Electronic doping of transition metal oxide perovskites

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

Cammarata, Antonio, E-mail: cammaant@fel.cvut.cz; Rondinelli, James M.

2016-05-23

CaFeO{sub 3} is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO{sub 3}. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

High-Performance Asymmetric Supercapacitors of MnCo2O4 Nanofibers and N-Doped Reduced Graphene Oxide Aerogel.

PubMed

Pettong, Tanut; Iamprasertkun, Pawin; Krittayavathananon, Atiweena; Sukha, Phansiri; Sirisinudomkit, Pichamon; Seubsai, Anusorn; Chareonpanich, Metta; Kongkachuichay, Paisan; Limtrakul, Jumras; Sawangphruk, Montree

2016-12-14

The working potential of symmetric supercapacitors is not so wide because one type of material used for the supercapacitor electrodes prefers either positive or negative charge to both charges. To address this problem, a novel asymmetrical supercapacitor (ASC) of battery-type MnCo 2 O 4 nanofibers (NFs)//N-doped reduced graphene oxide aerogel (N-rGO AE ) was fabricated in this work. The MnCo 2 O 4 NFs at the positive electrode store the negative charges, i.e., solvated OH - , while the N-rGO AE at the negative electrode stores the positive charges, i.e., solvated K + . An as-fabricated aqueous-based MnCo 2 O 4 //N-rGO AE ASC device can provide a wide operating potential of 1.8 V and high energy density and power density at 54 W h kg -1 and 9851 W kg -1 , respectively, with 85.2% capacity retention over 3000 cycles. To understand the charge storage reaction mechanism of the MnCo 2 O 4 , the synchrotron-based X-ray absorption spectroscopy (XAS) technique was also used to determine the oxidation states of Co and Mn at the MnCo 2 O 4 electrode after being electrochemically tested. The oxidation number of Co is oxidized from +2.76 to +2.85 after charging and reduced back to +2.75 after discharging. On the other hand, the oxidation state of Mn is reduced from +3.62 to +3.44 after charging and oxidized to +3.58 after discharging. Understanding in the oxidation states of Co and Mn at the MnCo 2 O 4 electrode here leads to the awareness of the uncertain charge storage mechanism of the spinel-type oxide materials. High-performance ASC here in this work may be practically used in high-power applications.

In situ Charge Density Imaging of Metamaterials made with Switchable Two dimensionalElectron Gas at Oxide Heterointerfaces

DTIC Science & Technology

2017-11-28

AFRL-AFOSR-JP-TR-2018-0028 In-situ Charge-Density Imaging of Metamaterials from Switchable 2D electron gas CHANG BEOM EOM UNIVERSITY OF WISCONSIN...Imaging of Metamaterials made with Switchable Two-dimensional Electron Gas at Oxide Heterointerfaces 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA2386-16-1...using pulsed laser deposition atomic with in-situ reflection high-energy electron diffraction (RHEED). We have also demonstrated that the inline

Adsorption and oxidation of SO2 by graphene oxides: A van der Waals density functional theory study

NASA Astrophysics Data System (ADS)

Zhang, Huijuan; Cen, Wanglai; Liu, Jie; Guo, Jiaxiu; Yin, Huaqiang; Ning, Ping

2015-01-01

Carbon materials have been used for low temperature (20-150 °C) catalytic removal of SO2 from the coal-burned flue gases for a long time, but the mechanism at atomic level is still controversial. Density functional theory was used to investigate the adsorption and oxidation of SO2 on elaborated graphene oxides (GOs) to discover the insights. It is found that the hydroxyl groups on GO surface possess bi-functional effects: both enhancing the adsorption of SO2 through H-bonding interaction and reducing the reaction barrier for its oxidation to SO3. The promotion of oxidation is related to a pre-activation of the surface epoxy group. Based on Bader population, charge difference and electron localization function analysis, a charge transfer channel is proposed to explain the pre-activation.

Effect of charged impurities and morphology on oxidation reactivity of graphene

NASA Astrophysics Data System (ADS)

Yamamoto, Mahito; Cullen, William; Einstein, Theodore; Fuhrer, Michael

2012-02-01

Chemical reactivity of single layer graphene supported on a substrate is observed to be enhanced over thicker graphene. Possible mechanisms for the enhancement are Fermi level fluctuations due to ionized impurities on the substrate, and structural deformation of graphene induced by coupling to the substrate geometry. Here, we study the substrate-dependent oxidation reactivity of graphene, employing various substrates such as SiO2, mica, SiO2 nanoparticle thin film, and hexagonal boron nitride, which exhibit different charged impurity concentrations and surface roughness. Graphene is prepared on each substrate via mechanical exfoliation and oxidized in Ar/O2 mixture at temperatures from 400-600 ^oC. After oxidation, the Raman spectrum of graphene is measured, and the Raman D to G peak ratio is used to quantify the density of point defects introduced by oxidation. We will discuss the correlations among the defect density in oxidized graphene, substrate charge inhomogeneity, substrate corrugations, and graphene layer thickness. This work has been supported by the University of Maryland NSF-MRSEC under Grant No. DMR 05-20471 with supplemental funding from NRI, and NSF-DMR 08-04976.

Reply to ``Comment on `Spin- and charge-ordering in oxygen-vacancy-ordered mixed-valence Sr4Fe4O11 ' ''

NASA Astrophysics Data System (ADS)

Ravindran, P.; Vidya, R.; Fjellvåg, H.; Kjekshus, A.

2008-04-01

Recently, using density-functional theoretical calculations, we have reported [Phys. Rev. B 74, 054422 (2006)] that formal Fe3+ ions reside at the square-pyramidal site and Fe4+ ions in the octahedral site in Sr4Fe4O11 . Based on the interpretation of experimental structural and Mössbauer data from the literature, Adler concludes that our previous first-principles results disagree with experiments on the assignment of oxidation states to Fe in the square-pyramidal and octahedral environments in Sr4Fe4O11 . From a critical examination of the structure data for Sr4Fe4O11 and related oxides with Fe in different oxidation states and theoretically simulated Mössbauer parameters (hyperfine field, isomer shift, and quadrupole splitting), here we show that information on charges residing on the different constituents cannot be directly derived either from experimental structure or Mössbauer data. From additional analyses of the chemical bonding on the basis of charge density, charge transfer, electron localization function, crystal orbital Hamilton population, Born effective charge, and partial density of states, we substantiate our previous assignment of formal Fe3+ and Fe4+ to the square-pyramidal and octahedral sites, respectively, in Sr4Fe4O11 .

Dopant selection for control of charge carrier density and mobility in amorphous indium oxide thin-film transistors: Comparison between Si- and W-dopants

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

Mitoma, Nobuhiko, E-mail: MITOMA.Nobuhiko@nims.go.jp, E-mail: TSUKAGOSHI.Kazuhito@nims.go.jp; Kizu, Takio; Lin, Meng-Fang

The dependence of oxygen vacancy suppression on dopant species in amorphous indium oxide (a-InO{sub x}) thin film transistors (TFTs) is reported. In a-InO{sub x} TFTs incorporating equivalent atom densities of Si- and W-dopants, absorption of oxygen in the host a-InO{sub x} matrix was found to depend on difference of Gibbs free energy of the dopants for oxidation. For fully oxidized films, the extracted channel conductivity was higher in the a-InO{sub x} TFTs containing dopants of small ionic radius. This can be explained by a reduction in the ionic scattering cross sectional area caused by charge screening effects.

Multibit Polycristalline Silicon-Oxide-Silicon Nitride-Oxide-Silicon Memory Cells with High Density Designed Utilizing a Separated Control Gate

NASA Astrophysics Data System (ADS)

Rok Kim, Kyeong; You, Joo Hyung; Dal Kwack, Kae; Kim, Tae Whan

2010-10-01

Unique multibit NAND polycrystalline silicon-oxide-silicon nitride-oxide-silicon (SONOS) memory cells utilizing a separated control gate (SCG) were designed to increase memory density. The proposed NAND SONOS memory device based on a SCG structure was operated as two bits, resulting in an increase in the storage density of the NVM devices in comparison with conventional single-bit memories. The electrical properties of the SONOS memory cells with a SCG were investigated to clarify the charging effects in the SONOS memory cells. When the program voltage was supplied to each gate of the NAND SONOS flash memory cells, the electrons were trapped in the nitride region of the oxide-nitride-oxide layer under the gate to supply the program voltage. The electrons were accumulated without affecting the other gate during the programming operation, indicating the absence of cross-talk between two trap charge regions. It is expected that the inference effect will be suppressed by the lower program voltage than the program voltage of the conventional NAND flash memory. The simulation results indicate that the proposed unique NAND SONOS memory cells with a SCG can be used to increase memory density.

Effect of surface charge density on the affinity of oxide nanoparticles for the vapor-water interface.

PubMed

Brown, Matthew A; Duyckaerts, Nicolas; Redondo, Amaia Beloqui; Jordan, Inga; Nolting, Frithjof; Kleibert, Armin; Ammann, Markus; Wörner, Hans Jakob; van Bokhoven, Jeroen A; Abbas, Zareen

2013-04-23

Using in-situ X-ray photoelectron spectroscopy at the vapor-water interface, the affinity of nanometer-sized silica colloids to adsorb at the interface is shown to depend on colloid surface charge density. In aqueous suspensions at pH 10 corrected Debye-Hückel theory for surface complexation calculations predict that smaller silica colloids have increased negative surface charge density that originates from enhanced screening of deprotonated silanol groups (≡Si-O(-)) by counterions in the condensed ion layer. The increased negative surface charge density results in an electrostatic repulsion from the vapor-water interface that is seen to a lesser extent for larger particles that have a reduced charge density in the XPS measurements. We compare the results and interpretation of the in-situ XPS and corrected Debye-Hückel theory for surface complexation calculations with traditional surface tension measurements. Our results show that controlling the surface charge density of colloid particles can regulate their adsorption to the interface between two dielectrics.

Stability of Li- and Mn-Rich Layered-Oxide Cathodes within the First-Charge Voltage Plateau

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

Iddir, Hakim; Bareño, Javier; Benedek, Roy

Li and Mn rich layered oxides xLi 2MnO 3•(1-x)LiMO 2 enable high capacity and energy density Li-ion batteries, but undergo structural transformations during the first charge that degrade their performance, and result in Voltage Fade upon cycling. First-principles density-functional-theory simulations reveal atomic transformations that occur in the bulk during the first charge. The simulations and experiment (particularly XRD) show that the O and Mn sublattices remain intact during the early part of the voltage plateau, and significant transformations occur only well into the voltage plateau, with perhaps close to half of the Li in the Li 2MnO 3 domains removed.more » That Voltage Fade is actually observed experimentally for a first charge with only minimal activation (extending only slightly beyond the onset of the voltage plateau) may be a consequence of surface and interface instabilities. Implications for the achievement of high energy-density, low-fade battery operation are discussed.« less

Quasi 2D Ultrahigh Carrier Density in a Complex Oxide Broken Gap Heterojunction

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

Xu, Peng; Droubay, Timothy C.; Jeong, Jong S.

2016-01-21

Two-dimensional (2D) ultra-high carrier densities at complex oxide interfaces are of considerable current research interest for novel plasmonic and high charge-gain devices. However, the highest 2D electron density obtained in oxide heterostructures is thus far limited to 3×1014 cm-2 (½ electron/unit cell/interface) at GdTiO3/SrTiO3 interfaces, and is typically an order of magnitude lower at LaAlO3/SrTiO3 interfaces. Here we show that carrier densities much higher than 3×1014 cm-2 can be achieved via band engineering. Transport measurements for 3 nm SrTiO3/t u.c. NdTiO3/3 nm SrTiO3/LSAT (001) show that charge transfer significantly in excess of the value expected from the polar discontinuity modelmore » occurs for higher t values. The carrier density remains unchanged, and equivalent to ½ electron/unit cell/interface for t < 6 unit cells. However, above a critical NdTiO3 thickness of 6 u.c., electrons from the valence band of NdTiO3 spill over into the SrTiO3 conduction band as a natural consequence of the band alignment. An atomistic model consistent with first-principle calculations and experimental results is proposed for the charge transfer mechanisms. These results may provide an exceptional route to the realization of the room-temperature oxide electronics.« less

Formation of intra-island grain boundaries in pentacene monolayers.

PubMed

Zhang, Jian; Wu, Yu; Duhm, Steffen; Rabe, Jürgen P; Rudolf, Petra; Koch, Norbert

2011-12-21

To assess the formation of intra-island grain boundaries during the early stages of pentacene film growth, we studied sub-monolayers of pentacene on pristine silicon oxide and silicon oxide with high pinning centre density (induced by UV/O(3) treatment). We investigated the influence of the kinetic energy of the impinging molecules on the sub-monolayer growth by comparing organic molecular beam deposition (OMBD) and supersonic molecular beam deposition (SuMBD). For pentacene films fabricated by OMBD, higher pentacene island-density and higher polycrystalline island density were observed on UV/O(3)-treated silicon oxide as compared to pristine silicon oxide. Pentacene films deposited by SuMBD exhibited about one order of magnitude lower island- and polycrystalline island densities compared to OMBD, on both types of substrates. Our results suggest that polycrystalline growth of single islands on amorphous silicon oxide is facilitated by structural/chemical surface pinning centres, which act as nucleation centres for multiple grain formation in a single island. Furthermore, the overall lower intra-island grain boundary density in pentacene films fabricated by SuMBD reduces the number of charge carrier trapping sites specific to grain boundaries and should thus help achieving higher charge carrier mobilities, which are advantageous for their use in organic thin-film transistors.

Tunnel field-effect transistor charge-trapping memory with steep subthreshold slope and large memory window

NASA Astrophysics Data System (ADS)

Kino, Hisashi; Fukushima, Takafumi; Tanaka, Tetsu

2018-04-01

Charge-trapping memory requires the increase of bit density per cell and a larger memory window for lower-power operation. A tunnel field-effect transistor (TFET) can achieve to increase the bit density per cell owing to its steep subthreshold slope. In addition, a TFET structure has an asymmetric structure, which is promising for achieving a larger memory window. A TFET with the N-type gate shows a higher electric field between the P-type source and the N-type gate edge than the conventional FET structure. This high electric field enables large amounts of charges to be injected into the charge storage layer. In this study, we fabricated silicon-oxide-nitride-oxide-semiconductor (SONOS) memory devices with the TFET structure and observed a steep subthreshold slope and a larger memory window.

Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics

PubMed Central

Ramana, CV; Becker, U; Shutthanandan, V; Julien, CM

2008-01-01

Molybdenum disulfide (MoS2), a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia. The present work was performed to understand thermal oxidation and metal-insertion processes of molybdenite surfaces. The analysis was performed using atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA). Structural studies using SEM and TEM indicate the local-disordering of the structure as a result of charge-transfer process between the inserted lithium and the molybdenite layer. Selected area electron diffraction measurements indicate the large variations in the diffusivity of lithium confirming that the charge-transfer is different along and perpendicular to the layers in molybdenite. Thermal heating of molybenite surface in air at 400°C induces surface oxidation, which is slow during the first hour of heating and then increases significantly. The SEM results indicate that the crystals formed on the molybdenite surface as a result of thermal oxidation exhibit regular thin-elongated shape. The average size and density of the crystals on the surface is dependent on the time of annealing; smaller size and high density during the first one-hour and significant increase in size associated with a decrease in density with further annealing. PMID:18534025

Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics.

PubMed

Ramana, C V; Becker, U; Shutthanandan, V; Julien, C M

2008-06-05

Molybdenum disulfide (MoS2), a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia.The present work was performed to understand thermal oxidation and metal-insertion processes of molybdenite surfaces. The analysis was performed using atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA).Structural studies using SEM and TEM indicate the local-disordering of the structure as a result of charge-transfer process between the inserted lithium and the molybdenite layer. Selected area electron diffraction measurements indicate the large variations in the diffusivity of lithium confirming that the charge-transfer is different along and perpendicular to the layers in molybdenite. Thermal heating of molybenite surface in air at 400 degrees C induces surface oxidation, which is slow during the first hour of heating and then increases significantly. The SEM results indicate that the crystals formed on the molybdenite surface as a result of thermal oxidation exhibit regular thin-elongated shape. The average size and density of the crystals on the surface is dependent on the time of annealing; smaller size and high density during the first one-hour and significant increase in size associated with a decrease in density with further annealing.

Aqueous Assembly of Oxide and Fluoride Nanoparticles into 3D Microassemblies.

PubMed

Cui, Shanying; Guan, Xin N; Ghantous, Eliana; Vajo, John J; Lucas, Matthew; Hsiao, Ming-Siao; Drummy, Lawrence F; Collins, Joshua; Juhl, Abigail; Roper, Christopher S; Gross, Adam F

2018-06-28

We demonstrate rapid [∼mm 3 /(h·L)] organic ligand-free self-assembly of three-dimensional, >50 μm single-domain microassemblies containing up to 10 7 individual aligned nanoparticles through a scalable aqueous process. Organization and alignment of aqueous solution-dispersed nanoparticles are induced by decreasing their pH-dependent surface charge without organic ligands, which could be temperature-sensitive or infrared light absorbing. This process is exhibited by transforming both dispersed iron oxide hydroxide nanorods and lithium yttrium fluoride nanoparticles into high packing density microassemblies. The approach is generalizable to nanomaterials with pH-dependent surface charge (e.g., oxides, fluorides, and sulfides) for applications requiring long-range alignment of nanostructures as well as high packing density.

Room-Temperature Activation of InGaZnO Thin-Film Transistors via He+ Irradiation.

PubMed

Stanford, Michael G; Noh, Joo Hyon; Mahady, Kyle; Ievlev, Anton V; Maksymovych, Peter; Ovchinnikova, Olga S; Rack, Philip D

2017-10-11

Amorphous indium gallium zinc oxide (a-IGZO) is a transparent semiconductor which has demonstrated excellent electrical performance as thin-film transistors (TFTs). However, a high-temperature activation process is generally required which is incompatible for next-generation flexible electronic applications. In this work, He + irradiation is demonstrated as an athermal activation process for a-IGZO TFTs. Controlling the He + dose enables the tuning of charge density, and a dose of 1 × 10 14 He + /cm 2 induces a change in charge density of 2.3 × 10 12 cm -2 . Time-dependent transport measurements and time-of-flight secondary ion mass spectroscopy (ToF-SIMS) indicate that the He + -induced trapped charge is introduced because of preferential oxygen-vacancy generation. Scanning microwave impedance microscopy confirms that He + irradiation improves the conductivity of the a-IGZO. For realization of a permanent activation, IGZO was exposed with a He + dose of 5 × 10 14 He + /cm 2 and then aged 24 h to allow decay of the trapped oxide charge originating for electron-hole pair generation. The resultant shift in the charge density is primarily attributed to oxygen vacancies generated by He + sputtering in the near-surface region.

Reliability of gamma-irradiated n-channel ZnO thin-film transistors: electronic and interface properties

NASA Astrophysics Data System (ADS)

Lee, Kin Kiong; Wang, Danna; Shinobu, Onoda; Ohshima, Takeshi

2018-04-01

Radiation-induced charge trapping and interface traps in n-channel ZnO thin film transistors are characterised as a function of total dose and irradiation bias following exposure to gamma-rays. Devices were irradiated up to ∼60 kGy(SiO?) and the electrical characteristic exhibits two distinct regimes. In the first regime, up to a total dose of 40 kGy(SiO?), the threshold voltage increases positively. However, in the second regime with irradiation greater than 40 kGy(SiO?), the threshold voltage moves in the opposite direction. This reversal of threshold voltage is attributed to the influence of the radiation-induced interface and oxide- charge, in which both have opposite polarity, on the electrical performance of the transistors. In the first regime, the generation of the oxide- charge is initially greater than the density of interface traps and caused a positive shift. In the second regime, when the total doses were greater than 40 kGy(SiO?), the radiation-induced interface traps are greater than the density of oxide- charge and caused the threshold voltage to switch direction. Further, the generated interface traps contributed to the degradation of the effective channel mobility, whereas the density of traps at the grain-boundaries did not increase significantly upon irradiation. Isothermal annealing of the devices at 363 K results in a reduction in the trap density and an improvement of the effective channel mobility to ∼90% of its pre-irradiation value.

