, we present a new approach to analyze chip reliability subject to electromigration (EM) whose fundamental causes and EM phenomenon happened in different materials are presented in this thesis. This new approach utilizes the statistical nature of EM failure in order to assess overall EM risk. It includes within-die temperature variations from the chip's temperature map extracted by an Electronic Design Automation (EDA) tool to estimate the failure probability of a design. Both the power estimation and thermal analysis are performed in the EDA flow. We first used the traditional EM approach to analyze the design with a single temperature across the entire chip that involves 6 metal and 5 via layers. Next, we used the same traditional approach but with a realistic temperature map. The traditional EM analysis approach and that coupled with a temperature map and the comparison between the results of considering and not considering temperature map are presented in in this research. A comparison between these two results confirms that using a temperature map yields a less pessimistic estimation of the chip's EM risk. Finally, we employed the statistical methodology we developed considering a temperature map and different use-condition voltages and frequencies to estimate the overall failure probability of the chip. The statistical model established considers the scaling work with the usage of traditional Black equation and four major conditions. The statistical result comparisons are within our expectations. The results of this statistical analysis confirm that the chip level failure probability is higher i) at higher use-condition frequencies for all use-condition voltages, and ii) when a single temperature instead of a temperature map across the chip is considered. In this thesis, I start with an overall review on current design types, common flows, and necessary verifications and reliability checking steps used in this IC design industry. Furthermore, the important concepts about "Scripting Automation" which is used in all the integration of using diversified EDA tools in this research work are also described in detail with several examples and my completed coding works are also put in the appendix for your reference. Hopefully, this construction of my thesis will give readers a thorough understanding about my research work from the automation of EDA tools to the statistical data generation, from the nature of EM to the statistical model construction, and the comparisons among the traditional EM analysis and the statistical EM analysis approaches.

Electrical Detection of Cancer Biomarker using Aptamers with Nanogap Break-Junctions

PubMed Central

Ilyas, Azhar; Asghar, Waseem; Allen, Peter B.; Duhon, Holli; Ellington, Andrew D.; Iqbal, Samir M.

2012-01-01

Epidermal Growth Factor Receptor (EGFR) is a cell surface protein overexpressed in cancerous cells. It is known to be the most common oncongene. EGFR concentration also increases in the serum of cancer patients. The detection of small changes in the concentration of EGFR can be critical for early diagnosis, resulting in better treatment and improved survival rate of cancer patients. This article reports an RNA aptamer based approach to selectively capture EGFR protein and an electrical scheme for its detection. Pairs of gold electrodes with nanometer separation were made through confluence of focused ion beam scratching and electromigration. The aptamer was hybridized to a single stranded DNA molecule, which in turn was immobilized on SiO2 surface between the gold nanoelectrodes. The selectivity of the aptamer was demonstrated by using control chips with mutated non–selective aptamer and with no aptamer. Surface functionalization was characterized by optical detection and two orders of magnitude increase in direct current (DC) was measured when selective capture of EGFR occurred. This represents an electronic biosensor for the detection of proteins of interest for medical applications. PMID:22706642

Effects of Pulse Parameters on Weld Microstructure and Mechanical Properties of Extra Pulse Current Aided Laser Welded 2219 Aluminum Alloy Joints.

PubMed

Zhang, Xinge; Li, Liqun; Chen, Yanbin; Yang, Zhaojun; Chen, Yanli; Guo, Xinjian

2017-09-15

In order to expand the application range of laser welding and improve weld quality, an extra pulse current was used to aid laser-welded 2219 aluminum alloy, and the effects of pulse current parameters on the weld microstructure and mechanical properties were investigated. The effect mechanisms of the pulse current interactions with the weld pool were evaluated. The results indicated that the coarse dendritic structure in the weld zone changed to a fine equiaxed structure using an extra pulse current, and the pulse parameters, including medium peak current, relatively high pulse frequency, and low pulse duty ratio benefited to improving the weld structure. The effect mechanisms of the pulse current were mainly ascribed to the magnetic pinch effect, thermal effect, and electromigration effect caused by the pulse current. The effect of the pulse parameters on the mechanical properties of welded joints were consistent with that of the weld microstructure. The tensile strength and elongation of the optimal pulse current-aided laser-welded joint increased by 16.4% and 105%, respectively, compared with autogenous laser welding.

Use of solar cell in electrokinetic remediation of cadmium-contaminated soil.

PubMed

Yuan, Songhu; Zheng, Zhonghua; Chen, Jing; Lu, Xiaohua

2009-03-15

This preliminary study used a solar cell, instead of direct current (DC) power supply, to generate electric field for electrokinetic (EK) remediation of cadmium-contaminated soil. Three EK tests were conducted and compared; one was conducted on a cloudy and rainy day with solar cell, one was conducted on a sunny day with solar cell and another was conducted periodically with DC power supply. It was found that the output potential of solar cell depended on daytime and was influenced by weather conditions; the applied potential in soil was affected by the output potential and weather conditions, and the current achieved by solar cell was comparable with that achieved by DC power supply. Solar cell could be used to drive the electromigration of cadmium in contaminated soil, and removal efficiency achieved by solar cell was comparable with that achieved by DC power supply. Compared with traditional DC power supply, using solar cell as power supply for EK remediation can greatly reduce energy expenditure. This study provided an alternative to improve the EK soil remediation and expanded the use of solar cell in environmental remediation.

Effects of Pulse Parameters on Weld Microstructure and Mechanical Properties of Extra Pulse Current Aided Laser Welded 2219 Aluminum Alloy Joints

PubMed Central

Zhang, Xinge; Li, Liqun; Chen, Yanbin; Yang, Zhaojun; Chen, Yanli; Guo, Xinjian

2017-01-01

In order to expand the application range of laser welding and improve weld quality, an extra pulse current was used to aid laser-welded 2219 aluminum alloy, and the effects of pulse current parameters on the weld microstructure and mechanical properties were investigated. The effect mechanisms of the pulse current interactions with the weld pool were evaluated. The results indicated that the coarse dendritic structure in the weld zone changed to a fine equiaxed structure using an extra pulse current, and the pulse parameters, including medium peak current, relatively high pulse frequency, and low pulse duty ratio benefited to improving the weld structure. The effect mechanisms of the pulse current were mainly ascribed to the magnetic pinch effect, thermal effect, and electromigration effect caused by the pulse current. The effect of the pulse parameters on the mechanical properties of welded joints were consistent with that of the weld microstructure. The tensile strength and elongation of the optimal pulse current-aided laser-welded joint increased by 16.4% and 105%, respectively, compared with autogenous laser welding. PMID:28914825

Assisting cultivation of photosynthetic microorganisms by microbial fuel cells to enhance nutrients recovery from wastewater.

PubMed

Colombo, Alessandra; Marzorati, Stefania; Lucchini, Giorgio; Cristiani, Pierangela; Pant, Deepak; Schievano, Andrea

2017-08-01

Spirulina was cultivated in cathodic compartments of photo-microbial fuel cells (P-MFC). Anodic compartments were fed with swine-farming wastewater, enriched with sodium acetate (2.34g COD L -1 ). Photosynthetic oxygen generation rates were sufficient to sustain cathodic oxygen reduction, significantly improving P-MFC electrochemical performances, as compared to water-cathode control experiments. Power densities (0.8-1Wm -2 ) approached those of air-cathode MFCs, run as control. COD was efficiently removed and only negligible fractions leaked to the cathodic chamber. Spirulina growth rates were comparable to those of control (MFC-free) cultures, while pH was significantly (0.5-1unit) higher in P-MFCs, due to cathodic reactions. Alkaliphilic photosynthetic microorganisms like Spirulina might take advantage of these selective conditions. Electro-migration along with diffusion to the cathodic compartment concurred for the recovery of most nutrients. Only P and Mg were retained in the anodic chamber. A deeper look into electro-osmotic mechanisms should be addressed in future studies. Copyright © 2017 Elsevier Ltd. All rights reserved.

Electrical characteristics in reverse electrodialysis using nanoporous membranes

NASA Astrophysics Data System (ADS)

Chanda, Sourayon; Tsai, Peichun Amy

2017-11-01

We experimentally and numerically investigate the effects of concentration difference and flow velocity on sustainable electricity generation and associated fluid dynamics using a single reverse electrodialysis (RED) cell. By exploiting the charge-selective nature of nanoporous interfaces, electrical energy is generated by reverse electrodialysis harnessing chemical Gibbs energy via a salinity gradient. Experimentally, a RED cell was designed with two reservoirs, which are separated by a nanoporous, cation-selective membrane. We injected deionized water through one reservoir, whereas a solution of high salt concentration through the other. The gradient of salt concentration primarily drives the flow in the charged nano-pores, due to the interplay between charge selectivity, diffusion processes, and electro-migration. The current-voltage characteristics of the single RED cell shows a linear current-voltage relationship, similar to an electrochemical cell. The membrane resistance is increased with increasing salt concentration difference and external flow rate. The present experimental work was further analyzed numerically to better understand the detailed electrical and flow fields under different concentration gradients and external flows. NSERC Discovery, Accelerator, and CRC Programs.

Computational and experimental model of transdermal iontophorethic drug delivery system.

PubMed

Filipovic, Nenad; Saveljic, Igor; Rac, Vladislav; Graells, Beatriz Olalde; Bijelic, Goran

2017-11-30

The concept of iontophoresis is often applied to increase the transdermal transport of drugs and other bioactive agents into the skin or other tissues. It is a non-invasive drug delivery method which involves electromigration and electroosmosis in addition to diffusion and is shown to be a viable alternative to conventional administration routs such as oral, hypodermic and intravenous injection. In this study we investigated, experimentally and numerically, in vitro drug delivery of dexamethasone sodium phosphate to porcine skin. Different current densities, delivery durations and drug loads were investigated experimentally and introduced as boundary conditions for numerical simulations. Nernst-Planck equation was used for calculation of active substance flux through equivalent model of homogeneous hydrogel and skin layers. The obtained numerical results were in good agreement with experimental observations. A comprehensive in-silico platform, which includes appropriate numerical tools for fitting, could contribute to iontophoretic drug-delivery devices design and correct dosage and drug clearance profiles as well as to perform much faster in-silico experiments to better determine parameters and performance criteria of iontophoretic drug delivery. Copyright © 2017 Elsevier B.V. All rights reserved.

Model creation of moving redox reaction boundary in agarose gel electrophoresis by traditional potassium permanganate method.

PubMed

Xie, Hai-Yang; Liu, Qian; Li, Jia-Hao; Fan, Liu-Yin; Cao, Cheng-Xi

2013-02-21

A novel moving redox reaction boundary (MRRB) model was developed for studying electrophoretic behaviors of analytes involving redox reaction on the principle of moving reaction boundary (MRB). Traditional potassium permanganate method was used to create the boundary model in agarose gel electrophoresis because of the rapid reaction rate associated with MnO(4)(-) ions and Fe(2+) ions. MRB velocity equation was proposed to describe the general functional relationship between velocity of moving redox reaction boundary (V(MRRB)) and concentration of reactant, and can be extrapolated to similar MRB techniques. Parameters affecting the redox reaction boundary were investigated in detail. Under the selected conditions, good linear relationship between boundary movement distance and time were obtained. The potential application of MRRB in electromigration redox reaction titration was performed in two different concentration levels. The precision of the V(MRRB) was studied and the relative standard deviations were below 8.1%, illustrating the good repeatability achieved in this experiment. The proposed MRRB model enriches the MRB theory and also provides a feasible realization of manual control of redox reaction process in electrophoretic analysis.

Exploring the Electrical Conductivity of Cytochrome P450 by Nano-Electrode and Conductive Atomic Force Microscopy

NASA Astrophysics Data System (ADS)

Li, Debin; Gu, Jianhua; Chye, Yewhee; Lederman, David; Kabulski, Jarod; Gannett, Peter; Tracy, Timothy

2006-03-01

There is a growing interest in measuring the conductivity of electron-transfer proteins. The cytochrome P450 (CP450) enzymes represent an important class of heme-containing enzymes. Immobilizing CP450 enzymes on a surface can be used for studying a single enzyme with respect to electron transfer. The spin state of the heme iron can change upon binding of a substrate. In our experiment, CP450 (diameter ˜ 5 nm) has been bonded to a metal surface. Nano-electrodes (gap < 10 nm) were fabricated by defining a bridge via e-beam lithography and then breaking the junction by electromigration at low temperatures. We have examined the electronic properties of CP450 by itself and after binding CP450 with flurbiprofen. The room temperature I-V conductivity is reminiscent to cyclic voltammetry measurements, indicating the presence of strong ionic transfer. At lower temperatures (100 K) the I-V characteristics indicate electronic transport dominated by tunneling processes. The conductive AFM is an additional method used to examine the enzyme's electronic properties. The results from two methods will be discussed..

On-chip isothermal, chemical cycling polymerase chain reaction (ccPCR)

NASA Astrophysics Data System (ADS)

Persat, Alexandre; Santiago, Juan

2008-11-01

We demonstrate a novel ccPCR technique for microfluidic DNA amplification where temperature is held constant in space and time. The polymerase chain reaction is a platform of choice for biological assays and typically based on a three-step thermal cycling: DNA denaturation, primers annealing and extension by an enzyme. We here demonstrate a novel technique where high concentration chemical denaturants (solvents) denature DNA. We leverage the high electrophoretic mobility of DNA and the electrical neutrality of denaturants to achieve chemical cycling. We focus DNA with isotachophoresis (ITP); a robust electrophoretic preconcentration technique which generates strong electric field gradients and protects the sample from dispersion. We apply a pressure-driven flow to balance electromigration velocity and keep the DNA sample stationary in a microchannel. We drive the DNA through a series of high denaturant concentration zones. DNA denatures at high denaturant concentration. At low denaturant concentration, the enzyme creates complementary strands. DNA reaction kinetics are slower than buffer reactions involved in ITP. We demonstrate successful ccPCR amplification for detection of E. Coli. The ccPCR has the potential for simpler chemistry than traditional PCR.

Microstructural changes in a cementitious membrane due to the application of a DC electric field.

PubMed

Covelo, Alba; Diaz, Belen; Freire, Lorena; Novoa, X Ramon; Perez, M Consuelo

2008-07-01

The use of electromigration techniques to accelerate chloride ions motion is commonly employed to characterise the permeability of cementitious samples to chlorides, a relevant parameter in reinforced concrete corrosion. This paper is devoted to the study of microstructure's changes occurring in mortar samples when submitted to natural diffusion and migration experiments. The application of an electric field reduces testing time in about one order of magnitude with respect to natural diffusion experiments. Nevertheless, the final sample's microstructure differs in both tests. Impedance Spectroscopy is employed for real time monitoring of microstructural changes. During migration experiments the global impedance undergoes important increase in shorter period of time compared to natural diffusion tests. So, the forced motion of ions through the concrete membrane induces significant variations in the porous structure, as confirmed by Mercury Intrusion Porosimetry. After migration experiments, an important increase in the capillary pore size (10-100 nm) was detected. Conversely, no relevant variations are found after natural diffusion tests. Results presented in this work cast doubt on the significance of diffusion coefficient values obtained under accelerated conditions.

Capillary electrophoresis and nanomaterials - Part I: Capillary electrophoresis of nanomaterials.

PubMed

Adam, Vojtech; Vaculovicova, Marketa

2017-10-01

Nanomaterials are in analytical science used for a broad range of purposes, covering the area of sample pretreatment as well as separation, detection, and identification of target molecules. This part of the review covers capillary electrophoresis (CE) of nanomaterials and focuses on the application of CE as a method for characterization used during nanomaterial synthesis and modification as well as the monitoring of their properties and interactions with other molecules. The heterogeneity of the nanomaterial family is extremely large. Depending on different definitions of the term Nanomaterial/Nanoparticle, the group may cover metal and polymeric nanoparticles, carbon nanomaterials, liposomes and even dendrimers. Moreover, these nanomaterials are usually subjected to some kind of surface modification or functionalization, which broadens the diversity even more. Not only for purposes of verification of nanomaterial synthesis and batch-to-batch quality check, but also for determination the polydispersity and for functionality characterization on the nanoparticle surface, has CE offered very beneficial capabilities. Finally, the monitoring of interactions between nanomaterials and other (bio)molecules is easily performed by some kind of capillary electromigration technique. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ SEM Study of Lithium Intercalation in individual V 2O 5 Nanowires

DOE PAGES

Strelcov, Evgheni; Cothren, Joshua E.; Leonard, Donovan N.; ...

2015-01-08

Progress in rational engineering of Li-ion batteries requires better understanding of the electrochemical processes and accompanying transformations in the electrode materials on multiple length scales. In spite of recent progress in utilizing transmission electron microscopy (TEM) to analyze these materials, in situ scanning electron microscopy (SEM) was mostly overlooked as a powerful tool that allows probing these phenomena on the nano and mesoscale. In this paper, we report on in situ SEM study of lithiation in a V 2O 5-based single-nanobelt battery with ionic liquid electrolyte. Coupled with cyclic voltammetry measurements, in situ SEM revealed the peculiarities of subsurface intercalation,more » formation of solid-electrolyte interface (SEI) and electromigration of liquid. We observed that single-crystalline vanadia nanobelts do not undergo large-scale amorphization or fracture during electrochemical cycling, but rather transform topochemically with only a slight shape distortion. Lastly, the SEI layer seems to have significant influence on the lithium ion diffusion and overall capacity of the single-nanobelt battery.« less

Structural transitions in electron beam deposited Co-carbonyl suspended nanowires at high electrical current densities.

PubMed

Gazzadi, Gian Carlo; Frabboni, Stefano

2015-01-01

Suspended nanowires (SNWs) have been deposited from Co-carbonyl precursor (Co2(CO)8) by focused electron beam induced deposition (FEBID). The SNWs dimensions are about 30-50 nm in diameter and 600-850 nm in length. The as-deposited material has a nanogranular structure of mixed face-centered cubic (FCC) and hexagonal close-packed (HCP) Co phases, and a composition of 80 atom % Co, 15 atom % O and 5 atom % C, as revealed by transmission electron microscopy (TEM) analysis and by energy-dispersive X-ray (EDX) spectroscopy, respectively. Current (I)-voltage (V) measurements with current densities up to 10(7) A/cm(2) determine different structural transitions in the SNWs, depending on the I-V history. A single measurement with a sudden current burst leads to a polycrystalline FCC Co structure extended over the whole wire. Repeated measurements at increasing currents produce wires with a split structure: one half is polycrystalline FCC Co and the other half is graphitized C. The breakdown current density is found at 2.1 × 10(7) A/cm(2). The role played by resistive heating and electromigration in these transitions is discussed.

Importance of core electrostatic properties on the electrophoresis of a soft particle

NASA Astrophysics Data System (ADS)

De, Simanta; Bhattacharyya, Somnath; Gopmandal, Partha P.

2016-08-01

The impact of the volumetric charged density of the dielectric rigid core on the electrophoresis of a soft particle is analyzed numerically. The volume charge density of the inner core of a soft particle can arise for a dendrimer structure or bacteriophage MS2. We consider the electrokinetic model based on the conservation principles, thus no conditions for Debye length or applied electric field is imposed. The fluid flow equations are coupled with the ion transport equations and the equation for the electric field. The occurrence of the induced nonuniform surface charge density on the outer surface of the inner core leads to a situation different from the existing analysis of a soft particle electrophoresis. The impact of this induced surface charge density together with the double-layer polarization and relaxation due to ion convection and electromigration is analyzed. The dielectric permittivity and the charge density of the core have a significant impact on the particle electrophoresis when the Debye length is in the order of the particle size. We find that by varying the ionic concentration of the electrolyte, the particle can exhibit reversal in its electrophoretic velocity. The role of the polymer layer softness parameter is addressed in the present analysis.

Electrokinetic remediation of manganese and ammonia nitrogen from electrolytic manganese residue.

PubMed

Shu, Jiancheng; Liu, Renlong; Liu, Zuohua; Du, Jun; Tao, Changyuan

2015-10-01

Electrolytic manganese residue (EMR) is a solid waste found in filters after sulphuric acid leaching of manganese carbonate ore, which mainly contains manganese and ammonia nitrogen and seriously damages the ecological environment. This work demonstrated the use of electrokinetic (EK) remediation to remove ammonia nitrogen and manganese from EMR. The transport behavior of manganese and ammonia nitrogen from EMR during electrokinetics, Mn fractionation before and after EK treatment, the relationship between Mn fractionation and transport behavior, as well as the effects of electrolyte and pretreatment solutions on removal efficiency and energy consumption were investigated. The results indicated that the use of H2SO4 and Na2SO4 as electrolytes and pretreatment of EMR with citric acid and KCl can reduce energy consumption, and the removal efficiencies of manganese and ammonia nitrogen were 27.5 and 94.1 %, respectively. In these systems, electromigration and electroosmosis were the main mechanisms of manganese and ammonia nitrogen transport. Moreover, ammonia nitrogen in EMR reached the regulated level, and the concentration of manganese in EMR could be reduced from 455 to 37 mg/L. In general, the electrokinetic remediation of EMR is a promising technology in the future.

Effects of Surface Finishes and Current Stressing on Interfacial Reaction Characteristics of Sn-3.0Ag-0.5Cu Solder Bumps

NASA Astrophysics Data System (ADS)

Kim, Jae-Myeong; Jeong, Myeong-Hyeok; Yoo, Sehoon; Park, Young-Bae

2012-04-01

The effects of surface finishes on the in situ interfacial reaction characteristics of ball grid array (BGA) Sn-3.0Ag-0.5Cu lead-free solder bumps were investigated under annealing and electromigration (EM) test conditions of 130°C to 175°C with 5.0 × 103 A/cm2. During reflow and annealing, (Cu,Ni)6Sn5 intermetallic compound (IMC) formed at the interface of electroless nickel immersion gold (ENIG) finish. In the case of both immersion Sn and organic solderability preservative (OSP) finishes, Cu6Sn5 and Cu3Sn IMCs formed. Overall, the IMC growth velocity of ENIG was much lower than that of the other finishes. The activation energies of total IMCs were found to be 0.52 eV for ENIG, 0.78 eV for immersion Sn, and 0.72 eV for OSP. The ENIG finish appeared to present an effective diffusion barrier between the Cu substrate and the solder, which leads to better EM reliability in comparison with Cu-based pad systems. The failure mechanisms were explored in detail via in situ EM tests.

Oxidation/reduction reactions at the metal contact-TlBr interface: an x-ray photoelectron spectroscopy study

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Swanberg, E. L.; Voss, L. F.; Graff, R. T.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Kim, H.; Cirignano, L.; Shah, K.

2014-09-01

TlBr radiation detector operation degrades with time at room temperature and is thought to be due to electromigration of Tl and Br vacancies within the crystal as well as the metal contacts migrating into the TlBr crystal itself due to electrochemical reactions at the metal/TlBr interface. X-ray photoemission spectroscopy (XPS) was used to investigate the metal contact surface/interfacial structure on TlBr devices. Device-grade TlBr was polished and subjected to a 32% HCl etch to remove surface damage prior to Mo or Pt contact deposition. High-resolution photoemission measurements on the Tl 4f, Br 3d, Cl 2p, Mo 3d and Pt 4f core lines were used to evaluate surface chemistry and non-equilibrium interfacial diffusion. Results indicate that anion substitution at the TlBr surface due to the HCl etch forms TlBr1-xClx with consequent formation of a shallow heterojunction. In addition, a reduction of Tl1+ to Tl0 is observed at the metal contacts after device operation in both air and N2 at ambient temperature. Understanding contact/device degradation versus operating environment is useful for improving radiation detector performance.

Measurement of resistance switching dynamics in copper sulfide memristor structures

NASA Astrophysics Data System (ADS)

McCreery, Kaitlin; Olson, Matthew; Teitsworth, Stephen

Resistance switching materials are the subject of current research in large part for their potential to enable novel computing devices and architectures such as resistance random access memories and neuromorphic chips. A common feature of memristive structures is the hysteretic switching between high and low resistance states which is induced by the application of a sufficiently large electric field. Here, we describe a relatively simple wet chemistry process to fabricate Cu2 S / Cu memristive structures with Cu2 S film thickness ranging up to 150 micron. In this case, resistance switching is believed to be mediated by electromigration of Cu ions from the Cu substrate into the Cu2 S film. Hysteretic current-voltage curves are measured and reveal switching voltages of about 0.8 Volts with a relatively large variance and independent of film thickness. In order to gain insight into the dynamics and variability of the switching process, we have measured the time-dependent current response to voltage pulses of varying height and duration with a time resolution of 1 ns. The transient response consists of a deterministic RC component as well as stochastically varying abrupt current steps that occur within a few microseconds of the pulse application.

High power vertical stacked diode laser development using macro-channel water cooling and hard solder bonding technology

NASA Astrophysics Data System (ADS)

Yu, Dongshan; Liang, Xuejie; Wang, Jingwei; Li, Xiaoning; Nie, Zhiqiang; Liu, Xingsheng

2017-02-01

A novel marco channel cooler (MaCC) has been developed for packaging high power diode vertical stacked (HPDL) lasers, which eliminates many of the issues in commercially-available copper micro-channel coolers (MCC). The MaCC coolers, which do not require deionized water as coolant, were carefully designed for compact size and superior thermal dissipation capability. Indium-free packaging technology was adopted throughout product design and fabrication process to minimize the risk of solder electromigration and thermal fatigue at high current density and long pulse width under QCW operation. Single MaCC unit with peak output power of up to 700W/bar at pulse width in microsecond range and 200W/bar at pulse width in millisecond range has been recorded. Characteristic comparison on thermal resistivity, spectrum, near filed and lifetime have been conducted between a MaCC product and its counterpart MCC product. QCW lifetime test (30ms 10Hz, 30% duty cycle) has also been conducted with distilled water as coolant. A vertical 40-MaCC stack product has been fabricated, total output power of 9 kilowatts has been recorded under QCW mode (3ms, 30Hz, 9% duty cycle).

Application of design of experiments for formulation development and mechanistic evaluation of iontophoretic tacrine hydrochloride delivery.

PubMed

Patel, Niketkumar; Jain, Shashank; Madan, Parshotam; Lin, Senshang

2016-11-01

The objective of this investigation is to develop mathematical equation to understand the impact of variables and establish statistical control over transdermal iontophoretic delivery of tacrine hydrochloride. In addition, possibility of using conductivity measurements as a tool of predicting ionic mobility of the participating ions for the application of iontophoretic delivery was explored. Central composite design was applied to study effect of independent variables like current strength, buffer molarity, and drug concentration on iontophoretic tacrine permeation flux. Molar conductivity was determined to evaluate electro-migration of tacrine ions with application of Kohlrausch's law. The developed mathematic equation not only reveals drug concentration as the most significant variable regulating tacrine permeation, followed by current strength and buffer molarity, but also is capable to optimize tacrine permeation with respective combination of independent variables to achieve desired therapeutic plasma concentration of tacrine in treatment of Alzheimer's disease. Moreover, relative higher mobility of sodium and chloride ions was observed as compared to estimated tacrine ion mobility. This investigation utilizes the design of experiment approach and extends the primary understanding of imapct of electronic and formulation variables on the tacrine permeation for the formulation development of iontophoretic tacrine delivery.

Biological permeable reactive barriers coupled with electrokinetic soil flushing for the treatment of diesel-polluted clay soil.

PubMed

Mena, Esperanza; Ruiz, Clara; Villaseñor, José; Rodrigo, Manuel A; Cañizares, Pablo

2015-01-01

Removal of diesel from spiked kaolin has been studied in the laboratory using coupled electrokinetic soil flushing (EKSF) and bioremediation through an innovative biological permeable reactive barriers (Bio-PRBs) positioned between electrode wells. The results show that this technology is efficient in the removal of pollutants and allows the soil to maintain the appropriate conditions for microorganism growth in terms of pH, temperature, and nutrients. At the same time, EKSF was demonstrated to be a very interesting technology for transporting pollutants, microorganisms and nutrients, although results indicate that careful management is necessary to avoid the depletion of nutrients, which are effectively transported by electro-migration. After two weeks of operation, 30% of pollutants are removed and energy consumption is under 70 kWh m(-3). Main fluxes (electroosmosis and evaporation) and changes in the most relevant parameters (nutrients, diesel, microorganisms, surfactants, moisture conductivity and pH) during treatment and in a complete post-study analysis are studied to give a comprehensive description of the most relevant processes occurring in the soil (pollutant transport and biodegradation). Copyright © 2014 Elsevier B.V. All rights reserved.

Dependence of magnetic field and electronic transport of Mn4 Single-molecule magnet in a Single-Electron Transistor

NASA Astrophysics Data System (ADS)

Rodriguez, Alvar; Singh, Simranjeet; Haque, Firoze; Del Barco, Enrique; Nguyen, Tu; Christou, George

2012-02-01

Dependence of magnetic field and electronic transport of Mn4 Single-molecule magnet in a Single-Electron Transistor A. Rodriguez, S. Singh, F. Haque and E. del Barco Department of Physics, University of Central Florida, 4000 Central Florida Blvd., Orlando, Florida 32816 USA T. Nguyen and G. Christou Department of Chemistry, University of Florida, Gainesville, Florida 32611 USA Abstract We have performed single-electron transport measurements on a series of Mn-based low-nuclearity single-molecule magnets (SMM) observing Coulomb blockade. SMMs with well isolated and low ground spin states, i.e. S = 9/2 (Mn4) and S = 6 (Mn3) were chosen for these studies, such that the ground spin multiplet does not mix with levels of other excited spin states for the magnetic fields (H = 0-8 T) employed in the experiments. Different functionalization groups were employed to change the mechanical, geometrical and transport characteristics of the molecules when deposited from liquid solution on the transistors. Electromigration-broken three-terminal single-electron transistors were used. Results obtained at temperatures down to 240 mK and in the presence of high magnetic fields will be shown.

Capillary electromigration separation of proteins and microorganisms dynamically modified by chromophoric nonionogenic surfactant.

PubMed

Horká, Marie; Růzicka, Filip; Holá, Veronika; Kahle, Vladislav; Moravcová, Dana; Slais, Karel

2009-08-15

A chromophoric nonionogenic surfactant poly(ethylene glycol) 3-(2-hydroxy-5-n-octylphenylazo)-benzoate, HOPAB, has been prepared and used as a buffer additive for a dynamic modification of proteins and/or microorganisms including Escherichia coli , Staphylococcus epidermidis (biofilm-positive and biofilm-negative), and the strains of yeast cells Candida albicans and Candida parapsilosis (biofilm-positive and biofilm-negative) during a capillary electrophoresis and a capillary isoelectric focusing (CIEF) with UV detection at 326 nm. Values of isoelectric points of labeled proteins and microorganisms have been calculated using UV-detectable pI markers and have been found comparable with pI of the native compounds. Minimum detectable amount has been assessed lower than picograms of proteins and lower than a hundred cells injected into a separation capillary. The introduced labeling method facilitates CIEF separation of microorganisms from the clinical sample of the infected urine at their clinically important levels in the pH gradient pH range of 2-5 and their subsequent cultivation. At the same time, it has enabled the determination of albumin in human urine as a major clinical marker of urinary tract infections and kidney diseases.

Surface functional groups in capacitive deionization with porous carbon electrodes

NASA Astrophysics Data System (ADS)

Hemmatifar, Ali; Oyarzun, Diego I.; Palko, James W.; Hawks, Steven A.; Stadermann, Michael; Santiago, Juan G.; Stanford Microfluidics Lab Team; Lawrence Livermore National Lab Team

2017-11-01

Capacitive deionization (CDI) is a promising technology for removal of toxic ions and salt from water. In CDI, an applied potential of about 1 V to pairs of porous electrodes (e.g. activated carbon) induces ion electromigration and electrostatic adsorption at electrode surfaces. Immobile surface functional groups play a critical role in the type and capacity of ion adsorption, and this can dramatically change desalination performance. We here use models and experiments to study weak electrolyte surface groups which protonate and/or depropotante based on their acid/base dissociation constants and local pore pH. Net chemical surface charge and differential capacitance can thus vary during CDI operation. In this work, we present a CDI model based on weak electrolyte acid/base equilibria theory. Our model incorporates preferential cation (anion) adsorption for activated carbon with acidic (basic) surface groups. We validated our model with experiments on custom built CDI cells with a variety of functionalizations. To this end, we varied electrolyte pH and measured adsorption of individual anionic and cationic ions using inductively coupled plasma mass spectrometry (ICP-MS) and ion chromatography (IC) techniques. Our model shows good agreement with experiments and provides a framework useful in the design of CDI control schemes.

Two-dimensional self-organization of an ordered Au silicide nanowire network on a Si(110)-16 x 2 surface.

PubMed

Hong, Ie-Hong; Yen, Shang-Chieh; Lin, Fu-Shiang

2009-08-17

A well-ordered two-dimensional (2D) network consisting of two crossed Au silicide nanowire (NW) arrays is self-organized on a Si(110)-16 x 2 surface by the direct-current heating of approximately 1.5 monolayers of Au on the surface at 1100 K. Such a highly regular crossbar nanomesh exhibits both a perfect long-range spatial order and a high integration density over a mesoscopic area, and these two self-ordering crossed arrays of parallel-aligned NWs have distinctly different sizes and conductivities. NWs are fabricated with widths and pitches as small as approximately 2 and approximately 5 nm, respectively. The difference in the conductivities of two crossed-NW arrays opens up the possibility for their utilization in nanodevices of crossbar architecture. Scanning tunneling microscopy/spectroscopy studies show that the 2D self-organization of this perfect Au silicide nanomesh can be achieved through two different directional electromigrations of Au silicide NWs along different orientations of two nonorthogonal 16 x 2 domains, which are driven by the electrical field of direct-current heating. Prospects for this Au silicide nanomesh are also discussed.

Monitoring exocytosis and release from individual mast cells by capillary electrophoresis and UV imaging microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yeung, E.S.; Lillard, S.J.; McCloskey, M.A.

1997-12-31

The complex temporal evolution of on-column exocytotic release of serotonin from individual peritoneal mast cells (RPMCs) was monitored by using capillary electrophoresis and UV imaging microscopy. Laser-induced native fluorescence detection with 275-nm excitation was used, and a detection limit of 1.7 amol (S/N = 3; rms) was obtained for serotonin. A physiological running buffer was used to ensure that the cell remained viable throughout. The secretagogue was polymyxin B sulfate (Pmx). Following the injection of a single mast cell into the capillary, electromigration of Pmx toward and past the cell induced degranulation and release of serotonin. The time course ofmore » release was registered in the electropherograms with subsecond resolution. Subsequent introduction of SDS caused the cell to lyse completely and allowed the residual serotonin to be quantified. The average amount of serotonin observed per RPMC was 1.6 {+-} 0.6 fmol; the average percentage of serotonin released was 28 {+-} 14%. Events that are consistent with released serontonin from single submicron granules (250 aL each) were evident, each of which contained an average amount of 5.9 {+-} 3 amol. Alternatively, UV movies can be taken of the entire event to provide temporal and spatial information.« less

Thermal stability, adhesion and electrical studies on (Ti,Zr)N x thin films as low resistive diffusion barriers between Cu and Si

NASA Astrophysics Data System (ADS)

Huang, Cheng-Lin; Lai, Chih-Huang; Tsai, Po-Hao; Kuo, Yu-Lin; Lin, Jing-Cheng; Lee, Chiapyng

2014-05-01

In this study, we investigated the thermal stability, wettability, adhesion and reliability of (Ti,Zr)N x films used as the diffusion barrier between Cu and Si. (Ti,Zr)N x films were prepared by DC reactive magnetron sputtering from a Ti-5 at. % Zr alloy target in N2/Ar gas mixtures. A minimum film resistivity of 59.3 µω cm was obtained at an N2/Ar flow ratio of 2.75, which corresponds to the near stoichiometric composition (N/(Ti,Zr) ratio ˜0.95). The sheet resistance of Cu/(Ti,Zr)N0.95/Si was not significantly increased until annealing above 750°C, indicating good thermal stability. On the other hand, the adhesion energy between Cu and the (Ti,Zr)Nx film was reduced as the N/Ti ratio was increased. To obtain reliable performance on stress-induced-voiding (SIV) and electromigration (EM) tests, we proposed to use (Ti,Zr)/(Ti,Zr)N x /(Ti,Zr) tri-layers. We suggest that the interfacial adhesion between barrier and Cu plays an important role in reliability. The proposed tri-layer structure may be a promising candidate for a barrier, as it exhibits excellent reliability without increasing resistance.

Nonuniformity of carrier injection and the degradation of blue LEDs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bochkareva, N. I.; Efremov, A. A.; Rebane, Yu. T.

The distribution of electroluminescence (EL) intensity over the area and in the course of time before and after the optical degradation of blue InGaN/GaN LEDs is studied. Current-voltage characteristics have been recorded. It is found that the initially bright luminescence near the region of metallization of the p-contact turns weak after the degradation of an LED. The time delay of {approx}20-40 ns is observed in the distribution of EL intensity over the area of LEDs after their degradation. We suppose that a rise in the excess current after degradation is due to the density increasing of the InGaN/GaN interface statesmore » and the formation of an electrical dipole, which lowers the potential barriers in p-GaN and n-GaN layers. The corresponding increase of capacitance leads to a time delay in the spreading of the injection current and in the distribution of the emission brightness over the area. The lateral nonuniformity of the carrier injection into the quantum, well before and after optical degradation, is attributed to diffusion and electromigration of hydrogen, induced by mechanical stress. The metallization of the p-contact may be the source of mechanical stress.« less

Conceptual design and experiments of electrochemistry-flushing technology for the remediation of historically Cr(Ⅵ)-contaminated soil.

PubMed

Li, Dong; Sun, Delin; Hu, Siyang; Hu, Jing; Yuan, Xingzhong

2016-02-01

A conceptual design and experiments, electrochemistry-flushing (E-flushing), using electrochemistry to enhance flushing efficiency for the remediation of Cr(Ⅵ)-contaminated soil is presented. The rector contained three compartments vertically superposed. The upper was airtight cathode compartment containing an iron-cathode. The middle was soil layer. The bottom was anode compartment containing an iron-anode and connected to a container by circulation pumps. H2 and OH(-) ions were produced at cathode. H2 increased the gas pressure in cathode compartment and drove flushing solution into soil layer forming flushing process. OH(-) ions entered into soil layer by eletromigration and hydraulic flow to enhance the desorption of Cr(Ⅵ). High potential gradient was applied to accelerate the electromigration of desorbed Cr(Ⅵ) ions and produced joule heat to increase soil temperature to enhance Cr(Ⅵ) desorption. In anode compartment, Fe(2+) ions produced at iron-anode reduced the desorbed Cr(Ⅵ) into Cr(3+) ions, which reacted with OH(-) ions forming Cr(OH)3. Experimental results show that Cr(Ⅵ) removal efficiency of E-flushing experiments was more than double of flushing experiments and reached the maximum of removal efficiency determined by desorption kinetics. All electrochemistry processes were positively used in E-flushing technology. Copyright © 2015 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Menglu; Tu, K. N., E-mail: kntu@ucla.edu; Kim, Dong Wook

Thermal-crosstalk induced thermomigration failure in un-powered microbumps has been found in 2.5D integrated circuit (IC) circuit. In 2.5D IC, a Si interposer was used between a polymer substrate and a device chip which has transistors. The interposer has no transistors. If transistors are added to the interposer chip, it becomes 3D IC. In our test structure, there are two Si chips placed horizontally on a Si interposer. The vertical connections between the interposer and the Si chips are through microbumps. We powered one daisy chain of the microbumps under one Si chip; however, the un-powered microbumps in the neighboring chipmore » are failed with big holes in the solder layer. We find that Joule heating from the powered microbumps is transferred horizontally to the bottom of the neighboring un-powered microbumps, and creates a large temperature gradient, in the order of 1000 °C/cm, through the un-powered microbumps in the neighboring chip, so the latter failed by thermomigration. In addition, we used synchrotron radiation tomography to compare three sets of microbumps in the test structure: microbumps under electromigration, microbumps under thermomigration, and microbumps under a constant temperature thermal annealing. The results show that the microbumps under thermomigration have the largest damage. Furthermore, simulation of temperature distribution in the test structure supports the finding of thermomigration.« less

Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals.

PubMed

Luo, Yanqi; Khoram, Parisa; Brittman, Sarah; Zhu, Zhuoying; Lai, Barry; Ong, Shyue Ping; Garnett, Erik C; Fenning, David P

2017-11-01

Optoelectronic devices based on hybrid perovskites have demonstrated outstanding performance within a few years of intense study. However, commercialization of these devices requires barriers to their development to be overcome, such as their chemical instability under operating conditions. To investigate this instability and its consequences, the electric field applied to single crystals of methylammonium lead bromide (CH 3 NH 3 PbBr 3 ) is varied, and changes are mapped in both their elemental composition and photoluminescence. Synchrotron-based nanoprobe X-ray fluorescence (nano-XRF) with 250 nm resolution reveals quasi-reversible field-assisted halide migration, with corresponding changes in photoluminescence. It is observed that higher local bromide concentration is correlated to superior optoelectronic performance in CH 3 NH 3 PbBr 3 . A lower limit on the electromigration rate is calculated from these experiments and the motion is interpreted as vacancy-mediated migration based on nudged elastic band density functional theory (DFT) simulations. The XRF mapping data provide direct evidence of field-assisted ionic migration in a model hybrid-perovskite thin single crystal, while the link with photoluminescence proves that the halide stoichiometry plays a key role in the optoelectronic properties of the perovskite. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanical integrity of a carbon nanotube/copper-based through-silicon via for 3D integrated circuits: a multi-scale modeling approach.

PubMed

Awad, Ibrahim; Ladani, Leila

2015-12-04

Carbon nanotube (CNT)/copper (Cu) composite material is proposed to replace Cu-based through-silicon vias (TSVs) in micro-electronic packages. The proposed material is believed to offer extraordinary mechanical and electrical properties and the presence of CNTs in Cu is believed to overcome issues associated with miniaturization of Cu interconnects, such as electromigration. This study introduces a multi-scale modeling of the proposed TSV in order to evaluate its mechanical integrity under mechanical and thermo-mechanical loading conditions. Molecular dynamics (MD) simulation was used to determine CNT/Cu interface adhesion properties. A cohesive zone model (CZM) was found to be most appropriate to model the interface adhesion, and CZM parameters at the nanoscale were determined using MD simulation. CZM parameters were then used in the finite element analysis in order to understand the mechanical and thermo-mechanical behavior of composite TSV at micro-scale. From the results, CNT/Cu separation does not take place prior to plastic deformation of Cu in bending, and separation does not take place when standard thermal cycling is applied. Further investigation is recommended in order to alleviate the increased plastic deformation in Cu at the CNT/Cu interface in both loading conditions.

High power vertical stacked and horizontal arrayed diode laser bar development based on insulation micro-channel cooling (IMCC) and hard solder bonding technology

NASA Astrophysics Data System (ADS)

Wang, Boxue; Jia, Yangtao; Zhang, Haoyu; Jia, Shiyin; Liu, Jindou; Wang, Weifeng; Liu, Xingsheng

2018-02-01

An insulation micro-channel cooling (IMCC) has been developed for packaging high power bar-based vertical stack and horizontal array diode lasers, which eliminates many issues caused in its congener packaged by commercial copper formed micro-channel cooler(MCC), such as coefficient of thermal expansion (CTE) mismatch between cooler and diode laser bar, high coolant quality requirement (DI water) and channel corrosion and electro-corrosion induced by DI water if the DI-water quality is not well maintained The IMCC cooler separates water flow route and electrical route, which allows tap-water as coolant without electro-corrosion and therefore prolongs cooler lifetime dramatically and escalated the reliability of these diode lasers. The thickness of ceramic and copper in an IMCC cooler is well designed to minimize the CTE mismatch between laser bar and cooler, consequently, a very low "SMILE" of the laser bar can be achieved for small fast axis divergence after collimation. In additional, gold-tin hard solder bonding technology was also developed to minimize the risk of solder electromigration at high current density and thermal fatigue under hard-pulse operation mode. Testing results of IMCC packaged diode lasers are presented in this report.

Modeling and experimental characterization of electromigration in interconnect trees

NASA Astrophysics Data System (ADS)

Thompson, C. V.; Hau-Riege, S. P.; Andleigh, V. K.

1999-11-01

Most modeling and experimental characterization of interconnect reliability is focussed on simple straight lines terminating at pads or vias. However, laid-out integrated circuits often have interconnects with junctions and wide-to-narrow transitions. In carrying out circuit-level reliability assessments it is important to be able to assess the reliability of these more complex shapes, generally referred to as `trees.' An interconnect tree consists of continuously connected high-conductivity metal within one layer of metallization. Trees terminate at diffusion barriers at vias and contacts, and, in the general case, can have more than one terminating branch when they include junctions. We have extended the understanding of `immortality' demonstrated and analyzed for straight stud-to-stud lines, to trees of arbitrary complexity. This leads to a hierarchical approach for identifying immortal trees for specific circuit layouts and models for operation. To complete a circuit-level-reliability analysis, it is also necessary to estimate the lifetimes of the mortal trees. We have developed simulation tools that allow modeling of stress evolution and failure in arbitrarily complex trees. We are testing our models and simulations through comparisons with experiments on simple trees, such as lines broken into two segments with different currents in each segment. Models, simulations and early experimental results on the reliability of interconnect trees are shown to be consistent.

A review of combinations of electrokinetic applications.

PubMed

Moghadam, Mohamad Jamali; Moayedi, Hossein; Sadeghi, Masoud Mirmohamad; Hajiannia, Alborz

2016-12-01

Anthropogenic activities contaminate many lands and underground waters with dangerous materials. Although polluted soils occupy small parts of the land, the risk they pose to plants, animals, humans, and groundwater is too high. Remediation technologies have been used for many years in order to mitigate pollution or remove pollutants from soils. However, there are some deficiencies in the remediation in complex site conditions such as low permeability and complex composition of some clays or heterogeneous subsurface conditions. Electrokinetic is an effective method in which electrodes are embedded in polluted soil, usually vertically but in some cases horizontally, and a low direct current voltage gradient is applied between the electrodes. The electric gradient initiates movement of contaminants by electromigration (charged chemical movement), electro-osmosis (movement of fluid), electrolysis (chemical reactions due to the electric field), and diffusion. However, sites that are contaminated with heavy metals or mixed contaminants (e.g. a combination of organic compounds with heavy metals and/or radionuclides) are difficult to remediate. There is no technology that can achieve the best results, but combining electrokinetic with other remediation methods, such as bioremediation and geosynthetics, promises to be the most effective method so far. This review focuses on the factors that affect electrokinetic remediation and the state-of-the-art methods that can be combined with electrokinetic.

Intermetallic Growth Induced Large-Scale Void Growth and Cracking Failure in Line-Type Cu/Solder/Cu Joints Under Current Stressing

NASA Astrophysics Data System (ADS)

Chen, Zhuo; Tian, Wenya; Li, Junhui; Zhu, Wenhui

2018-04-01

In order to study the electromigration (EM) behavior of solder joints in electronics packaging, especially under high-current and high-temperature working conditions, line-type Cu/solder/Cu butting samples were prepared to observe the microstructural evolution under 1.0 × 104 A/cm2 current stressing. A prominent polarity effect was found such that the Cu6Sn5 intermetallic compound (IMC) layer at the anode side, which thickened linearly with time, was much thicker than that at the cathode side. Compared to the samples subjected to thermal aging at the same temperature of 180°C, EM enhanced the Cu3Sn growth at both the anode and the cathode. Two distinct types of damage were observed after extended duration of current stressing. Back-flow of Cu into Cu3Sn was found at the Cu3Sn/Cu6Sn5 interface of the anode side, causing large voids, while strip cracks developed at the cathode solder/Cu6Sn5 interface, causing a significant increase of joint electrical resistance. With the mass transport characteristics that determine the IMC growth and vacancy accumulation analyzed in detail at each interface, formation mechanisms of the two types of damages are discussed.

Influence of reinforcement mesh configuration for improvement of concrete durability

NASA Astrophysics Data System (ADS)

Pan, Chong-gen; Jin, Wei-liang; Mao, Jiang-hong; Zhang, Hua; Sun, Li-hao; Wei, Dong

2017-10-01

Steel bar in concrete structures under harsh environmental conditions, such as chlorine corrosion, seriously affects its service life. Bidirectional electromigration rehabilitation (BIEM) is a new method of repair technology for reinforced concrete structures in such chloride corrosion environments. By applying the BIEM, chloride ions can be removed from the concrete and the migrating corrosion inhibit can be moved to the steel surface. In conventional engineering, the concrete structure is often configured with a multi-layer steel mesh. However, the effect of the BIEM in such structures has not yet been investigated. In this paper, the relevant simulation test is carried out to study the migration law of chloride ions and the migrating corrosion inhibitor in a concrete specimen with complex steel mesh under different energizing modes. The results show that the efficiency of the BIEM increases 50% in both the monolayer steel mesh and the double-layer steel mesh. By using the single-sided BIEM, 87% of the chloride ions are removed from the steel surface. The different step modes can affect the chloride ion removal. The chloride ions within the range of the reinforcement protective cover are easier to be removed than those in the concrete between the two layers of steel mesh. However, the amount of migrating corrosion inhibitor is larger in the latter circumstances.

Understanding the poor iontophoretic transport of lysozyme across the skin: when high charge and high electrophoretic mobility are not enough.

PubMed

Dubey, S; Kalia, Y N

2014-06-10

The original aim of the study was to investigate the transdermal iontophoretic delivery of lysozyme and to gain further insight into the factors controlling protein electrotransport. Initial experiments were done using porcine skin. Lysozyme transport was quantified by using an activity assay based on the lysis of Micrococcus lysodeikticus and was corrected for the release of endogenous enzyme from the skin during current application. Cumulative iontophoretic permeation of lysozyme during 8h at 0.5mA/cm(2) (0.7mM; pH6) was surprisingly low (5.37±3.46μg/cm(2) in 8h) as compared to electrotransport of cytochrome c (Cyt c) and ribonuclease A (RNase A) under similar conditions (923.0±496.1 and 170.71±92.13μg/cm(2), respectively) - despite its having a higher electrophoretic mobility. The focus of the study then became to understand and explain the causes of its poor iontophoretic transport. Lowering formulation pH to 5 increased histidine protonation in the protein and decreased the ionisation of fixed negative charges in the skin (pI ~4.5) and resulted in a small but statistically significant increase in permeation. Co-iontophoresis of acetaminophen revealed a significant inhibition of electroosmosis; inhibition factors of 12-16 were indicative of strong lysozyme binding to skin. Intriguingly, lidocaine electrotransport, which is due almost exclusively to electromigration, was also decreased (approximately 2.7-fold) following skin pre-treatment by lysozyme iontophoresis (cf. iontophoresis of buffer solution) - suggesting that lysozyme was also able to influence subsequent cation electromigration. In order to elucidate the site of skin binding, different porcine skin models were tested (dermatomed skin with thicknesses of 250 and 750μm, tape-stripped skin and heat-separated dermis). Although no difference was seen between permeation across 250 and 750μm dermatomed skin (13.57±12.20 and 5.37±3.46μg/cm(2), respectively), there was a statistically significant increase across tape-stripped skin and heat-separated dermis (36.86±7.48 and 43.42±13.11μg/cm(2), respectively) - although transport was still much less than that seen across intact skin for Cyt c or RNase A. Furthermore, electroosmotic inhibition factors fell to 2.2 and 1.0 for tape-stripped skin and heat-separated dermis - indicating that lysozyme affected convective solvent flow through interactions with the epidermis and predominantly the stratum corneum. Finally, cation exchange and hydrophobic interaction chromatography confirmed that although lysozyme had greater positive charge than Cyt c or RNase A under the conditions used for iontophoresis, it also possessed the highest surface hydrophobicity, which may have facilitated the interactions with the transport pathways and encouraged aggregation in the skin microenvironment. Thus, high charge and electrophoretic mobility seem to be inadequate descriptors to predict the transdermal iontophoretic transport of proteins whose complex three dimensional structures can facilitate interactions with cutaneous transport pathways. Copyright © 2014 Elsevier B.V. All rights reserved.

Electromembrane extraction of gonadotropin-releasing hormone agonists from plasma and wastewater samples.

PubMed

Nojavan, Saeed; Bidarmanesh, Tina; Mohammadi, Ali; Yaripour, Saeid

2016-03-01

In the present study, for the first time electromembrane extraction followed by high performance liquid chromatography coupled with ultraviolet detection was optimized and validated for quantification of four gonadotropin-releasing hormone agonist anticancer peptides (alarelin, leuprolide, buserelin and triptorelin) in biological and aqueous samples. The parameters influencing electromigration were investigated and optimized. The membrane consists 95% of 1-octanol and 5% di-(2-ethylhexyl)-phosphate immobilized in the pores of a hollow fiber. A 20 V electrical field was applied to make the analytes migrate from sample solution with pH 7.0, through the supported liquid membrane into an acidic acceptor solution with pH 1.0 which was located inside the lumen of hollow fiber. Extraction recoveries in the range of 49 and 71% within 15 min extraction time were obtained in different biological matrices which resulted in preconcentration factors in the range of 82-118 and satisfactory repeatability (7.1 < RSD% < 19.8). The method offers good linearity (2.0-1000 ng/mL) with estimation of regression coefficient higher than 0.998. The procedure allows very low detection and quantitation limits of 0.2 and 0.6 ng/mL, respectively. Finally, it was applied to determination and quantification of peptides in human plasma and wastewater samples and satisfactory results were yielded. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electromigration of Contaminated Soil by Electro-Bioremediation Technique

NASA Astrophysics Data System (ADS)

Azhar, A. T. S.; Nabila, A. T. A.; Nurshuhaila, M. S.; Shaylinda, M. Z. N.; Azim, M. A. M.

2016-07-01

Soil contamination with heavy metals poses major environmental and human health problems. This problem needs an efficient method and affordable technological solution such as electro-bioremediation technique. The electro-bioremediation technique used in this study is the combination of bacteria and electrokinetic process. The aim of this study is to investigate the effectiveness of Pseudomonas putida bacteria as a biodegradation agent to remediate contaminated soil. 5 kg of kaolin soil was spiked with 5 g of zinc oxide. During this process, the anode reservoir was filled with Pseudomonas putida while the cathode was filled with distilled water for 5 days at 50 V of electrical gradient. The X-Ray Fluorescent (XRF) test indicated that there was a significant reduction of zinc concentration for the soil near the anode with 89% percentage removal. The bacteria count is high near the anode which is 1.3x107 cfu/gww whereas the bacteria count at the middle and near the cathode was 5.0x106 cfu/gww and 8.0x106 cfu/gww respectively. The migration of ions to the opposite charge of electrodes during the electrokinetic process resulted from the reduction of zinc. The results obtained proved that the electro-bioremediation reduced the level of contaminants in the soil sample. Thus, the electro-bioremediation technique has the potential to be used in the treatment of contaminated soil.

Frequency-dependent failure mechanisms of nanocrystalline gold interconnect lines under general alternating current

NASA Astrophysics Data System (ADS)

Luo, X. M.; Zhang, B.; Zhang, G. P.