Probing charge transfer during metal-insulator transitions in graphene-LaAlO3/SrTiO3 systems

NASA Astrophysics Data System (ADS)

Aliaj, I.; Sambri, A.; Miseikis, V.; Stornaiuolo, D.; di Gennaro, E.; Coletti, C.; Pellegrini, V.; Miletto Granozio, F.; Roddaro, S.

2018-06-01

Two-dimensional electron systems (2DESs) at the interface between LaAlO3 (LAO) and SrTiO3 (STO) perovskite oxides display a wide class of tunable phenomena ranging from superconductivity to metal-insulator transitions. Most of these effects are strongly sensitive to surface physics and often involve charge transfer mechanisms, which are, however, hard to detect. In this work, we realize hybrid field-effect devices where graphene is used to modulate the transport properties of the LAO/STO 2DES. Different from a conventional gate, graphene is semimetallic and allows us to probe charge transfer with the oxide structure underneath the field-effect electrode. In LAO/STO samples with a low initial carrier density, graphene-covered regions turn insulating when the temperature is lowered to 3 K, but conduction can be restored in the oxide structure by increasing the temperature or by field effect. The evolution of graphene's electron density is found to be inconsistent with a depletion of LAO/STO, but it rather points to a localization of interfacial carriers in the oxide structure.

Hierarchical porous nickel oxide-carbon nanotubes as advanced pseudocapacitor materials for supercapacitors

NASA Astrophysics Data System (ADS)

Su, Aldwin D.; Zhang, Xiang; Rinaldi, Ali; Nguyen, Son T.; Liu, Huihui; Lei, Zhibin; Lu, Li; Duong, Hai M.

2013-03-01

Hierarchical porous carbon anode and metal oxide cathode are promising for supercapacitor with both high energy density and high power density. This Letter uses NiO and commercial carbon nanotubes (CNTs) as electrode materials for electrochemical capacitors with high energy storage capacities. Experimental results show that the specific capacitance of the electrode materials for 10%, 30% and 50% CNTs are 279, 242 and 112 F/g, respectively in an aqueous 1 M KOH electrolyte at a charge rate of 0.56 A/g. The maximum specific capacitance is 328 F/g at a charge rate of 0.33 A/g.

Far Infrared and Electrical Transport Studies of Oxide - Charge - Induced Localized States in a Model Two-Dimensional System.

NASA Astrophysics Data System (ADS)

Glaser, Evan R.

Far-infrared measurements of intersubband absorption spectra and dc electrical transport studies of n-inversion layers in (100) Si. Metal-Oxide-Semiconductor-Field-Effect-Transistors (MOSFETs) with mobile positive ions in the oxide are performed at temperatures between 1.7 and 80K. The results provide evidence for the existence of impurity bands and for screening of these localized states in this quasi two-dimensional electronic system. The properties of the elec- tronic states in the sub-micron (<10('-6)m) conducting layer of the MOS devices are probed in detail by conductance, capacitance and trans- conductance measurements and by optical absorption measure- ments with the aid of a Far-Infrared Fourier Transform Spectrometer. Data are obtained with positive oxide charge density as a parameter, varied by the drifting at room temperature of controlled amounts of. positive ions ((DELTA)N(,ox)) to the oxide-semiconductor interface (1.3 x 10('11) (LESSTHEQ) (DELTA)N(,ox) (LESSTHEQ) 7.0 x 10('11) cm('-2)) in the presence of positive gate voltages. (3-7V). In addition, high mobility devices in which no positive impurity ions had been purposely introduced are investigated to provide a basis for comparison with the corresponding results from poor mobil- ity devices. Studies are carried out for a wide range of net interfacial. oxide charge densities (2 x 10('10) cm('-2) (LESSTHEQ) N(,ox) (LESSTHEQ) 1 x 10('12) cm('-2)), and substrate source bias voltages (-9V (LESSTHEQ) V(,S) (LESSTHEQ) 1V) with the goal of. attaining a better understanding of the nature of localization effects (e.g., two-dimensional carrier localization), interface scattering, and many-body Coulombic interactions (e.g., screening effects) in these structures. The present measurements provide evidence for the existence of impurity bands and long band tails at low electron densities (n(,s) (LESSTHEQ) N(,ox)) associated with subbands due to both the inequivalent conduction-band valleys and for screening of these. localized states at high electron densities (n(,s) >(, )N(,ox)). In addition, at high inversion layer electron densities the intersubband resonance linewidths at 4.2K as a function of positive oxide charge density are found to be correlated with the corresponding scattering rates determined from the low temperature effective mobilities. The results of these studies are compared with recent experimental investigations of this and similar systems and with predictions of available theoretical models.

Possible origin and roles of nano-porosity in ZrO2 scales for hydrogen pick-up in Zr alloys

NASA Astrophysics Data System (ADS)

Lindgren, Mikaela; Geers, Christine; Panas, Itai

2017-08-01

A mechanistic understanding of Wagnerian build-up and subsequent non-Wagnerian break-down of barrier oxide upon oxidation of zirconium alloys by water is reiterated. Hydrogen assisted build-up of nano-porosity is addressed. Growth of sub-nanometer wide stalactitic pores owing to increasing aggregation of neutral oxygen vacancies offering a means to permeate hydrogen into the alloy is explored by density functional theory. The Wagnerian channel utilizes charge separation allowing charged oxygen vacancies and electrons to move separately from nominal anode to nominal cathode. This process becomes increasingly controlled by the charging of the barrier oxide resulting in sub-parabolic rate law for oxide growth. The break-down of the barrier oxide is understood to be preceded by avalanching hydrogen pick-up in the alloy. Pore mediated diffusion allows water to effectively short circuit the barrier oxide.

Polyelectrolyte assisted charge titration spectrometry: Applications to latex and oxide nanoparticles.

PubMed

Mousseau, F; Vitorazi, L; Herrmann, L; Mornet, S; Berret, J-F

2016-08-01

The electrostatic charge density of particles is of paramount importance for the control of the dispersion stability. Conventional methods use potentiometric, conductometric or turbidity titration but require large amount of samples. Here we report a simple and cost-effective method called polyelectrolyte assisted charge titration spectrometry or PACTS. The technique takes advantage of the propensity of oppositely charged polymers and particles to assemble upon mixing, leading to aggregation or phase separation. The mixed dispersions exhibit a maximum in light scattering as a function of the volumetric ratio X, and the peak position XMax is linked to the particle charge density according to σ∼D0XMax where D0 is the particle diameter. The PACTS is successfully applied to organic latex, aluminum and silicon oxide particles of positive or negative charge using poly(diallyldimethylammonium chloride) and poly(sodium 4-styrenesulfonate). The protocol is also optimized with respect to important parameters such as pH and concentration, and to the polyelectrolyte molecular weight. The advantages of the PACTS technique are that it requires minute amounts of sample and that it is suitable to a broad variety of charged nano-objects. Copyright © 2016 Elsevier Inc. All rights reserved.

Characterization of Defects in Scaled Mis Dielectrics with Variable Frequency Charge Pumping

NASA Astrophysics Data System (ADS)

Paulsen, Ronald Eugene

1995-01-01

Historically, the interface trap has been extensively investigated to determine the effects on device performance. Recently, much attention has been paid to trapping in near-interface oxide traps. Performance of high precision analog circuitry is affected by charge trapping in near-interface oxide traps which produces hysteresis, charge redistribution errors, and dielectric relaxation effects. In addition, the performance of low power digital circuitry, with reduced noise margins, may be drastically affected by the threshold voltage shifts associated with charge trapping in near -interface oxide traps. Since near-interface oxide traps may substantially alter the performance of devices, complete characterization of these defects is necessary. In this dissertation a new characterization technique, variable frequency charge pumping, is introduced which allows charge trapped at the interface to be distinguished from the charge trapped within the oxide. The new experimental technique is an extension of the charge pumping technique to low frequencies such that tunneling may occur from interface traps to near-interface oxide traps. A generalized charge pumping model, based on Shockley-Read-Hall statistics and trap-to-trap tunneling theory, has been developed which allows a more complete characterization of near-interface oxide traps. A pair of coupled differential equations governing the rate of change of occupied interface and near-interface oxide traps have been developed. Due to the experimental conditions in the charge pumping technique the equations may be decoupled, leading to an equation governing the rate of change of occupied interface traps and an equation governing the rate of change of occcupied near-interface oxide traps. Solving the interface trap equation and applying non-steady state charge dynamics leads to an interface trap component of the charge pumping current. In addition, solution to the near-interface oxide trap equation leads to an additional oxide trap component to the charge pumping current. Numerical simulations have been performed to support the analytical development of the generalized charge pumping model. By varying the frequency of the applied charge pumping waveform and monitoring the charge recombined per cycle, the contributions from interface traps may be separated from the contributions of the near-interface oxide traps. The generalized charge pumping model allows characterization of the density and spatial distribution of near-interface oxide traps from this variable frequency charge pumping technique. Characterization of interface and near-interface oxide trap generation has been performed on devices exposed to ionizing radiation, hot electron injection, and high -field/Fowler-Nordheim stressing. Finally, using SONOS nonvolatile memory devices, a framework has been established for experimentally determining not only the spatial distribution of near-interface oxide traps, but also the energetic distribution. An experimental approach, based on tri-level charge pumping, is discussed which allows the energetic distribution of near-interface oxide traps to be determined.

Aligned carbon nanotube/zinc oxide nanowire hybrids as high performance electrodes for supercapacitor applications

NASA Astrophysics Data System (ADS)

Al-Asadi, Ahmed S.; Henley, Luke Alexander; Wasala, Milinda; Muchharla, Baleeswaraiah; Perea-Lopez, Nestor; Carozo, Victor; Lin, Zhong; Terrones, Mauricio; Mondal, Kanchan; Kordas, Krisztian; Talapatra, Saikat

2017-03-01

Carbon nanotube/metal oxide based hybrids are envisioned as high performance electrochemical energy storage electrodes since these systems can provide improved performances utilizing an electric double layer coupled with fast faradaic pseudocapacitive charge storage mechanisms. In this work, we show that high performance supercapacitor electrodes with a specific capacitance of ˜192 F/g along with a maximum energy density of ˜3.8 W h/kg and a power density of ˜ 28 kW/kg can be achieved by synthesizing zinc oxide nanowires (ZnO NWs) directly on top of aligned multi-walled carbon nanotubes (MWCNTs). In comparison to pristine MWCNTs, these constitute a 12-fold of increase in specific capacitance as well as corresponding power and energy density values. These electrodes also possess high cycling stability and were able to retain ˜99% of their specific capacitance value over 2000 charging discharging cycles. These findings indicate potential use of a MWCNT/ZnO NW hybrid material for future electrochemical energy storage applications.

Time and voltage dependences of nanoscale dielectric constant modulation on indium tin oxide films

NASA Astrophysics Data System (ADS)

Li, Liang; Hao, Haoyue; Zhao, Hua

2017-01-01

The modulation of indium tin oxide (ITO) films through surface charge accumulation plays an important role in many different applications. In order to elaborately study the modulation, we measured the dielectric constant of the modulated layer through examining the excitation of surface plasmon polaritons. Charges were pumped on the surfaces of ITO films through applying high voltage in appropriate directions. Experiments unveiled that the dielectric constant of the modulated layer had large variation along with the nanoscale charge accumulation. Corresponding numerical results were worked out through combining Drude model and Mayadas-Shatzkes model. Based on the above results, we deduced the time and voltage dependences of accumulated charge density, which revealed a long-time charge accumulation process.

One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

PubMed Central

Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

2015-01-01

Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries. PMID:25563733

Floating gate memory with charge storage dots array formed by Dps protein modified with site-specific binding peptides

NASA Astrophysics Data System (ADS)

Kamitake, Hiroki; Uenuma, Mutsunori; Okamoto, Naofumi; Horita, Masahiro; Ishikawa, Yasuaki; Yamashita, Ichro; Uraoka, Yukiharu

2015-05-01

We report a nanodot (ND) floating gate memory (NFGM) with a high-density ND array formed by a biological nano process. We utilized two kinds of cage-shaped proteins displaying SiO2 binding peptide (minTBP-1) on their outer surfaces: ferritin and Dps, which accommodate cobalt oxide NDs in their cavities. The diameters of the cobalt NDs were regulated by the cavity sizes of the proteins. Because minTBP-1 is strongly adsorbed on the SiO2 surface, high-density cobalt oxide ND arrays were obtained by a simple spin coating process. The densities of cobalt oxide ND arrays based on ferritin and Dps were 6.8 × 1011 dots cm-2 and 1.2 × 1012 dots cm-2, respectively. After selective protein elimination and embedding in a metal-oxide-semiconductor (MOS) capacitor, the charge capacities of both ND arrays were evaluated by measuring their C-V characteristics. The MOS capacitor embedded with the Dps ND array showed a wider memory window than the device embedded with the ferritin ND array. Finally, we fabricated an NFGM with a high-density ND array based on Dps, and confirmed its competent writing/erasing characteristics and long retention time.

Scaling of Device Variability and Subthreshold Swing in Ballistic Carbon Nanotube Transistors

NASA Astrophysics Data System (ADS)

Cao, Qing; Tersoff, Jerry; Han, Shu-Jen; Penumatcha, Ashish V.

2015-08-01

In field-effect transistors, the inherent randomness of dopants and other charges is a major cause of device-to-device variability. For a quasi-one-dimensional device such as carbon nanotube transistors, even a single charge can drastically change the performance, making this a critical issue for their adoption as a practical technology. Here we calculate the effect of the random charges at the gate-oxide surface in ballistic carbon nanotube transistors, finding good agreement with the variability statistics in recent experiments. A combination of experimental and simulation results further reveals that these random charges are also a major factor limiting the subthreshold swing for nanotube transistors fabricated on thin gate dielectrics. We then establish that the scaling of the nanotube device uniformity with the gate dielectric, fixed-charge density, and device dimension is qualitatively different from conventional silicon transistors, reflecting the very different device physics of a ballistic transistor with a quasi-one-dimensional channel. The combination of gate-oxide scaling and improved control of fixed-charge density should provide the uniformity needed for large-scale integration of such novel one-dimensional transistors even at extremely scaled device dimensions.

Determination of intrinsic mobility of a bilayer oxide thin-film transistor by pulsed I-V method

NASA Astrophysics Data System (ADS)

Woo, Hyunsuk; Kim, Taeho; Hur, Jihyun; Jeon, Sanghun

2017-04-01

Amorphous oxide semiconductor thin-film transistors (TFT) have been considered as outstanding switch devices owing to their high mobility. However, because of their amorphous channel material with a certain level of density of states, a fast transient charging effect in an oxide TFT occurs, leading to an underestimation of the mobility value. In this paper, the effects of the fast charging of high-performance bilayer oxide semiconductor TFTs on mobility are examined in order to determine an accurate mobility extraction method. In addition, an approach based on a pulse I D -V G measurement method is proposed to determine the intrinsic mobility value. Even with the short pulse I D -V G measurement, a certain level of fast transient charge trapping cannot be avoided as long as the charge-trap start time is shorter than the pulse rising time. Using a pulse-amplitude-dependent threshold voltage characterization method, we estimated a correction factor for the apparent mobility, thus allowing us to determine the intrinsic mobility.

High frequency capacitance-voltage characteristics of thermally grown SiO2 films on beta-SiC

NASA Technical Reports Server (NTRS)

Tang, S. M.; Berry, W. B.; Kwor, R.; Zeller, M. V.; Matus, L. G.

1990-01-01

Silicon dioxide films grown under dry and wet oxidation environment on beta-SiC films have been studied. The beta-SiC films had been heteroepitaxially grown on both on-axis and 2-deg off-axis (001) Si substrates. Capacitance-voltage and conductance-voltage characteristics of metal-oxide-semiconductor structures were measured in a frequency range of 10 kHz to 1 MHz. From these measurements, the interface trap density and the effective fixed oxide charge density were observed to be generally lower for off-axis samples.

Covalent surface modification of chemically derived graphene and its application as supercapacitor electrode material.

PubMed

Jana, Milan; Khanra, Partha; Murmu, Naresh Chandra; Samanta, Pranab; Lee, Joong Hee; Kuila, Tapas

2014-04-28

A simple and effective method using 6-amino-4-hydroxy-2-naphthalenesulfonic acid (ANS) for the synthesis of water dispersible graphene has been described. Ultraviolet-visible (UV-vis) spectroscopy reveals that ANS-modified reduced graphene oxide (ANS-rGO) obeys Beers law at moderate concentrations. Fourier transform infrared and X-ray photoelectron spectroscopies provide quantitative information regarding the removal of oxygen functional groups from graphene oxide (GO) and the appearance of new functionalities in ANS-rGO. The electrochemical performances of ANS-rGO have been determined by cyclic voltammetry, charge-discharge and electrochemical impedance spectroscopy analysis. Charge-discharge experiments show that ANS-rGO is an outstanding supercapacitor electrode material due to its high specific capacitance (375 F g(-1) at a current density of 1.3 A g(-1)) and very good electrochemical cyclic stability (∼97.5% retention in specific capacitance after 1000 charge-discharge cycles). ANS-rGO exhibits promising characteristics with a very high power density (1328 W kg(-1)) and energy density (213 W h kg(-1)).

Interface effects on calculated defect levels for oxide defects

NASA Astrophysics Data System (ADS)

Edwards, Arthur; Barnaby, Hugh; Schultz, Peter; Pineda, Andrew

2014-03-01

Density functional theory (DFT) has had impressive recent success predicting defect levels in insulators and semiconductors [Schultz and von Lillienfeld, 2009]. Such success requires care in accounting for long-range electrostatic effects. Recently, Komsa and Pasquarello have started to address this problem in systems with interfaces. We report a multiscale technique for calculating electrostatic energies for charged defects in oxide of the metal-oxide-silicon (MOS) system, but where account is taken of substrate doping density, oxide thickness, and gate bias. We use device modeling to calculate electric fields for a point charge a fixed distance from the interface, and used the field to numerically calculate the long-range electrostatic interactions. We find, for example, that defect levels in the oxide do depend on both the magnitude and the polarity the substrate doping density. Furthermore, below 20 Å, oxide thickness also has significant effects. So, transferring results directly from bulk calculations leads to inaccuracies up to 0.5 eV- half of the silicon band gap. We will present trends in defect levels as a function of device parameters. We show that these results explain previous experimental results, and we comment on their potential impact on models for NBTI. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the United States Department of Energy's National Nuclear Security Administration under co.

Extraction method of interfacial injected charges for SiC power MOSFETs

NASA Astrophysics Data System (ADS)

Wei, Jiaxing; Liu, Siyang; Li, Sheng; Song, Haiyang; Chen, Xin; Li, Ting; Fang, Jiong; Sun, Weifeng

2018-01-01

An improved novel extraction method which can characterize the injected charges along the gate oxide interface for silicon carbide (SiC) power metal-oxide-semiconductor field-effect transistors (MOSFETs) is proposed. According to the different interface situations of the channel region and the junction FET (JFET) region, the gate capacitance versus gate voltage (Cg-Vg) curve of the device can be divided into three relatively independent parts, through which the locations and the types of the charges injected in to the oxide above the interface can be distinguished. Moreover, the densities of these charges can also be calculated by the amplitudes of the shifts in the Cg-Vg curve. The correctness of this method is proved by TCAD simulations. Moreover, experiments on devices stressed by unclamped-inductive-switching (UIS) stress and negative bias temperature stress (NBTS) are performed to verify the validity of this method.

A Rechargeable High-Temperature Molten Salt Iron-Oxygen Battery.