2014-09-01

Thermal fatigue failure of metallization interconnect lines subjected to alternating currents (AC) is becoming a severe threat to the long-term reliability of micro/nanodevices with increasing electrical current density/power. Here, thermal fatigue failure behaviors and damage mechanisms of nanocrystalline Au interconnect lines on the silicon glass substrate have been investigated by applying general alternating currents (the pure alternating current coupled with a direct current (DC) component) with different frequencies ranging from 0.05 Hz to 5 kHz. We observed both thermal fatigue damages caused by Joule heating-induced cyclic strain/stress and electromigration (EM) damages caused by the DC component. Besides, the damage formation showed a strong electrically-thermally-mechanically coupled effect and frequency dependence. At lower frequencies, thermal fatigue damages were dominant and the main damage forms were grain coarsening with grain boundary (GB) cracking/voiding and grain thinning. At higher frequencies, EM damages took over and the main damage forms were GB cracking/voiding of smaller grains and hillocks. Furthermore, the healing effect of the reversing current was considered to elucidate damage mechanisms of the nanocrystalline Au lines generated by the general AC. Lastly, a modified model was proposed to predict the lifetime of the nanocrystalline metal interconnect lines, i.e., that was a competing drift velocity-based approach based on the threshold time required for reverse diffusion/healing to occur.

A new model for the spectral induced polarization signature of bacterial growth in porous media

NASA Astrophysics Data System (ADS)

Revil, A.; Atekwana, E.; Zhang, C.; Jardani, A.; Smith, S.

2012-09-01

The complex conductivity of porous materials and colloidal suspensions comprises two components: an in-phase conductivity associated with electromigration of the charge carriers and a quadrature conductivity associated with the reversible storage of the charges at some polarization length scales. We developed a quantitative model to investigate the frequency domain induced polarization response of suspensions of bacteria and bacteria growth in porous media. Induced polarization of bacteria (α polarization) is related to the properties of the electrical double layer of the bacteria. Surface conductivity and α polarization are due to the Stern layer of counterions occurring in a brush of polymers coating the surface of the bacteria. These phenomena can be related to their cation exchange capacity. The mobility of the counterions in this Stern layer is found to be very small (4.7 × 10-10 m2 s-1 V-1 at 25°C). This implies a very low relaxation frequency for the αpolarization of the bacteria cells (typically around 0.1-5 Hz), in agreement with experimental observations. This new model can be coupled to reactive transport modeling codes in which the evolution of bacterial populations are usually described by Monod kinetics. We show that the growth rate and endogenous decay coefficients of bacteria in a porous sand can be inferred nonintrusively from time-lapse frequency domain induced polarization data.

Product assurance technology for procuring reliable, radiation-hard, custom LSI/VLSI electronics

NASA Technical Reports Server (NTRS)

Buehler, M. G.; Allen, R. A.; Blaes, B. R.; Hicks, K. A.; Jennings, G. A.; Lin, Y.-S.; Pina, C. A.; Sayah, H. R.; Zamani, N.

1989-01-01

Advanced measurement methods using microelectronic test chips are described. These chips are intended to be used in acquiring the data needed to qualify Application Specific Integrated Circuits (ASIC's) for space use. Efforts were focused on developing the technology for obtaining custom IC's from CMOS/bulk silicon foundries. A series of test chips were developed: a parametric test strip, a fault chip, a set of reliability chips, and the CRRES (Combined Release and Radiation Effects Satellite) chip, a test circuit for monitoring space radiation effects. The technical accomplishments of the effort include: (1) development of a fault chip that contains a set of test structures used to evaluate the density of various process-induced defects; (2) development of new test structures and testing techniques for measuring gate-oxide capacitance, gate-overlap capacitance, and propagation delay; (3) development of a set of reliability chips that are used to evaluate failure mechanisms in CMOS/bulk: interconnect and contact electromigration and time-dependent dielectric breakdown; (4) development of MOSFET parameter extraction procedures for evaluating subthreshold characteristics; (5) evaluation of test chips and test strips on the second CRRES wafer run; (6) two dedicated fabrication runs for the CRRES chip flight parts; and (7) publication of two papers: one on the split-cross bridge resistor and another on asymmetrical SRAM (static random access memory) cells for single-event upset analysis.

The electrodeposition of multilayers on a polymeric substrate in Flexible Organic Light Emitting Diode (OLED)

NASA Astrophysics Data System (ADS)

Guedes, Andre F. S.; Guedes, Vilmar P.; Tartari, Simone; Cunha, Idaulo Jose

2016-09-01

The development of Organic Light Emitting Diode (OLED), using an optically transparent substrate material and organic semiconductor materials, has been widely utilized by the electronic industry when producing new technological products. The OLED are the base Poly(3,4-ethylenedioxythiophene), PEDOT, Poly(p-phenylenevinylene), PPV, and Polyaniline, PANI, were deposited in Indium Tin Oxide, ITO, and characterized by UV-Visible Spectroscopy (UV-Vis), Optical Parameters (OP) and Scanning Electron Microscopy (SEM). In addition, the thin film obtained by the deposition of PANI, prepared in perchloric acid solution, was identified through PANI-X1. The result obtained by UV-Vis has demonstrated that the PET/ITO/PEDOT/PPV/PANI-X1/Al layer does not have displacement of absorption for wavelengths greaters after spin-coating and electrodeposition. Thus, the spectral irradiance of the OLED informed the irradiance of 100 W/m2, and this result, compared with the standard Light Emitting Diode (LED), has indicated that the OLED has higher irradiance. After 1200 hours of electrical OLED tests, the appearance of nanoparticles visible for images by SEM, to the migration process of organic semiconductor materials, was present, then. Still, similar to the phenomenon of electromigration observed in connections and interconnections of microelectronic devices, the results have revealed a new mechanism of migration, which raises the passage of electric current in OLED.

Electroviscous Effects in Ceramic Nanofiltration Membranes.

PubMed

Farsi, Ali; Boffa, Vittorio; Christensen, Morten Lykkegaard

2015-11-16

Membrane permeability and salt rejection of a γ-alumina nanofiltration membrane were studied and modeled for different salt solutions. Salt rejection was predicted by using the Donnan-steric pore model, in which the extended Nernst-Planck equation was applied to predict ion transport through the pores. The solvent flux was modeled by using the Hagen-Poiseuille equation by introducing electroviscosity instead of bulk viscosity. γ-Alumina particles were used for ζ-potential measurements. The ζ-potential measurements show that monovalent ions did not adsorb on the γ-alumina surface, whereas divalent ions were highly adsorbed. Thus, for divalent ions, the model was modified, owing to pore shrinkage caused by ion adsorption. The ζ-potential lowered the membrane permeability, especially for membranes with a pore radius lower than 3 nm, a ζ-potential higher than 20 mV, and an ionic strength lower than 0.01 m. The rejection model showed that, for a pore radius lower than 3 nm and for solutions with ionic strengths lower than 0.01 m, there is an optimum ζ-potential for rejection, because of the concurrent effects of electromigration and convection. Hence, the model can be used as a prediction tool to optimize membrane perm-selectivity by designing a specific pore size and surface charge for application at specific ionic strengths and pH levels. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guo, Rui; Gao, Liming, E-mail: liming.gao@sjtu.edu.cn; Li, Ming, E-mail: mingli90@sjtu.edu.cn

As the continuous shrinkage of the interconnect line width in microelectronics devices, there is a growing concern about the electromigration (EM) failure of bonding wire. In addition, an innovative Ag–8Au–3Pd alloy wire has shown promise as an economical substitute for gold wire interconnects due to the cost pressure of gold in the last decade. In present study of the Ag–8Au–3Pd alloy wire, the surface diffusion occupied the dominant position during EM failure, and the activation energy was found to be 0.61 eV. In order to reveal the failure mechanism, the cross-sections of the Ag–8Au–3Pd alloy wire during EM were preparedmore » by focused ion beam (FIB) micro-machining for electron backscatter diffraction (EBSD) analysis. The microstructure evolution of the Ag–8Au–3Pd alloy wire was characterized by the grain size and grain boundary. As a result, the EM failure originates in the atom transportation, which causes grain size increasing and atom diffusion on the wire surface. - Highlights: • The activation energy of Ag–8Au–3Pd alloy wire was obtained as 0.61 eV. • During EM, the silver atoms diffused from negative to the positive terminal on the wire surface. • The microstructure (grain size and grain boundary) was characterized by FIB-EBSD. • During EM, the atom transportation was found to cause grain size growth and atom diffusion on the wire surface.« less

Transport of water and ions in partially water-saturated porous media. Part 1. Constitutive equations

NASA Astrophysics Data System (ADS)

Revil, A.

2017-05-01

I developed a model of cross-coupled flow in partially saturated porous media based on electrokinetic coupling including the effect of ion filtration (normal and reverse osmosis) and the multi-component nature of the pore water (wetting) phase. The model also handles diffusion and membrane polarization but is valid only for saturations above the irreducible water saturation. I start with the local Nernst-Planck and Stokes equations and I use a volume-averaging procedure to obtain the generalized Ohm, Fick, and Darcy equations with cross-coupling terms at the scale of a representative elementary volume of the porous rock. These coupling terms obey Onsager's reciprocity, which is a required condition, at the macroscale, to keep the total dissipation function of the system positive. Rather than writing the electrokinetic terms in terms of zeta potential (the double layer electrical potential on the slipping plane located in the pore water), I developed the model in terms of an effective charge density dragged by the flow of the pore water. This effective charge density is found to be strongly controlled by the permeability and the water saturation. I also developed an electrical conductivity equation including the effect of saturation on both bulk and surface conductivities, the surface conductivity being associated with electromigration in the electrical diffuse layer coating the grains. This surface conductivity depends on the CEC of the porous material.

A Single-Level Tunnel Model to Account for Electrical Transport through Single Molecule- and Self-Assembled Monolayer-based Junctions

PubMed Central

Garrigues, Alvar R.; Yuan, Li; Wang, Lejia; Mucciolo, Eduardo R.; Thompon, Damien; del Barco, Enrique; Nijhuis, Christian A.

2016-01-01

We present a theoretical analysis aimed at understanding electrical conduction in molecular tunnel junctions. We focus on discussing the validity of coherent versus incoherent theoretical formulations for single-level tunneling to explain experimental results obtained under a wide range of experimental conditions, including measurements in individual molecules connecting the leads of electromigrated single-electron transistors and junctions of self-assembled monolayers (SAM) of molecules sandwiched between two macroscopic contacts. We show that the restriction of transport through a single level in solid state junctions (no solvent) makes coherent and incoherent tunneling formalisms indistinguishable when only one level participates in transport. Similar to Marcus relaxation processes in wet electrochemistry, the thermal broadening of the Fermi distribution describing the electronic occupation energies in the electrodes accounts for the exponential dependence of the tunneling current on temperature. We demonstrate that a single-level tunnel model satisfactorily explains experimental results obtained in three different molecular junctions (both single-molecule and SAM-based) formed by ferrocene-based molecules. Among other things, we use the model to map the electrostatic potential profile in EGaIn-based SAM junctions in which the ferrocene unit is placed at different positions within the molecule, and we find that electrical screening gives rise to a strongly non-linear profile across the junction. PMID:27216489

Reliability Improvement By Adopting Ti-barrier Metal For Porous Low-k ILD Structure

NASA Astrophysics Data System (ADS)

Sakata, A.; Yamashita, S.; Omoto, S.; Hatano, M.; Wada, J.; Higashi, K.; Yamaguchi, H.; Yosho, T.; Imamizu, K.; Yamada, M.; Hasunuma, M.; Takahashi, S.; Yamada, A.; Hasegawa, T.; Motoyama, K.; Tagami, M.; Kitano, T.; Kaneko, H.

2007-10-01

Titanium (Ti) has been proposed as an excellent barrier metal (BM) material for ULSI's Cu metallization from the stand point of two characteristics. One is the oxidation property, especially for the porous low-k ILD materials for 45 nm node device; the other is the interface behavior of Ti with Cu. Both stress induced voiding (SIV) suppression and one order longer electromigration (EM) lifetime were obtained by the adoption of Ti-BM instead of the conventional Tantalum (Ta)-BM. SIV failure is accelerated in porous low-k ILD by the following steps; 1) BM oxidation by the absorbed moisture in porous low-k ILD, 2) Adhesion degradation caused by the BM oxidation results in micro delamination of Cu film (void nucleation), 3) Void growth induced by the stress gradient in the Cu interconnect. It has been considered that the small volume change of Ti oxidation and the existence of metallic Ti-O solid-solution phase would be the reason for control of moisture penetration from the low-k ILD materials. In addition, Ti/Cu intermetallic reaction and the segregation of Ti atoms at Cu grain boundaries suppress Cu migration at BM/Cu interface and Cu grain boundaries, respectively. This is supported by higher EM activation energy of Cu line with Ti-BM than that with Ta-BM. These phenomena contribute to higher interconnect reliability.

Al-Si-Cu/TiN multilayer interconnection and Al-Ge reflow sputtering technologies for quarter-micron devices

NASA Astrophysics Data System (ADS)

Kikkawa, Takamaro; Kikuta, Kuniko

1993-05-01

Issues of interconnection technologies for quarter-micron devices are the reliability of metal lines with quarter-micron feature sizes and the formation of contact-hole-plugs with high aspect ratios. This paper describes a TiN/Al-Si-Cu/TiN/Al-Si-Cu/TiN/Ti multilayer conductor structure as a quarter-micron interconnection technology and aluminum-germanium (Al-Ge) reflow sputtering as a contact-hole filling technology. The TiN/Al-Si-Cu/TiN/Al-Si-Cu/TiN/Ti multilayer conductor structure could suppress stress-induced voiding and improve the electromigration mean-time to failure. These improvements are attributed to the fact that the grain boundaries for the Al-Si-Cu film and the interfaces between the Al-Si-Cu and the TiN films are strengthened by the rigid intermetallic compound, TiAl3. The Al-Ge alloy reflow sputtering is a candidate for contact- and via-hole filling technologies in terms of reducing fabrication costs. The Al-Ge reflow sputtering achieved low temperature contact hole filling at 300 degree(s)C. Contact holes with a diameter of 0.25 micrometers and aspect ratio of 4 could be filled. This is attributed to the low eutectic temperature for Al-Ge (424 degree(s)C) and the effect of thin polysilicon underlayer on the enhancement of Al-Ge reflow.

Low power gas sensor array on flexible acetate substrate

NASA Astrophysics Data System (ADS)

Benedict, Samatha; Basu, Palash Kumar; Bhat, Navakanta

2017-07-01

In this paper, we present a novel approach of fabricating a low-cost and low power gas sensor array on flexible acetate sheets for sensing CO, SO2, H2 and NO2 gases. The array has four sensor elements with an integrated microheater which can be individually controlled enabling the monitoring of four gases. The thermal properties of the microheater characterized by IR imaging are presented. The microheater with an active area of 15 µm  ×  5 µm reaches a temperature of 300 °C, consuming 2 mW power, the lowest reported on flexible substrates. A sensing electrode is patterned on top of the microheater, and a nanogap (100 nm) is created by an electromigration process. This nanogap is bridged by four sensing materials doped with platinum, deposited using a solution dispensing technique. The sensing material characterization is completed using energy dispersive x-ray analysis. The sensing characteristics of ZnO for CO, V2O5 for SO2, SnO2 for H2 and WO3 for NO2 gases are studied at different microheater voltages. The sensing characteristics of ZnO at different bending angles is also studied, which shows that the microheater and the sensing material are intact without any breaking upto a bending angle of 20°. The ZnO CO sensor shows sensitivity of 146.2% at 1 ppm with good selectivity.

Single-step enantioselective amino acid flux analysis by capillary electrophoresis using on-line sample preconcentration with chemical derivatization.

PubMed

Ptolemy, Adam S; Tran, Lara; Britz-McKibbin, Philip

2006-07-15

Capillary electrophoresis (CE) represents a versatile platform for integrating sample pretreatment with chemical analysis because of its ability to tune analyte electromigration and band dispersion properties in discontinuous electrolyte systems. In this article, a single-step method that combines on-line sample preconcentration with in-capillary chemical derivatization is developed for rapid, sensitive, and enantioselective analysis of micromolar levels of amino acids that lack intrinsic chromophores by CE with UV detection. Time-resolved electrophoretic studies revealed two distinct stages of amino acid band narrowing within the original long sample injection plug occurring both prior to and after in-capillary labeling via zone passing by ortho-phthalaldehyde/N-acetyl l-cysteine (OPA/NAC). This technique enabled direct analysis of d-amino acids in a 95% enantiomeric excess mixture with sub-micromolar detection limits and minimal sample handling, where the capillary functions as a preconcentrator, microreactor, and chiral selector. On-line sample preconcentration with chemical derivatization CE (SPCD-CE) was applied to study the enantioselective amino acid flux in Escherichia coli bacteria cultures, which demonstrated a unique l-Ala efflux into the extracellular medium. New strategies for high-throughput analyses of low-abundance metabolites are important for understanding fundamental physiological processes in bacteria required for screening the efficacy of new classes of antibiotics as well as altered metabolism in genetically modified mutant strains.

Development of a fast capillary electrophoresis method for determination of carbohydrates in honey samples.

PubMed

Rizelio, Viviane Maria; Tenfen, Laura; da Silveira, Roberta; Gonzaga, Luciano Valdemiro; Costa, Ana Carolina Oliveira; Fett, Roseane

2012-05-15

In this study, the determination of fructose, glucose and sucrose by capillary electrophoresis (CE) was investigated. The tendency of the analyte to undergo electromigration dispersion and the buffer capacity were evaluated using the Peakmaster(®) software and considered in the optimization of the background electrolyte, which was composed of 20 mmol L(-1) sorbic acid, 0.2 mmol L(-1) CTAB and 40 mmol L(-1) NaOH at pH 12.2. Under optimal CE conditions, the separation of the substances investigated was achieved in less than 2 min. The detection limits for the three analytes were in the range of 0.022 and 0.029 g L(-1) and precision measurements within 0.62-4.69% were achieved. The proposed methodology was applied in the quantitative analysis by direct injection of in honey samples to determine the main sugars presents. The samples were previously dissolved in deionized water and filtered with no other sample treatment. The mean values for fructose, glucose and sucrose were in the ranges of 33.65-45.46 g 100g(-1), 24.63-35.06 g 100g(-1) and <0.22-1.32 g 100g(-1), respectively. The good analytical performance of the method makes it suitable for implementation in food laboratories for the routine analysis of honey samples. Copyright © 2012 Elsevier B.V. All rights reserved.

The trace analysis of microorganisms in real samples by combination of a filtration microcartridge and capillary isoelectric focusing.

PubMed

Horká, Marie; Horký, Jaroslav; Kubesová, Anna; Zapletalová, Eva; Slais, Karel

2011-07-01

Trace analysis of microorganisms in real biological samples needs very sensitive methods for their detection. Most procedures for detecting and quantifying pathogens require a sample preparation step including concentrating microorganisms from large sample volumes with high and reproducible efficiency. Electromigration techniques have great potential to include the preconcentration, separation, and detection of whole cells and therefore they can rapidly indicate the presence of pathogens. The preconcentration and separation of microorganisms from real suspensions utilising a combination of filtration and capillary isoelectric focusing was developed and the possibility for its application to real samples was verified. For our experiments, spores of Monilinia species and of Penicillium expansum were selected as model bioparticles, as they cause major losses in agrosystems. The isoelectric points of the spores of M. laxa, M. fructigena, M. fruticola, and P. expansum were determined and the method was verified using real samples taken directly from infected apples. The coupling of a filtration cartridge with a separation capillary can improve the detection limit of isoelectric focusing with UV detection by at least 4 orders of magnitude. Spores of M. fructigena and of M. laxa in numbers of hundreds of particles per milliliter were detected on a visually noninfected apple surface which was cross-contaminated during handling and storage. The efficiency of preconcentration and a preliminary identification was verified by the phenotyping technique after cultivation of the spores sampled from the apple surface.

Analyte concentration at the tip of a nanopipette.

PubMed

Calander, Nils

2009-10-15

Concentration of molecules within the tips of nanopipettes when applying a DC voltage is herein investigated using finite-element simulations. The ion concentrations and fluxes due to diffusion, electro-migration, and electro-osmotic flow, and the electric potential are determined by the simultaneous solution of the Nernst-Planck, Poisson, and Navier-Stokes equations within the water solution containing sodium and chloride ions and negatively charged molecules. The electric potential within the pipette glass wall is at the same time determined by the Poisson equation together with appropriate boundary conditions and accounts for a field effect through the wall. Fixed negative surface charge on both the internal and external glass surfaces of the nanopipette is included together with the field effect through the glass wall to account for the electric double layer and the electro-osmosis. The inclusion of the field effect through the pipette wall is new compared to previous modeling of similar structures and is shown to be crucial for the behavior at the tip. It is demonstrated that the concentration of molecules is a consequence of ionic charge accumulation at the tip screening the electric field, thereby slowing down the electrophoretic motion of the molecules, which is further slowed down or stopped by the oppositely directed electro-osmosis. It is also shown that the trapping is very sensitive to the properties of the molecule, that is, its electrophoretic mobility and diffusion coefficient, the properties of the pipette, the ionic strength of the solution, and the applied electric field.

Mechanisms of mineral membrane fouling growth modulated by pulsed modes of current during electrodialysis: evidences of water splitting implications in the appearance of the amorphous phases of magnesium hydroxide and calcium carbonate.

PubMed

Cifuentes-Araya, Nicolás; Astudillo-Castro, Carolina; Bazinet, Laurent

2014-07-15

Experiments revealed the fouling nature evolutions along different electrodialysis (ED) trials, and how it disappears when current pulsation acts repetitively on the interfaces of ion-exchange membranes (IEMs). Fouling was totally controlled on the diluate side of cation-exchange membrane (CEM) by the repetitive pulsation frequency of the higher on-duty ratios applied. They created steady water splitting proton-barriers that neutralized OH(-) leakage through the membrane, decreasing the interfacial pH, and fouling of the concentrate side. The anion-exchange membrane (AEM) on the diluate side was similarly protected, but it was fouled once water splitting OH(-) generation became either intense enough or excessively weak. Interestingly, amorphous magnesium hydroxide (AMH) stemmed on the CEM-diluate side from brucite under intense water splitting OH(-) generation, and/or strong OH(-) leakage electromigration through the membrane. Water dissociation and overlimiting current regimes triggered drastic water molecule removal from crystal lattices through an accelerated cascade water splitting reaction. Also, amorphous calcium carbonate (ACC) appeared on CEM under intense water splitting reaction, and disappeared once intense OH(-) leakage was allowed by the water splitting proton-barrier dissipation. Our findings have implications for membrane fouling control, as well as for the understanding of the growth behavior of CaCO3 and Mg(OH)2 species on electromembrane interfaces. Copyright © 2014 Elsevier Inc. All rights reserved.

Electromigration of Mn, Fe, Cu and Zn with citric acid in contaminated clay.

PubMed

Pazos, M; Gouveia, S; Sanroman, M A; Cameselle, C

2008-07-01

Metal reactivity, speciation and solubility have an important influence in its transportation through a porous matrix by electrokinetics and, therefore, they dramatically affect the removal efficiency. This work deals with the effect of solubility and transport competition among several metals (Mn, Fe, Cu and Zn) during their transport through polluted clay. The unenhancement electrokinetic treatment results in a limited removal of the tested metals because they were retained into the kaolinite sample by the penetration of the alkaline front. Metals showed a removal degree in accordance with the solubility of the corresponding hydroxide and its formation pH. In 7 days of treatment, the removal results were: 75.6% of Mn; 68.5% of Zn, 40.6% of Cu and 14.8% of Fe. In order to avoid the negative effects of the basic front generated at the cathode, two different techniques were proposed and tested: the addition of citric acid as complexing agent to the polluted kaolinite sample and the use of citric acid to control de pH on the cathode chamber. Both techniques are based on the capability of citric acid to act as a complexing and neutralizing agent. Almost complete removal of Mn, Cu and Zn was achieved when citric acid was used (as neutralizing or complexing agent). But Fe only reached 33% of removal because it formed a negatively charged complex with citrate that retarded its transportation to the cathode.

Fate of zinc in an electroplating sludge during electrokinetic treatments.

PubMed

Liu, Shou-Heng; Wang, H Paul

2008-08-01

Chemical structure of zinc in the electrokinetic treatments of an electroplating sludge has been studied by in situ extended X-ray absorption fine structural (EXAFS) and X-ray absorption near edge structural (XANES) spectroscopies in the present work. The least-square fitted XANES spectra indicate that the main zinc compounds in the sludge were ZnCO(3) (75%), ZnOSiO(2) (17%) and Zn(OH)(2) (7%). Zinc in the sludge possessed a Zn-O bond distance of 2.07 A with a coordination number (CN) of 5. In the second shells, the bond distance of Zn-(O)-Si was 3.05 A (CN=2). An increase of Zn-(O)-Si (0.05 A) with a decrease of its CN (from 5 to <1) was found in the early stage of the electrokinetic treatment. Prolong the electrokinetic treatment time to 180 min, about 34% of Zn(II) was dissolved into the aqueous phase and about 68% of Zn(II) in the sludge (or 23% of total zinc) was migrated to the cathode under the electric field (5 V cm(-1)). The dissolution and electromigration rates of Zn(II) in the sludge were 1.0 and 0.6 mmol h(-1)g(-1) sludge, respectively during the electrokinetic treatment. This work also exemplifies the utilization of in situ EXAFS and XANES for revealing speciation and possible reaction pathways during the course of zinc recycling from the sludge by electrokinetic treatments.

Insulation Resistance Degradation in Ni-BaTiO3 Multilayer Ceramic Capacitors

NASA Technical Reports Server (NTRS)

Liu, Donhang (David)

2015-01-01

Insulation resistance (IR) degradation in Ni-BaTiO3 multilayer ceramic capacitors has been characterized by the measurement of both time to failure and direct-current (DC) leakage current as a function of stress time under highly accelerated life test conditions. The measured leakage current-time dependence data fit well to an exponential form, and a characteristic growth time ?SD can be determined. A greater value of tau(sub SD) represents a slower IR degradation process. Oxygen vacancy migration and localization at the grain boundary region results in the reduction of the Schottky barrier height and has been found to be the main reason for IR degradation in Ni-BaTiO3 capacitors. The reduction of barrier height as a function of time follows an exponential relation of phi (??)=phi (0)e(exp -2?t), where the degradation rate constant ??=??o??(????/????) is inversely proportional to the mean time to failure (MTTF) and can be determined using an Arrhenius plot. For oxygen vacancy electromigration, a lower barrier height phi(0) will favor a slow IR degradation process, but a lower phi(0) will also promote electronic carrier conduction across the barrier and decrease the insulation resistance. As a result, a moderate barrier height phi(0) (and therefore a moderate IR value) with a longer MTTF (smaller degradation rate constant ??) will result in a minimized IR degradation process and the most improved reliability in Ni-BaTiO3 multilayer ceramic capacitors.

Ligand-enhanced electrokinetic remediation of metal-contaminated marine sediments with high acid buffering capacity.

PubMed

Masi, Matteo; Iannelli, Renato; Losito, Gabriella

2016-06-01

The suitability of electrokinetic remediation for removing heavy metals from dredged marine sediments with high acid buffering capacity was investigated. Laboratory-scale electrokinetic remediation experiments were carried out by applying two different voltage gradients to the sediment (0.5 and 0.8 V/cm) while circulating water or two different chelating agents at the electrode compartments. Tap water, 0.1 M citric acid and 0.1 M ethylenediaminetetraacetic acid (EDTA) solutions were used respectively. The investigated metals were Zn, Pb, V, Ni and Cu. In the unenhanced experiment, the acid front could not propagate due to the high acid buffering capacity of the sediments; the production of OH(-) ions at the cathode resulted in a high-pH environment causing the precipitation of CaCO3 and metal hydroxides. The use of citric acid prevented the formation of precipitates, but solubilisation and mobilisation of metal species were not sufficiently achieved. Metal removal was relevant when EDTA was used as the conditioning agent, and the electric potential was raised up to 0.8 V/cm. EDTA led to the formation of negatively charged complexes with metals which migrated towards the anode compartment by electromigration. This result shows that metal removal from sediments with high acid buffering capacity may be achieved by enhancing the electrokinetic process by EDTA addition when the acidification of the medium is not economically and/or environmentally sustainable.