PubMed

Peng, Cheng; Guan, Chengzhi; Lin, Jun; Zhang, Shiyu; Bao, Hongliang; Wang, Yu; Xiao, Guoping; Chen, George Zheng; Wang, Jian-Qiang

2018-06-11

The energy and power density of conventional batteries are far lower than their theoretical expectations, primarily because of slow reaction kinetics that are often observed under ambient conditions. Here we describe a low-cost and high-temperature rechargeable iron-oxygen battery containing a bi-phase electrolyte of molten carbonate and solid oxide. This new design merges the merits of a solid-oxide fuel cell and molten metal-air battery, offering significantly improved battery reaction kinetics and power capability without compromising the energy capacity. The as-fabricated battery prototype can be charged at high current density, and exhibits excellent stability and security in the highly charged state. It typically exhibits specific energy, specific power, energy density, and power density of 129.1 Wh kg -1 , 2.8 kW kg -1 , 388.1 Wh L -1 , and 21.0 kW L -1 , respectively, based on the mass and volume of the molten salt. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

GaAs metal-oxide-semiconductor based non-volatile flash memory devices with InAs quantum dots as charge storage nodes

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

Islam, Sk Masiul, E-mail: masiulelt@gmail.com; Chowdhury, Sisir; Sarkar, Krishnendu

2015-06-24

Ultra-thin InP passivated GaAs metal-oxide-semiconductor based non-volatile flash memory devices were fabricated using InAs quantum dots (QDs) as charge storing elements by metal organic chemical vapor deposition technique to study the efficacy of the QDs as charge storage elements. The grown QDs were embedded between two high-k dielectric such as HfO{sub 2} and ZrO{sub 2}, which were used for tunneling and control oxide layers, respectively. The size and density of the QDs were found to be 5 nm and 1.8×10{sup 11} cm{sup −2}, respectively. The device with a structure Metal/ZrO{sub 2}/InAs QDs/HfO{sub 2}/GaAs/Metal shows maximum memory window equivalent to 6.87 V. Themore » device also exhibits low leakage current density of the order of 10{sup −6} A/cm{sup 2} and reasonably good charge retention characteristics. The low value of leakage current in the fabricated memory device is attributed to the Coulomb blockade effect influenced by quantum confinement as well as reduction of interface trap states by ultra-thin InP passivation on GaAs prior to HfO{sub 2} deposition.« less

High magnetic field studies of the charge density wave state of the quasi-two-dimensional conductor KMO 6O 17

NASA Astrophysics Data System (ADS)

Dumas, Jean; Guyot, Hervé; Balaska, Hafid; Marcus, Jacques; Vignolles, David; Sheikin, Ilya; Audouard, Alain; Brossard, Luc; Schlenker, Claire

2004-04-01

Magnetic torque and magnetoresistance measurements have been performed in high magnetic field on the quasi-two-dimensional charge density wave (CDW) oxide bronze KMo 6O 17 . Several anomalies have been found below 28 T either on the torque or on the magnetoresistance data. They can be attributed predominantly to orbital effects. Magnetoresistance data obtained up to 55 T show that a transition takes place above 30 T. This transition may be due to the Pauli coupling. The new field-induced density wave state exhibits Shubnikov-de Haas (SdH) oscillations.

A Hydrogen-Evolving Hybrid-Electrolyte Battery with Electrochemical/Photoelectrochemical Charging from Water Oxidation.

PubMed

Jin, Zhaoyu; Li, Panpan; Xiao, Dan

2017-02-08

Decoupled hydrogen and oxygen production were successfully embedded into an aqueous dual-electrolyte (acid-base) battery for simultaneous energy storage and conversion. A three-electrode configuration was adopted, involving an electrocatalytic hydrogen-evolving electrode as cathode, an alkaline battery-type or capacitor-type anode as shuttle, and a charging-assisting electrode for electro-/photoelectrochemically catalyzing water oxidation. The conceptual battery not only synergistically outputs electricity and chemical fuels with tremendous specific energy and power densities, but also supports various approaches to be charged by pure or solar-assisted electricity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of poly(ethylene oxide) on smectite: Effect of layer charge.

PubMed

Su, Chia-Chi; Shen, Yun-Hwei

2009-04-01

The adsorption of polymers on clay is important in many applications. However the mechanisms of poly(ethylene oxide) (PEO) adsorption on smectite is not well elucidated at present. The aim of this study was to investigate the effect of layer charge density on the adsorption of PEO by smectite. The results indicated that both the hydrophobic interaction (between CH(2)CH(2) groups and siloxane surface) and the hydrogen bonding (between ether oxygen of PEO and structure OH of smectite) lead to PEO preferential adsorption on the surface of low-charge smectite. In addition, the delamination of low-charge smectite in water is enhanced upon PEO adsorption presumably due to the hydrophilic ether oxygen of adsorbed PEO.

Some modification of cellulose nanocrystals for functional Pickering emulsions

PubMed Central

Saidane, Dorra; Perrin, Emilie; Cherhal, Fanch; Guellec, Florian

2016-01-01

Cellulose nanocrystals (CNCs) are negatively charged colloidal particles well known to form highly stable surfactant-free Pickering emulsions. These particles can vary in surface charge density depending on their preparation by acid hydrolysis or applying post-treatments. CNCs with three different surface charge densities were prepared corresponding to 0.08, 0.16 and 0.64 e nm−2, respectively. Post-treatment might also increase the surface charge density. The well-known TEMPO-mediated oxidation substitutes C6-hydroxyl groups by C6-carboxyl groups on the surface. We report that these different modified CNCs lead to stable oil-in-water emulsions. TEMPO-oxidized CNC might be the basis of further modifications. It is shown that they can, for example, lead to hydrophobic CNCs with a simple method using quaternary ammonium salts that allow producing inverse water-in-oil emulsions. Different from CNC modification before emulsification, modification can be carried out on the droplets after emulsification. This way allows preparing functional capsules according to the layer-by-layer process. As a result, it is demonstrated here the large range of use of these biobased rod-like nanoparticles, extending therefore their potential use to highly sophisticated formulations. This article is part of the themed issue ‘Soft interfacial materials: from fundamentals to formulation’. PMID:27298429

Understanding and Enhancing the Photostability of Nanoporous Metal Oxide Thin Films for Solar Hydrogen Generation

NASA Astrophysics Data System (ADS)

Chitrada, Kalyan Chakravarthi

Solar water splitting is an environmentally benign process which has received wide attention in the recent years as an alternate method for a clean and safe production of hydrogen. This process employs a semiconductor based photocatalyst, water, and sunlight to produce hydrogen. Metal-oxide based semiconductors are considered to be ideal photocatalytic materials because of their stability against photo-corrosion combined with relatively narrow energy band-gap, appropriately placed band edge positions with reference to oxygen and hydrogen energy levels, less scattering of charges due to wider valence band, high dielectric constant, natural abundance, and non-toxicity. In this dissertation, two metal oxide based semiconductors viz., iron (III) oxide and bismuth (III) oxide were investigated to understand and enhance their photo activity as photoanodes for solar water splitting application. Iron (III) oxide has a well suited band gap to capture solar spectrum but it suffers from inappropriately positioned band edges, recombination losses due to low electron mobility, and a small minority carrier diffusion length. However, it was hypothesized that the Iron (III) oxide might show interesting photoelectrochemical properties by alloying with 4f elements and shifting the conduction band minimum of the iron oxide favorably to more negative potentials. In the present study, a nanoporous iron oxide layer incorporated with Nd3+ and B3+ was synthesized by electrochemical anodization of a FeNdB alloy. The photoelectrochemical behavior of this oxide was compared with thermally oxidized FeNdB alloy and the iron oxides obtained by anodization and thermal oxidation of pure iron foil. Incorporation of Nd3+ and B3+ in the iron oxide showed a direct bandgap of 2.05 eV, an indirect bandgap of 1.9 eV and shifted the flatband potentials to --0.8 VAg/AgCl in 1 M KOH solution. The FeNdB oxide showed marginally better catalytic activity for the oxygen evolution reaction than pure iron oxide under dark conditions. The binary bismuth (III) oxide, in spite being a good photocatalytic material, did not receive as much attention as other bismuth based ternary oxides for photoelectrochemical water splitting application. In this present study, large surface area nanoporous bismuth oxide thin films were synthesized by the electrochemical anodization. These anodic oxides exhibited a dual layered structure having a planar inner oxide and nanoporous outer oxide. Effect of the nanoscale dimensions of the oxides on the photoelectrochemical behavior was studied to understand the charge transport, charge recombination behavior, and long term stability of the material. A maximum photo current density of 0.97 mA/cm2 was observed for the sample anodized at 10 V at 1.53 VRHE. The nanoporous anodic oxides showed a charge carrier density in the range of 1.2 x 1017 -- 4.8 x 1018 cm-3 without illumination and about 60% increase in the charge carrier density upon illumination. However a decay in photo current was observed for the bismuth oxide samples was due to accumulation of holes on the electrode surface. This hole-accumulation was mitigated by the addition of hole scavengers. Addition of hydrogen peroxide as hole scavenger increased the photo current density by about 4 times in 0.5 M Na2SO 4 (pH: 5.8) electrolyte. Addition of H2O2 in 1 M KOH (pH: 13.7) showed an increase-decrease behavior and high photo current density of ~10 mA/cm2 at a bias potential of 0.65 VRHE . The high photo activity observed in this electrolyte was attributed to the in-situ formation of Bi2O4-x phase by the photo-conversion of the beta-Bi2O3 at the surface. The photo-converted Bi2O4-x has a smaller band gap (1.4 eV) and therefore harvested more light in the visible region. This in-situ formation of low band gap phases in the presence of H2O2 during solar water splitting is an interesting observation which has been reported for the first time and this will help design material with very high photo-activity.

Effect of 30 MeV Li3+ ion and 8 MeV electron irradiation on N-channel MOSFETs

NASA Astrophysics Data System (ADS)

Prakash, A. P. G.; Ganesh, K. C. P.; Nagesha, Y. N.; Umakanth, D.; Arora, S. K.; Siddappa, K.

The effect of 30 MeV Li3+ ion and 8 MeV electron irradiation on the threshold voltage (V-TH), the voltage shift due to interface trapped charge (DeltaV(Nit)), the voltage shift due to oxide trapped charge (DeltaV(Not)), the density of interface trapped charge (DeltaN(it)), the density of oxide trapped charge (DeltaN(ot) ) and the drain saturation current (I-D Sat) were studied as a function of fluence. Considerable increase in DeltaN(it) and DeltaN(ot) , and decrease in V-TH and I-D Sat were observed in both types of irradiation. The observed difference in the properties of Li3+ ion and electron irradiated MOSFETs are interpreted on the basis of energy loss process associated with the type of radiation. The study showed that the 30 MeV Li3+ ion irradiation produce more damage when compared to the 8 MeV electron irradiation because of the higher electronic energy loss value. High temperature annealing studies showed that trapped charge generated during ion and electron irradiation was annealed out at 500 degreesC.

Tuning charge transfer in the LaTiO3/RO/LaNiO3 (R = rare-earth) superlattices by the rare-earth oxides interfaces from a first-principles calculation

NASA Astrophysics Data System (ADS)

Yao, Fen; Zhang, Lifang; Meng, Junling; Liu, Xiaojuan; Zhang, Xiong; Zhang, Wenwen; Meng, Jian; Zhang, Hongjie

2018-03-01

We investigate the internal charge transfer at the isopolar interfaces in LaTiO3/RO/LaNiO3 (R = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu) superlattices by means of density functional theory calculations. The charge transfer from Ti sites to Ni sites in all superlattices is induced by the electronegativity difference between the elements Ti and Ni, and the lanthanide oxides interfaces can modulate the amount of charge transfer. Comparison of the perovskite heterostructures with the different rare-earth interfaces shows that increasing the deviations of bond angles from 180.0° and the oxygen motions near the interfaces enhance charge transfer. The 4f electrons themselves of rare-earth elements have faint influences on charge transfer. In addition, the reasons why our calculated 4f states of Sm and Tm elements disagree with the experimental systems have been provided. It is hoped that all the calculated results could be used to design new functional nanoelectronic devices in perovskite oxides.

Oxidation catalysis by polyoxometalates fundamental electron-transfer phenomena

Treesearch

Yurii V. Geletii; Rajai H. Atalla; Alan J. Bailey; Laurent Delannoy; Craig L. Hill; Ira A. Weinstock

2002-01-01

Early transition-metal oxygen-anion clusters (polyoxometalates, POMs) are a large and rapidly growing class of versatile and tunable oxidation catalysts. All key molecular properties of these clusters (composition, size, shape, charge density, reduction potential, solubility, etc.) can be systematically altered, and the clusters themselves can serve as tunable ligands...

Instability of phosphorous doped SiO2 in 4H-SiC MOS capacitors at high temperatures

NASA Astrophysics Data System (ADS)

Idris, M. I.; Weng, M. H.; Chan, H.-K.; Murphy, A. E.; Clark, D. T.; Young, R. A. R.; Ramsay, E. P.; Wright, N. G.; Horsfall, A. B.

2016-12-01

In this paper, the effect of inclusion of phosphorous (at a concentration below 1%) on the high temperature characteristics (up to 300 °C) of the SiO2/SiC interface is investigated. Capacitance-voltage measurements taken for a range of frequencies have been utilized to extract parameters including flatband voltage, threshold voltage, effective oxide charge, and interface state density. The variation of these parameters with temperature has been investigated for bias sweeps in opposing directions and a comparison made between phosphorous doped and as-grown oxides. At room temperature, the effective oxide charge for SiO2 may be reduced by the phosphorous termination of dangling bonds at the interface. However, at high temperatures, the effective charge in the phosphorous doped oxide remains unstable and effects such as flatband voltage shift and threshold voltage shift dominate the characteristics. The instability in these characteristics was found to result from the trapped charges in the oxide (±1012 cm-3) or near interface traps at the interface of the gate oxide and the semiconductor (1012-1013 cm-2 eV-1). Hence, the performance enhancements observed for phosphorous doped oxides are not realised in devices operated at elevated temperatures.

Charge transfer in rectifying oxide heterostructures and oxide access elements in ReRAM

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

Stefanovich, G. B.; Pergament, A. L.; Boriskov, P. P.

2016-05-15

The main aspects of the synthesis and experimental research of oxide diode heterostructures are discussed with respect to their use as selector diodes, i.e., access elements in oxide resistive memory. It is shown that charge transfer in these materials differs significantly from the conduction mechanism in p–n junctions based on conventional semiconductors (Si, Ge, A{sup III}–B{sup V}), and the model should take into account the electronic properties of oxides, primarily the low carrier drift mobility. It is found that an increase in the forward current requires an oxide with a small band gap (<1.3 eV) in the heterostructure composition. Heterostructuresmore » with Zn, In–Zn (IZO), Ti, Ni, and Cu oxides are studied; it is found that the CuO–IZO heterojunction has the highest forward current density (10{sup 4} A/cm{sup 2}).« less

Resolving the degradation pathways in high-voltage oxides for high-energy-density lithium-ion batteries; Alternation in chemistry, composition and crystal structures

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

Mohanty, Debasish; Mazumder, Baishakhi; Devaraj, Arun

Our development of stable high-voltage (HV), high capacity (HC) cathode oxides is indispensable to enhancing the performance of current high-energy-density (HED) lithium-ion batteries. Overstoichiometric, layered Li- and Mn-rich (LMR) composite oxides are promising materials for HV-HC cathodes for HED batteries; however, their practical use is limited. By probing the crystal structure, magnetic structure, and microstructure of the Li 1.2Mn 0.55Ni 0.15Co 0.1O 2 LMR oxide, we demonstrate that the oxide loses its pristine chemistry, structure, and composition during the first charge-discharge cycle and that it proceeds through a series of progressive events that introduce impediments on the ion mobility pathways.more » Here, we discovered i) the presence of tetrahedral Mn 3+, interlayer cation intermixing, interface of layered-spinel, and structurally rearranged domains, cation segregation at an HV charged state, and ii) the loss of Li ions, inhomogeneous distribution of Li/Ni, and structurally transformed domains after the first discharge. Our results will advance our fundamental understanding of the obstacles related to ion migration pathways in HV-HC cathode systems and will enable us to formulate design rules for use of such materials in high-energy-density electrochemical-energy-storage devices.« less

Resolving the degradation pathways in high-voltage oxides for high-energy-density lithium-ion batteries; Alternation in chemistry, composition and crystal structures

DOE PAGES

Mohanty, Debasish; Mazumder, Baishakhi; Devaraj, Arun; ...

2017-04-05

Our development of stable high-voltage (HV), high capacity (HC) cathode oxides is indispensable to enhancing the performance of current high-energy-density (HED) lithium-ion batteries. Overstoichiometric, layered Li- and Mn-rich (LMR) composite oxides are promising materials for HV-HC cathodes for HED batteries; however, their practical use is limited. By probing the crystal structure, magnetic structure, and microstructure of the Li 1.2Mn 0.55Ni 0.15Co 0.1O 2 LMR oxide, we demonstrate that the oxide loses its pristine chemistry, structure, and composition during the first charge-discharge cycle and that it proceeds through a series of progressive events that introduce impediments on the ion mobility pathways.more » Here, we discovered i) the presence of tetrahedral Mn 3+, interlayer cation intermixing, interface of layered-spinel, and structurally rearranged domains, cation segregation at an HV charged state, and ii) the loss of Li ions, inhomogeneous distribution of Li/Ni, and structurally transformed domains after the first discharge. Our results will advance our fundamental understanding of the obstacles related to ion migration pathways in HV-HC cathode systems and will enable us to formulate design rules for use of such materials in high-energy-density electrochemical-energy-storage devices.« less

Charge localization and ordering in A 2 Mn 8 O 16 hollandite group oxides: Impact of density functional theory approaches

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

Kaltak, Merzuk; Fernandez-Serra, Marivi; Hybertsen, Mark S.

The phases of A 2Mn 8O 16 hollandite group oxides emerge from the competition between ionic interactions, Jahn-Teller effects, charge ordering, and magnetic interactions. Their balanced treatment with feasible computational approaches can be challenging for commonly used approximations in density functional theory. Three examples (A = Ag, Li, and K) are studied with a sequence of different approximate exchange-correlation functionals. Starting from a generalized gradient approximation (GGA), an extension to include van der Waals interactions and a recently proposed meta-GGA are considered. Then local Coulomb interactions for the Mn 3d electrons are more explicitly considered with the DFT + Umore » approach. Finally, selected results from a hybrid functional approach provide a reference. Results for the binding energy of the A species in the parent oxide highlight the role of van der Waals interactions. Relatively accurate results for insertion energies can be achieved with a low-U and a high-U approach. In the low-U case, the materials are described as band metals with a high-symmetry, tetragonal crystal structure. In the high-U case, the electrons donated by A result in formation of local Mn 3+ centers and corresponding Jahn-Teller distortions characterized by a local order parameter. The resulting degree of monoclinic distortion depends on charge ordering and magnetic interactions in the phase formed. The reference hybrid functional results show charge localization and ordering. Comparison to low-temperature experiments of related compounds suggests that charge localization is the physically correct result for the hollandite group oxides studied here. Lastly, while competing effects in the local magnetic coupling are subtle, the fully anisotropic implementation of DFT + U gives the best overall agreement with results from the hybrid functional.« less

Charge localization and ordering in A 2 Mn 8 O 16 hollandite group oxides: Impact of density functional theory approaches

DOE PAGES

Kaltak, Merzuk; Fernandez-Serra, Marivi; Hybertsen, Mark S.

2017-12-01

The phases of A 2Mn 8O 16 hollandite group oxides emerge from the competition between ionic interactions, Jahn-Teller effects, charge ordering, and magnetic interactions. Their balanced treatment with feasible computational approaches can be challenging for commonly used approximations in density functional theory. Three examples (A = Ag, Li, and K) are studied with a sequence of different approximate exchange-correlation functionals. Starting from a generalized gradient approximation (GGA), an extension to include van der Waals interactions and a recently proposed meta-GGA are considered. Then local Coulomb interactions for the Mn 3d electrons are more explicitly considered with the DFT + Umore » approach. Finally, selected results from a hybrid functional approach provide a reference. Results for the binding energy of the A species in the parent oxide highlight the role of van der Waals interactions. Relatively accurate results for insertion energies can be achieved with a low-U and a high-U approach. In the low-U case, the materials are described as band metals with a high-symmetry, tetragonal crystal structure. In the high-U case, the electrons donated by A result in formation of local Mn 3+ centers and corresponding Jahn-Teller distortions characterized by a local order parameter. The resulting degree of monoclinic distortion depends on charge ordering and magnetic interactions in the phase formed. The reference hybrid functional results show charge localization and ordering. Comparison to low-temperature experiments of related compounds suggests that charge localization is the physically correct result for the hollandite group oxides studied here. Lastly, while competing effects in the local magnetic coupling are subtle, the fully anisotropic implementation of DFT + U gives the best overall agreement with results from the hybrid functional.« less

Charge localization and ordering in A2Mn8O16 hollandite group oxides: Impact of density functional theory approaches

NASA Astrophysics Data System (ADS)

Kaltak, Merzuk; Fernández-Serra, Marivi; Hybertsen, Mark S.