Stable room-temperature thallium bromide semiconductor radiation detectors

NASA Astrophysics Data System (ADS)

Datta, A.; Fiala, J.; Becla, P.; Motakef, Shariar

2017-10-01

Thallium bromide (TlBr) is a highly efficient ionic semiconductor with excellent radiation detection properties. However, at room temperature, TlBr devices polarize under an applied electric field. This phenomenon not only degrades the charge collection efficiency of the detectors but also promotes chemical reaction of the metal electrodes with bromine, resulting in an unstable electric field and premature failure of the device. This drawback has been crippling the TlBr semiconductor radiation detector technology over the past few decades. In this exhaustive study, this polarization phenomenon has been counteracted using innovative bias polarity switching schemes. Here the highly mobile Br- species, with an estimated electro-diffusion velocity of 10-8 cm/s, face opposing electro-migration forces during every polarity switch. This minimizes the device polarization and availability of Br- ions near the metal electrode. Our results indicate that it is possible to achieve longer device lifetimes spanning more than 17 000 h (five years of 8 × 7 operation) for planar and pixelated radiation detectors using this technique. On the other hand, at constant bias, 2500 h is the longest reported lifetime with most devices less than 1000 h. After testing several biasing switching schemes, it is concluded that the critical bias switching frequency at an applied bias of 1000 V/cm is about 17 μHz. Using this groundbreaking result, it will now be possible to deploy this highly efficient room temperature semiconductor material for field applications in homeland security, medical imaging, and physics research.

Detection and Separation of Inorganic Cations in Natural, Potable, and Wastewater Samples Using Capillary Zone Electrophoresis with Indirect UV Detection

PubMed Central

Varden, Lara; Bou-Abdallah, Fadi

2017-01-01

Capillary zone electrophoresis (CZE) is a sensitive and rapid technique for determining traces of inorganic cations in water samples. CZE with indirect UV-diode array detection (CZE-DAD) was utilized to identify several inorganic cations in natural, potable, and wastewater samples. A pH 4.35 background electrolyte system was employed and consisted of 15 mM imidazole, 8 mM malonic acid, 2 mM 18-crown-6 ether as complexing agents, 10% v/v methanol as an organic modifier with indirect absorbance reference at 214 nm. The CZE method involved electromigration injection at 5 kV for 5 s, a separation voltage of 20 kV at 25°C, and a detection wavelength of 280 nm. Six main cations (ammonium NH4+, potassium K+, calcium Ca2+, sodium Na+, magnesium Mg2+, and lead Pb2+) were tested, and all but lead, were detected in the water samples at concentrations between 0.03 and 755 ppm with a detection limit ranging between 0.023 and 0.084 ppm. The successful evaluation of the proposed methodology allowed us to reliably detect and separate six metal ions in different water samples without any pretreatment. All water samples were collected from Northern New York towns and the Raquette River water system, the third longest river in New York State and the largest watershed of the central and western Adirondacks. PMID:29057144

Insulation Resistance Degradation in Ni-BaTiO3 Multilayer Ceramic Capacitors

NASA Technical Reports Server (NTRS)

Liu, Donhang David

2015-01-01

Insulation resistance (IR) degradation in NiBaTiO3 multilayer ceramic capacitors has been characterized by the measurement of both time to failure (TTF) and direct current leakage current as a function of stress time under highly accelerated life test conditions. The measured leakage current time dependence data fit well to an exponential form, and a characteristic growth time tau (sub SD) can be determined. A greater value of tau (sub SD) represents a slower IR degradation process. Oxygen vacancy migration and localization at the grain boundary region results in the reduction of the Schottky barrier height and has been found to be the main reason for IR degradation in NiBaTiO3 capacitors. The reduction of barrier height as a function oftime follows an exponential relation of phi (t ) = phi (0) e (exp -2Kt), where 13 the degradation rate constant K Koe (Ek/kT) is inversely proportional to the mean TTF (MTTF) and can be determined using an Arrhenius plot. For oxygen vacancy electromigration, a lower barrier height phi (0) will favor a slow IR degradation process, but a lower phi (0) will also promote electronic carrier conduction across the barrier and decrease the IR. As a result, a moderate barrier height phi (0) (and therefore a moderate IR value) with a longer MTTF (smaller degradation rate constant K) will result in a minimized IR degradation process and the most improved reliability in NiBaTiO3 multilayer ceramic capacitors.

Physicochemical effects on uncontaminated kaolinite due to electrokinetic treatment using inert electrodes.

PubMed

Liaki, Christina; Rogers, Christopher D F; Boardman, David I

2008-07-01

To determine the consequences of applying electrokinetics to clay soils, in terms of mechanisms acting and resulting effects on the clay, tests were conducted in which an electrical gradient was applied across controlled specimens of English China Clay (ECC) using 'inert' electrodes and a 'Reverse Osmosis' water feed to the electrodes (i.e., to mimic electrokinetic stabilisation without the stabiliser added or electrokinetic remediation without the contaminant being present). The specimens in which electromigration was induced over time periods of 3, 7, 14 and 28 days were subsequently tested for Atterberg Limits, undrained shear strength using a hand shear vane, water content, pH, conductivity and zeta potential. Water flowed through the system from anode to cathode and directly affected the undrained shear strength of the clay. Acid and alkali fronts were created around the anode and cathode, respectively, causing changes in the pH, conductivity and zeta potential of the soil. Variations in zeta potential were linked to flocculation and dispersion of the soil particles, thus raising or depressing the Liquid Limit and Plastic Limit, and influencing the undrained shear strength. Initial weakening around the anode and cathode was replaced by a regain of strength at the anode once acidic conditions had been created, while highly alkaline conditions at the cathode induced a marked improvement in strength. A novel means of indicating strength improvement by chemical means, i.e., free from water content effects, is presented to assist in interpretation of the results.

New pathway for the formation of metallic cubic phase Ge-Sb-Te compounds induced by an electric current

PubMed Central

Park, Yong-Jin; Cho, Ju-Young; Jeong, Min-Woo; Na, Sekwon; Joo, Young-Chang

2016-01-01

The novel discovery of a current-induced transition from insulator to metal in the crystalline phase of Ge2Sb2Te5 and GeSb4Te7 have been studied by means of a model using line-patterned samples. The resistivity of cubic phase Ge-Sb-Te compound was reduced by an electrical current (~1 MA/cm2), and the final resistivity was determined based on the stress current density, regardless of the initial resistivity and temperature, which indicates that the conductivity of Ge-Sb-Te compound can be modulated by an electrical current. The minimum resistivity of Ge-Sb-Te materials can be achieved at high kinetic rates by applying an electrical current, and the material properties change from insulating to metallic behavior without a phase transition. The current-induced metal transition is more effective in GeSb4Te7 than Ge2Sb2Te5, which depends on the intrinsic vacancy of materials. Electromigration, which is the migration of atoms induced by a momentum transfer from charge carriers, can easily promote the rearrangement of vacancies in the cubic phase of Ge-Sb-Te compound. This behavior differs significantly from thermal annealing, which accompanies a phase transition to the hexagonal phase. This result suggests a new pathway for modulating the electrical conductivity and material properties of chalcogenide materials by applying an electrical current. PMID:26902593

Localized Pulsed Electrodeposition Process for Three-Dimensional Printing of Nanotwinned Metallic Nanostructures.

PubMed

Daryadel, Soheil; Behroozfar, Ali; Morsali, S Reza; Moreno, Salvador; Baniasadi, Mahmoud; Bykova, Julia; Bernal, Rodrigo A; Minary-Jolandan, Majid

2018-01-10

Nanotwinned-metals (nt-metals) offer superior mechanical (high ductility and strength) and electrical (low electromigration) properties compared to their nanocrystalline (nc) counterparts. These properties are advantageous in particular for applications in nanoscale devices. However, fabrication of nt-metals has been limited to films (two-dimensional) or template-based (one-dimensional) geometries, using various chemical and physical processes. In this Letter, we demonstrate the ambient environment localized pulsed electrodeposition process for direct printing of three-dimensional (3D) freestanding nanotwinned-Copper (nt-Cu) nanostructures. 3D nt-Cu structures were additively manufactured using pulsed electrodeposition at the tip of an electrolyte-containing nozzle. Focused ion beam (FIB) and transmission electron microscopy (TEM) analysis revealed that the printed metal was fully dense, and was mostly devoid of impurities and microstructural defects. FIB and TEM images also revealed nanocrystalline-nanotwinned-microstructure (nc-nt-microstructure), and confirmed the formation of coherent twin boundaries in the 3D-printed Cu. Mechanical properties of the 3D-printed nc-nt-Cu were characterized by direct printing (FIB-less) of micropillars for in situ SEM microcompression experiments. The 3D-printed nc-nt-Cu exhibited a flow stress of over 960 MPa, among the highest ever reported, which is remarkable for a 3D-printed material. The microstructure and mechanical properties of the nc-nt-Cu were compared to those of nc-Cu printed using the same process under direct current (DC) voltage.

Controllable Switching Filaments Prepared via Tunable and Well-Defined Single Truncated Conical Nanopore Structures for Fast and Scalable SiOx Memory.

PubMed

Kwon, Soonbang; Jang, Seonghoon; Choi, Jae-Wan; Choi, Sanghyeon; Jang, Sukjae; Kim, Tae-Wook; Wang, Gunuk

2017-12-13

The controllability of switching conductive filaments is one of the central issues in the development of reliable metal-oxide resistive memory because the random dynamic nature and formation of the filaments pose an obstacle to desirable switching performance. Here, we introduce a simple and novel approach to control and form a single silicon nanocrystal (Si-NC) filament for use in SiO x memory devices. The filament is formed with a confined vertical nanoscale gap by using a well-defined single vertical truncated conical nanopore (StcNP) structure. The physical dimensions of the Si-NC filaments such as number, size, and length, which have a significant influence on the switching properties, can be simply engineered by the breakdown of an Au wire through different StcNP structures. In particular, we demonstrate that the designed SiO x memory junction with a StcNP of pore depth of ∼75 nm and a bottom diameter of ∼10 nm exhibited a switching speed of up to 6 ns for both set and reset process, significantly faster than reported SiO x memory devices. The device also exhibited a high ON-OFF ratio, multistate storage ability, acceptable endurance, and retention stability. The influence of the physical dimensions of the StcNP on the switching features is discussed based on the simulated temperature profiles of the Au wire and the nanogap size generated inside the StcNP structure during electromigration.

Time-resolved mapping of water diffusion coefficients in a working soft actuator device.

PubMed

Naji, Leila; Chudek, John A; Baker, Richard T

2008-08-14

Diffusion-weighted imaging was employed to spatially map the distribution of the diffusion coefficient of water, D, in bare, water-soaked, Li(+)-exchanged, cast Nafion and in an ionic polymer-metal composite (IPMC) soft actuator element, prepared from this bare Nafion by impregnation with Pt electrodes. D was evaluated in two orthogonal directions: along one of the long dimensions of the sample (Dx) and through its thickness (Dz). D-maps of the IPMC element were obtained both in the absence of an applied potential and in situ during the application of a 3 V dc potential across the thickness of the sample. In the bare Nafion, D-maps showed uniform values of both Dx and Dz of about 6 x 10 (-10) m(2) s(-1). In the IPMC two effects were observed: (i) D at the electroded surfaces of the IPMC was higher than at the center of the sample; (ii) this difference was much greater in Dz than in Dx . Both effects were explained by the influence of the impregnated Pt electrodes on polymer structure. The D-maps in the electrochemical measurements showed high values of D (up to 8 x 10(-10) m(2) s(-1)) at the cathode and low values (from 1 x 10(-10) m(2) s(-1)) at the anode. This was explained in terms of the effect on the Nafion nanostructure of the forced electro-migration of Li(H2O)x(+) species toward the cathode.

Excitation of propagating spin waves by pure spin current

NASA Astrophysics Data System (ADS)

Demokritov, Sergej

Recently it was demonstrated that pure spin currents can be utilized to excite coherent magnetization dynamics, which enables development of novel magnetic nano-oscillators. Such oscillators do not require electric current flow through the active magnetic layer, which can help to reduce the Joule power dissipation and electromigration. In addition, this allows one to use insulating magnetic materials and provides an unprecedented geometric flexibility. The pure spin currents can be produced by using the spin-Hall effect (SHE). However, SHE devices have a number of shortcomings. In particular, efficient spin Hall materials exhibit a high resistivity, resulting in the shunting of the driving current through the active magnetic layer and a significant Joule heating. These shortcomings can be eliminated in devices that utilize spin current generated by the nonlocal spin-injection (NLSI) mechanism. Here we review our recent studies of excitation of magnetization dynamics and propagating spin waves by using NLSI. We show that NLSI devices exhibit highly-coherent dynamics resulting in the oscillation linewidth of a few MHz at room temperature. Thanks to the geometrical flexibility of the NLSI oscillators, one can utilize dipolar fields in magnetic nano-patterns to convert current-induced localized oscillations into propagating spin waves. The demonstrated systems exhibit efficient and controllable excitation and directional propagation of coherent spin waves characterized by a large decay length. The obtained results open new perspectives for the future-generation electronics using electron spin degree of freedom for transmission and processing of information on the nanoscale.

Sample preconcentration with chemical derivatization in capillary electrophoresis. Capillary as preconcentrator, microreactor and chiral selector for high-throughput metabolite screening.

PubMed

Ptolemy, Adam S; Britz-McKibbin, Philip

2006-02-17

New strategies for integrating sample pretreatment with chemical analyses under a single format is required for rapid, sensitive and enantioselective analyses of low abundance metabolites in complex biological samples. Capillary electrophoresis (CE) offers a unique environment for controlling analyte/reagent band dispersion and electromigration properties using discontinuous electrolyte systems. Recent work in our laboratory towards developing a high-throughput CE platform for low abundance metabolites via on-line sample preconcentration with chemical derivatization (SPCD) is primarily examined in this review, as there have been surprisingly only a few strategies reported in the literature to date. In-capillary sample preconcentration serves to enhance concentration sensitivity via electrokinetic focusing of long sample injection volumes for lower detection limits, whereas chemical derivatization by zone passing is used to expand detectability and selectivity, notably for enantiomeric resolution of metabolites lacking intrinsic chromophores using nanolitre volumes of reagent. Together, on-line SPCD-CE can provide over a 100-fold improvement in concentration sensitivity, shorter total analysis times, reduced sample handling and improved reliability for a variety of amino acid and amino sugar metabolites, which is also amenable to automated high-throughput screening. This review will highlight basic method development and optimization parameters relevant to SPCD-CE, including applications to bacterial metabolite flux and biomarker analyses. Insight into the mechanism of analyte focusing and labeling by SPCD-CE is also discussed, as well as future directions for continued research.

New barrierless copper-alloy film for future applications

NASA Astrophysics Data System (ADS)

Lin, Chon-Hsin Lin

2015-09-01

Since Cu metallization results in a conductivity and an electromigration resistance greater than those of Al, it has become popular for making Si-based interconnects for numerous devices in the field of microelectronics. Following the current trend of miniaturization required for most electronic components, there is a greater need for further size reduction in Si-based devices. The most critical side effect of size reduction is the increase in electronic scattering and resistivity when the barrier-layer thickness is further reduced. To explore advanced Cu-metallization methods and to develop a more economical manufacturing process for Cu-alloy films, the development of Cu materials having better quality and higher thermal stability becomes imperative for the metallization and annealing processes. For this purpose, we first fabricated Cu(GeNx) films and examined their thermal stability and electrical reliability after either cyclic or isothermal annealing. The excellent thermal and electrical properties make these new Cu-alloy films highly promising for applications that require more reliable and inexpensive copper interconnects. In this study, we fabricated Cu alloy films by doping a minute amount of Ge or GeNx, respectively, into the Cu films via barrierless Cu metallization, an inexpensive manufacturing method. Using these newly fabricated alloy films, we were able to eliminate or at least substantially reduce the detrimental interaction between the alloy and the barrierless Si substrate. The Cu(GeNx) films also exhibited high thermal stability, low resistivity and leakage current, and long time-dependent dielectric breakdown (TDDB) lifetimes, making such novel films a candidate for high-quality, economical, and more reliable Cu interconnects.

Analysis of current-driven oscillatory dynamics of single-layer homoepitaxial islands on crystalline conducting substrates

NASA Astrophysics Data System (ADS)

Dasgupta, Dwaipayan; Kumar, Ashish; Maroudas, Dimitrios

2018-03-01

We report results of a systematic study on the complex oscillatory current-driven dynamics of single-layer homoepitaxial islands on crystalline substrate surfaces and the dependence of this driven dynamical behavior on important physical parameters, including island size, substrate surface orientation, and direction of externally applied electric field. The analysis is based on a nonlinear model of driven island edge morphological evolution that accounts for curvature-driven edge diffusion, edge electromigration, and edge diffusional anisotropy. Using a linear theory of island edge morphological stability, we calculate a critical island size at which the island's equilibrium edge shape becomes unstable, which sets a lower bound for the onset of time-periodic oscillatory dynamical response. Using direct dynamical simulations, we study the edge morphological dynamics of current-driven single-layer islands at larger-than-critical size, and determine the actual island size at which the migrating islands undergo a transition from steady to time-periodic asymptotic states through a subcritical Hopf bifurcation. At the highest symmetry of diffusional anisotropy examined, on {111} surfaces of face-centered cubic crystalline substrates, we find that more complex stable oscillatory states can be reached through period-doubling bifurcation at island sizes larger than those at the Hopf points. We characterize in detail the island morphology and dynamical response at the stable time-periodic asymptotic states, determine the range of stability of these oscillatory states terminated by island breakup, and explain the morphological features of the stable oscillating islands on the basis of linear stability theory.

Ultrafast DNA sequencing on a microchip by a hybrid separation mechanism that gives 600 bases in 6.5 minutes.

PubMed

Fredlake, Christopher P; Hert, Daniel G; Kan, Cheuk-Wai; Chiesl, Thomas N; Root, Brian E; Forster, Ryan E; Barron, Annelise E

2008-01-15

To realize the immense potential of large-scale genomic sequencing after the completion of the second human genome (Venter's), the costs for the complete sequencing of additional genomes must be dramatically reduced. Among the technologies being developed to reduce sequencing costs, microchip electrophoresis is the only new technology ready to produce the long reads most suitable for the de novo sequencing and assembly of large and complex genomes. Compared with the current paradigm of capillary electrophoresis, microchip systems promise to reduce sequencing costs dramatically by increasing throughput, reducing reagent consumption, and integrating the many steps of the sequencing pipeline onto a single platform. Although capillary-based systems require approximately 70 min to deliver approximately 650 bases of contiguous sequence, we report sequencing up to 600 bases in just 6.5 min by microchip electrophoresis with a unique polymer matrix/adsorbed polymer wall coating combination. This represents a two-thirds reduction in sequencing time over any previously published chip sequencing result, with comparable read length and sequence quality. We hypothesize that these ultrafast long reads on chips can be achieved because the combined polymer system engenders a recently discovered "hybrid" mechanism of DNA electromigration, in which DNA molecules alternate rapidly between repeating through the intact polymer network and disrupting network entanglements to drag polymers through the solution, similar to dsDNA dynamics we observe in single-molecule DNA imaging studies. Most importantly, these results reveal the surprisingly powerful ability of microchip electrophoresis to provide ultrafast Sanger sequencing, which will translate to increased system throughput and reduced costs.

Ultrafast DNA sequencing on a microchip by a hybrid separation mechanism that gives 600 bases in 6.5 minutes

PubMed Central

Fredlake, Christopher P.; Hert, Daniel G.; Kan, Cheuk-Wai; Chiesl, Thomas N.; Root, Brian E.; Forster, Ryan E.; Barron, Annelise E.

2008-01-01

To realize the immense potential of large-scale genomic sequencing after the completion of the second human genome (Venter's), the costs for the complete sequencing of additional genomes must be dramatically reduced. Among the technologies being developed to reduce sequencing costs, microchip electrophoresis is the only new technology ready to produce the long reads most suitable for the de novo sequencing and assembly of large and complex genomes. Compared with the current paradigm of capillary electrophoresis, microchip systems promise to reduce sequencing costs dramatically by increasing throughput, reducing reagent consumption, and integrating the many steps of the sequencing pipeline onto a single platform. Although capillary-based systems require ≈70 min to deliver ≈650 bases of contiguous sequence, we report sequencing up to 600 bases in just 6.5 min by microchip electrophoresis with a unique polymer matrix/adsorbed polymer wall coating combination. This represents a two-thirds reduction in sequencing time over any previously published chip sequencing result, with comparable read length and sequence quality. We hypothesize that these ultrafast long reads on chips can be achieved because the combined polymer system engenders a recently discovered “hybrid” mechanism of DNA electromigration, in which DNA molecules alternate rapidly between reptating through the intact polymer network and disrupting network entanglements to drag polymers through the solution, similar to dsDNA dynamics we observe in single-molecule DNA imaging studies. Most importantly, these results reveal the surprisingly powerful ability of microchip electrophoresis to provide ultrafast Sanger sequencing, which will translate to increased system throughput and reduced costs. PMID:18184818

Desalination and hydrogen, chlorine, and sodium hydroxide production via electrophoretic ion exchange and precipitation.

PubMed

Shkolnikov, Viktor; Bahga, Supreet S; Santiago, Juan G

2012-08-28

We demonstrate and analyze a novel desalination method which works by electrophoretically replacing sodium and chloride in feed salt water with a pair of ions, calcium and carbonate, that react and precipitate out. The resulting calcium carbonate precipitate is benign to health, and can be filtered or settled out, yielding low ionic strength product water. The ion exchange and precipitation employs self-sharpening interfaces induced by movement of multiple ions in an electric field to prevent contamination of the product water. Simultaneously, the electrolysis associated with the electromigration produces hydrogen gas, chlorine gas, and sodium hydroxide. We conducted an experimental study of this method's basic efficacy to desalinate salt water from 100 to 600 mol m(-3) sodium chloride. We also present physicochemical models of the process, and analyze replacement reagents consumption, permeate recovery ratio, and energy consumption. We hypothesize that the precipitate can be recycled back to replacement reagents using the well-known, commercially implemented Solvay process. We show that the method's permeate recovery ratio is 58% to 46%, which is on par with that of reverse osmosis. We show that the method's energy consumption requirement over and above that necessary to generate electrolysis is 3 to 10 W h l(-1), which is on par with the energy consumed by state-of-the-art desalination methods. Furthermore, the method operates at ambient temperature and pressure, and uses no specialized membranes. The process may be feasible as a part of a desalination-co-generation facility: generating fresh water, hydrogen and chlorine gas, and sodium hydroxide.

Influences of electric current on the wettability and interfacial microstructure in Sn/Fe system

NASA Astrophysics Data System (ADS)

Shen, Ping; Gu, Yan; Yang, Nan-Nan; Zheng, Rui-Peng; Ren, Li-Hua

2015-02-01

The wettability of oxidized and clean Fe substrates by liquid Sn was investigated using a dispensed sessile drop method with and without the application of a direct current (DC) and their interfacial microstructures were compared. The initial contact angles were 107 ± 3° at 623 K when the Fe substrate was covered by an oxide film, and they did not show an appreciable decrease during isothermal dwells in the absence of DC application but progressively decreased to 42 ± 3° when a 7.5 ampere current was applied. However, in the case of the oxide film being removed by a high-vacuum pre-annealing treatment at 1073 K, the current and its polarity had a negligible effect on the wetting behavior. Nevertheless, they had a noticeable influence on the interfacial microstructure. In the absence of DC, the interface was covered by a product layer consisting of a single FeSn2 phase for the samples tested at 623 K and the FeSn2/FeSn2 grain boundaries were incompletely wetted by the Sn melt; whereas, under DC, the reaction layer was much thicker and the Sn melt wet well the FeSn2/FeSn2 grain boundaries. Moreover, a FeSn phase also formed as a result of enhanced mass transfer. The amount of the FeSn phase was larger and the grain boundary wetting of FeSn2 by liquid Sn was better for the current flowing from the molten Sn drop to the Fe substrate due to an electromigration effect.

Integrative metabolomics for characterizing unknown low-abundance metabolites by capillary electrophoresis-mass spectrometry with computer simulations.

PubMed

Lee, Richard; Ptolemy, Adam S; Niewczas, Liliana; Britz-McKibbin, Philip

2007-01-15

Characterization of unknown low-abundance metabolites in biological samples is one the most significant challenges in metabolomic research. In this report, an integrative strategy based on capillary electrophoresis-electrospray ionization-ion trap mass spectrometry (CE-ESI-ITMS) with computer simulations is examined as a multiplexed approach for studying the selective nutrient uptake behavior of E. coli within a complex broth medium. On-line sample preconcentration with desalting by CE-ESI-ITMS was performed directly without off-line sample pretreatment in order to improve detector sensitivity over 50-fold for cationic metabolites with nanomolar detection limits. The migration behavior of charged metabolites were also modeled in CE as a qualitative tool to support MS characterization based on two fundamental analyte physicochemical properties, namely, absolute mobility (muo) and acid dissociation constant (pKa). Computer simulations using Simul 5.0 were used to better understand the dynamics of analyte electromigration, as well as aiding de novo identification of unknown nutrients. There was excellent agreement between computer-simulated and experimental electropherograms for several classes of cationic metabolites as reflected by their relative migration times with an average error of <2.0%. Our studies revealed differential uptake of specific amino acids and nucleoside nutrients associated with distinct stages of bacterial growth. Herein, we demonstrate that CE can serve as an effective preconcentrator, desalter, and separator prior to ESI-MS, while providing additional qualitative information for unambiguous identification among isobaric and isomeric metabolites. The proposed strategy is particularly relevant for characterizing unknown yet biologically relevant metabolites that are not readily synthesized or commercially available.

Nanocrystallized SrHA/SrHA SrTiO3/SrTiO3 TiO2 multilayer coatings formed by micro-arc oxidation for photocatalytic application

NASA Astrophysics Data System (ADS)

Han, Y.; Chen, D. H.; Zhang, L.

2008-08-01

Novel photocatalytic coatings containing strontium hydroxyapatite (SrHA), strontium titanate (SrTiO3), and TiO2 were formed by micro-arc oxidation (MAO) in an aqueous electrolyte containing strontium acetate and β-glycerophosphate disodium at 530 V for 0.1-5 min. The structure evolution of the coatings was investigated as a function of processing time, and the photocatalytic activity of the coatings was evaluated by measuring the decomposition rate of methyl orange under ultraviolet irradiation. During the MAO processing of the coatings, it was observed that some granules appeared in the electrolyte adjacent to the anode and they increased in amount as the processing time was prolonged. The obtained results show that the granules are amorphous and poorly crystallized SrHA with negative charges. The coating prepared for 5 min presents a microporous structure of SrHA/SrHA-SrTiO3/SrTiO3-TiO2 multilayers, in which the SrHA outermost layer and the SrHA-SrTiO3 intermediate layer are nanocrystallized. It is suggested that formation of the granules, electro-migration of the granules onto the pre-formed layer, and crystallization of the adhered granules are possible mechanisms for the formation of a SrHA/SrHA-SrTiO3/SrTiO3-TiO2 multilayer coating. This coating shows much higher photocatalytic decomposition efficiency relative to the MAO-formed TiO2 coating, and is expected to have an important photocatalytic application.

Self-consistent modeling of electrochemical strain microscopy of solid electrolytes

DOE PAGES

Tselev, Alexander; Morozovska, Anna N.; Udod, Alexei; ...