2017-12-01

The phases of A2Mn8O16 hollandite group oxides emerge from the competition between ionic interactions, Jahn-Teller effects, charge ordering, and magnetic interactions. Their balanced treatment with feasible computational approaches can be challenging for commonly used approximations in density functional theory. Three examples (A = Ag, Li, and K) are studied with a sequence of different approximate exchange-correlation functionals. Starting from a generalized gradient approximation (GGA), an extension to include van der Waals interactions and a recently proposed meta-GGA are considered. Then local Coulomb interactions for the Mn 3 d electrons are more explicitly considered with the DFT + U approach. Finally, selected results from a hybrid functional approach provide a reference. Results for the binding energy of the A species in the parent oxide highlight the role of van der Waals interactions. Relatively accurate results for insertion energies can be achieved with a low-U and a high-U approach. In the low-U case, the materials are described as band metals with a high-symmetry, tetragonal crystal structure. In the high-U case, the electrons donated by A result in formation of local Mn3 + centers and corresponding Jahn-Teller distortions characterized by a local order parameter. The resulting degree of monoclinic distortion depends on charge ordering and magnetic interactions in the phase formed. The reference hybrid functional results show charge localization and ordering. Comparison to low-temperature experiments of related compounds suggests that charge localization is the physically correct result for the hollandite group oxides studied here. Finally, while competing effects in the local magnetic coupling are subtle, the fully anisotropic implementation of DFT + U gives the best overall agreement with results from the hybrid functional.

Structural and Electronic Properties of Transition-Metal Oxides Attached to a Single-Walled CNT as a Lithium-Ion Battery Electrode: A First-Principles Study.

PubMed

Tack, Liew Weng; Azam, Mohd Asyadi; Seman, Raja Noor Amalina Raja

2017-04-06

Single-walled carbon nanotubes (SWCNTs) and metal oxides (MOs), such as manganese(IV) oxide (MnO 2 ), cobalt(II, III) oxide (Co 3 O 4 ), and nickel(II) oxide (NiO) hybrid structures, have received great attention because of their promising application in lithium-ion batteries (LIBs). As electrode materials for LIBs, the structure of SWCNT/MOs provides high power density, good electrical conductivity, and excellent cyclic stability. In this work, first-principles calculations were used to investigate the structural and electronic properties of MOs attached to (5, 5) SWCNT and Li-ion adsorption to SWCNT/metal oxide composites as electrode materials in LIBs. Emphasis was placed on the synergistic effects of the composite on the electrochemical performance of LIBs in terms of adsorption capabilities and charge transfer of Li-ions attached to (5, 5) SWCNT and metal oxides. Also, Li adsorption energy on SWCNTs and three different metal oxides (NiO, MnO 2 , and Co 3 O 4 ) and the accompanying changes in the electronic properties, such as band structure, density of states and charge distribution as a function of Li adsorption were calculated. On the basis of the calculation results, the top C atom was found to be the most stable position for the NiO and MnO 2 attachment to SWCNT, while the Co 3 O 4 molecule, the Co 2+ , was found to be the most stable attachment on SWCNT. The obtained results show that the addition of MOs to the SWCNT electrode enables an increase in specific surface area and improves the electronic conductivity and charge transfer of an LIB.

Solid-State Thin-Film Supercapacitors with Ultrafast Charge/Discharge Based on N-Doped-Carbon-Tubes/Au-Nanoparticles-Doped-MnO2 Nanocomposites.

PubMed

Lv, Qiying; Wang, Shang; Sun, Hongyu; Luo, Jun; Xiao, Jian; Xiao, JunWu; Xiao, Fei; Wang, Shuai

2016-01-13

Although carbonaceous materials possess long cycle stability and high power density, their low-energy density greatly limits their applications. On the contrary, metal oxides are promising pseudocapacitive electrode materials for supercapacitors due to their high-energy density. Nevertheless, poor electrical conductivity of metal oxides constitutes a primary challenge that significantly limits their energy storage capacity. Here, an advanced integrated electrode for high-performance pseudocapacitors has been designed by growing N-doped-carbon-tubes/Au-nanoparticles-doped-MnO2 (NCTs/ANPDM) nanocomposite on carbon fabric. The excellent electrical conductivity and well-ordered tunnels of NCTs together with Au nanoparticles of the electrode cause low internal resistance, good ionic contact, and thus enhance redox reactions for high specific capacitance of pure MnO2 in aqueous electrolyte, even at high scan rates. A prototype solid-state thin-film symmetric supercapacitor (SSC) device based on NCTs/ANPDM exhibits large energy density (51 Wh/kg) and superior cycling performance (93% after 5000 cycles). In addition, the asymmetric supercapacitor (ASC) device assembled from NCTs/ANPDM and Fe2O3 nanorods demonstrates ultrafast charge/discharge (10 V/s), which is among the best reported for solid-state thin-film supercapacitors with both electrodes made of metal oxide electroactive materials. Moreover, its superior charge/discharge behavior is comparable to electrical double layer type supercapacitors. The ASC device also shows superior cycling performance (97% after 5000 cycles). The NCTs/ANPDM nanomaterial demonstrates great potential as a power source for energy storage devices.

Optimization of the parameters of ITO-CdTe photovoltaic cells

NASA Astrophysics Data System (ADS)

Adib, N.; Simashkevich, A. V.; Sherban, D. A.

The effect of the surface state density at the interface and of the static charge in the intermediate oxide layer on the photoelectric parameters of solar cells based on ITO-nCdTe semiconductor-insulator-semiconductor structures is calculated theoretically. It is shown that,under AMI conditions, the conversion efficiency of such cells can be as high as 12 percent (short-circuit current, 23 mA/sq cm; open-circuit voltage, 0.65 V; fill factor, 0.8), provided that the surface states are acceptors and the oxide is negatively charged. It is concluded that surface states and the dielectric layer charge have a positive effect on the efficiency of solar cells of this type.

Controlled growth of semiconductor crystals

DOEpatents

Bourret-Courchesne, Edith D.

1992-01-01

A method for growth of III-V, II-VI and related semiconductor single crystals that suppresses random nucleation and sticking of the semiconductor melt at the crucible walls. Small pieces of an oxide of boron B.sub.x O.sub.y are dispersed throughout the comminuted solid semiconductor charge in the crucible, with the oxide of boron preferably having water content of at least 600 ppm. The crucible temperature is first raised to a temperature greater than the melt temperature T.sub.m1 of the oxide of boron (T.sub.m1 =723.degree. K. for boron oxide B.sub.2 O.sub.3), and the oxide of boron is allowed to melt and form a reasonably uniform liquid layer between the crucible walls and bottom surfaces and the still-solid semiconductor charge. The temperature is then raised to approximately the melt temperature T.sub.m2 of the semiconductor charge material, and crystal growth proceeds by a liquid encapsulated, vertical gradient freeze process. About half of the crystals grown have a dislocation density of less than 1000/cm.sup.2. If the oxide of boron has water content less than 600 ppm, the crucible material should include boron nitride, a layer of the inner surface of the crucible should be oxidized before the oxide of boron in the crucible charge is melted, and the sum of thicknesses of the solid boron oxide layer and liquid boron oxide layer should be at least 50 .mu.m.

Controlled growth of semiconductor crystals

DOEpatents

Bourret-Courchesne, E.D.

1992-07-21

A method is disclosed for growth of III-V, II-VI and related semiconductor single crystals that suppresses random nucleation and sticking of the semiconductor melt at the crucible walls. Small pieces of an oxide of boron B[sub x]O[sub y] are dispersed throughout the comminuted solid semiconductor charge in the crucible, with the oxide of boron preferably having water content of at least 600 ppm. The crucible temperature is first raised to a temperature greater than the melt temperature T[sub m1] of the oxide of boron (T[sub m1]=723 K for boron oxide B[sub 2]O[sub 3]), and the oxide of boron is allowed to melt and form a reasonably uniform liquid layer between the crucible walls and bottom surfaces and the still-solid semiconductor charge. The temperature is then raised to approximately the melt temperature T[sub m2] of the semiconductor charge material, and crystal growth proceeds by a liquid encapsulated, vertical gradient freeze process. About half of the crystals grown have a dislocation density of less than 1000/cm[sup 2]. If the oxide of boron has water content less than 600 ppm, the crucible material should include boron nitride, a layer of the inner surface of the crucible should be oxidized before the oxide of boron in the crucible charge is melted, and the sum of thicknesses of the solid boron oxide layer and liquid boron oxide layer should be at least 50 [mu]m. 7 figs.

Degradation of the electrical characteristics of MOS structures with erbium, gadolinium, and dysprosium oxides under the effect of an electric field

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

Shalimova, M. B., E-mail: shamb@samsu.ru; Sachuk, N. V.

2015-08-15

The degradation of the characteristics of silicon metal-oxide-semiconductor (MOS) structures with oxides of rare-earth elements under the effect of electric fields with intensities of 0.1–4 MV/cm during the course of electroforming is studied. A specific feature of electroforming consists in the possibility of multiple switching of the structures from the insulating state to the low-resistivity one and back. The temporal characteristics of the degradation of MOS structures during the course of electroforming are exponential. The current-voltage characteristics follow the power law in the range of 0.2–3 V; the effect of an electric field brings about a variation in the distributionmore » of the energy density of traps responsible for currents limited by space charge. It is established that multiple cycles of electroforming lead to an increase in the density of surface states at the Si-oxide interface and to a variation in the energy position of the trap levels, which affects the charge state of the traps.« less

Energetics of edge oxidization of graphene nanoribbons

NASA Astrophysics Data System (ADS)

Yasuma, Airi; Yamanaka, Ayaka; Okada, Susumu

2018-06-01

On the basis of the density functional theory, we studied the geometries and energetics of O atoms adsorbed on graphene edges for simulating the initial stage of the edge oxidization of graphene. Our calculations showed that oxygen atoms are preferentially adsorbed onto the graphene edges with the zigzag portion, resulting in a large adsorption energy of about 5 eV. On the other hand, the edges with armchair shape are rarely oxidized, or the oxidization causes substantial structural reconstructions, because of the stable covalent bond at the armchair edge with the triple bond nature. Furthermore, the energetics sensitively depends on the edge angles owing to the inhomogeneity of the charge density at the edge atomic sites.

Conduction mechanism change with transport oxide layer thickness in oxide hetero-interface diode

NASA Astrophysics Data System (ADS)

Nam, Bu-il; Park, Jong Seo; Lim, Keon-Hee; Ahn, Yong-keon; Lee, Jinwon; Park, Jun-woo; Cho, Nam-Kwang; Lee, Donggun; Lee, Han-Bo-Ram; Kim, Youn Sang

2017-07-01

An effective and facile strategy is proposed to demonstrate an engineered oxide hetero-interface of a thin film diode with a high current density and low operating voltage. The electrical characteristics of an oxide hetero-interface thin film diode are governed by two theoretical models: the space charge-limited current model and the Fowler-Nordheim (F-N) tunneling model. Interestingly, the dominant mechanism strongly depends on the insulator thickness, and the mechanism change occurs at a critical thickness. This paper shows that conduction mechanisms of oxide hetero-interface thin film diodes depend on thicknesses of transport oxide layers and that current densities of these can be exponentially increased through quantum tunneling in the diodes with the thicknesses less than 10 nm. These oxide hetero-interface diodes have great potential for low-powered transparent nanoscale applications.

Electric charging/discharging characteristics of super capacitor, using de-alloying and anodic oxidized Ti-Ni-Si amorphous alloy ribbons.

PubMed

Fukuhara, Mikio; Sugawara, Kazuyuki

2014-01-01

Charging/discharging behaviors of de-alloyed and anodic oxidized Ti-Ni-Si amorphous alloy ribbons were measured as a function of current between 10 pA and 100 mA, using galvanostatic charge/discharging method. In sharp contrast to conventional electric double layer capacitor (EDLC), discharging behaviors for voltage under constant currents of 1, 10 and 100 mA after 1.8 ks charging at 100 mA show parabolic decrease, demonstrating direct electric storage without solvents. The supercapacitors, devices that store electric charge on their amorphous TiO2-x surfaces that contain many 70-nm sized cavities, show the Ragone plot which locates at lower energy density region near the 2nd cells, and RC constant of 800 s (at 1 mHz), which is 157,000 times larger than that (5 ms) in EDLC.

Electric charging/discharging characteristics of super capacitor, using de-alloying and anodic oxidized Ti-Ni-Si amorphous alloy ribbons

PubMed Central

2014-01-01

Charging/discharging behaviors of de-alloyed and anodic oxidized Ti-Ni-Si amorphous alloy ribbons were measured as a function of current between 10 pA and 100 mA, using galvanostatic charge/discharging method. In sharp contrast to conventional electric double layer capacitor (EDLC), discharging behaviors for voltage under constant currents of 1, 10 and 100 mA after 1.8 ks charging at 100 mA show parabolic decrease, demonstrating direct electric storage without solvents. The supercapacitors, devices that store electric charge on their amorphous TiO2-x surfaces that contain many 70-nm sized cavities, show the Ragone plot which locates at lower energy density region near the 2nd cells, and RC constant of 800 s (at 1 mHz), which is 157,000 times larger than that (5 ms) in EDLC. PMID:24959106

Quantitative Analysis of Charge Injection and Discharging of Si Nanocrystals and Arrays by Electrostatic Force Microscopy

NASA Technical Reports Server (NTRS)

Bell, L. D.; Boer, E.; Ostraat, M.; Brongersma, M. L.; Flagan, R. C.; Atwater, H. A.

2000-01-01

NASA requirements for computing and memory for microspacecraft emphasize high density, low power, small size, and radiation hardness. The distributed nature of storage elements in nanocrystal floating-gate memories leads to intrinsic fault tolerance and radiation hardness. Conventional floating-gate non-volatile memories are more susceptible to radiation damage. Nanocrystal-based memories also offer the possibility of faster, lower power operation. In the pursuit of filling these requirements, the following tasks have been accomplished: (1) Si nanocrystal charging has been accomplished with conducting-tip AFM; (2) Both individual nanocrystals on an oxide surface and nanocrystals formed by implantation have been charged; (3) Discharging is consistent with tunneling through a field-lowered oxide barrier; (4) Modeling of the response of the AFM to trapped charge has allowed estimation of the quantity of trapped charge; and (5) Initial attempts to fabricate competitive nanocrystal non-volatile memories have been extremely successful.

Status in calculating electronic excited states in transition metal oxides from first principles.

PubMed

Bendavid, Leah Isseroff; Carter, Emily Ann

2014-01-01

Characterization of excitations in transition metal oxides is a crucial step in the development of these materials for photonic and optoelectronic applications. However, many transition metal oxides are considered to be strongly correlated materials, and their complex electronic structure is challenging to model with many established quantum mechanical techniques. We review state-of-the-art first-principles methods to calculate charged and neutral excited states in extended materials, and discuss their application to transition metal oxides. We briefly discuss developments in density functional theory (DFT) to calculate fundamental band gaps, and introduce time-dependent DFT, which can model neutral excitations. Charged excitations can be described within the framework of many-body perturbation theory based on Green's functions techniques, which predominantly employs the GW approximation to the self-energy to facilitate a feasible solution to the quasiparticle equations. We review the various implementations of the GW approximation and evaluate each approach in its calculation of fundamental band gaps of many transition metal oxides. We also briefly review the related Bethe-Salpeter equation (BSE), which introduces an electron-hole interaction between GW-derived quasiparticles to describe accurately neutral excitations. Embedded correlated wavefunction theory is another framework used to model localized neutral or charged excitations in extended materials. Here, the electronic structure of a small cluster is modeled within correlated wavefunction theory, while its coupling to its environment is represented by an embedding potential. We review a number of techniques to represent this background potential, including electrostatic representations and electron density-based methods, and evaluate their application to transition metal oxides.

High quality factor graphene varactors for wireless sensing applications

NASA Astrophysics Data System (ADS)

Koester, Steven J.

2011-10-01

A graphene wireless sensor concept is described. By utilizing thin gate dielectrics, the capacitance in a metal-insulator-graphene structure varies with charge concentration through the quantum capacitance effect. Simulations using realistic structural and transport parameters predict quality factors, Q, >60 at 1 GHz. When placed in series with an ideal inductor, a resonant frequency tuning ratio of 25% (54%) is predicted for sense charge densities ranging from 0.32 to 1.6 μC/cm2 at an equivalent oxide thickness of 2.0 nm (0.5 nm). The resonant frequency has a temperature sensitivity, df/dT, less than 0.025%/K for sense charge densities >0.32 μC/cm2.

Influence of controlled surface oxidation on the magnetic anisotropy of Co ultrathin films

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

Di, N.; Maroun, F., E-mail: fouad.maroun@polytechnique.fr; Allongue, P.

2015-03-23

We studied the influence of controlled surface-limited oxidation of electrodeposited epitaxial Co(0001)/Au(111) films on their magnetic anisotropy energy using real time in situ magneto optical Kerr effect and density functional theory (DFT) calculations. We investigated the Co first electrochemical oxidation step which we demonstrate to be completely reversible and determined the structure of this oxide layer. We show that the interface magnetic anisotropy of the Co film increases by 0.36 erg/cm{sup 2} upon Co surface oxidation. We performed DFT calculations to determine the different surface structures in a wide potential range as well as the charge transfer at the Co surface.more » Our results suggest that the magnetic anisotropy change is correlated with a positive charge increase of 0.54 e{sup −} for the Co surface atom upon oxidation.« less

Homogeneous dispersion of organic p-dopants in an organic semiconductor as an origin of high charge generation efficiency

NASA Astrophysics Data System (ADS)

Lee, Jae-Hyun; Kim, Hyun-Mi; Kim, Ki-Bum; Kabe, Ryota; Anzenbacher, Pavel; Kim, Jang-Joo

2011-04-01

We report that an organic p-dopant tri[1,2-bis(trifluoromethyl)ethane-1,2-dithiolene] [Mo(tfd)3] resulted in higher density of holes than inorganic metal oxide dopants of ReO3 or MoO3 in 1,4-bis[N-(1-naphthyl)-N'-phenylamino]-4,4'-diamine even though the metal oxide dopants possess deeper work functions compared to Mo(tfd)3. Higher charge generation efficiency results largely from the homogeneous dispersion of Mo(tfd)3 in the host. In contradistinction, the transmission electron microscopy analysis revealed a formation of metal oxide nanoclusters. This highlights the importance of homogeneous dispersion for an efficient doping.

Effects of low-temperature (120 °C) annealing on the carrier concentration and trap density in amorphous indium gallium zinc oxide thin film transistors

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

Kim, Jae-sung; Piao, Mingxing; Jang, Ho-Kyun

2014-12-28

We report an investigation of the effects of low-temperature annealing on the electrical properties of amorphous indium gallium zinc oxide (a-IGZO) thin-film transistors (TFTs). X-ray photoelectron spectroscopy was used to characterize the charge carrier concentration, which is related to the density of oxygen vacancies. The field-effect mobility was found to decrease as a function of the charge carrier concentration, owing to the presence of band-tail states. By employing the transmission line method, we show that the contact resistance did not significantly contribute to the changes in device performance after annealing. In addition, using low-frequency noise analyses, we found that themore » trap density decreased by a factor of 10 following annealing at 120 °C. The switching operation and on/off ratio of the a-IGZO TFTs improved considerably after low-temperature annealing.« less

Thermal treatment effects on charge storage performance of graphene-based materials for supercapacitors.

PubMed

Zhang, Hongxin; Bhat, Vinay V; Gallego, Nidia C; Contescu, Cristian I

2012-06-27

Graphene materials were synthesized by reduction of exfoliated graphite oxide and then thermally treated in nitrogen to improve the surface area and their electrochemical performance as electrical double-layer capacitor electrodes. The structural and surface properties of the prepared reduced graphite oxide (RGO) were investigated using atomic force microscopy, scanning electron microscopy, Raman spectra, X-ray diffraction pattern analysis, and nitrogen adsorption/desorption studies. RGO forms a continuous network of crumpled sheets, which consist of large amounts of few-layer and single-layer graphenes. Electrochemical studies were conducted by cyclic voltammetry, impedance spectroscopy, and galvanostatic charge-discharge measurements. The modified RGO materials showed enhanced electrochemical performance, with maximum specific capacitance of 96 F/g, energy density of 12.8 Wh/kg, and power density of 160 kW/kg. These results demonstrate that thermal treatment of RGO at selected conditions is a convenient and efficient method for improving its specific capacitance, energy, and power density.