2014-10-10

Electrochemical strain microscopy (ESM) employs a strong electromechanical coupling in solid ionic conductors to map ionic transport and electrochemical processes with nanometer-scale spatial resolution. To elucidate the mechanisms of the ESM image formation, we performed self-consistent numerical modeling of the electromechanical response in solid electrolytes under the probe tip in a linear, small-signal regime using the Boltzmann–Planck–Nernst–Einstein theory and Vegard's law while taking account of the electromigration and diffusion. We identified the characteristic time scales involved in the formation of the ESM response and found that the dynamics of the charge carriers in the tip-electrolyte system with blocking interfaces canmore » be described as charging of the diffuse layer at the tip-electrolyte interface through the tip contact spreading resistance. At the high frequencies used in the detection regime, the distribution of the charge carriers under the tip is governed by evanescent concentration waves generated at the tip-electrolyte interface. The ion drift length in the electric field produced by the tip determines the ESM response at high frequencies, which follows a 1/f asymptotic law. The electronic conductivity, as well as the electron transport through the electrode-electrolyte interface, do not have a significant effect on the ESM signal in the detection regime. The results indicate, however, that for typical solid electrolytes at room temperature, the ESM response originates at and contains information about the very surface layer of a sample, and the properties of the one-unit-cell-thick surface layer may significantly contribute to the ESM response, implying a high surface sensitivity and a high lateral resolution of the technique. On the other hand, it follows that a rigorous analysis of the ESM signals requires techniques that account for the discrete nature of a solid.« less

Partially Ionized Beam Deposition of Silicon-Dioxide and Aluminum Thin Films - Defects Generation.

NASA Astrophysics Data System (ADS)

Wong, Justin Wai-Chow

1987-09-01

Detect formation in SiO_2 and Al thin films and interfaces were studied using a partially ionized beam (PIB) deposition technique. The evaporated species (the deposition material) were partially ionized to give an ion/atom ratio of <=q0.1% and the substrate was biased at 0-5kV during the deposition. The results suggest that due to the ion bombardment, stoichiometric SiO_2 films can be deposited at a low substrate temperature (~300 ^circC) and low oxygen pressure (<=q10^{-4} Torr). Such deposition cannot be achieved using conventional evaporation-deposition techniques. However, traps and mobile ions were observed in the oxide and local melt-down was observed when a sufficiently high electric field was applied to the film. For the PIB Al deposition on the Si substrate, stable Al/Si Schottky contact was formed when the substrate bias was <=q1kV. For a substrate bias of 2.5kV, the capacitance of the Al/Si interface increased dramatically. A model of self-ion implantation with a p-n junction created by the Al^+ ion implantation was proposed and tested to explain the increase of the interface capacitance. Several deep level states at the Al/Si interface were observed using Deep Level Transient Spectroscopy (DLTS) technique when the film was deposited at a bias of 3kV. The PIB Al films deposited on the Si substrate showed unusually strong electromigration resistance under high current density operation. This phenomenon was explained by the highly oriented microstructure of the Al films created by the self-ion bombardment during deposition. These findings show that PIB has potential applications in a number of areas, including low temperature thin film deposition, and epitaxial growth of thin films in the microelectronics thin film industry.

In Situ Bioremediation of Chlorinated Ethenes in Hydraulically-Tight Sediments: Challenges and Limitations

NASA Astrophysics Data System (ADS)

Zhang, M.; Yoshikawa, M.; Takeuchi, M.; Komai, T.

2011-12-01

Chlorinated ethenes, like perchloroethene (PCE) and trichloroethene (TCE), have been widely used by many industries, especially in developed countries like Japan. Because of their wide applications, lack of proper regulation, poor handing, storage and disposal practices in the past, chlorinated ethenes have become a type of the most prevalent contaminants for soils and groundwater pollution. For the sake of their degradability, bioremediation has been considered as a potentially cost-effective and environmentally friendly approach for cleanup of chlorinated ethenes in situ. In this presentation, we briefly overview the status of soil and groundwater pollution, the recent amendment of the Soil Contamination Countermeasures Act in Japan, comparison between the bioremediation and other techniques like pump and treat, and the mechanisms of reductive dechlorination, direct oxidation and co-metabolism of chlorinated ethenes. We then introduce and discuss some recent challenges and advancements in in-situ bioremediation including technologies for accelerating bio-degradation of chlorinated ethenes, technologies for assessing diffusive properties of dissolved hydrogen in hydraulically-tight soil samples, and combination of bioremediation with other techniques like electro-kinetic approach. Limiting factors that may cause incomplete remediation and/or ineffectiveness of bioremediation are examined from biochemical, geochemical and hydro-geological aspects. This study reconfirmed and illustrated that: 1) The key factor for an effective bioremediation is how to disperse a proper accelerating agent throughout the polluted strata, 2) The effective diffusion coefficient of dissolved hydrogen in geologic media is relatively big and is almost independent on their permeability, and 3) To effectively design and perform an accelerated bioremediation, a combination of natural migration with pressurized injection and/or other approaches, like electro-migration, for stimulating mass transport could be necessary depending on the hydraulic properties, like porosity and permeability of a stratum.

Metal-filled carbon nanotube based optical nanoantennas: bubbling, reshaping, and in situ characterization.

PubMed

Fan, Zheng; Tao, Xinyong; Cui, Xudong; Fan, Xudong; Zhang, Xiaobin; Dong, Lixin

2012-09-21

Controlled fabrication of metal nanospheres on nanotube tips for optical antennas is investigated experimentally. Resembling soap bubble blowing using a straw, the fabrication process is based on nanofluidic mass delivery at the attogram scale using metal-filled carbon nanotubes (m@CNTs). Two methods have been investigated including electron-beam-induced bubbling (EBIB) and electromigration-based bubbling (EMBB). EBIB involves the bombardment of an m@CNT with a high energy electron beam of a transmission electron microscope (TEM), with which the encapsulated metal is melted and flowed out from the nanotube, generating a metallic particle on a nanotube tip. In the case where the encapsulated materials inside the CNT have a higher melting point than what the beam energy can reach, EMBB is an optional process to apply. Experiments show that, under a low bias (2.0-2.5 V), nanoparticles can be formed on the nanotube tips. The final shape and crystallinity of the nanoparticles are determined by the cooling rate. Instant cooling occurs with a relatively large heat sink and causes the instant shaping of the solid deposit, which is typically similar to the shape of the molten state. With a smaller heat sink as a probe, it is possible to keep the deposit in a molten state. Instant cooling by separating the deposit from the probe can result in a perfect sphere. Surface and volume plasmons characterized with electron energy loss spectroscopy (EELS) prove that resonance occurs between a pair of as-fabricated spheres on the tip structures. Such spheres on pillars can serve as nano-optical antennas and will enable devices such as scanning near-field optical microscope (SNOM) probes, scanning anodes for field emitters, and single molecule detectors, which can find applications in bio-sensing, molecular detection, and high-resolution optical microscopy.

Potassium Sodium Niobate-Based Lead-Free Piezoelectric Multilayer Ceramics Co-Fired with Nickel Electrodes.

PubMed

Kawada, Shinichiro; Hayashi, Hiroyuki; Ishii, Hideki; Kimura, Masahiko; Ando, Akira; Omiya, Suetake; Kubodera, Noriyuki

2015-11-03

Although lead-free piezoelectric ceramics have been extensively studied, many problems must still be overcome before they are suitable for practical use. One of the main problems is fabricating a multilayer structure, and one solution attracting growing interest is the use of lead-free multilayer piezoelectric ceramics. The paper reviews work that has been done by the authors on lead-free alkali niobate-based multilayer piezoelectric ceramics co-fired with nickel inner electrodes. Nickel inner electrodes have many advantages, such as high electromigration resistance, high interfacial strength with ceramics, and greater cost effectiveness than silver palladium inner electrodes. However, widely used lead zirconate titanate-based ceramics cannot be co-fired with nickel inner electrodes, and silver palladium inner electrodes are usually used for lead zirconate titanate-based piezoelectric ceramics. A possible alternative is lead-free ceramics co-fired with nickel inner electrodes. We have thus been developing lead-free alkali niobate-based multilayer ceramics co-fired with nickel inner electrodes. The normalized electric-field-induced thickness strain ( S max / E max ) of a representative alkali niobate-based multilayer ceramic structure with nickel inner electrodes was 360 pm/V, where S max denotes the maximum strain and E max denotes the maximum electric field. This value is about half that for the lead zirconate titanate-based ceramics that are widely used. However, a comparable value can be obtained by stacking more ceramic layers with smaller thicknesses. In the paper, the compositional design and process used to co-fire lead-free ceramics with nickel inner electrodes are introduced, and their piezoelectric properties and reliabilities are shown. Recent advances are introduced, and future development is discussed.

Spatiotemporal pH dynamics in concentration polarization near ion-selective membranes.

PubMed

Andersen, Mathias B; Rogers, David M; Mai, Junyu; Schudel, Benjamin; Hatch, Anson V; Rempe, Susan B; Mani, Ali

2014-07-08

We present a detailed analysis of the transient pH dynamics for a weak, buffered electrolyte subject to voltage-driven transport through an ion-selective membrane. We show that pH fronts emanate from the concentration polarization zone next to the membrane and that these propagating fronts change the pH in the system several units from its equilibrium value. The analysis is based on a 1D model using the unsteady Poisson-Nernst-Planck equations with nonequilibrium chemistry and without assumptions of electroneutrality or asymptotically thin electric double layers. Nonequilibrium chemical effects, especially for water splitting, are shown to be important for the dynamical and spatiotemporal evolution of the pH fronts. Nonetheless, the model also shows that at steady state the assumption of chemical equilibrium can still lead to good approximations of the global pH distribution. Moreover, our model shows that the transport of the hydronium ion in the extended space charge region is governed by a balance between electromigration and water self-ionization. On the basis of this observation, we present a simple model showing that the net flux of the hydronium ion is proportional to the length of the extended space charge region and the water self-ionization rate. To demonstrate these effects in practice, we have adopted the experiment of Mai et al. (Mai, J.; Miller, H.; Hatch, A. V. Spatiotemporal Mapping of Concentration Polarization Induced pH Changes at Nanoconstrictions. ACS Nano 2012, 6, 10206) as a model problem, and by including the full chemistry and transport, we show that the present model can capture the experimentally observed pH fronts. Our model can, among other things, be used to predict and engineer pH dynamics, which can be essential to the performance of membrane-based systems for biochemical separation and analysis.

Numerical modelling of electrochemical polarization around charged metallic particles

NASA Astrophysics Data System (ADS)

Bücker, Matthias; Undorf, Sabine; Flores Orozco, Adrián; Kemna, Andreas

2017-04-01

We extend an existing analytical model and carry out numerical simulations to study the polarization process around charged metallic particles immersed in an electrolyte solution. Electro-migration and diffusion processes in the electrolyte are described by the Poisson-Nernst-Planck system of partial differential equations. To model the surface charge density, we consider a time- and frequency-invariant electric potential at the particle surface, which leads to the build-up of a static electrical double layer (EDL). Upon excitation by an external electric field at low frequencies, we observe the superposition of two polarization processes. On the one hand, the induced dipole moment on the metallic particle leads to the accumulation of opposite charges in the electrolyte. This charge polarization corresponds to the long-known response of uncharged metallic particles. On the other hand, the unequal cation and anion concentrations in the EDL give rise to a salinity gradient between the two opposite sides of the metallic particle. The resulting concentration polarization enhances the magnitude of the overall polarization response. Furthermore, we use our numerical model to study the effect of relevant model parameters such as surface charge density and ionic strength of the electrolyte on the resulting spectra of the effective conductivity of the composite model system. Our results do not only give interesting new insight into the time-harmonic variation of electric potential and ion concentrations around charged metallic particle. They are also able to reduce incongruities between earlier model predictions and geophysical field and laboratory measurements. Our model thereby improves the general understanding of IP signatures of metallic particles and represents the next step towards a quantitative interpretation of IP imaging results. Part of this research is funded by the Austrian Federal Ministry of Science, Research and Economy under the Raw Materials Initiative.

Mobilization of phenol and dichlorophenol in unsaturated soils by non-uniform electrokinetics.

PubMed

Luo, Qishi; Zhang, Xihui; Wang, Hui; Qian, Yi

2005-06-01

The poor mobility of organic pollutants in contaminated sites frequently results in slow remediation processes. Organics, especially hydrophobic compounds, are generally retained strongly in soil matrix as a result of sorption, sequestration, or even formation into non-aqueous-phase liquids and their mobility is thus greatly reduced. The objective of this study was to evaluate the feasibility of using non-uniform electrokinetic transport processes to enhance the mobility of organic pollutants in unsaturated soils with no injection reagents. Phenol and 2,4-dichlorophenol (2,4-DCP), and kaolin and a natural sandy loam soil were selected as model organics and soils, respectively. The results showed that non-uniform electrokinetics can accelerate the desorption and movement of phenol and 2,4-DCP in unsaturated soils. Electromigration and electroosmotic flow were the main driving forces, and their role in the mobilization of phenol and 2,4-DCP varied with soil pH. The movement of 2,4-DCP in the sandy loam towards the anode (about 1.0 cmd(-1)V(-1)) was 1.0-1.5 cmd(-1)V(-1) slower than that in the kaolin soil, but about 0.5 cmd(-1)V(-1) greater than that of phenol in the sandy loam. When the sandy loam was adjusted to pH 9.3, the movement of phenol and 2,4-DCP towards the anode was about twice and five times faster than that at pH 7.7, respectively. The results also demonstrated that the movement of phenol and 2,4-DCP in soils can be easily controlled by regulating the operational mode of electric field. It is believed that non-uniform electrokinetics has the potential for practical application to in situ remediation of organics-contaminated sites.

Potassium Sodium Niobate-Based Lead-Free Piezoelectric Multilayer Ceramics Co-Fired with Nickel Electrodes

PubMed Central

Kawada, Shinichiro; Hayashi, Hiroyuki; Ishii, Hideki; Kimura, Masahiko; Ando, Akira; Omiya, Suetake; Kubodera, Noriyuki

2015-01-01

Although lead-free piezoelectric ceramics have been extensively studied, many problems must still be overcome before they are suitable for practical use. One of the main problems is fabricating a multilayer structure, and one solution attracting growing interest is the use of lead-free multilayer piezoelectric ceramics. The paper reviews work that has been done by the authors on lead-free alkali niobate-based multilayer piezoelectric ceramics co-fired with nickel inner electrodes. Nickel inner electrodes have many advantages, such as high electromigration resistance, high interfacial strength with ceramics, and greater cost effectiveness than silver palladium inner electrodes. However, widely used lead zirconate titanate-based ceramics cannot be co-fired with nickel inner electrodes, and silver palladium inner electrodes are usually used for lead zirconate titanate-based piezoelectric ceramics. A possible alternative is lead-free ceramics co-fired with nickel inner electrodes. We have thus been developing lead-free alkali niobate-based multilayer ceramics co-fired with nickel inner electrodes. The normalized electric-field-induced thickness strain (Smax/Emax) of a representative alkali niobate-based multilayer ceramic structure with nickel inner electrodes was 360 pm/V, where Smax denotes the maximum strain and Emax denotes the maximum electric field. This value is about half that for the lead zirconate titanate-based ceramics that are widely used. However, a comparable value can be obtained by stacking more ceramic layers with smaller thicknesses. In the paper, the compositional design and process used to co-fire lead-free ceramics with nickel inner electrodes are introduced, and their piezoelectric properties and reliabilities are shown. Recent advances are introduced, and future development is discussed. PMID:28793646

E-field induced resistive switch in metal/praseodymium calcium manganite interfaces: A model for future nonvolatile memory devices

NASA Astrophysics Data System (ADS)

Das, Nilanjan

Among the various candidates for non-volatile random access memory (RAM), interfacial resistive switch in Ag/Pr0.7Ca0.3 MnO3 (PCMO) configuration has drawn major attention in recent years due to its potential as a high storage density (˜ terabyte) device. However, the diverse nature of the resistive switch in different systems makes the development of a unifying model for its underlying physics very difficult. This dissertation will address both issues, namely, characterization of switches for device applications and development of a system-independent generic model, in detail. In our work, we have studied the properties electric pulse induced interfacial switch in electrode/PCMO system. A very fast speed ("write speed") of 100 ns, threshold ("programming voltage") as low as 2 V (for micro electrodes), and non-volatility ("data retention") of switched states have been achieved. A clear distinction between fast switch and sub-threshold slow quasistatic-dc switch has been made. Results obtained from time-dependence studies and impedance spectroscopy suggest that defect creation/annihilation, such as broken bonds (under very high field at interface, 107V/cm), is likely the mechanism for the sub-micros fast switching. On the other hand, slow accumulative process, such as electromigration of point defects, are responsible for the subthreshold quasi-dc switch. Scanning probe imaging has revealed the nanoscale inhomogeneity of the switched surfaces, essential for observing a resistive switch. Evolution of such structures has been observed under surface pre-training. Device scalability has been tested by creating reversible modification of surface conductivities with atomic force microscopy, thus creating the "nano-switch" (limited to a region of 10--100 nm).

Mathematical modeling based evaluation and simulation of boron removal in bioelectrochemical systems.

PubMed

Ping, Qingyun; Abu-Reesh, Ibrahim M; He, Zhen

2016-11-01

Boron removal is an arising issue in desalination plants due to boron's toxicity. As an emerging treatment concept, bioelectrochemical systems (BES) can achieve potentially cost-effective boron removal by taking advantage of cathodic-produced alkali. Prior studies have demonstrated successful removal of boron in microbial desalination cells (MDCs) and microbial fuel cells (MFCs), both of which are representative BES. Herein, mathematical models were developed to further evaluate boron removal by different BES and understand the key operating factors. The models delivered very good prediction of the boron concentration in the MDC integrated with Donnan Dialysis (DD) system with the lowest relative root-mean-square error (RMSE) of 0.00%; the predication of the MFC performance generated the highest RMSE of 18.55%. The model results of salt concentration, solution pH, and current generation were well fitted with experimental data for RMSE values mostly below 10%. The long term simulation of the MDC-DD system suggests that the accumulation of salt in the catholyte/stripping solution could have a positive impact on the removal of boron due to osmosis-driven convection. The current generation in the MDC may have little influence on the boron removal, while in the MFC the current-driven electromigration can contribute up to 40% of boron removal. Osmosis-induced convection transport of boron could be the major driving force for boron removal to a low level <2mgL(-1). The ratio between the anolyte and the catholyte flow rates should be kept >22.2 in order to avoid boron accumulation in the anolyte effluent. Copyright © 2016 Elsevier B.V. All rights reserved.

Hair analysis for abused drugs by capillary zone electrophoresis with field-amplified sample stacking.

PubMed

Tagliaro, F; Manetto, G; Crivellente, F; Scarcella, D; Marigo, M

1998-04-05

The present paper describes the methodological optimisation and validation of a capillary zone electrophoresis method for the determination of morphine, cocaine and 3,4-methylenedioxymethamphetamine (MDMA) in hair, with injection based on field-amplified sample stacking. Diode array UV absorption detection was used to improve analytical selectivity and identification power. Analytical conditions: running buffer 100 mM potassium phosphate adjusted to pH 2.5 with phosphoric acid, applied potential 10 kV, temperature 20 degrees C, injection by electromigration at 10 kV for 10 s, detection by UV absorption at the fixed wavelength of 200 nm or by recording the full spectrum between 190 and 400 nm. Injection conditions: the dried hair extracts were reconstituted with a low-conductivity solvent (0.1 mM formic acid), the injection end of the capillary was dipped in water for 5 s without applying pressure (external rinse step), then a plug of 0.1 mM phosphoric acid was loaded by applying 0.5 psi for 10 s and, finally, the sample was injected electrokinetically at 10 kV for 10 s. Under the described conditions, the limit of detection was 2 ng/ml for MDMA, 8 ng/ml for cocaine and 6 ng/ml for morphine (with a signal-to-noise ratio of 5). The lowest concentration suitable for recording interpretable spectra was about 10-20-times the limit of detection of each analyte. The intraday and day-to-day reproducibility of migration times (n = 6), with internal standardisation, was characterised by R.S.D. values < or = 0.6%; peak area R.S.D.s were better than 10% in intraday and than 15% in day-to-day experiments. Analytical linearity was good with R2 better than 0.9990 for all the analytes.

Electrokinetic treatment of polluted soil at pilot level coupled to an advanced oxidation process of its wastewater

NASA Astrophysics Data System (ADS)

Ochoa, B.; Ramos, L.; Garibay, A.; Pérez-Corona, M.; Cuevas, M. C.; Cárdenas, J.; Teutli, M.; Bustos, E.

2016-02-01

Soil contaminated with hydrocarbons is a current problem of great importance. These contaminants may be toxic, can retain water and block gas exchange with the atmosphere, which produces a poor-quality soil unsuitable for ecological health. Electroremediation is among the treatments for the removal of such contaminants. In this research, a pilot-level electroremediation test was applied using a circular arrangement of electrodes with a Ti cathode at the middle of the cell surrounded by six IrO2-Ta2O5 | Ti anodes. The presence of an NaOH electrolyte helps to develop the electromigration and electro-osmosis of gasoline molecules (at 1126 mg kg-1) surrounded by Na+ ions. The hydrocarbons are directed towards the cathode and subsequently removed in an aqueous Na+ - hydrocarbon solution, and the -OH migrates to the anode. During electrokinetic treatment, the physicochemical characteristics of the soil close to either the cathode or anode and at the half-cell were evaluated during the three weeks of treatment. During that time, more than 80% of hydrocarbons were removed. Hydrocarbons removed by the electrokinetic treatment of gasoline-polluted soil were collected in a central wastewater compartment and subsequently treated with a Fenton-type advanced oxidation process. This achieved more than 70% mineralization of the hydrocarbons to CO2 and H2O within 1.5 h; its low toxicity status was verified using the Deltatox® kit test. With this approach, the residual water complied with the permissible limits of COD, pH, and electrical conductivity for being discharged into water bodies, according to Mexican norm NOM-001-SEMARNAT-1996.

Probabilistic immortality of Cu damascene interconnects

NASA Astrophysics Data System (ADS)

Hau-Riege, Stefan P.

2002-02-01

We have studied electromigration short-line effects in Cu damascene interconnects through experiments on lines of various lengths L, stressed at a variety of current densities j, and embedded in different dielectric materials. We observed two modes of resistance evolution: Either the resistance of the lines remains constant for the duration of the test, so that the lines are considered immortal, or the lines fail due to abrupt open-circuit failure. The resistance was not observed to gradually increase and then saturate, as commonly observed in Al-based interconnects, because the barrier is too thin and resistive to serve as a redundant current path should voiding occur. The critical stress for void nucleation was found to be smaller than 41 MPa, since voiding occurred even under the mildest test conditions of j=2 MA/cm2 and L=10.5 μm at 300 °C. A small fraction of short Cu lines failed even at low current densities, which deems necessary a concept of probabilistic immortality rather than deterministic immortality. Experiments and modeling suggest that the probability of immortality is described by (jL2/B), where B is the effective elastic modulus of the metallization scheme. By contrast, the immortality of Al-based interconnects with shunt layers is described by (jL) if no voids nucleate, and (jL/B) if voids do nucleate. Even though the phenomenology of short-line effects differs for Al- and Cu-based interconnects, the immortality of interconnects of either materials system can be explained by the phenomena of nucleation barriers for void formation and void-growth saturation. The differences are due solely to the absence of a shunt layer and the low critical stress for void nucleation in the case of Cu.

Accelerated Metastable Solid-liquid Interdiffusion Bonding with High Thermal Stability and Power Handling

NASA Astrophysics Data System (ADS)

Huang, Ting-Chia; Smet, Vanessa; Kawamoto, Satomi; Pulugurtha, Markondeya R.; Tummala, Rao R.

2018-01-01

Emerging high-performance systems are driving the need for advanced packaging solutions such as 3-D integrated circuits (ICs) and 2.5-D system integration with increasing performance and reliability requirements for off-chip interconnections. Solid-liquid interdiffusion (SLID) bonding resulting in all-intermetallic joints has been proposed to extend the applicability of solders, but faces fundamental and manufacturing challenges hindering its wide adoption. This paper introduces a Cu-Sn SLID interconnection technology, aiming at stabilization of the microstructure in the Cu6Sn5 metastable phase rather than the usual stable Cu3Sn phase. This enables formation of a void-free interface yielding higher mechanical strength than standard SLID bonding, as well as significantly reducing the transition time. The metastable SLID technology retains the benefits of standard SLID with superior I/O pitch scalability, thermal stability and current handling capability, while advancing assembly manufacturability. In the proposed concept, the interfacial reaction is controlled by introducing Ni(P) diffusion barrier layers, designed to effectively isolate the metastable Cu6Sn5 phase preventing any further transformation. Theoretical diffusion and kinetic models were applied to design the Ni-Cu-Sn interconnection stack to achieve the targeted joint composition. A daisy chain test vehicle was used to demonstrate this technology as a first proof of concept. Full transition to Cu6Sn5 was successfully achieved within a minute at 260°C as confirmed by scanning electron microscope (SEM) and x-ray energy dispersive spectroscopy (XEDS) analysis. The joint composition was stable through 10× reflow, with outstanding bond strength averaging 90 MPa. The metastable SLID interconnections also showed excellent electromigration performance, surviving 500 h of current stressing at 105 A/cm2 at 150°C.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lawrence R. Sita

Ferrocene-based molecular components for nanoelectronics offer a number of distinct advantages relative to all carbon frameworks due to metal-centered molecular states that should be closer in energy to the Fermi levels of the metal electrodes in metal / molecule / metal heterojunctions. Given this, the overall goal of the project was to investigate the conduction physics of a variety of proposed ferrocene diode / transistor designs in order to address the fundamental question; can electron transport within nm-length scale structures be modulated in a controlled fashion? During the funded period, substantial progress towards achieving this goal was made by surmountingmore » a number of scientific and technical obstacles. More specifically, a concise and general synthetic route to several mono- and diferrocene dithiols and monothiols was achieved that now allows for the directed and controlled assembly of a variety of metal / molecule /metal test structures for the single molecule conductance measurements and the fabrication of self-assembled monolayers (SAMs) on Au(111) that are amenable to quantitative electrochemical characterization of electron-transfer rates. Most importantly, by using an electromigrated test structure, reproducible I/V data for one of the ferrocene dithiol molecules have been collected which exhibit surprisingly high conductance. Exceptional agreement of this result with theory serves to substantiate the original hypothesis that metal-centered states within a molecular bridge can indeed serve to establish higher conductance relative to all-organic molecular bridges. Overall, the successful demonstration of the ability of ferrocene-molecular frameworks to serve as exceptional molecular conductors will play an important role in the continued evolution in design of molecular components for nanoelectronic devices, which in turn, will have a positive impact on the science and potential technologies associated with these systems.« less

Reliability and Characteristics of Wafer-Level Chip-Scale Packages under Current Stress

NASA Astrophysics Data System (ADS)

Chen, Po-Ying; Kung, Heng-Yu; Lai, Yi-Shao; Hsiung Tsai, Ming; Yeh, Wen-Kuan

2008-02-01

In this work, we present a novel approach and method for elucidating the characteristics of wafer-level chip-scale packages (WLCSPs) for electromigration (EM) tests. The die in WLCSP was directly attached to the substrate via a soldered interconnect. The shrinking of the area of the die that is available for power, and the solder bump also shrinks the volume and increases the density of electrons for interconnect efficiency. The bump current density now approaches to 106 A/cm2, at which point the EM becomes a significant reliability issue. As known, the EM failure depends on numerous factors, including the working temperature and the under bump metallization (UBM) thickness. A new interconnection geometry is adopted extensively with moderate success in overcoming larger mismatches between the displacements of components during current and temperature changes. Both environments and testing parameters for WLCSP are increasingly demanded. Although failure mechanisms are considered to have been eliminated or at least made manageable, new package technologies are again challenging its process, integrity and reliability. WLCSP technology was developed to eliminate the need for encapsulation to ensure compatibility with smart-mount technology (SMT). The package has good handing properties but is now facing serious reliability problems. In this work, we investigated the reliability of a WLCSP subjected to different accelerated current stressing conditions at a fixed ambient temperature of 125 °C. A very strong correlation exists between the mean time to failure (MTTF) of the WLCSP test vehicle and the mean current density that is carried by a solder joint. A series of current densities were applied to the WLCSP architecture; Black's power law was employed in a failure mode simulation. Additionally, scanning electron microscopy (SEM) was adopted to determine the differences existing between high- and low-current-density failure modes.