Designing New Materials for Converting Solar Energy to Fuels via Quantum Mechanics

DTIC Science & Technology

2014-07-11

dopants can also be exploited to increase charge carrier concentration without creating traps and hence improve the conductivity of these materials...e.g., Mn(II) in hematite for hole transport, Y(III) in MnO:ZnO for electron transport). • We discovered that dopants derived from covalent oxides...e.g., Si from silica, as a dopant in hematite) can also be used to increase charge carrier density without creating traps. Charge carriers stay

Graphite oxide/β-Ni(OH)2 composites for application in supercapacitors

NASA Astrophysics Data System (ADS)

Singh, Arvinder; Chandra, Amreesh

2013-06-01

Graphite oxide/β-Ni(OH)2 composites have been investigated as electrode material in supercapacitors. Phase formation of electrode material is investigated using diffraction measurements. Particle shape-size studies show deposition of β-Ni(OH)2 nanoparticles on graphite oxide (GO) sheets. Electrochemical performance of GO/β-Ni(OH)2 composite in supercapacitors is discussed based on the analysis of electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and galvanostatic charge-discharge studies. Excellent energy density of ˜53 Wh/kg in 1M Na2SO4 aqueous electrolyte is reported at power density of ˜1364W/kg. The significance of results is discussed in the paper.

POx/Al2O3 stacks: Highly effective surface passivation of crystalline silicon with a large positive fixed charge

NASA Astrophysics Data System (ADS)

Black, Lachlan E.; Kessels, W. M. M. Erwin

2018-05-01

Thin-film stacks of phosphorus oxide (POx) and aluminium oxide (Al2O3) are shown to provide highly effective passivation of crystalline silicon (c-Si) surfaces. Surface recombination velocities as low as 1.7 cm s-1 and saturation current densities J0s as low as 3.3 fA cm-2 are obtained on n-type (100) c-Si surfaces passivated by 6 nm/14 nm thick POx/Al2O3 stacks deposited in an atomic layer deposition system and annealed at 450 °C. This excellent passivation can be attributed in part to an unusually large positive fixed charge density of up to 4.7 × 1012 cm-2, which makes such stacks especially suitable for passivation of n-type Si surfaces.

Cyclic voltammetry on sputter-deposited films of electrochromic Ni oxide: Power-law decay of the charge density exchange

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

Wen, Rui-Tao, E-mail: Ruitao.Wen@angstrom.uu.se; Granqvist, Claes G.; Niklasson, Gunnar A.

2014-10-20

Ni-oxide-based thin films were produced by reactive direct-current magnetron sputtering and were characterized by X-ray diffraction and Rutherford backscattering spectroscopy. Intercalation of Li{sup +} ions was accomplished by cyclic voltammetry (CV) in an electrolyte of LiClO{sub 4} in propylene carbonate, and electrochromism was documented by spectrophotometry. The charge density exchange, and hence the optical modulation span, decayed gradually upon repeated cycling. This phenomenon was accurately described by an empirical power law, which was valid for at least 10{sup 4} cycles when the applied voltage was limited to 4.1 V vs Li/Li{sup +}. Our results allow lifetime assessments for one of themore » essential components in an electrochromic device such as a “smart window” for energy-efficient buildings.« less

Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review

NASA Astrophysics Data System (ADS)

Zhi, Mingjia; Xiang, Chengcheng; Li, Jiangtian; Li, Ming; Wu, Nianqiang

2012-12-01

This paper presents a review of the research progress in the carbon-metal oxide composites for supercapacitor electrodes. In the past decade, various carbon-metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon-metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review.

PubMed

Zhi, Mingjia; Xiang, Chengcheng; Li, Jiangtian; Li, Ming; Wu, Nianqiang

2013-01-07

This paper presents a review of the research progress in the carbon-metal oxide composites for supercapacitor electrodes. In the past decade, various carbon-metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon-metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

Environmental Electrometry with Luminescent Carbon Nanotubes.

PubMed

Noé, Jonathan C; Nutz, Manuel; Reschauer, Jonathan; Morell, Nicolas; Tsioutsios, Ioannis; Reserbat-Plantey, Antoine; Watanabe, Kenji; Taniguchi, Takashi; Bachtold, Adrian; Högele, Alexander

2018-06-25

We demonstrate that localized excitons in luminescent carbon nanotubes can be utilized to study electrostatic fluctuations in the nanotube environment with sensitivity down to the elementary charge. By monitoring the temporal evolution of the cryogenic photoluminescence from individual carbon nanotubes grown on silicon oxide and hexagonal boron nitride, we characterize the dynamics of charge trap defects for both dielectric supports. We find a one order of magnitude reduction in the photoluminescence spectral wandering for nanotubes on extended atomically flat terraces of hexagonal boron nitride. For nanotubes on hexagonal boron nitride with pronounced spectral fluctuations, our analysis suggests proximity to terrace ridges where charge fluctuators agglomerate to exhibit areal densities exceeding those of silicon oxide. Our results establish carbon nanotubes as sensitive probes of environmental charge fluctuations and highlight their potential for applications in electrometric nanodevices with all-optical readout.

Buffer-eliminated, charge-neutral epitaxial graphene on oxidized 4H-SiC (0001) surface

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

Sirikumara, Hansika I., E-mail: hansi.sirikumara@siu.edu; Jayasekera, Thushari, E-mail: thushari@siu.edu

Buffer-eliminated, charge-neutral epitaxial graphene (EG) is important to enhance its potential in device applications. Using the first principles Density Functional Theory calculations, we investigated the effect of oxidation on the electronic and structural properties of EG on 4H-SiC (0001) surface. Our investigation reveals that the buffer layer decouples from the substrate in the presence of both silicate and silicon oxy-nitride at the interface, and the resultant monolayer EG is charge-neutral in both cases. The interface at 4H-SiC/silicate/EG is characterized by surface dangling electrons, which opens up another route for further engineering EG on 4H-SiC. Dangling electron-free 4H-SiC/silicon oxy-nitride/EG is idealmore » for achieving charge-neutral EG.« less

Electrochemical comparison of nickel and nickel hydroxide nanoparticles composited with reduced graphene oxide and polyaniline for their supercapacitor application

NASA Astrophysics Data System (ADS)

Viswanthan, Aranganathan; Shetty, Adka Nityananda

2018-04-01

The reduced graphene oxide/polyaniline/Ni(OH)2 (GP-Ni(OH)2) and reduced graphene oxide/polyaniline/Ni (GP-Ni) nanocomposites were synthesized by facile in situ single step chemical method. The constituents were confirmed by powder-XRD, and the electrochemical characterizations were carried out using cyclic voltammetry(CV), galvanostatic charge/discharge (GCD) and electrochemical impedance spectroscopy (EIS). The electrochemical contribution of Ni(OH)2 and Ni to their supercapacitance along with reduced graphene oxide and polyaniline was compared. The GP-Ni nanocomposite exhibited a specific capacitance of 266.66 F g-1, energy density of 53.33 W h kg-1 and power density of 1385 W kg-1 at a current density of 0.25 A g-1 and the results were enhanced to 21% and more promising than that of nanocomposite GP-Ni(OH)2.

Semiconductor technology program. Progress briefs

NASA Technical Reports Server (NTRS)

Bullis, W. M.

1980-01-01

Measurement technology for semiconductor materials, process control, and devices is reviewed. Activities include: optical linewidth and thermal resistance measurements; device modeling; dopant density profiles; resonance ionization spectroscopy; and deep level measurements. Standardized oxide charge terminology is also described.

An accurate MOS measurement procedure for work function difference in the Al/SiO 2/Si system

NASA Astrophysics Data System (ADS)

Krautschneider, W. H.; Laschinski, J.; Seifert, W.; Wagemann, H. G.

1986-05-01

Determination of Al/Si work function difference φMS is achieved by means of capacitance measurements of differently manufactured MOS varactors (Al/SiO 2/ n-Si) with variable oxide thickness ("step varactor"). For the φMS evaluation the influences of interface (fQ it) and oxide (ifQ f) charges have been considered, and models of their charges and dipole behaviour are described. Midgap band bending has been chosen as best condition for the evaluation of ΦMSO as basic amount of work function difference with negligible interference of Qit. Plots of Φ MSvs ψS for numerous specimens indicate that, usually, dipole voltage ΔΦ is closely connected to ΦMS within the voltage drop across the MOS varactor according to ΦMS = ΦMSO + qΔΦ. For the evaluation of dipole voltage ΔΦ models of charge density Qit within interface states are presented which assume dominating donor or acceptor states within the two halves of the band gap. Corrections of impurity homogeneity across the wafer and of impurity profile into the depth of the chips are considered. For the work function difference extrapolated to intrinsic density, ΦMSO = (-0.26 ± 0.05) eV holds. Additionally from midgap through inversion of n-Si, dipole voltage was observed ( ΔΦ = 0.015 V) which was caused by interface states and oxide charge 3 nm apart from one another.

COMPARATIVE ASSESSMENT OF THE COMPOSITION AND CHARGE STATE OF NITROGENASE FeMo-COFACTOR

PubMed Central

Harris, Travis V.; Szilagyi, Robert K.

2011-01-01

A significant limitation in our understanding of the molecular mechanism of biological nitrogen fixation is the uncertain composition of the FeMo-cofactor (FeMo-co) of nitrogenase. In this study we present a systematic, density functional theory-based evaluation of spin coupling schemes, iron oxidation states, ligand protonation states, and interstitial ligand composition using a wide range of experimental criteria. The employed functionals and basis sets were validated with molecular orbital information from X-ray absorption spectroscopic data of relevant iron-sulfur clusters. Independently from the employed level of theory, the electronic structure with the greatest number of antiferromagnetic interactions corresponds to the lowest energy state for a given charge and oxidation state distribution of the iron ions. The relative spin state energies of resting and oxidized FeMo-co already allowed the exclusion of certain iron oxidation state distributions and interstitial ligand compositions. Geometry optimized FeMo-co structures of several models further eliminated additional states and compositions, while reduction potentials indicated a strong preference for the most likely charge state of FeMo-co. Mössbauer and ENDOR parameter calculations were found to be remarkably dependent on the employed training set, density functional and basis set. Overall, we found that a more oxidized [MoIV-2FeII-5FeIII-9S2−-C4−] composition with a hydroxyl-protonated homocitrate ligand satisfies all of the available experimental criteria, and is thus favored over the currently preferred composition of [MoIV-4FeII-3FeIII-9S2−-N3−] from the literature. PMID:21545160

Photoelectron Spectroscopy of Free Polyoxoanions Mo6O19 2- and W6O19 2- in the Gas Phase

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

Infante, Ivan A.; Visscher, Lucas; Wang, Xue B.

2004-09-22

Two doubly charged polyoxoanions, Mo6O19 2- and W6O19 2-, were observed in the gas phase using electrospray ionization. Their electronic structures were investigated using photoelectron spectroscopy and quasi-relativistic density functional calculations. Each dianion was found to be highly stable despite the presence of strong intramolecular coulomb repulsion, estimated to be about 2 eV for each system. The valence detachment features were all shown to originate from electronic excitations involving oxygen lone-pair type orbitals. Their observed energies were in excellent agreement with the theoretical vertical detachment energies calculated using time-dependent density functional theory. Despite being multiply charged, polyoxometalate oxide clusters canmore » be studied in the gas phase, providing the opportunity for detailed benchmark theoretical studies on the electronic structures of these important transition-metal oxide systems.« less

Comparison and characterization of different tunnel layers, suitable for passivated contact formation

NASA Astrophysics Data System (ADS)

Ling, Zhi Peng; Xin, Zheng; Ke, Cangming; Jammaal Buatis, Kitz; Duttagupta, Shubham; Lee, Jae Sung; Lai, Archon; Hsu, Adam; Rostan, Johannes; Stangl, Rolf

2017-08-01

Passivated contacts for solar cells can be realized using a variety of differently formed ultra-thin tunnel oxide layers. Assessing their interface properties is important for optimization purposes. In this work, we demonstrate the ability to measure the interface defect density distribution D it(E) and the fixed interface charge density Q f for ultra-thin passivation layers operating within the tunnel regime (<2 nm). Various promising tunnel layer candidates [i.e., wet chemically formed SiO x , UV photo-oxidized SiO x , and atomic layer deposited (ALD) AlO x ] are investigated for their potential application forming electron or hole selective tunnel layer passivated contacts. In particular, ALD AlO x is identified as a promising tunnel layer candidate for hole-extracting passivated contact formation, stemming from its high (negative) fixed interface charge density in the order of -6 × 1012 cm-2. This is an order of magnitude higher compared to wet chemically or UV photo-oxidized formed silicon oxide tunnel layers, while keeping the density of interface defect states D it at a similar level (in the order of ˜2 × 1012 cm-2 eV-1). This leads to additional field effect passivation and therefore to significantly higher measured effective carrier lifetimes (˜2 orders of magnitude). A surface recombination velocity of ˜40 cm/s has been achieved for a 1.5 nm thin ALD AlO x tunnel layer prior to capping by an additional hole transport material, like p-doped poly-Si or PEDOT:PSS.

Merely Measuring the UV-Visible Spectrum of Gold Nanoparticles Can Change Their Charge State.

PubMed

Navarrete, Jose; Siefe, Chris; Alcantar, Samuel; Belt, Michael; Stucky, Galen D; Moskovits, Martin

2018-02-14

Metallic nanostructures exhibit a strong plasmon resonance at a wavelength whose value is sensitive to the charge density in the nanostructure, its size, shape, interparticle coupling, and the dielectric properties of its surrounding medium. Here we use UV-visible transmission and reflectance spectroscopy to track the shifts of the plasmon resonance in an array of gold nanoparticles buried under metal-oxide layers of varying thickness produced using atomic layer deposition (ALD) and then coated with bulk layers of one of three metals: aluminum, silver, or gold. A significant shift in the plasmon resonance was observed and a precise value of ω p , the plasmon frequency of the gold comprising the nanoparticles, was determined by modeling the composite of gold nanoparticles and metal-oxide layer as an optically homogeneous film of core-shell particles bounded by two substrates: one of quartz and the other being one of the aforementioned metals, then using a Maxwell-Garnett effective medium expression to extract ω p for the gold nanoparticles before and after coating with the bulk metals. Under illumination, the change in the charge density of the gold nanoparticles per particle determined from the change in the values of ω p is found to be some 50-fold greater than what traditional electrostatic contact electrification models compute based on the work function difference of the two conductive materials. Moreover, when using bulk gold as the capping layer, which should have resulted in a negligible charge exchange between the gold nanoparticles and the bulk gold, a significant charge transfer from the bulk gold layer to the nanoparticles was observed as with the other metals. We explain these observations in terms of the "plasmoelectric effect", recently described by Atwater and co-workers, in which the gold nanoparticles modify their charge density to allow their resonant wavelength to match that of the incident light, thereby achieving, a lower value of the chemical potential due to the entropy increase resulting from the conversion of the plasmon's energy to heat. We conclude that even the act of registering the spectrum of nanoparticles is at times sufficient to alter their charge densities and hence their UV-visible spectra.

Charge Behaviors around Oxide Device/Pseudo-Physiological Solution Interface with Molecular Dynamic Simulations

NASA Astrophysics Data System (ADS)

Maekawa, Yuki; Shibuta, Yasushi; Sakata, Toshiya

2013-12-01

In this study, we investigated the charge behaviors of ions and water molecules at the oxide device/pseudo-physiological solution interface by use of molecular dynamics (MD) simulations because the detection principle of semiconductor-based biosensors is based on the detection of charge density changes at the oxide sensing surface in physiological environments. In particular, we designed an alpha-quartz (100) surface with some charges corresponding to pH=5.5 so that the ionic behaviors for 500 mM each of Na+ and Cl- around the interface were calculated under the surface condition with charges, considering a real system. As a result of the simulation, we defined the region of Debye length from the calculated potential distribution, in which some parameters such as diffusion coefficient and the vibration of water molecules around the interface differed from those of the bulk solution. The elucidation of the solid/liquid interfacial behaviors by the simulation technique should deepen our understanding of the detection principle of semiconductor-based biosensors and will give guidelines for the design of a bio-interface in the field of biosensing technology, because they cannot be demonstrated experimentally.

Bipolar charge storage characteristics in copper and cobalt co-doped zinc oxide (ZnO) thin film.

PubMed

Kumar, Amit; Herng, Tun Seng; Zeng, Kaiyang; Ding, Jun

2012-10-24

The bipolar charge phenomenon in Cu and Co co-doped zinc oxide (ZnO) film samples has been studied using scanning probe microscopy (SPM) techniques. Those ZnO samples are made using a pulsed laser deposition (PLD) technique. It is found that the addition of Cu and Co dopants suppresses the electron density in ZnO and causes a significant change in the work function (Fermi level) value of the ZnO film; this results in the ohmic nature of the contact between the electrode (probe tip) and codoped sample, whereas this contact exhibits a Schottky nature in the undoped and single-element-doped samples. These results are verified by Kelvin probe force microscopy (KPFM) and ultraviolet photoelectron spectroscopy (UPS) measurements. It is also found that the co-doping (Cu and Co) can stabilize the bipolar charge, whereas Cu doping only stabilizes the positive charge in ZnO thin films.

Modulated two-dimensional charge-carrier density in LaTiO3-layer-doped LaAlO3/SrTiO3 heterostructure.

PubMed

Nazir, Safdar; Bernal, Camille; Yang, Kesong

2015-03-11

The highly mobile two-dimensional electron gas (2DEG) formed at the polar/nonpolar LaAlO3/SrTiO3 (LAO/STO) heterostructure (HS) is a matter of great interest because of its potential applications in nanoscale solid-state devices. To realize practical implementation of the 2DEG in device design, desired physical properties such as tuned charge carrier density and mobility are necessary. In this regard, polar perovskite-based transition metal oxides can act as doping layers at the interface and are expected to tune the electronic properties of 2DEG of STO-based HS systems dramatically. Herein, we investigated the doping effects of LaTiO3(LTO) layers on the electronic properties of 2DEG at n-type (LaO)(+1)/(TiO2)(0) interface in the LAO/STO HS using spin-polarized density functional theory calculations. Our results indicate an enhancement of orbital occupation near the Fermi energy, which increases with respect to the number of LTO unit cells, resulting in a higher charge carrier density of 2DEG than that of undoped system. The enhanced charge carrier density is attributed to an extra electron introduced by the Ti 3d(1) orbitals from the LTO dopant unit cells. This conclusion is consistent with the recent experimental findings (Appl. Phys. Lett. 2013, 102, 091601). Detailed charge density and partial density of states analysis suggests that the 2DEG in the LTO-doped HS systems primarily comes from partially occupied dyz and dxz orbitals.

Ion-ion correlation, solvent excluded volume and pH effects on physicochemical properties of spherical oxide nanoparticles.

PubMed

Ovanesyan, Zaven; Aljzmi, Amal; Almusaynid, Manal; Khan, Asrar; Valderrama, Esteban; Nash, Kelly L; Marucho, Marcelo

2016-01-15

One major source of complexity in the implementation of nanoparticles in aqueous electrolytes arises from the strong influence that biological environments has on their physicochemical properties. A key parameter for understanding the molecular mechanisms governing the physicochemical properties of nanoparticles is the formation of the surface charge density. In this article, we present an efficient and accurate approach that combines a recently introduced classical solvation density functional theory for spherical electrical double layers with a surface complexation model to account for ion-ion correlation and excluded volume effects on the surface titration of spherical nanoparticles. We apply the proposed computational approach to account for the charge-regulated mechanisms on the surface chemistry of spherical silica (SiO2) nanoparticles. We analyze the effects of the nanoparticle size, as well as pH level and electrolyte concentration of the aqueous solution on the nanoparticle's surface charge density and Zeta potential. We validate our predictions for 580Å and 200Å nanoparticles immersed in acid, neutral and alkaline mono-valent aqueous electrolyte solutions against experimental data. Our results on mono-valent electrolyte show that the excluded volume and ion-ion correlations contribute significantly to the surface charge density and Zeta potential of the nanoparticle at high electrolyte concentration and pH levels, where the solvent crowding effects and electrostatic screening have shown a profound influence on the protonation/deprotonation reactions at the liquid/solute interface. The success of this approach in describing physicochemical properties of silica nanoparticles supports its broader application to study other spherical metal oxide nanoparticles. Copyright © 2015 Elsevier Inc. All rights reserved.