Electrical field: a historical review of its application and contributions in wastewater sludge dewatering.

PubMed

Mahmoud, Akrama; Olivier, Jérémy; Vaxelaire, Jean; Hoadley, Andrew F A

2010-04-01

Electric field-assisted dewatering, also called electro-dewatering, is a technology in which a conventional dewatering mechanism such a pressure dewatering is combined with electrokinetic effects to realize an improved liquid/solids separation, to increase the final dry solids content and to accelerate the dewatering process with low energy consumption compared to thermal drying. Electro-dewatering is not a new idea, but the practical industrial applications have been limited to niche areas in soil mechanics, civil engineering, and the ceramics industry. Recently, it has received great attention, specially, in the fields of fine-particle sludge, gelatinous sludge, sewage sludge, pharmaceutical industries, food waste and bull kelp, which could not be successfully dewatered with conventional mechanical methods. This review focuses on the scientific and practical aspects of the application of an electrical field in laboratory/industrial dewatering, and discusses this in relation to conventional dewatering techniques. A comprehensive bibliography of research in the electro-dewatering of wastewater sludges is included. As the fine-particle suspensions possess a surface charge, usually negative, they are surrounded by a layer with a higher density of positive charges, the electric double layer. When an electric field is applied, the usually negative charged particles move towards the electrode of the opposite charge. The water, commonly with cations, is driven towards the negative electrode. Electro-dewatering thus involves the well-known phenomena of electrophoresis, electro-osmosis, and electromigration. Following a detailed outline of the role of the electric double layer and electrokinetic phenomena, an analysis of the components of applied voltage and their significance is presented from an electrochemical viewpoint. The aim of this elementary analysis is to provide a fundamental understanding of the different process variables and configurations in order to identify potential improvements. Also discussed herein is the investigation of the electrical behaviour of a porous medium, with particular emphasis on porous medium conductivity determination. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Diffuse charge dynamics in ionic thermoelectrochemical systems.

PubMed

Stout, Robert F; Khair, Aditya S

2017-08-01

Thermoelectrics are increasingly being studied as promising electrical generators in the ongoing search for alternative energy sources. In particular, recent experimental work has examined thermoelectric materials containing ionic charge carriers; however, the majority of mathematical modeling has been focused on their steady-state behavior. Here, we determine the time scales over which the diffuse charge dynamics in ionic thermoelectrochemical systems occur by analyzing the simplest model thermoelectric cell: a binary electrolyte between two parallel, blocking electrodes. We consider the application of a temperature gradient across the device while the electrodes remain electrically isolated from each other. This results in a net voltage, called the thermovoltage, via the Seebeck effect. At the same time, the Soret effect results in migration of the ions toward the cold electrode. The charge dynamics are described mathematically by the Poisson-Nernst-Planck equations for dilute solutions, in which the ion flux is driven by electromigration, Brownian diffusion, and thermal diffusion under a temperature gradient. The temperature evolves according to the heat equation. This nonlinear set of equations is linearized in the (experimentally relevant) limit of a "weak" temperature gradient. From this, we show that the time scale on which the thermovoltage develops is the Debye time, 1/Dκ^{2}, where D is the Brownian diffusion coefficient of both ion species, and κ^{-1} is the Debye length. However, the concentration gradient due to the Soret effect develops on the bulk diffusion time, L^{2}/D, where L is the distance between the electrodes. For thin diffuse layers, which is the condition under which most real devices operate, the Debye time is orders of magnitude less than the diffusion time. Therefore, rather surprisingly, the majority of ion motion occurs after the steady thermovoltage has developed. Moreover, the dynamics are independent of the thermal diffusion coefficients, which simply set the magnitude of the steady-state thermovoltage.

Nonequilibrium electrokinetic effects in beds of ion-permselective particles.

PubMed

Leinweber, Felix C; Tallarek, Ulrich

2004-12-21

Electrokinetic transport of fluorescent tracer molecules in a bed of porous glass beads was investigated by confocal laser scanning microscopy. Refractive index matching between beads and the saturating fluid enabled a quantitative analysis of intraparticle and extraparticle fluid-side concentration profiles. Kinetic data were acquired for the uptake and release of electroneutral and counterionic tracer under devised conditions with respect to constant pressure-driven flow through the device and the effect of superimposed electrical fields. Transport of neutral tracer is controlled by intraparticle mass transfer resistance which can be strongly reduced by electroosmotic flow, while steady-state distributions and bead-averaged concentrations are unaffected by the externally applied fields. Electrolytes of low ionic strength caused the transport through the charged (mesoporous) beads to become highly ion-permselective, and concentration polarization is induced in the bulk solution due to the superimposed fields. The depleted concentration polarization zone comprises extraparticle fluid-side mass transfer resistance. Ionic concentrations in this diffusion boundary layer decrease at increasing field strength, and the flux densities approach an upper limit. Meanwhile, intraparticle transport of counterions by electromigration and electroosmosis continues to increase and finally exceeds the transport from bulk solution into the beads. A nonequilibrium electrical double layer is induced which consists of mobile and immobile space charge regions in the extraparticle bulk solution and inside a bead, respectively. These electrical field-induced space charges form the basis for nonequilibrium electrokinetic phenomena. Caused by the underlying transport discrimination (intraparticle electrokinetic vs extraparticle boundary-layer mass transfer), the dynamic adsorption capacity for counterions can be drastically reduced. Further, the extraparticle mobile space charge region leads to nonlinear electroosmosis. Flow patterns can become highly chaotic, and electrokinetic instability mixing is shown to increase lateral dispersion. Under these conditions, the overall axial dispersion of counterionic tracer can be reduced by more than 2 orders of magnitude, as demonstrated by pulse injections.

Statistical analysis of electroconvection near an ion-selective membrane in the highly chaotic regime

NASA Astrophysics Data System (ADS)

Druzgalski, Clara; Mani, Ali

2016-11-01

We investigate electroconvection and its impact on ion transport in a model system comprised of an ion-selective membrane, an aqueous electrolyte, and an external electric field applied normal to the membrane. We develop a direct numerical simulation code to solve the governing Poisson-Nernst-Planck and Navier-Stokes equations in three dimensions using a specialized parallel numerical algorithm and sufficient resolution to capture the high frequency and high wavenumber physics. We show a comprehensive statistical analysis of the transport phenomena in the highly chaotic regime. Qualitative and quantitative comparisons of two-dimensional (2D) and 3D simulations include prediction of the mean concentration fields as well as the spectra of concentration, charge density, and velocity signals. Our analyses reveal a significant quantitative difference between 2D and 3D electroconvection. Furthermore, we show that high-intensity yet short-lived current density hot spots appear randomly on the membrane surface, contributing significantly to the mean current density. By examining cross correlations between current density on the membrane and other field quantities we explore the physical mechanisms leading to current hot spots. We also present analysis of transport fluxes in the context of ensemble-averaged equations. Our analysis reveals that in the highly chaotic regime the mixing layer (ML), which spans the majority of the domain extent, is governed by advective fluctuations. Furthermore, we show that in the ML the mean electromigration fluxes cancel out for positive and negative ions, indicating that the mean transport of total salt content within the ML can be represented via the electroneutral approximation. Finally, we present an assessment of the importance of different length scales in enhancing transport by computing the cross covariance of concentration and velocity fluctuations in the wavenumber space. Our analysis indicates that in the majority of the domain the large scales contribute most significantly to transport, while the effects of small scales become more appreciable in regions very near the membrane.

Diffuse charge dynamics in ionic thermoelectrochemical systems

NASA Astrophysics Data System (ADS)

Stout, Robert F.; Khair, Aditya S.

2017-08-01

Thermoelectrics are increasingly being studied as promising electrical generators in the ongoing search for alternative energy sources. In particular, recent experimental work has examined thermoelectric materials containing ionic charge carriers; however, the majority of mathematical modeling has been focused on their steady-state behavior. Here, we determine the time scales over which the diffuse charge dynamics in ionic thermoelectrochemical systems occur by analyzing the simplest model thermoelectric cell: a binary electrolyte between two parallel, blocking electrodes. We consider the application of a temperature gradient across the device while the electrodes remain electrically isolated from each other. This results in a net voltage, called the thermovoltage, via the Seebeck effect. At the same time, the Soret effect results in migration of the ions toward the cold electrode. The charge dynamics are described mathematically by the Poisson-Nernst-Planck equations for dilute solutions, in which the ion flux is driven by electromigration, Brownian diffusion, and thermal diffusion under a temperature gradient. The temperature evolves according to the heat equation. This nonlinear set of equations is linearized in the (experimentally relevant) limit of a "weak" temperature gradient. From this, we show that the time scale on which the thermovoltage develops is the Debye time, 1 /D κ2 , where D is the Brownian diffusion coefficient of both ion species, and κ-1 is the Debye length. However, the concentration gradient due to the Soret effect develops on the bulk diffusion time, L2/D , where L is the distance between the electrodes. For thin diffuse layers, which is the condition under which most real devices operate, the Debye time is orders of magnitude less than the diffusion time. Therefore, rather surprisingly, the majority of ion motion occurs after the steady thermovoltage has developed. Moreover, the dynamics are independent of the thermal diffusion coefficients, which simply set the magnitude of the steady-state thermovoltage.

Mapping Ionic Currents and Reactivity on the Nanoscale: Electrochemical Strain Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kalinin, S.V.

2010-10-19

Solid-state electrochemical processes in oxides underpin a broad spectrum of energy and information storage devices, ranging from Li-ion and Li-air batteries, to solid oxide fuel cells (SOFC) to electroresistive and memristive systems. These functionalities are controlled by the bias-driven diffusive and electromigration transport of mobile ionic species, as well as intricate a set of electrochemical and defect-controlled reactions at interfaces and in bulk. Despite the wealth of device-level and atomistic studies, little is known on the mesoscopic mechanisms of ion diffusion and electronic transport on the level of grain clusters, individual grains, and extended defects. The development of the capabilitymore » for probing ion transport on the nanometer scale is a key to deciphering complex interplay between structure, functionality, and performance in these systems. Here we introduce Electrochemical Strain Microscopy, a scanning probe microscopy technique based on strong strain-bias coupling in the systems in which local ion concentrations are changed by electrical fields. The imaging capability, as well as time- and voltage spectroscopies analogous to traditional current based electrochemical characterization methods are developed. The reversible intercalation of Li and mapping electrochemical activity in LiCoO2 is demonstrated, illustrating higher Li diffusivity at non-basal planes and grain boundaries. In Si-anode device structure, the direct mapping of Li diffusion at extended defects and evolution of Li-activity with charge state is explored. The electrical field-dependence of Li mobility is studied to determine the critical bias required for the onset of electrochemical transformation, allowing reaction and diffusion processes in the battery system to be separated at each location. Finally, the applicability of ESM for probing oxygen vacancy diffusion and oxygen reduction/evolution reactions is illustrated, and the high resolution ESM maps are correlated with aberration corrected scanning transmission electron microscopy imaging. The future potential for deciphering mechanisms of electrochemical transformations on an atomically-defined single-defect level is discussed.« less

Molecular Dynamics Simulations of Grain Boundary and Bulk Diffusion in Metals.

NASA Astrophysics Data System (ADS)

Plimpton, Steven James

Diffusion is a microscopic mass transport mechanism that underlies many important macroscopic phenomena affecting the structural, electrical, and mechanical properties of metals. This thesis presents results from atomistic simulation studies of diffusion both in bulk and in the fast diffusion paths known as grain boundaries. Using the principles of molecular dynamics single boundaries are studied and their structure and dynamic properties characterized. In particular, tilt boundary bicrystal and bulk models of fcc Al and bcc alpha-Fe are simulated. Diffusion coefficients and activation energies for atomic motion are calculated for both models and compared to experimental data. The influence of the interatomic pair potential on the diffusion is studied in detail. A universal relation between the melting temperature that a pair potential induces in a simulated bulk model and the potential energy barrier height for atomic hopping is derived and used to correlate results for a wide variety of pair potentials. Using these techniques grain boundary and bulk diffusion coefficients for any fcc material can be estimated from simple static calculations without the need to perform more time-consuming dynamic simulations. The influences of two other factors on grain boundary diffusion are also studied because of the interest of the microelectronics industry in the diffusion related reliability problem known as electromigration. The first factor, known to affect the self diffusion rate of Al, is the presence of Cu impurity atoms in Al tilt boundaries. The bicrystal model for Al is seeded randomly with Cu atoms and a simple hybrid Morse potential used to model the Al-Cu interaction. While some effect due to the Cu is noted, it is concluded that pair potentials are likely an inadequate approximation for the alloy system. The second factor studied is the effect of the boundary orientation angle on the diffusion rate. Symmetric bcc Fe boundaries are relaxed to find optimal structures and their diffusion coefficients calculated. Good agreement is found with the dislocation pipe model for tilt boundary diffusion.

Insulation-resistance degradation kinetics of bulk BaTi1-ξAξO3-Δ and defect-chemical origin of acceptor-type(A) and doping-level(ξ) effect

NASA Astrophysics Data System (ADS)

Kwon, Hyung-Soon; Yoon, Seok-Hyun; Yoo, Han-Ill

2016-07-01

Dearth of the reproducible, consistent observations on insulation-resistance (IR) degradation kinetics of bulk dielectric BaTiO3 may be attributed to their conventional measurement method, two-probe potentiostatic, which would be by no means free from the electrode effect for a finite- dimension specimen in particular. We hereby measured the IR-degradation kinetics galvanostatically by using a series of inner probes on bulk BaTi1-ξAξO3-Δ (A = Al, Mn; ξ = 0.001, 0.003, 0.010) with their high-temperature (1000 °C) equilibrium ionic-defect-structure in air being frozen-in at 250 °C and compared with the kinetics as calculated on the basis of the electromigration of frozen-in oxygen vacancies ( cV o ) in association with the A-ionization or hole-trapping equilibria. It has turned out that the calculated depict sufficiently precisely all the as-observed kinetics as well as the effects of acceptor type(A) and doping level(ξ), thus, quantitatively establishing the correlation between the frozen-in ionic-defect-structure and IR-degradation kinetics with new insights into the degradation inner-workings: IR-degradation is triggered as soon as the oxygen vacancy concentration at the cathode reaches that corresponding to the insulator-to-semiconductor transition ( cV S / I ) and proceeds with the front of just-turned, n-type semiconducting region ( c V = cV S / I ) moving towards the anode at a fixed velocity. The healthy lifetime of the dielectric is, thus, essentially the time duration for the cathode to achieve cV S / I from cV o , and the final stage of degradation is approximated to be the length fraction χs of the semiconductor such that χs = cV o / cV S / I . A new suggestion is finally made to further suppress the IR degradation kinetics of the bulk dielectric BaTiO3.

Immortality of Cu damascene interconnects

NASA Astrophysics Data System (ADS)

Hau-Riege, Stefan P.

2002-04-01

We have studied short-line effects in fully-integrated Cu damascene interconnects through electromigration experiments on lines of various lengths and embedded in different dielectric materials. We compare these results with results from analogous experiments on subtractively-etched Al-based interconnects. It is known that Al-based interconnects exhibit three different behaviors, depending on the magnitude of the product of current density, j, and line length, L: For small values of (jL), no void nucleation occurs, and the line is immortal. For intermediate values, voids nucleate, but the line does not fail because the current can flow through the higher-resistivity refractory-metal-based shunt layers. Here, the resistance of the line increases but eventually saturates, and the relative resistance increase is proportional to (jL/B), where B is the effective elastic modulus of the metallization system. For large values of (jL/B), voiding leads to an unacceptably high resistance increase, and the line is considered failed. By contrast, we observed only two regimes for Cu-based interconnects: Either the resistance of the line stays constant during the duration of the experiment, and the line is considered immortal, or the line fails due to an abrupt open-circuit failure. The absence of an intermediate regime in which the resistance saturates is due to the absence of a shunt layer that is able to support a large amount of current once voiding occurs. Since voids nucleate much more easily in Cu- than in Al-based interconnects, a small fraction of short Cu lines fails even at low current densities. It is therefore more appropriate to consider the probability of immortality in the case of Cu rather than assuming a sharp boundary between mortality and immortality. The probability of immortality decreases with increasing amount of material depleted from the cathode, which is proportional to (jL2/B) at steady state. By contrast, the immortality of Al-based interconnects is described by (jL) if no voids nucleate, and (jL/B) if voids nucleate.

Multi-dimensional modeling of atmospheric copper-sulfidation corrosion on non-planar substrates.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Ken Shuang

2004-11-01

This report documents the author's efforts in the deterministic modeling of copper-sulfidation corrosion on non-planar substrates such as diodes and electrical connectors. A new framework based on Goma was developed for multi-dimensional modeling of atmospheric copper-sulfidation corrosion on non-planar substrates. In this framework, the moving sulfidation front is explicitly tracked by treating the finite-element mesh as a pseudo solid with an arbitrary Lagrangian-Eulerian formulation and repeatedly performing re-meshing using CUBIT and re-mapping using MAPVAR. Three one-dimensional studies were performed for verifying the framework in asymptotic regimes. Limited model validation was also carried out by comparing computed copper-sulfide thickness with experimentalmore » data. The framework was first demonstrated in modeling one-dimensional copper sulfidation with charge separation. It was found that both the thickness of the space-charge layers and the electrical potential at the sulfidation surface decrease rapidly as the Cu{sub 2}S layer thickens initially but eventually reach equilibrium values as Cu{sub 2}S layer becomes sufficiently thick; it was also found that electroneutrality is a reasonable approximation and that the electro-migration flux may be estimated by using the equilibrium potential difference between the sulfidation and annihilation surfaces when the Cu{sub 2}S layer is sufficiently thick. The framework was then employed to model copper sulfidation in the solid-state-diffusion controlled regime (i.e. stage II sulfidation) on a prototypical diode until a continuous Cu{sub 2}S film was formed on the diode surface. The framework was also applied to model copper sulfidation on an intermittent electrical contact between a gold-plated copper pin and gold-plated copper pad; the presence of Cu{sub 2}S was found to raise the effective electrical resistance drastically. Lastly, future research needs in modeling atmospheric copper sulfidation are discussed.« less

Application of Lattice Boltzmann Methods in Complex Mass Transfer Systems

NASA Astrophysics Data System (ADS)

Sun, Ning

Lattice Boltzmann Method (LBM) is a novel computational fluid dynamics method that can easily handle complex and dynamic boundaries, couple local or interfacial interactions/reactions, and be easily parallelized allowing for simulation of large systems. While most of the current studies in LBM mainly focus on fluid dynamics, however, the inherent power of this method makes it an ideal candidate for the study of mass transfer systems involving complex/dynamic microstructures and local reactions. In this thesis, LBM is introduced to be an alternative computational method for the study of electrochemical energy storage systems (Li-ion batteries (LIBs) and electric double layer capacitors (EDLCs)) and transdermal drug design on mesoscopic scale. Based on traditional LBM, the following in-depth studies have been carried out: (1) For EDLCs, the simulation of diffuse charge dynamics is carried out for both the charge and the discharge processes on 2D systems of complex random electrode geometries (pure random, random spheres and random fibers). Steric effect of concentrated solutions is considered by using modified Poisson-Nernst-Plank (MPNP) equations and compared with regular Poisson-Nernst-Plank (PNP) systems. The effects of electrode microstructures (electrode density, electrode filler morphology, filler size, etc.) on the net charge distribution and charge/discharge time are studied in detail. The influence of applied potential during discharging process is also discussed. (2) For the study of dendrite formation on the anode of LIBs, it is shown that the Lattice Boltzmann model can capture all the experimentally observed features of microstructure evolution at the anode, from smooth to mossy to dendritic. The mechanism of dendrite formation process in mesoscopic scale is discussed in detail and compared with the traditional Sand's time theories. It shows that dendrite formation is closely related to the inhomogeneous reactively at the electrode-electrolyte interface. When the inhomogeneity is small, dendrites form mainly under high current densities, in which the mass transfer is dominated by electromigration; when the inhomogeneity is very large, dendrites may form under both high and low current densities, which is dominated by electromigration in high current density and by surface reactivity in low current density. We show that the critical current density for dendrite formation is sensitive to surface inhomogeneous reactivity and the onset time of dendrite formation is sensitive to the initial roughness of electrode. A new analysis method is introduced, which can predict the formation of dendrites in batteries at a very early stage even before large dendrites form. Charge/discharge cyclic properties of the system are also studied, which shows that electrode roughness will increase during cycles and the break-off of dendritic structures is inevitable once big dendrites form; however, it is possible to minimize the amount of break-off materials by optimizing the rate of discharge. (3) The LBM is also used to simulate intercalation reactions in a Li-Ion battery with graphite as anode and pure Li metal as counter electrode. Both galvanostatic and potentiostatic conditions were studied. The relation between operation parameters (current and potential) and electrode parameters (porosity, thickness and diffusivity) and plating times were discussed. Different equilibrium potentials forms (empirical fitting, fitting of SONY 18650 cell, and staged profiles) were also compared. By modifying the morphology of electrode with a density gradient, it was shown that much better electrode performance can be obtained, which can be helpful for the designing and manufacturing of better batteries. (4) The transdermal drug delivery system is also simulated by using LBM. Two kinds of transdermal structures are discussed: "brick and mortar" structure and a simple homogenized structure. It is demonstrated that the homogenized system is able to obtain similar steady state flux as the "brick and mortar" structure; however, in the early transient region, their flux value can be different. The influence of different system parameters (amount of drug in patch, patch thickness, partition coefficient at patch/ Stratum Corneum (SC) interface, and the diffusion coefficient of drug in each component) is discussed in details. It turns out that in this system, the rate-determine step for mass transfer should be the partition between patch and SC layers and the diffusion in the SC layer. The influence of enhancer is also tested. It is shown that by adding enhancers, the drug flux can be significantly increased. However, the peak time of drug does not necessarily match the peak flux time of enhancer. The peak time of drug could be adjusted (pushed earlier or dragged later) by using different kinds of enhancers, which has higher/smaller diffusivity than drug in the SC layer.

Microscale solution manipulation using photopolymerized hydrogel membranes and induced charge electroosmosis micropumps

NASA Astrophysics Data System (ADS)

Paustian, Joel Scott

Microfluidic technology is playing an ever-expanding role in advanced chemical and biological devices, with diverse applications including medical diagnostics, high throughput research tools, chemical or biological detection, separations, and controlled particle fabrication. Even so, local (microscale) modification of solution properties within microchannels, such as pressure, solute concentration, and voltage remains a challenge, and improved spatiotemporal control would greatly enhance the capabilities of microfluidics. This thesis demonstrates and characterizes two microfluidic tools to enhance local solution control. I first describe a microfluidic pump that uses an electrokinetic effect, Induced-Charge Electroosmosis (ICEO), to generate pressure on-chip. In ICEO, steady flows are driven by AC fields along metal-electrolyte interfaces. I design and microfabricate a pump that exploits this effect to generate on-chip pressures. The ICEO pump is used to drive flow along a microchannel, and the pressure is measured as a function of voltage, frequency, and electrolyte composition. This is the first demonstration of chip-scale flows driven by ICEO, which opens the possibility for ICEO pumping in self-contained microfluidic devices. Next, I demonstrate a method to create thin local membranes between microchannels, which enables local diffusive delivery of solute. These ``Hydrogel Membrane Microwindows'' are made by photopolymerizing a hydrogel which serves as a local ``window'' for solute diffusion and electromigration between channels, but remains a barrier to flow. I demonstrate three novel experimental capabilities enabled by the hydrogel membranes: local concentration gradients, local electric currents, and rapid diffusive composition changes. I conclude by applying the hydrogel membranes to study solvophoresis, the migration of particles in solvent gradients. Solvent gradients are present in many chemical processes, but migration of particles within these gradients is not well understood. An improved understanding would allow solvophoresis to be engineered (e.g. for coatings and thin film deposition) or reduced (e.g. in fouling processes during reactions and separations). Toward this end, I perform velocity measurements of colloidal particles at various ethanol-water concentrations and gradient strengths. The velocity was found to depend on the mole fraction via the equation u = DSP▿ln X, where u is the velocity, DSP is the mobility, and X is the ethanol mole fraction.

Electrokinetically Emplaced Amendments for Enhanced Bioremediation of Chlorinated Solvents in Clay: a Pilot Field Test

NASA Astrophysics Data System (ADS)

O'Carroll, D. M.; Inglis, A.; Head, N.; Chowdhury, A. I.; Garcia, A. N.; Reynolds, D. A.; Hogberg, D.; Edwards, E.; Lomheim, L.; Austrins, L. M.; Hayman, J.; Auger, M.; Sidebottom, A.; Eimers, J.; Gerhard, J.

2017-12-01

Bioremediation is an increasingly popular treatment technology for contaminated sites due to the proven success of biostimulation and bioaugmentation. However, bioremediation, along with other in-situ remediation technologies, faces limitations due to challenges with amendment delivery in low permeability media. Studies have suggested that electrokinetics (EK) can enhance the delivery of amendments in low permeability soils, such as clay. A pilot field trial was conducted to evaluate the potential for electrokinetics to support anaerobic dechlorination in clay by improving the transport of lactate and microorganisms. The study was performed on a former chlorinated solvent production facility in Ontario, Canada. Five transect cells were set up within the contaminated clay test area. Different amendments were injected in three of these cells to test various remediation strategies under the influence of EK. The other two cells were used as controls, one with EK applied and the other with no EK. This study focuses on the cell that applied electrokinetics for lactate emplacement followed by bioremediation (EK-Bio). This cell had an initial single injection of KB-1 bioaugmentation culture (SiREM, Canada) followed by injection of sodium lactate as a biostimulant while direct current was applied for 45 days between two electrodes 3 m apart. EK can enhance lactate migration by electromigration, while microorganisms have the potential to be influenced by electroosmosis of the bulk fluid or by electrophoresis of the charged bacteria themselves. All monitoring well locations in the EK-Bio cell exhibited evidence of successful lactate delivery corresponding to an increase in dissolved organic carbon. Reduction in chlorinated volatile organic compound (cVOC) concentrations, in particular 1,2-dichloroethane (1,2-DCA), were evident in monitoring locations coinciding with significant lactate breakthrough. Further investigation into the influence of EK-Bio on the abundance and distribution of microbial communities is being explored using soil and groundwater samples collected throughout the duration of the field trial. This study provides original insights into the application of electrokinetically-enhanced bioremediation as a treatment strategy for contaminated, low permeability porous media.

Using transdermal iontophoresis to increase granisetron delivery across skin in vitro and in vivo: effect of experimental conditions and a comparison with other enhancement strategies.

PubMed

Cázares-Delgadillo, Jennyfer; Ganem-Rondero, Adriana; Quintanar-Guerrero, David; López-Castellano, Alicia C; Merino, Virginia; Kalia, Yogeshvar N

2010-03-18

The objectives of the study were (i) to investigate the effect of experimental parameters on the iontophoretic transport of granisetron, (ii) to identify the relative contributions of electromigration (EM) and electroosmosis (EO), (iii) to determine the feasibility of delivering therapeutic amounts of drug for the treatment of chemotherapy-induced nausea and vomiting and (iv) to test the in vitro results in a simple animal model in vivo. Preliminary in vitro studies using aqueous granisetron formulations investigating the effect of drug concentration (5, 10, 20 and 40 mM) and current density (0.1, 0.2, 0.3 mA cm(-2)) were performed using porcine ear skin. As expected, cumulative delivery in vitro at the 20 and 40 mM concentrations was significantly greater than that at 5 and 10mM, which were not statistically different (p<0.05). Increasing the applied current density from 0.1 to 0.3 mA cm(-2) resulted in a approximately 4.2-fold increase in iontophoretic flux. Furthermore, in the absence of Na(+) in the formulation, no dependence of iontophoretic flux on drug concentration was reported (at a granisetron concentration of 40 mM, the transport rate was 2.93+/-0.62 microg cm(-2)min(-1)). Co-iontophoresis of acetaminophen was used to show that EM was the predominant transport mechanism accounting for 71-86% of total granisetron delivery. In vivo studies in Wistar rats (40 mM granisetron; application of 0.3 mA cm(-2) for 5h with Ag/AgCl electrodes and salt bridges) showed an average iontophoretic input rate (k(input)) of 0.83+/-0.26 microg min(-1) and a maximum plasma concentration (C(max)) of 0.092+/-0.004 microg ml(-1). Based on these results and given the known pharmacokinetics, transdermal iontophoresis could achieve therapeutic drug levels for the management of chemotherapy-induced emesis using a reasonably sized (4-6 cm(2)) patch. Copyright 2010 Elsevier B.V. All rights reserved.