Plane wave density functional molecular dynamics study of exothermic reactions of Al/CuO thermites

NASA Astrophysics Data System (ADS)

Oloriegbe, Suleiman; Sewell, Thomas; Chen, Zhen; Jiang, Shan; Gan, Yong

2014-03-01

Exothermic reactions between nanosize aluminum (Al) and copper oxide (CuO) structures are of current interest because of their high reaction enthalpy and energy density which exceed those of traditional monomolecular energetic compounds such as TNT, RDX, and HMX. In this work, molecular dynamics simulations with forces obtained from plane wave density functional theory are used to investigate the atomic-scale and electronic processes that occur during the fast thermite reactions between Al and CuO nanostructures under adiabatic conditions. Aluminum surfaces in contact with O-exposed and Cu-exposed CuO surfaces are studied. Starting from initial temperature T = 800 K, we have observed: faster chemical reaction at the oxygen-rich interface during the initial 0.5 ps, linear temperature rise, and fast oxygen diffusion into the Al region with the rate 1.87 X 10-3 cm2/s. The density-derived electrostatic and chemical method is used to evaluate the net atomic charges and charge transfer during the important redox processes. High charge density around the oxygen-exposed interface may be responsible for the faster initial reactions at that interface. The overall reaction rate, determined using the time evolution of Cu-O charge orbital overlap population, is approximately first order.

Density gradient in SiO 2 films on silicon as revealed by positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Revesz, A. G.; Anwand, W.; Brauer, G.; Hughes, H. L.; Skorupa, W.

2002-06-01

Positron annihilation spectroscopy of thermally grown and deposited SiO 2 films on silicon shows in a non-destructive manner that these films have a gradient in their density. The gradient is most pronounced for the oxide grown in dry oxygen. Oxidation in water-containing ambient results in an oxide with reduced gradient, similarly to the gradient in the deposited oxide. These observations are in accordance with earlier optical and other studies using stepwise etching or a set of samples of varying thickness. The effective oxygen charge, which is very likely one of the reasons for the difference in the W parameters of silica glass and quartz crystal, could be even higher at some localized configurations in the SiO 2 films resulting in increased positron trapping.

Charge injection and accumulation in organic light-emitting diode with PEDOT:PSS anode

NASA Astrophysics Data System (ADS)

Weis, Martin; Otsuka, Takako; Taguchi, Dai; Manaka, Takaaki; Iwamoto, Mitsumasa

2015-04-01

Organic light-emitting diode (OLED) displays using flexible substrates have many attractive features. Since transparent conductive oxides do not fit the requirements of flexible devices, conductive polymer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) has been proposed as an alternative. The charge injection and accumulation in OLED devices with PEDOT:PSS anodes are investigated and compared with indium tin oxide anode devices. Higher current density and electroluminescence light intensity are achieved for the OLED device with a PEDOT:PSS anode. The electric field induced second-harmonic generation technique is used for direct observation of temporal evolution of electric fields. It is clearly demonstrated that the improvement in the device performance of the OLED device with a PEDOT:PSS anode is associated with the smooth charge injection and accumulation.

Effects of dc bias on the kinetics and electrical properties of silicon dioxide grown in an electron cyclotron resonance plasma

NASA Astrophysics Data System (ADS)

Carl, D. A.; Hess, D. W.; Lieberman, M. A.; Nguyen, T. D.; Gronsky, R.

1991-09-01

Thin (3-300-nm) oxides were grown on single-crystal silicon substrates at temperatures from 523 to 673 K in a low-pressure electron cyclotron resonance (ECR) oxygen plasma. Oxides were grown under floating, anodic or cathodic bias conditions, although only the oxides grown under floating or anodic bias conditions are acceptable for use as gate dielectrics in metal-oxide-semiconductor technology. Oxide thickness uniformity as measured by ellipsometry decreased with increasing oxidation time for all bias conditions. Oxidation kinetics under anodic conditions can be explained by negatively charged atomic oxygen, O-, transport limited growth. Constant current anodizations yielded three regions of growth: (1) a concentration gradient dominated regime for oxides thinner than 10 nm, (2) a field dominated regime with ohmic charged oxidant transport for oxide thickness in the range of 10 nm to approximately 100 nm, and (3) a space-charge limited regime for films thicker than approximately 100 nm. The relationship between oxide thickness (xox), overall potential drop (Vox) and ion current (ji) in the space-charge limited transport region was of the form: ji ∝ V2ox/x3ox. Transmission electron microscopy analysis of 5-60-nm-thick anodized films indicated that the silicon-silicon dioxide interface was indistinguishable from that of thermal oxides grown at 1123 K. High-frequency capacitance-voltage (C-V) and ramped bias current-voltage (I-V) studies performed on 5.4-30-nm gate thickness capacitors indicated that the as-grown ECR films had high levels of fixed oxide charge (≳1011 cm-2) and interface traps (≳1012 cm-2 eV-1). The fixed charge level could be reduced to ≊4×1010 cm-2 by a 20 min polysilicon gate activation anneal at 1123 K in nitrogen; the interface trap density at mid-band gap decreased to ≊(1-2)×1011 cm-2 eV-1 after this process. The mean breakdown strength for anodic oxides grown under optimum conditions was 10.87±0.83 MV cm-1. Electrical properties of the 5.4-8-nm gates compared well with thicker films and control dry thermal oxides of similar thicknesses.

films on silicon at different annealing temperatures

NASA Astrophysics Data System (ADS)

Zhao, Yan; Zhou, Chunlan; Zhang, Xiang; Zhang, Peng; Dou, Yanan; Wang, Wenjing; Cao, Xingzhong; Wang, Baoyi; Tang, Yehua; Zhou, Su

2013-03-01

Thermal atomic layer-deposited (ALD) aluminum oxide (Al2O3) acquires high negative fixed charge density ( Q f) and sufficiently low interface trap density after annealing, which enables excellent surface passivation for crystalline silicon. Q f can be controlled by varying the annealing temperatures. In this study, the effect of the annealing temperature of thermal ALD Al2O3 films on p-type Czochralski silicon wafers was investigated. Corona charging measurements revealed that the Q f obtained at 300°C did not significantly affect passivation. The interface-trapping density markedly increased at high annealing temperature (>600°C) and degraded the surface passivation even at a high Q f. Negatively charged or neutral vacancies were found in the samples annealed at 300°C, 500°C, and 750°C using positron annihilation techniques. The Al defect density in the bulk film and the vacancy density near the SiO x /Si interface region decreased with increased temperature. Measurement results of Q f proved that the Al vacancy of the bulk film may not be related to Q f. The defect density in the SiO x region affected the chemical passivation, but other factors may dominantly influence chemical passivation at 750°C.

Amorphous GeOx-Coated Reduced Graphene Oxide Balls with Sandwich Structure for Long-Life Lithium-Ion Batteries.

PubMed

Choi, Seung Ho; Jung, Kyeong Youl; Kang, Yun Chan

2015-07-01

Amorphous GeOx-coated reduced graphene oxide (rGO) balls with sandwich structure are prepared via a spray-pyrolysis process using polystyrene (PS) nanobeads as sacrificial templates. This sandwich structure is formed by uniformly coating the exterior and interior of few-layer rGO with amorphous GeOx layers. X-ray photoelectron spectroscopy analysis reveals a Ge:O stoichiometry ratio of 1:1.7. The amorphous GeOx-coated rGO balls with sandwich structure have low charge-transfer resistance and fast Li(+)-ion diffusion rate. For example, at a current density of 2 A g(-1), the GeOx-coated rGO balls with sandwich and filled structures and the commercial GeO2 powders exhibit initial charge capacities of 795, 651, and 634 mA h g(-1), respectively; the corresponding 700th-cycle charge capacities are 758, 579, and 361 mA h g(-1). In addition, at a current density of 5 A g(-1), the rGO balls with sandwich structure have a 1600th-cycle reversible charge capacity of 629 mA h g(-1) and a corresponding capacity retention of 90.7%, as measured from the maximum reversible capacity at the 100th cycle.

Nitrogen-doped partially reduced graphene oxide rewritable nonvolatile memory.

PubMed

Seo, Sohyeon; Yoon, Yeoheung; Lee, Junghyun; Park, Younghun; Lee, Hyoyoung

2013-04-23

As memory materials, two-dimensional (2D) carbon materials such as graphene oxide (GO)-based materials have attracted attention due to a variety of advantageous attributes, including their solution-processability and their potential for highly scalable device fabrication for transistor-based memory and cross-bar memory arrays. In spite of this, the use of GO-based materials has been limited, primarily due to uncontrollable oxygen functional groups. To induce the stable memory effect by ionic charges of a negatively charged carboxylic acid group of partially reduced graphene oxide (PrGO), a positively charged pyridinium N that served as a counterion to the negatively charged carboxylic acid was carefully introduced on the PrGO framework. Partially reduced N-doped graphene oxide (PrGODMF) in dimethylformamide (DMF) behaved as a semiconducting nonvolatile memory material. Its optical energy band gap was 1.7-2.1 eV and contained a sp2 C═C framework with 45-50% oxygen-functionalized carbon density and 3% doped nitrogen atoms. In particular, rewritable nonvolatile memory characteristics were dependent on the proportion of pyridinum N, and as the proportion of pyridinium N atom decreased, the PrGODMF film lost memory behavior. Polarization of charged PrGODMF containing pyridinium N and carboxylic acid under an electric field produced N-doped PrGODMF memory effects that followed voltage-driven rewrite-read-erase-read processes.

Synthesis and Characterisation of Reduced Graphene Oxide/Bismuth Composite for Electrodes in Electrochemical Energy Storage Devices.

PubMed

Wang, Jiabin; Zhang, Han; Hunt, Michael R C; Charles, Alasdair; Tang, Jie; Bretcanu, Oana; Walker, David; Hassan, Khalil T; Sun, Yige; Šiller, Lidija

2017-01-20

A reduced graphene oxide/bismuth (rGO/Bi) composite was synthesized for the first time using a polyol process at a low reaction temperature and with a short reaction time (60 °C and 3 hours, respectively). The as-prepared sample is structured with 20-50 nm diameter bismuth particles distributed on the rGO sheets. The rGO/Bi composite displays a combination of capacitive and battery-like charge storage, achieving a specific capacity value of 773 C g -1 at a current density of 0.2 A g -1 when charged to 1 V. The material not only has good power density but also shows moderate stability in cycling tests with current densities as high as 5 A g -1 . The relatively high abundance and low price of bismuth make this rGO/Bi material a promising candidate for use in electrode materials in future energy storage devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dependence of interface charge trapping on channel engineering in pentacene field effect transistors.

PubMed

Lee, Sunwoo; Park, Junghyuck; Park, In-Sung; Ahn, Jinho

2014-07-01

We investigate the dependence of charge carrier mobility by trap states at various interface regions through channel engineering. Prior to evaluation of interface trap density, the electrical performance in pentaene field effect transistors (FET) with high-k gate oxide are also investigated depending on four channel engineering. As a channel engineering, gas treatment, coatings of thin polymer layer, and chemical surface modification using small molecules were carried out. After channel engineering, the performance of device as well as interface trap density calculated by conductance method are remarkably improved. It is found that the reduced interface trap density is closely related to decreasing the sub-threshold swing and improving the mobility. Particularly, we also found that performance of device such as mobility, subthreshold swing, and interface trap density after gas same is comparable to those of OTS.

Criteria for selecting electrodes for electrical stimulation: theoretical and practical considerations.

PubMed

Brummer, S B; Robblee, L S; Hambrecht, F T

1983-01-01

Smaller, more charge-intensive electrodes are needed for "safe" stimulation of the nervous system. In this paper we review critical concepts and the state of the art in electrodes. Control of charge density and charge balance are essential to avoid tissue electrolysis. Chemical criteria for "safe" stimulation are reviewed ("safe" is equated with "chemically reversible"). An example of a safe, but generally impractical, charge-injection process is double-layer charging. The limit here is the onset of irreversible faradaic processes. More charge can be safely injected with so-called "capacitor" electrodes, such as porous intermixtures of Ta/Ta2O5. BaTiO3 has excellent dielectric properties and may provide a new generation of capacitor electrodes. Faradaic charge injection is usually partially irreversible since some of the products escape into the solution. With Pt, up to 400 muc/cm2 real area can be absorbed by faradaic reactions of surface-adsorbed species, but a small part is lost due to metal dissolution. The surface of "activated" Ir is covered with a multilayer hydrated oxide. Charge injection occurs via rapid valence change within this oxide. Little or no metal dissolution is observed, and gassing limits are not exceeded even under stringent conditions.

Low-crystalline iron oxide hydroxide nanoparticle anode for high-performance supercapacitors

PubMed Central

Owusu, Kwadwo Asare; Qu, Longbing; Li, Jiantao; Wang, Zhaoyang; Zhao, Kangning; Yang, Chao; Hercule, Kalele Mulonda; Lin, Chao; Shi, Changwei; Wei, Qiulong; Zhou, Liang; Mai, Liqiang

2017-01-01

Carbon materials are generally preferred as anodes in supercapacitors; however, their low capacitance limits the attained energy density of supercapacitor devices with aqueous electrolytes. Here, we report a low-crystalline iron oxide hydroxide nanoparticle anode with comprehensive electrochemical performance at a wide potential window. The iron oxide hydroxide nanoparticles present capacitances of 1,066 and 716 F g−1 at mass loadings of 1.6 and 9.1 mg cm−2, respectively, a rate capability with 74.6% of capacitance retention at 30 A g−1, and cycling stability retaining 91% of capacitance after 10,000 cycles. The performance is attributed to a dominant capacitive charge-storage mechanism. An aqueous hybrid supercapacitor based on the iron oxide hydroxide anode shows stability during float voltage test for 450 h and an energy density of 104 Wh kg−1 at a power density of 1.27 kW kg−1. A packaged device delivers gravimetric and volumetric energy densities of 33.14 Wh kg−1 and 17.24 Wh l−1, respectively. PMID:28262797

Investigation of Oxygen and Hydrogen Associated Charge Trapping and Electrical Characteristics of Silicon Nitride Films for Mnos Devices.

NASA Astrophysics Data System (ADS)

Xu, Dan

Silicon nitride (Si_3N _4) and silicon oxynitride (SiO _{rm x}N_ {rm y}) films in the form of metal -nitride-oxide-silicon (MNOS) structures were investigated to determine the correlation between their electrical characteristics and the nature of the chemical bonding so as to provide guidelines for the next generation of nonvolatile memory devices. The photoionization cross section of electron traps in the oxynitride films of MNOS devices were also measured as a function photon energy and oxygen concentration of the silicon oxynitride films. An effective photoionization cross section associated with electron traps was determined to be between 4.9 times 10 ^{-19} cm^2 to 10.8 times 10^ {-19} cm^2 over the photon energy of 2.06 eV to 3.1 eV for silicon oxynitride films containing 7 atomic % to 17 atomic % of oxygen. The interface state density of metal-nitride-oxide -silicon (MNOS) devices was investigated as a function of processing conditions. The interface state density around the midgap of the oxide-silicon interface of the MNOS structures for deposition temperature between 650^ circC to 850^circC increased from 1.1 to 8.2 times 10 ^{11} cm^ {-2}eV^{-1}, for as-deposited silicon nitride films; but decreased from 5.0 to 3.5 times 10^ {11} cm^{-2} eV^{-1}, for films annealed in nitrogen at 900^circC for 60 minutes; and further decreased and remained constant at 1.5 times 10^{11 } cm^{-2}eV ^{-1}, for films which were further annealed in hydrogen at 900^ circC for an additional 60 minutes. The interface state density increase was due to an increase in the loss of hydrogen at the interfacial region and also due to an increase in the thermal stress caused by differences in thermal expansion coefficients of silicon nitride and silicon dioxide films at higher deposition temperatures. The interface state density was subject to two opposing influences; an increase by thermal stress, and a reduction by hydrogen compensation of these states. The photocurrent-voltage (photoI-V) technique in combination with internal photo-electric technique were employed to determine the trapped charge density and its centroid as a function of processing conditions. Results showed that the trapped charge density was of the order of 10^{18} cm ^{-3}. However, the charge trapping density increased about 30% as the atomic percentage of hydrogen decreased from 6 to 2 atomic %.

Effects of Different Manufacturing Processes on TEMPO-Oxidized Carboxylated Cellulose Nanofiber Performance as Binder for Flexible Lithium-Ion Batteries.

PubMed

Lu, Huiran; Guccini, Valentina; Kim, Hyeyun; Salazar-Alvarez, German; Lindbergh, Göran; Cornell, Ann

2017-11-01

Carboxylated cellulose nanofibers (CNF) prepared using the TEMPO-route are good binders of electrode components in flexible lithium-ion batteries (LIB). However, the different parameters employed for the defibrillation of CNF such as charge density and degree of homogenization affect its properties when used as binder. This work presents a systematic study of CNF prepared with different surface charge densities and varying degrees of homogenization and their performance as binder for flexible LiFePO 4 electrodes. The results show that the CNF with high charge density had shorter fiber lengths compared with those of CNF with low charge density, as observed with atomic force microscopy. Also, CNF processed with a large number of passes in the homogenizer showed a better fiber dispersibility, as observed from rheological measurements. The electrodes fabricated with highly charged CNF exhibited the best mechanical and electrochemical properties. The CNF at the highest charge density (1550 μmol g -1 ) and lowest degree of homogenization (3 + 3 passes in the homogenizer) achieved the overall best performance, including a high Young's modulus of approximately 311 MPa and a good rate capability with a stable specific capacity of 116 mAh g -1 even up to 1 C. This work allows a better understanding of the influence of the processing parameters of CNF on their performance as binder for flexible electrodes. The results also contribute to the understanding of the optimal processing parameters of CNF to fabricate other materials, e.g., membranes or separators.

Growing Platinum-Ruthenium-Tin ternary alloy nanoparticles on reduced graphene oxide for strong ligand effect toward enhanced ethanol oxidation reaction.

PubMed

Xia, Qing Qing; Zhang, Lian Ying; Zhao, Zhi Liang; Li, Chang Ming

2017-11-15

Uniform Pt 1 Ru 0.5 Sn 0.5 ternary alloy nanoparticles are in situ deposited on reduced graphene oxide (Pt 1 Ru 0.5 Sn 0.5 -RGO) through its functional groups and defects as nucleation sites to greatly electrocatalyze ethanol oxidation reaction for much higher mass current densities, larger apparent specific current densities and better stability than commercial Pt-C catalyst (Pt-C(commer)). Mechanistic studies indicate that the excellent electrocatalytic activity and anti-poisoning are resulted from a strong ligand effect of the ternary alloy components, in which the charge transfer is boosted while decreasing the density of states close to the Fermi level of Pt to reduce bond energy between Pt and CO-like adsorbates for greatly improved anti-poisoning ability. This work holds a great promise to fabricate a high performance anode catalyst with a low Pt loading for direct ethanol fuel cells. Copyright © 2017. Published by Elsevier Inc.

Band Alignment and Charge Transfer in Complex Oxide Interfaces

NASA Astrophysics Data System (ADS)

Zhong, Zhicheng; Hansmann, Philipp

2017-01-01

The synthesis of transition metal heterostructures is currently one of the most vivid fields in the design of novel functional materials. In this paper, we propose a simple scheme to predict band alignment and charge transfer in complex oxide interfaces. For semiconductor heterostructures, band-alignment rules like the well-known Anderson or Schottky-Mott rule are based on comparison of the work function or electron affinity of the bulk components. This scheme breaks down for oxides because of the invalidity of a single work-function approximation as recently shown in [Phys. Rev. B 93, 235116 (2016), 10.1103/PhysRevB.93.235116; Adv. Funct. Mater. 26, 5471 (2016), 10.1002/adfm.201600243]. Here, we propose a new scheme that is built on a continuity condition of valence states originating in the compounds' shared network of oxygen. It allows for the prediction of sign and relative amplitude of the intrinsic charge transfer, taking as input only information about the bulk properties of the components. We support our claims by numerical density functional theory simulations as well as (where available) experimental evidence. Specific applications include (i) controlled doping of SrTiO3 layers with the use of 4 d and 5 d transition metal oxides and (ii) the control of magnetic ordering in manganites through tuned charge transfer.