A new model for the spectral induced polarization signature of bacterial growth in porous media

NASA Astrophysics Data System (ADS)

Zhang, C.; Revil, A.; Atekwana, E. A.; Jardani, A.; Smith, S.

2012-12-01

Recent biogeophysics studies demonstrated the sensitivity of complex conductivity to bacterial growth and microbial mediated mineral transformations in porous media. Frequency-domain induced polarization is a minimally invasive manner to measure the complex conductivity of a material over a broad range of frequencies. The real component of complex conductivity is associated with electromigration of the charge carriers, and the imaginary component represents reversible energy storage of charge carriers at polarization length scales. Quantitative relationship between frequency-domain induced polarization responses and bacterial growth and decay in porous media is analyzed in this study using a new developed model. We focus on the direct contribution of bacteria themselves to the complex conductivity in porous media in the absence of biomineralization. At low frequencies, the induced polarization of bacteria (α-polarization) is related to the properties of the electrical double layer surrounding the membrane surface of bacteria. Surface conductivity and α-polarization are due to the Stern layer of the counterions occurring in a brush of polymers coating the surface of the bacteria, and can be related to the cation exchange capacity of the bacteria. From the modeling results, at low frequencies (< 10 Hz), the mobility of the counterions (K+) in the Stern layer of bacteria is found to be extremely small (4.7×10-10 m2s-1 V-1 at 25°C), and is close to the mobility of the same counterions along the surface of clay minerals (Na+, 1.5×10-10 m2s-1 V-1 at 25°C). This result is in agreement with experimental observations and it indicates a very low relaxation frequency for the α-polarization of the bacteria cells (typically around 0.1 to 5 Hertz). By coupling this new model with reactive transport modeling in which the evolution of bacterial populations are usually described by Monod kinetics, we show that the changes in imaginary conductivity with time can be used to determine bacterial growth kinetics parameters such as the growth and endogenous decay coefficient.

Electrokinetic transport phenomena: Mobility measurement and electrokinetic instability

NASA Astrophysics Data System (ADS)

Oddy, Michael Huson

Miniaturization and integration of traditional bioassay procedures into microfabricated on-chip assay systems, commonly referred to as "Micro Total Analysis" (muTAS) systems, may have a significant impact on the fields of genomics, proteomics, and clinical analysis. These bioanalytical microsystems leverage electroosmosis and electrophoresis for sample transport, mixing, manipulation, and separation. This dissertation addresses the following three topics relevant to such systems: a new diagnostic for measuring the electrophoretic mobility of sub-micron, fluorescently-labeled particles and the electroosmotic mobility of a microchannel; a novel method and device for rapidly stirring micro- and nanoliter volume solutions for microfluidic bioanalytical applications; and a multiple-species electrokinetic instability model. Accurate measurement of the electrophoretic particle mobility and the electroosmotic mobility of microchannel surfaces is crucial to understanding the stability of colloidal suspensions, obtaining particle tracking-based velocimetry measurements of electroosmotic flow fields, and the quantification of electrokinetic bioanalytical device performance. A method for determining these mobilities from alternating and direct current electrokinetic particle tracking measurements is presented. The ability to rapidly mix fluids at low Reynolds numbers is important to the functionality of many bioanalytical, microfluidic devices. We present an electrokinetic process for rapidly stirring microflow streams by initiating an electrokinetic flow instability. The design, fabrication and performance analysis of two micromixing devices capable of rapidly stirring two low Reynolds number fluid streams are presented. Electroosmotic and electrophoretic transport in the presence of conductivity mismatches between reagent streams and the background electrolytes, can lead to an unstable flow field generating significant sample dispersion. In the multiple-species electrokinetic instability model, we consider a high aspect ratio microchannel geometry, a conductivity gradient orthogonal to the applied electric field, and a four-species chemistry model. A linear stability analysis of the depth-averaged governing equations shows unstable eigenmodes for conductivity ratios as close to unity as 1.01. Experiments and full nonlinear simulations of the governing equations were conducted for a conductivity ratio of 1.05. Images of the disturbance dye field from the nonlinear simulations show good qualitative and quantitative agreement with experiment. Species electromigration is shown to a have significant influence on the development of the conductivity field and instability dynamics in multi-ion configurations.

Electrochemical oxidation of ciprofloxacin in two different processes: the electron transfer process on the anode surface and the indirect oxidation process in bulk solutions.

PubMed

Shen, Bo; Wen, Xianghua; Korshin, Gregory V

2018-05-14

Herein, the rotating disk electrode technique was used for the first time to investigate the effects of mass-transfer limitations and pH on the electrochemical oxidation of CPX, to determine the kinetics of CPX oxidation and to explore intrinsic mechanisms during the electron transfer process. Firstly, cyclic voltammetry revealed that an obvious irreversible CPX oxidation peak was observed within the potential window from 0.70 to 1.30 V at all pHs. Based on the Levich equation, the electrochemical oxidation of CPX in the electron transfer process was found to be controlled by both diffusion and kinetic processes when pH = 2, 5, 7 and 9; the diffusion coefficient of CPX at pH = 2 was calculated to be 1.5 × 10-7 cm2 s-1. Kinetic analysis indicated that the reaction on the electrode surface was adsorption-controlled compared to a diffusion process; the surface concentration of electroactive species was estimated to be 1.15 × 10-9 mol cm-2, the standard rate constant of the surface reaction was calculated to be 1.37 s-1, and CPX oxidation was validated to be a two-electron transfer process. Finally, a possible CPX oxidation pathway during the electron transfer process was proposed. The electrochemical degradation of CPX on a Ti-based anode was also conducted subsequently to investigate the electrochemical oxidation of CPX in the indirect oxidation process in bulk solutions. The effects of pH and current density were determined and compared to related literature results. The oxidation of CPX at different pHs is believed to be the result of a counterbalance between favorable and unfavorable factors, namely electromigration and side reactions of oxygen evolution, respectively. The effects of current density indicated a diffusion- and reaction-controlled process at low currents followed by a reaction-controlled process at high currents. The results presented in this study provide better understanding of the electrochemical oxidation of CPX and would enable the development of new treatment methods based on electrochemistry.

Electrokinetic transport properties of deoxynucleotide monophosphates (dNMPs) through thermoplastic nanochannels.

PubMed

O'Neil, Colleen; Amarasekara, Charuni A; Weerakoon-Ratnayake, Kumuditha M; Gross, Bethany; Jia, Zheng; Singh, Varshni; Park, Sunggook; Soper, Steven A

2018-10-16

The electrokinetic behavior of molecules in nanochannels (<100 nm in length) have generated interest due to the unique transport properties observed that are not seen in microscale channels. These nanoscale dependent transport properties include transverse electromigration arising from partial electrical double layer overlap, enhanced solute/wall interactions due to the small channel diameter, and field-dependent intermittent motion produced by surface roughness. In this study, the electrokinetic transport properties of deoxynucleotide monophosphates (dNMPs) were investigated, including the effects of electric field strength, surface effects, and composition of the carrier electrolyte (ionic concentration and pH). The dNMPs were labeled with a fluorescent reporter (ATTO 532) to allow tracking of the electrokinetic transport of the dNMPs through a thermoplastic nanochannel fabricated via nanoimprinting (110 nm × 110 nm, width × depth, and 100 μm in length). We discovered that the transport properties in plastic nanochannels of the dye-labeled dNMPs produced differences in their apparent mobilities that were not seen using microscale columns. We built histograms for each dNMP from their apparent mobilities under different operating conditions and fit the histograms to Gaussian functions from which the separation resolution could be deduced as a metric to gage the ability to identify the molecule based on their apparent mobility. We found that the resolution ranged from 0.73 to 2.13 at pH = 8.3. Changing the carrier electrolyte pH > 10 significantly improved separation resolution (0.80-4.84) and reduced the standard deviation in the Gaussian fit to the apparent mobilities. At low buffer concentrations, decreases in separation resolution and increased standard deviations in Gaussian fits to the apparent mobilities of dNMPs were observed due to the increased thickness of the electric double layer leading to a partial parabolic flow profile. The results secured for the dNMPs in thermoplastic nanochannels revealed a high identification efficiency (>99%) in most cases for the dNMPs due to differences in their apparent mobilities when using nanochannels, which could not be achieved using microscale columns. Copyright © 2018. Published by Elsevier B.V.

Characterization of crystallographic properties of thin films using X-ray diffraction

NASA Astrophysics Data System (ADS)

Zoo, Yeongseok

2007-12-01

Silver (Ag) has been recognized as one of promising candidates in Ultra-Large Scale Integrated (ULSI) applications in that it has the lowest bulk electrical resistivity of all pure metals and higher electromigration resistance than other interconnect materials. However, low thermal stability on Silicon Dioxide (Si02) at high temperatures (e.g., agglomeration) is considered a drawback for the Ag metallization scheme. Moreover, if a thin film is attached on a substrate, its properties may differ significantly from that of the bulk, since the properties of thin films can be significantly affected by the substrate. In this study, the Coefficient of Thermal Expansion (CTE) and texture evolution of Ag thin films on different substrates were characterized using various analytical techniques. The experimental results showed that the CTE of the Ag thin film was significantly affected by underlying substrate and the surface roughness of substrate. To investigate the alloying effect for Ag meatallization, small amounts of Copper (Cu) were added and characterized using theta-2theta X-ray Diffraction (XRD) scan and pole figure analysis. These XRD techniques are useful for investigating the primary texture of a metal film, (111) in this study, which (111) is the notation of a specific plane in the orthogonal coordinate system. They revealed that the (111) textures of Ag and Ag(Cu) thin films were enhanced with increasing temperature. Comparison of texture profiles between Ag and Ag(Cu) thin films showed that Cu additions enhanced (111) texture in Ag thin films. Accordingly, the texture enhancement in Ag thin films by Cu addition was discussed. Strained Silicon-On-Insulator (SSOI) is being considered as a potential substrate for Complementary Metal-Oxide-Semiconductor (CMOS) technology since the induced strain results in a significant improvement in device performance. High resolution X-ray diffraction (XRD) techniques were used to characterize the perpendicular and parallel strains in SSOI layers. XRD diffraction profiles generated from the crystalline SSOI layer provided a direct measurement of the layer's strain components. In addition, it has demonstrated that the rotational misalignment between the layer and the substrate can be incorporated within the biaxial strain equations for epitaxial layers. Based on these results, the strain behavior of the SSOI layer and the relation between strained Si and SiO2 layers are discussed for annealed samples.

A Reliability Model for Ni-BaTiO3-Based (BME) Ceramic Capacitors

NASA Technical Reports Server (NTRS)

Liu, Donhang

2014-01-01

The evaluation of multilayer ceramic capacitors (MLCCs) with base-metal electrodes (BMEs) for potential NASA space project applications requires an in-depth understanding of their reliability. The reliability of an MLCC is defined as the ability of the dielectric material to retain its insulating properties under stated environmental and operational conditions for a specified period of time t. In this presentation, a general mathematic expression of a reliability model for a BME MLCC is developed and discussed. The reliability model consists of three parts: (1) a statistical distribution that describes the individual variation of properties in a test group of samples (Weibull, log normal, normal, etc.), (2) an acceleration function that describes how a capacitors reliability responds to external stresses such as applied voltage and temperature (All units in the test group should follow the same acceleration function if they share the same failure mode, independent of individual units), and (3) the effect and contribution of the structural and constructional characteristics of a multilayer capacitor device, such as the number of dielectric layers N, dielectric thickness d, average grain size r, and capacitor chip size S. In general, a two-parameter Weibull statistical distribution model is used in the description of a BME capacitors reliability as a function of time. The acceleration function that relates a capacitors reliability to external stresses is dependent on the failure mode. Two failure modes have been identified in BME MLCCs: catastrophic and slow degradation. A catastrophic failure is characterized by a time-accelerating increase in leakage current that is mainly due to existing processing defects (voids, cracks, delamination, etc.), or the extrinsic defects. A slow degradation failure is characterized by a near-linear increase in leakage current against the stress time; this is caused by the electromigration of oxygen vacancies (intrinsic defects). The two identified failure modes follow different acceleration functions. Catastrophic failures follow the traditional power-law relationship to the applied voltage. Slow degradation failures fit well to an exponential law relationship to the applied electrical field. Finally, the impact of capacitor structure on the reliability of BME capacitors is discussed with respect to the number of dielectric layers in an MLCC unit, the number of BaTiO3 grains per dielectric layer, and the chip size of the capacitor device.

Exchange biased and closed-flux pseudo spin-valve materials, device applications, and electrical reliability

NASA Astrophysics Data System (ADS)

Bae, Seongtae

Since giant magnetoresistance (GMR) and tunneling magnetoresistance (TMR) spinvalve effects were developed for the last two decades after discovered, world wide researches on applying these effects for various kinds of solid state active devices has provided a strong impact on challenging new functional micro-magnetoelectronic devices. In particular, recently developed nano-structured magnetic spin-valve thin film materials for spin-electronic devices are now considered as building blocks of state-of-the-art electronic engineering. This research has been concentrated on developing and designing magneto-electronic solid state devices with high thermal and electrical stability using an alpha-Fe 2O3 and NiO oxide anti-ferromagnetic exchange biased GMR bottom spin-valves (BSV), NiFe/Cu/Co and NiFe/Cu/CoFe based closed-flux metallic pseudo spin-valves, and PtMn exchange biased TMR spin-valves. The category covering this research is divided into four main research steps. First is to investigate exchange bias coupling characteristics of alpha-Fe2 O3 and NiO oxide Anti-ferromagnetic materials (AF)/Ferromagnetic (F) layer systems for optimizing exchange biased BSV and to study magnetic properties of various kinds of magnetic thin films including single through multi-layered structures for the fundamental research on NiFe/Cu/Co and NiFe/Cu/CoFe closed-flux metallic pseudo spin-valves. Second is to develop and improve new kinds of BSVs and closed-flux metallic spinvalves by controlling process parameters in terms of crystalline orientation texture of AF and F layers, interfacial surface roughness, grain size (its size distribution), chemical composition, and kinetics of sputtering film growth. Third is to design, to fabricate, and to investigate the magnetic and electrical properties of magneto-electronic devices as well as their applications such as GMR magnetoresistive random access memory (MRAM), GMR read head, TMR read head, and new kinds of GMR solid state devices, which can be promisingly substituted for current microelectronic devices. Finally, the last is to focus on studying electrical reliability of GMR read sensor and GMR MRAM cell in terms of electromigration-induced failures of various kinds of magnetic thin films, which are currently used in GMR spin-valve materials, and is to investigate the effects of current (or voltage) induced dielectric breakdown in aluminum oxide tunnel barrier under various testing conditions on the electrical stability of real TMR read sensors.

Characterization of Novel Thin-Films and Structures for Integrated Circuit and Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Zhao, Zhao

Thin films have been widely used in various applications. This research focuses on the characterization of novel thin films in the integrated circuits and photovoltaic techniques. The ion implanted layer in silicon can be treated as ion implanted thin film, which plays an essential role in the integrated circuits fabrication. Novel rapid annealing methods, i.e. microwave annealing and laser annealing, are conducted to activate ion dopants and repair the damages, and then are compared with the conventional rapid thermal annealing (RTA). In terms of As+ and P+ implanted Si, the electrical and structural characterization confirms that the microwave and laser annealing can achieve more efficient dopant activation and recrystallization than conventional RTA. The efficient dopant activation in microwave annealing is attributed to ion hopping under microwave field, while the liquid phase growth in laser annealing provides its efficient dopant activation. The characterization of dopants diffusion shows no visible diffusion after microwave annealing, some extent of end range of diffusion after RTA, and significant dopant diffusion after laser annealing. For photovoltaic applications, an indium-free novel three-layer thin-film structure (transparent composited electrode (TCE)) is demonstrated as a promising transparent conductive electrode for solar cells. The characterization of TCE mainly focuses on its optical and electrical properties. Transfer matrix method for optical transmittance calculation is validated and proved to be a desirable method for predicting transmittance of TCE containing continuous metal layer, and can estimate the trend of transmittance as the layer thickness changes. TiO2/Ag/TiO2 (TAgT) electrode for organic solar cells (OSCs) is then designed using numerical simulation and shows much higher Haacke figure of merit than indium tin oxide (ITO). In addition, TAgT based OSC shows better performance than ITO based OSC when compatible hole transfer layer is employed. The electrical and structural characterization of hole transfer layers (HTLs) in OSCs reveals MoO3 is the compatible HTL for TAgT anode. In the end, the reactive ink printed Ag film for solar cell contact application is studied by characterizing its electromigration lifetime. A percolative model is proposed and validated for predicting the resistivity and lifetime of printed Ag thin films containing porous structure.

The effect of an imposed current on the creep of tin silver copper interconnects

NASA Astrophysics Data System (ADS)

Kinney, Christopher Charles

There has been substantial work done on the properties of solder interconnects due to the global transition to lead free electronics. These interconnects create an electrical connection, which current will pass through for much of the interconnects' lifespan. As such, it is imperative in the testing of any solder alloy to examine the mechanical, thermal, and microstructural behavior of the interconnect while it is under an imposed current. The imposed current drives several internal effects that may impact the behavior of the interconnect; creating a complicated state within the interconnect. This thesis is the first study of the couple between current and mechanical properties of these interconnects. Idealized SnAgCu interconnects were made consisting of double-shear specimens that contained paired solder joints, 400x400mum in cross-section, 200mum in thickness on a Cu substrate. Different representative microstructures were prepared by pre-treating the interconnects via electromigration and isothermal aging. Samples were tested with and without an imposed current, and at a variety of temperatures. These tests consistently yielded two unexpected results. First, the relative increase in creep rate, for a given imposed current, is nearly the same over a range of temperatures and starting microstructures. Second, when tests are done at equivalent temperatures (to compensate for Joule heating) the creep rate is lower when under an imposed current than under isothermal conditions. To explain this phenomena, internal gradients within the interconnects were investigated. The temperature profile was shown to be constant at a given current density. Given constant temperature, and a microstructure that includes interfacial voids, the effect of the imposed current on the vacancy concentration was examined. It was found that the current depletes the joint of vacancies, lowering the average creep rate, and introducing observable heterogeneities in the creep pattern. This result was also found to be dependant on the specific locations of the voids, which act as vacancy sources or sinks. The usual Dom equation then provides a very useful basis for evaluating the change of creep rate with current. Actual microelectronic devices were also examined under an imposed current. Due to the complex geometry and composition of the samples, lower current densities were necessitated. As such, current induced effects were lessened, yet comparisons show similar behavior to the idealized interconnects. Our idealized model was applied to these devices, and yielded activation energies consistent with previous data. Finally, lifetime reliability projections were made for use in the future design of lead free microelectronic devices.

Mathematical models to describe iontophoretic transport in vitro and in vivo and the effect of current application on the skin barrier.

PubMed

Gratieri, Taís; Kalia, Yogeshvar N

2013-02-01

The architecture and composition of the stratum corneum make it a particularly effective barrier against the topical and transdermal delivery of hydrophilic molecules and ions. As a result, different strategies have been explored in order to expand the range of therapeutic agents that can be administered by this route. Iontophoresis involves the application of a small electric potential to increase transport into and across the skin. Since current flow is preferentially via transport pathways with at least some aqueous character, it is ideal for hydrosoluble molecules containing ionisable groups. Hence, the physicochemical properties that limit partitioning and passive diffusion through the intercellular lipid matrix are beneficial for electrically-assisted delivery. The presence of fixed ionisable groups in the skin (pI 4-4.5) means that application of the electric field results in a convective solvent flow (i.e., electroosmosis) in the direction of ion motion so as to neutralise membrane charge. Hence, under physiological conditions, cation electrotransport is due to both electromigration and electroosmosis-their relative contribution depends on the formulation conditions and the physicochemical properties of the permeant. Different mathematical models have been developed to provide a theoretical framework in order to explain iontophoretic transport kinetics. They usually involve solutions of the Nernst-Planck equation - using either the constant field (Goldman) or electroneutrality (Nernst) approximations - with or without terms for the convective solvent flow component. Investigations have also attempted to elucidate the nature of ion transport pathways and to explain the effect of current application on the electrical properties of the skin-more specifically, the stratum corneum. These studies have led to the development of different equivalent circuit models. These range from simple parallel arrangements of a resistor and a capacitor to the inclusion of the more esoteric "constant phase element"; the latter provides a better mathematical description of the "non-ideal" behaviour of skin impedance. However, in addition to simply providing a "mathematical" fit of the observed data, it is essential to relate these circuit elements to biological structures present in the skin. More recently, attention has also turned to what happens when the permeant crosses the epidermis and reaches the systemic circulation and pharmacokinetic models have been proposed to interpret data from iontophoretic delivery studies in vivo. Here, we provide an overview of mathematical models that have been proposed to describe (i) the effect of current application on the skin and the implications for potential iontophoretic transport pathways, (ii) electrotransport kinetics and (iii) the fate of iontophoretically delivered drugs once they enter the systemic circulation. Copyright © 2012 Elsevier B.V. All rights reserved.

Controlled iontophoretic transport of huperzine A across skin in vitro and in vivo: effect of delivery conditions and comparison of pharmacokinetic models.

PubMed

Kalaria, Dhaval R; Patel, Pratikkumar; Merino, Virginia; Patravale, Vandana B; Kalia, Yogeshvar N

2013-11-04

The aim of this study was to investigate constant current anodal iontophoresis of Huperzine A (HupA) in vitro and in vivo and hence to evaluate the feasibility of using electrically assisted delivery to administer therapeutic amounts of the drug across the skin for the treatment of Alzheimer's disease. Preliminary experiments were performed using porcine and human skin in vitro. Stability studies demonstrated that HupA was not degraded upon exposure to epidermis or dermis for 12 h and that it was also stable in the presence of an electric current (0.5 mA · cm(-2)). Passive permeation of HupA (2 mM) was minimal (1.1 ± 0.1 μg · cm(-2)); iontophoresis at 0.15, 0.3, and 0.5 mA · cm(-2) produced 106-, 134-, and 184-fold increases in its transport across the skin. Surprisingly, despite the use of a salt bridge to isolate the formulation compartment from the anodal chamber, which contained 133 mM NaCl, iontophoresis of HupA was shown to increase linearly with its concentration (1, 2, and 4 mM in 25 mM MES, pH 5.0) (r(2) = 0.99). This was attributed to the low ratio of drug to Cl¯ (in the skin and in the receiver compartment) which competed strongly to carry current, its depletion, and to possible competition from the zwitterionic MES. Co-iontophoresis of acetaminophen confirmed that electromigration was the dominant electrotransport mechanism. Total delivery across human and porcine skin was found to be statistically equivalent (243.2 ± 33.1 and 235.6 ± 13.7 μg · cm(-2), respectively). Although the transport efficiency was ∼ 1%, the iontophoretic delivery efficiency (i.e., the fraction of the drug load delivered) was extremely high, in the range of 46-81% depending on the current density. Cumulative permeation of HupA from a Carbopol gel formulation after iontophoresis for 6 h at 0.5 mA · cm(-2) was less than that from solution (135.3 ± 25.2 and 202.9 ± 5.2 μg · cm(-2), respectively) but sufficient for therapeutic delivery. Pharmacokinetic parameters were determined in male Wistar rats in vivo (4 mM HupA; 0.5 mA · cm(-2) for 5 h with Ag/AgCl electrodes) using two-compartment models with either constant or time-variant input rates. A superior fit was obtained using the time-variant model, and the input rate in vivo was significantly greater than that in vitro. Based on these results and the known pharmacokinetics, it was estimated that therapeutic amounts of HupA could be delivered for the treatment of Alzheimer's disease using a reasonably sized patch.

Oxide materials for spintronic device applications

NASA Astrophysics Data System (ADS)

Prestgard, Megan Campbell

Spintronic devices are currently being researched as next-generation alternatives to traditional electronics. Electronics, which utilize the charge-carrying capabilities of electrons to store information, are fundamentally limited not only by size constraints, but also by limits on current flow and degradation, due to electro-migration. Spintronics devices are able to overcome these limitations, as their information storage is in the spin of electrons, rather than their charge. By using spin rather than charge, these current-limiting shortcomings can be easily overcome. However, for spintronic devices to be fully implemented into the current technology industry, their capabilities must be improved. Spintronic device operation relies on the movement and manipulation of spin-polarized electrons, in which there are three main processes that must be optimized in order to maximize device efficiencies. These spin-related processes are: the injection of spin-polarized electrons, the transport and manipulation of these carriers, and the detection of spin-polarized currents. In order to enhance the rate of spin-polarized injection, research has been focused on the use of alternative methods to enhance injection beyond that of a simple ferromagnetic metal/semiconductor injector interface. These alternatives include the use of oxide-based tunnel barriers and the modification of semiconductors and insulators for their use as ferromagnetic injector materials. The transport of spin-polarized carriers is heavily reliant on the optimization of materials' properties in order to enhance the carrier mobility and to quench spin-orbit coupling (SOC). However, a certain degree of SOC is necessary in order to allow for the electric-field, gate-controlled manipulation of spin currents. Spin detection can be performed via both optical and electrical techniques. Using electrical methods relies on the conversion between spin and charge currents via SOC and is often the preferred method for device-based applications. This dissertation presents experimental results on the use of oxides for fulfilling the three spintronic device requirements. In the case of spin injection, the study of dilute magnetic dielectrics (DMDs) shows the importance of doping on the magnetic properties of the resulting tunnel barriers. The study of spin transport in ZnO has shown that, even at room temperature, the spin diffusion length is relatively long, on the order of 100 nm. These studies have also probed the spin relaxation mechanics in ZnO and have shown that Dyakonov-Perel spin relaxation, operating according to Fermi-Dirac statistics, is the dominant spin relaxation mechanism in zinc oxide. Finally, spin detection in ZnO has shown that, similar to other semiconductors, by modifying the resistivity of the ZnO thin films, the spin Hall angle (SHA) can be enhanced to nearly that of metals. This is possible by enhancing extrinsic SOC due to skew-scattering from impurities as well as phonons. In addition, thermal spin injection has also been detected using ZnO, which results support the independently measured inverse spin-Hall effect studies. The work represented herein illustrates that oxide materials have the potential to enhance spintronic device potential in all processes pertinent to spintronic applications.

Improved Bacterial and Viral Recoveries from 'Complex' Samples using Electrophoretically Assisted Acoustic Focusing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ness, K; Rose, K; Jung, B

2008-03-27

Automated front-end sample preparation technologies can significantly enhance the sensitivity and reliability of biodetection assays [1]. We are developing advanced sample preparation technologies for biowarfare detection and medical point-of-care diagnostics using microfluidic systems with continuous sample processing capabilities. Here we report an electrophoretically assisted acoustic focusing technique to rapidly extract and enrich viral and bacterial loads from 'complex samples', applied in this case to human nasopharyngeal samples as well as simplified surrogates. The acoustic forces capture and remove large particles (> 2 {micro}m) such as host cells, debris, dust, and pollen from the sample. We simultaneously apply an electric fieldmore » transverse to the flow direction to transport small ({le} 2 {micro}m), negatively-charged analytes into a separate purified recovery fluid using a modified H-filter configuration [Micronics US Patent 5,716,852]. Hunter and O'Brien combined transverse electrophoresis and acoustic focusing to measure the surface charge on large particles, [2] but to our knowledge, our work is the first demonstration combining these two techniques in a continuous flow device. Marina et al. demonstrated superimposed dielectrophoresis (DEP) and acoustic focusing for enhanced separations [3], but these devices have limited throughput due to the rapid decay of DEP forces. Both acoustic standing waves and electric fields exert significant forces over the entire fluid volume in microchannels, thus allowing channels with larger dimensions (> 100 {micro}m) and high throughputs (10-100 {micro}L/min) necessary to process real-world volumes (1 mL). Previous work demonstrated acoustic focusing of microbeads [4] and biological species [5] in various geometries. We experimentally characterized our device by determining the biological size-cutoff where acoustic radiation pressure forces no longer transport biological particles. Figure 1 shows images of E.Coli ({approx}1 {micro}m) and yeast ({approx}4-5 {micro}m) flowing in a microchannel (200 {micro}m deep, 500 {micro}m wide) at a flow rate of 10 {micro}L/min. The E.Coli does not focus in the acoustic field while the yeast focuses at the channel centerline. This result suggests the acoustic size-cutoff for biological particles in our device lies between 2 and 3 {micro}m. Transverse electrophoresis has been explored extensively in electric field flow fractionation [6] and isoelectric focusing devices [7]. We demonstrated transverse electrophoretic transport of a wide variety of negatively-charged species, including fluorophores, beads, viruses, E.Coli, and yeast. Figure 2 shows the electromigration of a fluorescently labeled RNA virus (MS2) from the lower half of the channel to the upper half region with continuous flow. We demonstrated the effectiveness of our electrophoretically assisted acoustic focusing device by separating virus-like particles (40 nm fluorescent beads, selected to aid in visualization) from a high background concentration of yeast contaminants (see Figure 3). Our device allows for the efficient recovery of virus into a pre-selected purified buffer while background contaminants are acoustically captured and removed. We also tested the device using clinical nasopharyngeal samples, both washes and lavages, and demonstrated removal of unknown particulates (>2 ?m size) from the sample. Our future research direction includes spiking known amounts of bacteria and viruses into clinical samples and performing quantitative off-chip analysis (real-time PCR and flow cytometry).« less

Chip-package nano-structured copper and nickel interconnections with metallic and polymeric bonding interfaces

NASA Astrophysics Data System (ADS)

Aggarwal, Ankur

With the semiconductor industry racing toward a historic transition, nano chips with less than 45 nm features demand I/Os in excess of 20,000 that support computing speed in terabits per second, with multi-core processors aggregately providing highest bandwidth at lowest power. On the other hand, emerging mixed signal systems are driving the need for 3D packaging with embedded active components and ultra-short interconnections. Decreasing I/O pitch together with low cost, high electrical performance and high reliability are the key technological challenges identified by the 2005 International Technology Roadmap for Semiconductors (ITRS). Being able to provide several fold increase in the chip-to-package vertical interconnect density is essential for garnering the true benefits of nanotechnology that will utilize nano-scale devices. Electrical interconnections are multi-functional materials that must also be able to withstand complex, sustained and cyclic thermo-mechanical loads. In addition, the materials must be environmentally-friendly, corrosion resistant, thermally stable over a long time, and resistant to electro-migration. A major challenge is also to develop economic processes that can be integrated into back end of the wafer foundry, i.e. with wafer level packaging. Device-to-system board interconnections are typically accomplished today with either wire bonding or solders. Both of these are incremental and run into either electrical or mechanical barriers as they are extended to higher density of interconnections. Downscaling traditional solder bump interconnect will not satisfy the thermo-mechanical reliability requirements at very fine pitches of the order of 30 microns and less. Alternate interconnection approaches such as compliant interconnects typically require lengthy connections and are therefore limited in terms of electrical properties, although expected to meet the mechanical requirements. A novel chip-package interconnection technology is developed to address the IC packaging requirements beyond the ITRS projections and to introduce innovative design and fabrication concepts that will further advance the performance of the chip, the package, and the system board. The nano-structured interconnect technology simultaneously packages all the ICs intact in wafer form with quantum jump in the number of interconnections with the lowest electrical parasitics. The intrinsic properties of nano materials also enable several orders of magnitude higher interconnect densities with the best mechanical properties for the highest reliability and yet provide higher current and heat transfer densities. Nano-structured interconnects provides the ability to assemble the packaged parts on the system board without the use of underfill materials and to enable advanced analog/digital testing, reliability testing, and burn-in at wafer level. This thesis investigates the electrical and mechanical performance of nanostructured interconnections through modeling and test vehicle fabrication. The analytical models evaluate the performance improvements over solder and compliant interconnections. Test vehicles with nano-interconnections were fabricated using low cost electro-deposition techniques and assembled with various bonding interfaces. Interconnections were fabricated at 200 micron pitch to compare with the existing solder joints and at 50 micron pitch to demonstrate fabrication processes at fine pitches. Experimental and modeling results show that the proposed nano-interconnections could enhance the reliability and potentially meet all the system performance requirements for the emerging micro/nano-systems.

Materials with engineered mesoporosity for programmed mass transport

NASA Astrophysics Data System (ADS)

Gough, Dara V.

Transport in nanostructured materials is of great interest for scientists in various fields, including molecular sequestration, catalysis, artificial photosynthesis and energy storage. This thesis will present work on the transport of molecular and ionic species in mesoporous materials (materials with pore sizes between 2 and 50 nm). Initially, discussion will focus on the synthesis of mesoporous ZnS nanorattles and the size selected mass transport of small molecules through the mesopores. Discussion will then shift of exploration of cation exchange and electroless plating of metals to alter the mesoporous hollow sphere (MHS) materials and properties. The focus of discussion will then shift to the transport of ions into and out of a hierarchically structured gold electrode. Finally, a model gamma-bactiophage was developed to study the electromigration of charged molecules into and out of a confined geometry. A catalytically active biomolecular species was encapsulated within the central cavity of ZnS MHS. Both the activity of the encapsulated enzyme and the size-selective transport through the wall of the MHS were verified through the use of a common fluorogen, hydrogen peroxide, and sodium azide. Additionally, the protection of the enzyme was shown through size-selected blocking of a protease. The mesoporous hollow sphere system introduces size-selectivity to catalyzed chemical reactions; future work may include variations in pore sizes, and pore wall chemical functionalization. The pore size in ZnS mesoporous hollow spheres is controlled between 2.5 and 4.1 nm through swelling of the lyotropic liquid crystal template. The incorporation of a swelling agent is shown to linearly vary the hexagonal lyotropic liquid crystalline phase, which templates the mesopores, while allowing the high fidelity synthesis of mesoporous hollow spheres. Fluorescnently labeled ssDNA was utilized as a probe to explore the change in mesopore permeability afforded by the swollen template relative to the unswollen template. Electroless plating and cation exchange were explored as methods to vary the shell material of MHS. Mesoporous Ni MHS were obtained by the reduction of Ni2+ with dimethylamine borane onto a CML latex core. However, the resultant MHS were damaged due to core swelling during etch. To successfully obtain undeformed MHS, a silica core must be utilized; one possible route to explore, in order to reach this goal, is the surface chemistry/ligand effects on Ni2+. Cation exchange was performed in order to obtain CuS MHS; however, it proved an unsuccessful route to PbS, S and HgS. CdS-ZnS, Bi2S3 and Ag2S MHS were obtained only with significant defects. A novel hierarchically structured material, porous opal, was prepared using a colloidal crystal template and the dealloying of silver from gold and possed porosity on length scales range from 10s of nanometers (due to the colloidal crystal template) down to ca. 10 nm (due to dealloying). The transport properties of the material were studied using cyclic voltammetry and electrochemical impedance spectroscopy. The porous opal was found to posses enhanced charge transport properties relative to a unimodal porous gold film and a higher surface area than a gold opal. An equivalent circuit model was presented to explain the enhanced charge transport properties. A biomimetic system for studying the translocation of polymers through a channel and into a spherical cavity was developed based on inspiration from the gamma-bacteriophage. The nanocavity system was synthesized using two template length scales: 250 nm and 1.2 mum. Fabrication challenges that arose when using 1.2 mum colloidal templates were addressed, and the system was optimized for confinement studies of plasmid dsDNA.

Macroscopic Modeling of a One-Dimensional Electrochemical Cell using the Poisson-Nernst-Planck Equations

NASA Astrophysics Data System (ADS)

Yan, David

This thesis presents the one-dimensional equations, numerical method and simulations of a model to characterize the dynamical operation of an electrochemical cell. This model extends the current state-of-the art in that it accounts, in a primitive way, for the physics of the electrolyte/electrode interface and incorporates diffuse-charge dynamics, temperature coupling, surface coverage, and polarization phenomena. The one-dimensional equations account for a system with one or two mobile ions of opposite charge, and the electrode reaction we consider (when one is needed) is a one-electron electrodeposition reaction. Though the modeled system is far from representing a realistic electrochemical device, our results show a range of dynamics and behaviors which have not been observed previously, and explore the numerical challenges required when adding more complexity to a model. Furthermore, the basic transport equations (which are developed in three spatial dimensions) can in future accomodate the inclusion of additional physics, and coupling to more complex boundary conditions that incorporate two-dimensional surface phenomena and multi-rate reactions. In the model, the Poisson-Nernst-Planck equations are used to model diffusion and electromigration in an electrolyte, and the generalized Frumkin-Butler-Volmer equation is used to model reaction kinetics at electrodes. An energy balance equation is derived and coupled to the diffusion-migration equation. The model also includes dielectric polarization effects by introducing different values of the dielectric permittivity in different regions of the bulk, as well as accounting for surface coverage effects due to adsorption, and finite size "crowding", or steric effects. Advection effects are not modeled but could in future be incorporated. In order to solve the coupled PDE's, we use a variable step size second order scheme in time and finite differencing in space. Numerical tests are performed on a simplified system and the scheme's stability and convergence properties are discussed. While evaluating different methods for discretizing the coupled flux boundary condition, we discover a thresholding behaviour in the adaptive time stepper, and perform additional tests to investigate it. Finally, a method based on ghost points is chosen for its favorable numerical properties compared to the alternatives. With this method, we are able to run simulations with a large range of parameters, including any value of the nondimensionalized Debye length epsilon. The numerical code is first used to run simulations to explore the effects of polarization, surface coverage, and temperature. The code is also used to perform frequency sweeps of input signals in order to mimic impedance spectroscopy experiments. Finally, in Chapter 5, we use our model to apply ramped voltages to electrochemical systems, and show theoretical and simulated current-voltage curves for liquid and solid thin films, cells with blocking (polarized) electrodes, and electrolytes with background charge. Linear sweep and cyclic voltammetry techniques are important tools for electrochemists and have a variety of applications in engineering. Voltammetry has classically been treated with the Randles-Sevcik equation, which assumes an electroneutral supported electrolyte. No general theory of linear-sweep voltammetry is available, however, for unsupported electrolytes and for other situations where diffuse charge effects play a role. We show theoretical and simulated current-voltage curves for liquid and solid thin films, cells with blocking electrodes, and membranes with fixed background charge. The analysis focuses on the coupling of Faradaic reactions and diffuse charge dynamics, but capacitive charging of the double layers is also studied, for early time transients at reactive electrodes and for non-reactive blocking electrodes. The final chapter highlights the role of diffuse charge in the context of voltammetry, and illustrates which regimes can be approximated using simple analytical expressions and which require more careful consideration.

New precursors and chemistry for the growth of transition metal films by atomic layer deposition

NASA Astrophysics Data System (ADS)

Knisley, Thomas Joseph

The advancing complexity of advanced microelectronic devices is placing rigorous demands on currently used PVD and CVD deposition techniques. The ALD deposition method is proposed to meet the film thickness and conformality constraints needed by the semiconductor industry in future manufacturing processes. Unfortunately, there is a limited number of chemical precursors available that have high thermal stability, reactivity, and vapor pressure suitable for ALD film growth to occur. These properties collectively contribute to the lack of suitable transition metal precursors available for use in ALD. In this thesis, we report the discovery of a series of novel transition metal diazadienate precursors that promising properties deemed suitable for ALD. The volatility and thermal stability of the new transition metal diazadienyl compounds were studied by preparative sublimation and capillary tube melting point/decomposition experiments. Thermogravimetric analyses (TGA) demonstrate precursor residues of less than 4% at 500 °C. In addition, sublimation data, melting points, and decomposition temperatures for all complexes are presented. The manganese diazadienyl complex has the highest decomposition temperature of the series of complexes produced (325 °C). During preparative sublimations, the product recoveries of all transition metal diazadienyl complexes were greater than 92.0% with nonvolatile residues of less than 7.0%. This is an excellent indication that these complexes may be suitable candidates as metal precursors for ALD. Nickel nitride (NixN) films have been studied as an intermediate material for the formation of both nickel metal and nickel silicide using chemical vapor deposition. Herein, we describe the ALD growth of nickel nitride thin films from bis(1,4-di-tert-butyl-1,3-diazabutadiene) nickel(II) (Ni(tBu2DAD)2) and 1,1-dimethylhydrazine. An ALD window for the deposition of nickel nitride films on 500 nm thermal SiO2 substrates was observed between 225 and 240 °C with a constant growth rate of 0.70 Å/cycle. X-Ray photoelectron spectroscopy (XPS) showed all expected ionizations with carbon concentrations below the detection limit after argon ion sputtering. Due to preferential nitrogen sputtering in XPS, Rutherford backscattering spectrometry (RBS) and nuclear reaction analysis (NRA) were performed and subsequently revealed Ni:N ratios between 2-4 for films deposited within the ALD window. AFM measurements revealed a RMS roughness value of 10.8 nm on an as-deposited film at 225°C. All as-deposited films were amorphous as determined by X-ray diffraction. Copper is the primary interconnect material in microelectronics devices, due to its high conductivity and low affinity towards electromigration. With transistor gate lengths scheduled to reach 14 nm by 2014, there are severe demands upon the current film growth techniques used in device fabrication. The ALD film growth method is ideally suited for future microelectronics manufacturing, since it inherently provides highly conformal thin films, even in high aspect ratio nanoscale features, and allows sub-nanometer control over film thicknesses. In Chapter 4, we describe the atomic layer deposition of high purity, low resistivity copper metal thin films using a three precursor sequence entailing Cu(dmap)2, formic acid, and hydrazine. In this process, Cu(dmap) 2 is unreactive towards hydrazine but is transformed to copper(II) formate, which is then readily reduced to copper metal by subsequent hydrazine exposure. The present work therefore addresses a central problem with the ALD growth of metal thin films: low reactivity of metal precursors toward common reducing agents. A constant growth rate of 0.47-0.50 Å/cycle upon prime grade Si(100) was observed at substrate temperatures between 100 and 170 °C. Compositional analyses (XPS and TOF-ERDA) revealed copper films with low levels of carbon, oxygen, nitrogen, and hydrogen. Powder X-ray diffraction spectra of all films showed polycrystalline copper. The resistivities of films grown between 100 and 140 °C ranged between 9.6 and 16.4 μΩ·cm, demonstrating the growth of high purity, low resistivity copper films. An AFM measurement revealed a RMS roughness value of 3.5 nm on an as-deposited 50 nm Cu film at 120 °C.

Atomisti modeling of the microstructure and transport properties of lead-free solder alloys

NASA Astrophysics Data System (ADS)

Sellers, Michael S.

Damage mechanics models of lead-free solder joints in nanoelectronics continue to improve, and in doing so begin to utilize quantitative values describing processes at the atomic level, governing phenomena like electromigration and thermomigration. In particular, knowledge of the transport properties of specific microstructures helps continuum level models fully describe these larger-scale damage phenomena via multi-scale analysis. For example, diffusivities for different types of grain boundaries (fast diffusion paths for solvent and solute atoms, and vacancies), and a description of the boundary structure as a function of temperature, are critical in modeling solder microstructure evolution and, consequently, joint behavior under extreme temperature and electric current. Moreover, for damage that develops at larger length scales, surface energies and diffusivities play important roles in characterizing void stability and morphology. Unfortunately, experiments that investigate these kind of damage phenomena in the atomistic realm are often inconsistent or unable to directly quantify important parameters. One case is the particular transport and structural properties of grain boundaries in Sn (the main component in lead-free solder alloys) and their behavior in the presence of Ag and Cu impurities. This information is crucial in determining accurate diffusivity values for the common SnAgCu (SAC) type solder. Although an average grain boundary diffusivity has been reported for polycrystalline Sn in several works, the value for grain boundary width is estimated and specific diffusivities for boundaries known to occur in Sn have not been reported, to say nothing of solute effects on Sn diffusivity and grain boundary structure. Similarly, transport properties of Sn surfaces remain relatively uninvestigated as well. These gaps and inconsistencies in atomistic data must be remedied for micro- and macro-scale modeling to improve. As a complement to experimental work and possessing the ability to fill in the gaps, molecular simulation serves to reinforce experimental predictions and provide insight into the atomistic processes that govern studied phenomena. In the present body of work, we employ molecular statics and dynamics simulations in the characterization and computation of betaSn surface energies and surface diffusivities, the determination of diffusivities and structural properties of specific betaSn grain boundaries, and the investigation of Cu and Ag solute effects on betaSn grain boundaries. In our study of betaSn surfaces, energies for low number Miller index surfaces are computed and the (100) plane is found to have the lowest un-relaxed energy. We then find that two simple hopping mechanisms dominate adatom diffusion transitions on this surface. For each, we determine hopping rates of the adatom and compute its tracer diffusivity. Our work on grain boundaries investigates the self-diffusion properties and structure of several betaSn symmetric tilt grain boundaries using molecular dynamics simulations. We find that larger diffusive widths are exhibited by higher excess potential energy grain boundaries. Diffusivities in the directions parallel to the interface plane are also computed and activation energies are found with the Arrhenius relation. These are shown to agree well with experimental data. Finally, we examine the effect that solute atoms of Ag and Cu have on the microstructure of betaSn. Excess energies of the (101) symmetric tilt betaSn grain boundary are computed as a function of solute concentration at the interface, and we show that Ag lowers the energy at a greater rate than Cu. We also quantify segregation enthalpies and critical solute concentrations (where the excess energy of the boundary is reduced to zero). The effect of solute type on shear stress is also examined, and we show that solute has a strong effect on the stabilization of higher energy grain boundaries under shear stress. We then look at the self-diffusivity of Sn in the (101) symmetric tilt betaSn grain boundary and show that adding both Ag or Cu decrease the grain boundary self-diffusivity of Sn as solute amount in the interface increases. Effects of larger concentrations of Cu in particular are also investigated.

FOREWORD: Heterogenous nucleation and microstructure formation—a scale- and system-bridging approach Heterogenous nucleation and microstructure formation—a scale- and system-bridging approach

NASA Astrophysics Data System (ADS)

Emmerich, H.

2009-11-01

Scope and aim of this volume. Nucleation and initial microstructure formation play an important role in almost all aspects of materials science [1-5]. The relevance of the prediction and control of nucleation and the subsequent microstructure formation is fully accepted across many areas of modern surface and materials science and technology. One reason is that a large range of material properties, from mechanical ones such as ductility and hardness to electrical and magnetic ones such as electric conductivity and magnetic hardness, depend largely on the specific crystalline structure that forms in nucleation and the subsequent initial microstructure growth. A very demonstrative example for the latter is the so called bamboo structure of an integrated circuit, for which resistance against electromigration [6] , a parallel alignment of grain boundaries vertical to the direction of electricity, is most favorable. Despite the large relevance of predicting and controlling nucleation and the subsequent microstructure formation, and despite significant progress in the experimental analysis of the later stages of crystal growth in line with new theoretical computer simulation concepts [7], details about the initial stages of solidification are still far from being satisfactorily understood. This is in particular true when the nucleation event occurs as heterogenous nucleation. The Priority Program SPP 1296 'Heterogenous Nucleation and Microstructure Formation—a Scale- and System-Bridging Approach' [8] sponsored by the German Research Foundation, DFG, intends to contribute to this open issue via a six year research program that enables approximately twenty research groups in Germany to work interdisciplinarily together following this goal. Moreover, it enables the participants to embed themselves in the international community which focuses on this issue via internationally open joint workshops, conferences and summer schools. An outline of such activities can be found in [8]. Furthermore, the honorable invitation to publish a special issue in Journal of Physics: Condensed Matter dedicated to the Priority Program's topic allows the obtained results to be communicated to relevant international colleagues, which stimulates further interest and encourages future collaborations. The issue comprises the research results of the participants during the first two year period of the Priority Program as well as that of the international referees of the program. Now, what precisely is the research concept of the Priority Program and thus, what are the articles in this special issue dedicated to? Ever since the pioneering work of Volmer and Weber [9], Becker and Döring [10] as well as Turnbull and Fisher [11] nucleation has been modelled more or less phenomenologically. These traditional models describe nucleation by stochastic processes of single atoms, respectively, molecules, which attach at primary droplets. Those thereby growing droplets become stable by reaching a critical size. This concept has largely been employed to model thermal activated first-order phase transformations. However it contains basic weak points, which raises the question of its physical justification. For instance, the dependence of the interfacial free energy on the critical size of a nucleus is—from the point of view of recent experiments—not considered adequately. In the past years, several advances have been performed to put the modelling of nucleation and microstructure formation on a wider base [12-15]. Figure 1 Figure 1. Illustration of the interdisciplinary approach in the Research Priority Program 'Nucleation and Growth Kinetics in Colloids and Metals—Steps towards a Scale- and System-Bridging Understanding' [8]: to advance towards a system- and scale-bridging detailed understanding of the energetics and kinetics of heterogeneous nucleation and micro-structure formation, two different experimental (binary colloids and binary metallic alloys) model systems are investigated jointly by experimental scientists working with different experimental techniques together with theoreticians, whose expertise is likewise diverse, ranging from density functional theory (DFT), over molecular simulations (MC/MD) to the phase-field method and who at the same time aim at a rigorous connection of these methods. This sketch illustrates the different 'dimensions' of the interdisciplinary research setting of the Priority Program and thus underlying the articles in this issue. Still the comparison of these new approaches with experimental results leads to controversial conclusions [12, 16]. Hence the study and development of theoretical models for the understanding and in particular for the quantitative description of the heterogeneous nucleus- and microstructure-formation processes remains an open but successively more and more quantitatively approachable issue. The development of physically relevant models for nucleus- and initial microstructure-formation is based on reliable knowledge of key parameters as the interfacial energy between crystal nucleus and melt. The latter is still experimentally difficult to access in metallic systems due to limitations arising e.g. from non-transmittance of optical light. To accelerate the development of more quantitative models capable of addressing the open issues of heterogenous nucleation and microstructure formation further, it is therefore essential to find complementary experimental systems which are less limited in accessing the above key parameters than metals. For this reason, within the Priority Program 1296 'Heterogenous Nucleation and Microstructure Formation—a Scale- and System-Bridging Approach' [8], the emphasis is to investigate the energetics and kinetics of heterogeneous nucleation and microstructure-formation processes experimentally jointly with metals as well as colloids as mesoscopic model systems for these processes. Thereby the most comprehensive experimental picture shall be obtained. The research on colloidal systems is now at a point, at which it promises, in a symbiotic approach with metal physics, to make significant contributions to the identification of the above key parameters. So it has e.g. become possible to tune the interaction potential in colloids and thus to adjust it to display generic mechanisms of heterogeneous nucleation and microstructure-formation [17]. This offers several advantages compared to experimental investigations in metals: the crystallization of fluidic colloidal systems is much slower than the crystallization of metals. Moreover colloids are transparent in the field of optical light, so it is possible to study nucleation in situ by using novel optical research methods (confocal light microscopy)—thus, determining the above key parameters. For this reason the DFG Research Priority Program 1296 employs a system- and scale-bridging interdisciplinary scientific approach intended to thereby contribute to a comprehensive multiscale understanding of the basic mechanisms determining heterogenous nucleation and initial microstructure formation, which might successively be an applicable material system-independently. Initially its focus—and thus the focus of this issue—will be on the simplest types of model systems for heterogenous crystalline orders, on pure metals, binary metal alloys, and colloids. Theoretically and simulation based these systems are jointly studied based on density functional theory (DFT), molecular simulation methods (MC/MD) and the phase-field method at the same time aiming at a rigorous connection of these methods. The joint approach comprising theory and experiment is depicted in figure 1. More specifically the following questions are addressed and the first advances on these can be found in this issue: Heterogeneous nucleation: what does a critical nucleation grain look like? Does the classical concept of a contact angle make sense for heterogeneous nucleation? Can claims made about the dominant contributions to the nucleation barrier for heterogeneous nucleation, as they can be obtained from molecular simulations, be reconciled with results obtained via the phase-field method? What is the relation between interaction potentials and the relevant boundary energies? Transition from nucleus to microstructure: how does a microstructure develop out of a nucleus in the interplay between crystallization and segregation depending on the precise reference point in the phase diagram? How stable are those scenarios with respect to changes of that reference point? How well can these scenarios be reproduced via binary colloidal model systems? Microstructure development: what kind of consequences result from the new understanding of nucleation for the initial development of the microstructure? What kind of kinetic rules does the initial growth of the solidifying microstructure follow? Is it possible to identify conditions under which several microscopic morphologies of the same alloy composition are kinetically stable? This issue is organized as follows: it starts with three sections, where the main focus is on theoretical and simulation based advances beginning with the methods at the lowest scale, i.e. with a section on density functional theory and phase-field crystal method based contributions. This section is succeeded by a section devoted to the investigations of the molecular modelling groups inside the Priority Program, and a subsequent one on phase-field simulation. Sections 4, 5 and 6 are devoted to articles with a main focus on experimental contributions for the metallic and the colloidal systems and finally a section on applications. It is important to have in mind the term 'main focus' with an emphasis on main when reflecting this devision due to the interdisciplinary nature of the research reported here, which can already be seen in the articles as well. References [1] Chernov A A 1984 Modern Crystallography III-Crystal Growth (Berlin: Springer) [2] Mutaftschiev B 1993 Handbook on Crystal Growth ed D T J Hurle (Amsterdam: North-Holland) p 187 [3] Lacmann R and Schmidt P 1977 Current Topics in Materials Science ed E Kaldis and H J Scheel (Amsterdam: North-Holland) vol 2, pp 301-25 [4] Skripov V P 1977 Current Topics in Materials Scierce ed by E Kaldis and H J Scheel (Amsterdam: North-Holland) 327-78 [5] Chayen N E 1997 J. Appl. Crystallogr. 30 198 [6] Cho J and Thompson C V 1989 Appl. Phys. Lett. 54 2577 [7] Boettinger W J, Coriell S R, Greer A L, Karma A, Kurz W, Rappaz M, and Trivedi R 2000 Acta mater. 48 43 [8] www.spp1296.rwth-aachen.de [9] Volmer M and Weber A 1926 Z. Phys. Chemie. 119 227 [10] Becker R and Döring W 1935 Ann. Phys. 24 719 [11] Turnbull D and Fisher J C 1949 J. Chem. Phys. 17 71 [12] Oxtoby D W 1992 J. Phys.: Condens. Matter 4 7627 [13] Gránásy L and Iglói F 1997 J. Chem. Phys. 107 3634 [14] Gránásy L, Börzsönyi T, Pusztai T 2003 Interface and Transport Dynamics ed H Emmerich, B Nestler and M Schreckenberg (Berlin: Springer) p 190 [15] Emmerich H and Siquieri R 2005 Numerical Heat Transfer ed A Nowack and R A Bialecki [16] Gránásy L 1993 J. Non-Cryst. Solids 162 301 Dragnevski K I, Cochrane R F and Mullis A 2004 Mat. Sci. Eng. A 375-377 479 [17] Sood A K 1991 Solid State Physics 45 1