Electrofluidic gating of a chemically reactive surface.

PubMed

Jiang, Zhijun; Stein, Derek

2010-06-01

We consider the influence of an electric field applied normal to the electric double layer at a chemically reactive surface. Our goal is to elucidate how surface chemistry affects the potential for field-effect control over micro- and nanofluidic systems, which we call electrofluidic gating. The charging of a metal-oxide-electrolyte (MOE) capacitor is first modeled analytically. We apply the Poisson-Boltzmann description of the double layer and impose chemical equilibrium between the ionizable surface groups and the solution at the solid-liquid interface. The chemically reactive surface is predicted to behave as a buffer, regulating the charge in the double layer by either protonating or deprotonating in response to the applied field. We present the dependence of the charge density and the electrochemical potential of the double layer on the applied field, the density, and the dissociation constants of ionizable surface groups and the ionic strength and the pH of the electrolyte. We simulate the responses of SiO(2) and Al(2)O(3), two widely used oxide insulators with different surface chemistries. We also consider the limits to electrofluidic gating imposed by the nonlinear behavior of the double layer and the dielectric strength of oxide materials, which were measured for SiO(2) and Al(2)O(3) films in MOE configurations. Our results clarify the response of chemically reactive surfaces to applied fields, which is crucial to understanding electrofluidic effects in real devices.

Nanocrystal floating gate memory with solution-processed indium-zinc-tin-oxide channel and colloidal silver nanocrystals

NASA Astrophysics Data System (ADS)

Hu, Quanli; Ha, Sang-Hyub; Lee, Hyun Ho; Yoon, Tae-Sik

2011-12-01

A nanocrystal (NC) floating gate memory with solution-processed indium-zinc-tin-oxide (IZTO) channel and silver (Ag) NCs embedded in thin gate dielectric layer (SiO2(30 nm)/Al2O3(3 nm)) was fabricated. Both the IZTO channel and colloidal Ag NC layers were prepared by spin-coating and subsequent annealing, and dip-coating process, respectively. A threshold voltage shift up to ~0.9 V, corresponding to the electron density of 6.5 × 1011 cm-2, at gate pulsing <=10 V was achieved by the charging of high density NCs. These results present the successful non-volatile memory characteristics of an oxide-semiconductor transistor fabricated through solution processes.

Characterization, modeling and physical mechanisms of different surface treatment methods at room temperature on the oxide and interfacial quality of the SiO2 film using the spectroscopic scanning capacitance microscopy

NASA Astrophysics Data System (ADS)

Wong, Kin Mun

In this article, a simple, low cost and combined surface treatment method [pre-oxidation immersion of the p-type silicon (Si) substrate in hydrogen peroxide (H2O2) and post oxidation ultra-violet (UV) irradiation of the silicon-dioxide (SiO2) film] at room temperature is investigated. The interface trap density at midgap [Dit(mg)] of the resulting SiO2 film (denoted as sample 1A) is quantified from the full width at half-maximum of the scanning capacitance microscopy (SCM) differential capacitance (dC/dV) characteristics by utilizing a previously validated theoretical model. The Dit(mg) of sample 1A is significantly lower than the sample without any surface treatments which indicates that it is a viable technique for improving the interfacial quality of the thicker SiO2 films prepared by wet oxidation. Moreover, the proposed combined surface treatment method may possibly complement the commonly used forming gas anneal process to further improve the interfacial quality of the SiO2 films. The positive shift of the flatband voltage due to the overall oxide charges (estimated from the probe tip dc bias at the peak dC/dV spectra) of sample 1A suggests the presence of negative oxide fixed charge density (Nf) in the oxide. In addition, an analytical formula is derived to approximate the difference of the Nf values between the oxide samples that are immersed in H2O2 and UV irradiated from their measured SCM dC/dV spectra. Conversely, some physical mechanisms are proposed that result in the ionization of the SiO- species (which are converted from the neutral SiOH groups that originate from the pre-oxidation immersion in H2O2 and ensuing wet oxidation) during the UV irradiation as well as the UV photo-injected electrons from the Si substrate (which did not interact with the SiOH groups). They constitute the source of mobile electrons which partially passivate the positively charged empty donor-like interface traps at the Si-SiO2 interface.

Electrochemical characterization of high frequency stimulation electrodes: role of electrode material and stimulation parameters on electrode polarization

NASA Astrophysics Data System (ADS)

Ghazavi, Atefeh; Cogan, Stuart F.

2018-06-01

Objective. With recent interest in kilohertz frequency electrical stimulation for nerve conduction block, understanding the electrochemistry and role of electrode material is important for assessing the safety of these stimulus protocols. Here we describe an approach to determining electrode polarization in response to continuous kilohertz frequency sinusoidal current waveforms. We have also investigated platinum, iridium oxide, and titanium nitride as coatings for high frequency electrodes. The current density distribution at 50 kHz at the electrode–electrolyte interface was also modeled to demonstrate the importance of the primary current distribution in supporting charge injection at high frequencies. Approach. We determined electrode polarization in response to sinusoidal currents with frequencies in the 1–50 kHz range and current amplitudes from 100 to 500 µA and 1–5 mA, depending on the electrode area. The current density distribution at the interface was modeled using the finite element method (FEM). Main results. At low frequencies, 1–5 kHz, polarization on the platinum electrode was significant, exceeding the water oxidation potential for high amplitude (5 mA) waveforms. At frequencies of 20 kHz or higher, the polarization was less than 300 mV from the electrode open circuit potential. The choice of electrode material did not play a significant role in electrode polarization at frequencies higher than 10 kHz. The current density distribution modeled at 50 kHz is non-uniform and this non-uniformity persists throughout charge delivery. Significance. At high frequencies (>10 kHz) electrode double-layer charging is the principal mechanism of charge-injection and selection of the electrode material has little effect on polarization, with platinum, iridium oxide, and titanium nitride exhibiting similar behavior. High frequency stimulation is dominated by a highly nonuniform primary current distribution.

Experimental charge density analysis of a gallium(I) N-heterocyclic carbene analogue.

PubMed

Overgaard, Jacob; Jones, Cameron; Dange, Deepak; Platts, James A

2011-09-05

The experimental electron density of the only known example of a four-membered Ga(I) N-heterocyclic carbene analogue has been determined by multipole modeling of 90 K X-ray diffraction data and compared to theoretical data. In order to obtain a satisfactory model, it is necessary to modify the radial dependency of the core electrons of Ga using two separate scaling parameters for s,p- and d-electrons. Evidence for significant lone-pair density on Ga is found in the electron density and derived properties despite the partial positive charge of this atom. Static deformation density and molecular electrostatic potential clearly show a directional lone pair on Ga, whereas the Laplacian of the total electron density does not; this feature is, however, present in the Laplacian of the valence-only density. The Ga center also acts as an acceptor in four intramolecular C-H···Ga contacts, whose nature is probed by density properties. Substantial covalent character is apparent in the Ga-N bonds, but no sign of donation from filled N p-orbitals to empty Ga p-orbitals is found, whereas π-delocalization over the organic ligand is evident. This study highlights the utility of experimental charge density analysis as a technique to investigate the unusual bonding and electronic characteristics of low oxidation state/low coordinate p-block complexes.

Preparation of gallium nitride surfaces for atomic layer deposition of aluminum oxide

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

Kerr, A. J.; Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093; Chagarov, E.

2014-09-14

A combined wet and dry cleaning process for GaN(0001) has been investigated with XPS and DFT-MD modeling to determine the molecular-level mechanisms for cleaning and the subsequent nucleation of gate oxide atomic layer deposition (ALD). In situ XPS studies show that for the wet sulfur treatment on GaN(0001), sulfur desorbs at room temperature in vacuum prior to gate oxide deposition. Angle resolved depth profiling XPS post-ALD deposition shows that the a-Al{sub 2}O{sub 3} gate oxide bonds directly to the GaN substrate leaving both the gallium surface atoms and the oxide interfacial atoms with XPS chemical shifts consistent with bulk-like charge.more » These results are in agreement with DFT calculations that predict the oxide/GaN(0001) interface will have bulk-like charges and a low density of band gap states. This passivation is consistent with the oxide restoring the surface gallium atoms to tetrahedral bonding by eliminating the gallium empty dangling bonds on bulk terminated GaN(0001)« less

Charge injection and accumulation in organic light-emitting diode with PEDOT:PSS anode

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

Weis, Martin, E-mail: martin.weis@stuba.sk; Otsuka, Takako; Taguchi, Dai

2015-04-21

Organic light-emitting diode (OLED) displays using flexible substrates have many attractive features. Since transparent conductive oxides do not fit the requirements of flexible devices, conductive polymer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) has been proposed as an alternative. The charge injection and accumulation in OLED devices with PEDOT:PSS anodes are investigated and compared with indium tin oxide anode devices. Higher current density and electroluminescence light intensity are achieved for the OLED device with a PEDOT:PSS anode. The electric field induced second-harmonic generation technique is used for direct observation of temporal evolution of electric fields. It is clearly demonstrated that the improvement in the devicemore » performance of the OLED device with a PEDOT:PSS anode is associated with the smooth charge injection and accumulation.« less

Supercapacitors based on highly dispersed polypyrrole-reduced graphene oxide composite with a folded surface

NASA Astrophysics Data System (ADS)

Wang, Anqi; Zhou, Xi; Qian, Tao; Yu, Chenfei; Wu, Shishan; Shen, Jian

2015-08-01

Highly dispersed polypyrrole particles were decorated on reduced graphene oxide sheets using a facile in situ synthesis route. The prepared composite, which obtained a folded surface, shows remarkable performance as the electrode material of supercapacitors. The specific capacitance reaches 564.1 F g-1 at a current density of 1 A g-1 and maintains 86.4 % after 1000 charging-discharging cycles at a current density of 20 A g-1, which indicates a good cycling stability. Furthermore, the prepared supercapacitor demonstrates an ultrahigh energy density of 50.13 Wh kg-1 at power density of 0.40 kW kg-1, and remains of 45.33 Wh kg-1 even at high power density of 8.00 kW kg-1, which demonstrate that the hybrid supercapacitor can be a promising energy storage system for fast and efficient energy storage in the future.

Direct Imaging of Charge Density Modulation in Switchable Two-Dimensional Electron Gas at the Oxide Hetero-Interfaces by Using Electron Bean Inline Holography

DTIC Science & Technology

2015-08-16

Switchable Two-Dimensional Electron Gas at the Oxide Hetero-Interfaces by Using Electron Bean Inline Holography 5a. CONTRACT NUMBER FA2386-13-1-4136...Hetero-Interfaces by Using Electron Bean Inline Holography 5a. CONTRACT NUMBER FA2386-13-1-4136 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 61102F

Low temperature formation of electrode having electrically conductive metal oxide surface

DOEpatents

Anders, Simone; Anders, Andre; Brown, Ian G.; McLarnon, Frank R.; Kong, Fanping

1998-01-01

A low temperature process is disclosed for forming metal suboxides on substrates by cathodic arc deposition by either controlling the pressure of the oxygen present in the deposition chamber, or by controlling the density of the metal flux, or by a combination of such adjustments, to thereby control the ratio of oxide to metal in the deposited metal suboxide coating. The density of the metal flux may, in turn, be adjusted by controlling the discharge current of the arc, by adjusting the pulse length (duration of on cycle) of the arc, and by adjusting the frequency of the arc, or any combination of these parameters. In a preferred embodiment, a low temperature process is disclosed for forming an electrically conductive metal suboxide, such as, for example, an electrically conductive suboxide of titanium, on an electrode surface, such as the surface of a nickel oxide electrode, by such cathodic arc deposition and control of the deposition parameters. In the preferred embodiment, the process results in a titanium suboxide-coated nickel oxide electrode exhibiting reduced parasitic evolution of oxygen during charging of a cell made using such an electrode as the positive electrode, as well as exhibiting high oxygen overpotential, resulting in suppression of oxygen evolution at the electrode at full charge of the cell.

Investigation of 'surface donors' in Al2O3/AlGaN/GaN metal-oxide-semiconductor heterostructures: Correlation of electrical, structural, and chemical properties

NASA Astrophysics Data System (ADS)

Ťapajna, M.; Stoklas, R.; Gregušová, D.; Gucmann, F.; Hušeková, K.; Haščík, Š.; Fröhlich, K.; Tóth, L.; Pécz, B.; Brunner, F.; Kuzmík, J.

2017-12-01

III-N surface polarization compensating charge referred here to as 'surface donors' (SD) was analyzed in Al2O3/AlGaN/GaN metal-oxide-semiconductor (MOS) heterojunctions using scaled oxide films grown by metal-organic chemical vapor deposition at 600 °C. We systematically investigated impact of HCl pre-treatment prior to oxide deposition and post-deposition annealing (PDA) at 700 °C. SD density was reduced down to 1.9 × 1013 cm-2 by skipping HCl pre-treatment step as compared to 3.3 × 1013 cm-2 for structures with HCl pre-treatment followed by PDA. The nature and origin of SD was then analyzed based on the correlation between electrical, micro-structural, and chemical properties of the Al2O3/GaN interfaces with different SD density (NSD). From the comparison between distributions of interface traps of MOS heterojunction with different NSD, it is demonstrated that SD cannot be attributed to interface trapped charge. Instead, variation in the integrity of the GaOx interlayer confirmed by X-ray photoelectron spectroscopy is well correlated with NSD, indicating SD may be formed by border traps at the Al2O3/GaOx interface.

Preparation and characterization of flexible asymmetric supercapacitors based on transition-metal-oxide nanowire/single-walled carbon nanotube hybrid thin-film electrodes.

PubMed

Chen, Po-Chiang; Shen, Guozhen; Shi, Yi; Chen, Haitian; Zhou, Chongwu

2010-08-24

In the work described in this paper, we have successfully fabricated flexible asymmetric supercapacitors (ASCs) based on transition-metal-oxide nanowire/single-walled carbon nanotube (SWNT) hybrid thin-film electrodes. These hybrid nanostructured films, with advantages of mechanical flexibility, uniform layered structures, and mesoporous surface morphology, were produced by using a filtration method. Here, manganese dioxide nanowire/SWNT hybrid films worked as the positive electrode, and indium oxide nanowire/SWNT hybrid films served as the negative electrode in a designed ASC. In our design, charges can be stored not only via electrochemical double-layer capacitance from SWNT films but also through a reversible faradic process from transition-metal-oxide nanowires. In addition, to obtain stable electrochemical behavior during charging/discharging cycles in a 2 V potential window, the mass balance between two electrodes has been optimized. Our optimized hybrid nanostructured ASCs exhibited a superior device performance with specific capacitance of 184 F/g, energy density of 25.5 Wh/kg, and columbic efficiency of approximately 90%. In addition, our ASCs exhibited a power density of 50.3 kW/kg, which is 10-fold higher than obtained in early reported ASC work. The high-performance hybrid nanostructured ASCs can find applications in conformal electrics, portable electronics, and electrical vehicles.

Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Lang, Xingyou; Hirata, Akihiko; Fujita, Takeshi; Chen, Mingwei

2011-04-01

Electrochemical supercapacitors can deliver high levels of electrical power and offer long operating lifetimes, but their energy storage density is too low for many important applications. Pseudocapacitive transition-metal oxides such as MnO2 could be used to make electrodes in such supercapacitors, because they are predicted to have a high capacitance for storing electrical charge while also being inexpensive and not harmful to the environment. However, the poor conductivity of MnO2 (10-5-10-6 S cm-1) limits the charge/discharge rate for high-power applications. Here, we show that hybrid structures made of nanoporous gold and nanocrystalline MnO2 have enhanced conductivity, resulting in a specific capacitance of the constituent MnO2 (~1,145 F g-1) that is close to the theoretical value. The nanoporous gold allows electron transport through the MnO2, and facilitates fast ion diffusion between the MnO2 and the electrolytes while also acting as a double-layer capacitor. The high specific capacitances and charge/discharge rates offered by such hybrid structures make them promising candidates as electrodes in supercapacitors, combining high-energy storage densities with high levels of power delivery.

Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors.

PubMed

Lang, Xingyou; Hirata, Akihiko; Fujita, Takeshi; Chen, Mingwei

2011-04-01

Electrochemical supercapacitors can deliver high levels of electrical power and offer long operating lifetimes, but their energy storage density is too low for many important applications. Pseudocapacitive transition-metal oxides such as MnO(2) could be used to make electrodes in such supercapacitors, because they are predicted to have a high capacitance for storing electrical charge while also being inexpensive and not harmful to the environment. However, the poor conductivity of MnO(2) (10(-5)-10(-6) S cm(-1)) limits the charge/discharge rate for high-power applications. Here, we show that hybrid structures made of nanoporous gold and nanocrystalline MnO(2) have enhanced conductivity, resulting in a specific capacitance of the constituent MnO(2) (~1,145 F g(-1)) that is close to the theoretical value. The nanoporous gold allows electron transport through the MnO(2), and facilitates fast ion diffusion between the MnO(2) and the electrolytes while also acting as a double-layer capacitor. The high specific capacitances and charge/discharge rates offered by such hybrid structures make them promising candidates as electrodes in supercapacitors, combining high-energy storage densities with high levels of power delivery.

Voltage-Dependent Charge Storage in Cladded Zn0.56Cd0.44Se Quantum Dot MOS Capacitors for Multibit Memory Applications

NASA Astrophysics Data System (ADS)

Khan, J.; Lingalugari, M.; Al-Amoody, F.; Jain, F.

2013-11-01

As conventional memories approach scaling limitations, new storage methods must be utilized to increase Si yield and produce higher on-chip memory density. Use of II-VI Zn0.56Cd0.44Se quantum dots (QDs) is compatible with epitaxial gate insulators such as ZnS-ZnMgS. Voltage-dependent charging effects in cladded Zn0.56Cd0.44Se QDs are presented in a conventional metal-oxide-semiconductor capacitor structure. Charge storage capabilities in Si and ZnMgS QDs have been reported by various researchers; this work is focused on II-VI material Zn0.56Cd0.44Se QDs nucleated using photoassisted microwave plasma metalorganic chemical vapor deposition. Using capacitance-voltage hysteresis characterization, the multistep charging and discharging capabilities of the QDs at room temperature are presented. Three charging states are presented within a 10 V charging voltage range. These characteristics exemplify discrete charge states in the QD layer, perfect for multibit, QD-functionalized high-density memory applications. Multiple charge states with low operating voltage provide device characteristics that can be used for multibit storage by allowing varying charges to be stored in a QD layer based on the applied "write" voltage.

Impact of magnetite nanoparticle incorporation on optical and electrical properties of nanocomposite LbL assemblies.

PubMed

Yashchenok, Alexey M; Gorin, Dmitry A; Badylevich, Mikhail; Serdobintsev, Alexey A; Bedard, Matthieu; Fedorenko, Yanina G; Khomutov, Gennady B; Grigoriev, Dmitri O; Möhwald, Helmuth

2010-09-21

Optical and electrical properties of polyelectrolyte/iron oxide nanocomposite planar films on silicon substrates were investigated for different amount of iron oxide nanoparticles incorporated in the films. The nanocomposite assemblies prepared by the layer-by-layer assembly technique were characterized by ellipsometry, atomic force microscopy, and secondary ion mass-spectrometry. Absorption spectra of the films reveal a shift of the optical absorption edge to higher energy when the number of deposited layers decreases. Capacitance-voltage and current-voltage measurements were applied to study the electrical properties of metal-oxide-semiconductor structures prepared by thermal evaporation of gold electrodes on nanocomposite films. The capacitance-voltage measurements show that the dielectric constant of the film increases with the number of deposited layers and the fixed charge and the trapped charge densities have a negative sign.

Passivation mechanism of thermal atomic layer-deposited Al2O3 films on silicon at different annealing temperatures.

PubMed

Zhao, Yan; Zhou, Chunlan; Zhang, Xiang; Zhang, Peng; Dou, Yanan; Wang, Wenjing; Cao, Xingzhong; Wang, Baoyi; Tang, Yehua; Zhou, Su

2013-03-02

Thermal atomic layer-deposited (ALD) aluminum oxide (Al2O3) acquires high negative fixed charge density (Qf) and sufficiently low interface trap density after annealing, which enables excellent surface passivation for crystalline silicon. Qf can be controlled by varying the annealing temperatures. In this study, the effect of the annealing temperature of thermal ALD Al2O3 films on p-type Czochralski silicon wafers was investigated. Corona charging measurements revealed that the Qf obtained at 300°C did not significantly affect passivation. The interface-trapping density markedly increased at high annealing temperature (>600°C) and degraded the surface passivation even at a high Qf. Negatively charged or neutral vacancies were found in the samples annealed at 300°C, 500°C, and 750°C using positron annihilation techniques. The Al defect density in the bulk film and the vacancy density near the SiOx/Si interface region decreased with increased temperature. Measurement results of Qf proved that the Al vacancy of the bulk film may not be related to Qf. The defect density in the SiOx region affected the chemical passivation, but other factors may dominantly influence chemical passivation at 750°C.

Passivation mechanism of thermal atomic layer-deposited Al2O3 films on silicon at different annealing temperatures

PubMed Central

2013-01-01

Thermal atomic layer-deposited (ALD) aluminum oxide (Al2O3) acquires high negative fixed charge density (Qf) and sufficiently low interface trap density after annealing, which enables excellent surface passivation for crystalline silicon. Qf can be controlled by varying the annealing temperatures. In this study, the effect of the annealing temperature of thermal ALD Al2O3 films on p-type Czochralski silicon wafers was investigated. Corona charging measurements revealed that the Qf obtained at 300°C did not significantly affect passivation. The interface-trapping density markedly increased at high annealing temperature (>600°C) and degraded the surface passivation even at a high Qf. Negatively charged or neutral vacancies were found in the samples annealed at 300°C, 500°C, and 750°C using positron annihilation techniques. The Al defect density in the bulk film and the vacancy density near the SiOx/Si interface region decreased with increased temperature. Measurement results of Qf proved that the Al vacancy of the bulk film may not be related to Qf. The defect density in the SiOx region affected the chemical passivation, but other factors may dominantly influence chemical passivation at 750°C. PMID:23452508

Effects on Organic Photovoltaics Using Femtosecond-Laser-Treated Indium Tin Oxides.

PubMed

Chen, Mei-Hsin; Tseng, Ya-Hsin; Chao, Yi-Ping; Tseng, Sheng-Yang; Lin, Zong-Rong; Chu, Hui-Hsin; Chang, Jan-Kai; Luo, Chih-Wei

2016-09-28

The effects of femtosecond-laser-induced periodic surface structures (LIPSS) on an indium tin oxide (ITO) surface applied to an organic photovoltaic (OPV) system were investigated. The modifications of ITO induced by LIPPS in OPV devices result in more than 14% increase in power conversion efficiency (PCE) and short-circuit current density relative to those of the standard device. The basic mechanisms for the enhanced short-circuit current density are attributed to better light harvesting, increased scattering effects, and more efficient charge collection between the ITO and photoactive layers. Results show that higher PCEs would be achieved by laser-pulse-treated electrodes.

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

Okamura, M., E-mail: okamura@bnl.gov; Nishina Center for Accelerator-Based Science, RIKEN, Saitama; Palm, K.

Calcium and lithium ion beams are required by NASA Space Radiation Laboratory at Brookhaven National Laboratory to simulate the effects of cosmic radiation. To identify the difficulties in providing such highly reactive materials as laser targets, both species were experimentally tested. Plate shaped lithium and calcium targets were fabricated to create ablation plasmas with a 6 ns 1064 nm neodymium-doped yttrium aluminum garnet laser. We found significant oxygen contamination in both the Ca and Li high charge state beams due to the rapid oxidation of the surfaces. A large spot size, low power density laser was used to create lowmore » charge state beams without scanning the targets. The low charge state Ca beam did not have any apparent oxygen contamination, showing the potential to clean the target entirely of oxide with a low power beam once in the chamber. The Li target was clearly still oxidizing in the chamber after each low power shot. To measure the rate of oxidation, we shot the low power laser at the target repeatedly at 10 s, 30 s, 60 s, and 120 s interval lengths, showing a linear relation between the interval time and the amount of oxygen in the beam.« less

Intensive Study on the Catalytical Behavior of N-Methylphenothiazine as a Soluble Mediator to Oxidize the Li2O2 Cathode of the Li-O2 Battery.

PubMed

Feng, Ningning; Mu, Xiaowei; Zhang, Xueping; He, Ping; Zhou, Haoshen

2017-02-01

Aprotic Li-O 2 batteries have attracted worldwide interest owing to their ultrahigh theoretical energy density. However, the practical Li-O 2 batteries still suffer from high charge overpotential and low energy efficiency resulting from the sluggish kinetics in electrochemically oxidizing the insulating lithium peroxide (Li 2 O 2 ). Recently, dissolved redox mediators in the electrolyte have enabled the effective catalytic oxidation of Li 2 O 2 at the liquid-solid interface. Here, we report that the incorporation of N-methylphenothiazine (MPT), as a redox shuttle in Li-O 2 batteries, provides a dramatic reduction in charge overpotential to 0.67 V and an improved round-trip efficiency close to 76%. Moreover, the efficacy of MPT in Li-O 2 cells was further investigated by various characterizations. On charging, MPT + cations are first generated electrochemically at the cathode surface and subsequently oxidize the solid discharge products Li 2 O 2 through a chemical reaction. Furthermore, the presence of MPT has been demonstrated to improve the cycling stability of the cells and suppress side reactions arising from carbon and electrolytes at high potentials.

Orbital-occupancy versus charge ordering and the strength of electron correlations in electron-doped CaMnO3.

PubMed

Luo, Weidong; Franceschetti, Alberto; Varela, Maria; Tao, Jing; Pennycook, Stephen J; Pantelides, Sokrates T

2007-07-20

The structural, electronic, and magnetic properties of mixed-valence compounds are believed to be governed by strong electron correlations. Here we report benchmark density-functional calculations in the spin-polarized generalized-gradient approximation (GGA) for the ground-state properties of doped CaMnO(3). We find excellent agreement with all available data, while inclusion of strong correlations in the GGA+U scheme impairs this agreement. We demonstrate that formal oxidation states reflect only orbital occupancies, not charge transfer, and resolve outstanding controversies about charge ordering.

Orbital-Occupancy versus Charge Ordering and the Strength of Electron Correlations in Electron-Doped CaMnO3

NASA Astrophysics Data System (ADS)

Luo, Weidong; Franceschetti, Alberto; Varela, Maria; Tao, Jing; Pennycook, Stephen J.; Pantelides, Sokrates T.

2007-07-01

The structural, electronic, and magnetic properties of mixed-valence compounds are believed to be governed by strong electron correlations. Here we report benchmark density-functional calculations in the spin-polarized generalized-gradient approximation (GGA) for the ground-state properties of doped CaMnO3. We find excellent agreement with all available data, while inclusion of strong correlations in the GGA+U scheme impairs this agreement. We demonstrate that formal oxidation states reflect only orbital occupancies, not charge transfer, and resolve outstanding controversies about charge ordering.

Molecular receptors in metal oxide sol-gel materials prepared via molecular imprinting

DOEpatents

Sasaki, Darryl Y.; Brinker, C. Jeffrey; Ashley, Carol S.; Daitch, Charles E.; Shea, Kenneth J.; Rush, Daniel J.

2000-01-01

A method is provided for molecularly imprinting the surface of a sol-gel material, by forming a solution comprised of a sol-gel material, a solvent, an imprinting molecule, and a functionalizing siloxane monomer of the form Si(OR).sub.3-n X.sub.n, wherein n is an integer between zero and three and X is a functional group capable of reacting with the imprinting molecule, evaporating the solvent, and removing the imprinting molecule to form the molecularly imprinted metal oxide sol-gel material. The use of metal oxide sol-gels allows the material porosity, pore size, density, surface area, hardness, electrostatic charge, polarity, optical density, and surface hydrophobicity to be tailored and be employed as sensors and in catalytic and separations operations.

Interface properties of SiOxNy layer on Si prepared by atmospheric-pressure plasma oxidation-nitridation

PubMed Central

2013-01-01

SiOxNy films with a low nitrogen concentration (< 4%) have been prepared on Si substrates at 400°C by atmospheric-pressure plasma oxidation-nitridation process using O2 and N2 as gaseous precursors diluted in He. Interface properties of SiOxNy films have been investigated by analyzing high-frequency and quasistatic capacitance-voltage characteristics of metal-oxide-semiconductor capacitors. It is found that addition of N into the oxide increases both interface state density (Dit) and positive fixed charge density (Qf). After forming gas anneal, Dit decreases largely with decreasing N2/O2 flow ratio from 1 to 0.01 while the change of Qf is insignificant. These results suggest that low N2/O2 flow ratio is a key parameter to achieve a low Dit and relatively high Qf, which is effective for field effect passivation of n-type Si surfaces. PMID:23634872

Influence of surface oxidation on ion dynamics and capacitance in porous and nonporous carbon electrodes

DOE PAGES

Dyatkin, Boris; Zhang, Yu; Mamontov, Eugene; ...

2016-04-07

Here, we investigate the influence of surface chemistry and ion confinement on capacitance and electrosorption dynamics of room-temperature ionic liquids (RTILs) in supercapacitors. Using air oxidation and vacuum annealing, we produced defunctionalized and oxygen-rich surfaces of carbide-derived carbons (CDCs) and graphene nanoplatelets (GNPs). While oxidized surfaces of porous CDCs improve capacitance and rate handling abilities of ions, defunctionalized nonporous GNPs improve charge storage densities on planar electrodes. Quasi-elastic neutron scattering (QENS) and inelastic neutron scattering (INS) probed the structure, dynamics, and orientation of RTIL ions confined in divergently functionalized pores. Oxidized, ionophilic surfaces draw ions closer to pore surfaces andmore » enhance potential-driven ion transport during electrosorption. Molecular dynamics (MD) simulations corroborated experimental data and demonstrated the significance of surface functional groups on ion orientations, accumulation densities, and capacitance.« less

Low temperature solution processed high-κ ZrO2 gate dielectrics for nanoelectonics

NASA Astrophysics Data System (ADS)

Kumar, Arvind; Mondal, Sandip; Rao, K. S. R. Koteswara

2016-05-01

The high-κ gate dielectrics, specifically amorphous films offer salient features such as exceptional mechanical flexibility, smooth surfaces and better uniformity associated with low leakage current density. In this work, ∼35 nm thick amorphous ZrO2 films were deposited on silicon substrate at low temperature (300 °C, 1 h) from facile spin-coating method and characterized by various analytical techniques. The X-ray diffraction and X-ray photoelectron spectroscopy reveal the formation of amorphous phase ZrO2, while ellipsometry analysis together with the Atomic Force Microscope suggest the formation of dense film with surface roughness of 1.5 Å, respectively. The fabricated films were integrated in metal-oxide-semiconductor (MOS) structures to check the electrical capabilities. The oxide capacitance (Cox), flat band capacitance (CFB), flat band voltage (VFB), dielectric constant (κ) and oxide trapped charges (Qot) extracted from high frequency (1 MHz) C-V curve are 186 pF, 104 pF, 0.37 V, 15 and 2 × 10-11 C, respectively. The small flat band voltage 0.37 V, narrow hysteresis and very little frequency dispersion between 10 kHz-1 MHz suggest an excellent a-ZrO2/Si interface with very less trapped charges in the oxide. The films exhibit a low leakage current density 4.7 × 10-9 A/cm2 at 1 V. In addition, the charge transport mechanism across the MOSC is analyzed and found to have a strong bias dependence. The space charge limited conduction mechanism is dominant in the high electric field region (1.3-5 V) due to the presence of traps, while the trap-supported tunneling is prevailed in the intermediate region (0.35-1.3 V). Low temperature solution processed ZrO2 thin films obtained are of high quality and find their importance as a potential dielectric layer on Si and polymer based flexible electronics.

Charge Transport and the Nature of Traps in Oxygen Deficient Tantalum Oxide.

PubMed

Gritsenko, Vladimir A; Perevalov, Timofey V; Voronkovskii, Vitalii A; Gismatulin, Andrei A; Kruchinin, Vladimir N; Aliev, Vladimir Sh; Pustovarov, Vladimir A; Prosvirin, Igor P; Roizin, Yakov

2018-01-31

Optical and transport properties of nonstoichiometric tantalum oxide thin films grown by ion beam deposition were investigated in order to understand the dominant charge transport mechanisms and reveal the nature of traps. The TaO x films composition was analyzed by X-ray photoelectron spectroscopy and by quantum-chemistry simulation. From the optical absorption and photoluminescence measurements and density functional theory simulations, it was concluded that the 2.75 eV blue luminescence excited in a TaO x by 4.45 eV photons, originates from oxygen vacancies. These vacancies are also responsible for TaO x conductivity. The thermal trap energy of 0.85 eV determined from the transport experiments coincides with the half of the Stokes shift of the blue luminescence band. It is argued that the dominant charge transport mechanism in TaO x films is phonon-assisted tunneling between the traps.

Charge transfer in iridate-manganite superlattices

DOE PAGES

Okamoto, Satoshi; Nichols, John; Sohn, Changhee; ...

2017-03-03

Charge transfer in superlattices consisting of SrIrOmore » $$_3$$ and SrMnO$$_3$$ is investigated using density functional theory. Despite the nearly identical work function and non-polar interfaces between SrIrO$$_3$$ and SrMnO$$_3$$, rather large charge transfer was experimentally reported between them. Our results provide a qualitative understanding to such experimental reports. We further develop a microscopic model that captures the mechanism behind this phenomenon. This leads to unique strain dependence of such charge transfer in iridate-manganite superlattices. The predicted behavior is consistently verified by experiment. Lastly, our work thus demonstrates a new route to control electronic states in non-polar oxide heterostructures.« less

Nanostructured pseudocapacitive materials decorated 3D graphene foam electrodes for next generation supercapacitors.

PubMed

Patil, Umakant; Lee, Su Chan; Kulkarni, Sachin; Sohn, Ji Soo; Nam, Min Sik; Han, Suhyun; Jun, Seong Chan

2015-04-28

Nowadays, advancement in performance of proficient multifarious electrode materials lies conclusively at the core of research concerning energy storage devices. To accomplish superior capacitance performance the requirements of high capacity, better cyclic stability and good rate capability can be expected from integration of electrochemical double layer capacitor based carbonaceous materials (high power density) and pseudocapacitive based metal hydroxides/oxides or conducting polymers (high energy density). The envisioned three dimensional (3D) graphene foams are predominantly advantageous to extend potential applicability by offering a large active surface area and a highly conductive continuous porous network for fast charge transfer with decoration of nanosized pseudocapacitive materials. In this article, we review the latest methodologies and performance evaluation for several 3D graphene based metal oxides/hydroxides and conducting polymer electrodes with improved electrochemical properties for next-generation supercapacitors. The most recent research advancements of our and other groups in the field of 3D graphene based electrode materials for supercapacitors are discussed. To assess the studied materials fully, a careful interpretation and rigorous scrutiny of their electrochemical characteristics is essential. Auspiciously, both nano-structuration as well as confinement of metal hydroxides/oxides and conducting polymers onto a conducting porous 3D graphene matrix play a great role in improving the performance of electrodes mainly due to: (i) active material access over large surface area with fast charge transportation; (ii) synergetic effect of electric double layer and pseudocapacitive based charge storing.

The Effect of Oxidation and Charge/Discharge rates on Li Plating in All-Solid-State Batteries

NASA Astrophysics Data System (ADS)

Yulaev, Alexander; Oleshko, Vladimir; Talin, A. Alec; Leite, Marina S.; Kolmakov, Andrei

All-solid-state Li-ion batteries (SSLIBs) is currently an extensive area of research due to their promising specific power and energy density properties. Moreover, SSLIBs significantly mitigate the safety risks of the thermal runaway that may occur in liquid electrolyte batteries. We fabricated a model SSLIB, which consists of LiCoO2 cathode layer, LiPON as an electrolyte, and a model ultra-thin carbon anode. Using in operando scanning electron microscopy in conjunction with electrochemical measurements, we found that depending on ambient oxidizing conditions and charging rate, the morphology of plated lithium alternates between quasi-1D and 3D microstructures. In addition, we were able to use an electron beam as a virtual nano-electrode to selectively control the nucleation rate and Li growth structure during the SSLIB charging with high spatial resolution. Finally, we determined the conditions when lithium may be oxidized even during battery cycling under UHV conditions, leading to significant capacity losses. We foresee that our work will provide deeper insights into a safe SSLIB performance under real world operating conditions.

Modeling the Partial Atomic Charges in Inorganometallic Molecules and Solids and Charge Redistribution in Lithium-Ion Cathodes

DOE PAGES

Wang, Bo; Li, Shaohong L.; Truhlar, Donald G.

2014-10-30

Partial atomic charges are widely used for the description of charge distributions of molecules and solids. These charges are useful to indicate the extent of charge transfer and charge flow during chemical reactions in batteries, fuel cells, and catalysts and to characterize charge distributions in capacitors, liquid-phase electrolytes, and solids and at electrochemical interfaces. However, partial atomic charges given by various charge models differ significantly, especially for systems containing metal atoms. In the present study, we have compared various charge models on both molecular systems and extended systems, including Hirshfeld, CM5, MK, ChElPG, Mulliken, MBS, NPA, DDEC, LoProp, and Badermore » charges. Their merits and drawbacks are compared. The CM5 charge model is found to perform well on the molecular systems, with a mean unsigned percentage deviation of only 9% for the dipole moments. We therefore formulated it for extended systems and applied it to study charge flow during the delithiation process in lithium-containing oxides used as cathodes. Our calculations show that the charges given by the CM5 charge model are reasonable and that during the delithiation process, the charge flow can occur not only on the transition metal but also on the anions. The oxygen atoms can lose a significant density of electrons, especially for deeply delithiated materials. We also discuss other methods in current use to analyze the charge transfer and charge flow in batteries, in particular the use of formal charge, spin density, and orbital occupancy. Here, we conclude that CM5 charges provide useful information in describing charge distributions in various materials and are very promising for the study of charge transfer and charge flows in both molecules and solids.« less

Modeling the Partial Atomic Charges in Inorganometallic Molecules and Solids and Charge Redistribution in Lithium-Ion Cathodes.

PubMed

Wang, Bo; Li, Shaohong L; Truhlar, Donald G

2014-12-09

Partial atomic charges are widely used for the description of charge distributions of molecules and solids. These charges are useful to indicate the extent of charge transfer and charge flow during chemical reactions in batteries, fuel cells, and catalysts and to characterize charge distributions in capacitors, liquid-phase electrolytes, and solids and at electrochemical interfaces. However, partial atomic charges given by various charge models differ significantly, especially for systems containing metal atoms. In the present study, we have compared various charge models on both molecular systems and extended systems, including Hirshfeld, CM5, MK, ChElPG, Mulliken, MBS, NPA, DDEC, LoProp, and Bader charges. Their merits and drawbacks are compared. The CM5 charge model is found to perform well on the molecular systems, with a mean unsigned percentage deviation of only 9% for the dipole moments. We therefore formulated it for extended systems and applied it to study charge flow during the delithiation process in lithium-containing oxides used as cathodes. Our calculations show that the charges given by the CM5 charge model are reasonable and that during the delithiation process, the charge flow can occur not only on the transition metal but also on the anions. The oxygen atoms can lose a significant density of electrons, especially for deeply delithiated materials. We also discuss other methods in current use to analyze the charge transfer and charge flow in batteries, in particular the use of formal charge, spin density, and orbital occupancy. We conclude that CM5 charges provide useful information in describing charge distributions in various materials and are very promising for the study of charge transfer and charge flows in both molecules and solids.

CO oxidation on Alsbnd Au nano-composite systems

NASA Astrophysics Data System (ADS)

Rajesh, C.; Majumder, C.

2018-03-01

Using first principles method we report the CO oxidation behaviour of Alsbnd Au nano-composites in three different size ranges: Al6Au8, Al13Au42 and a periodic slab of Alsbnd Au(1 1 1) surface. The clusters prefer enclosed structures with alternating arrangement of Al and Au atoms, maximising Auδ-sbnd Alδ+ bonds. Charge distribution analysis suggests the charge transfer from Al to Au atoms, corroborated by the red shift in the density of states spectrum. Further, CO oxidation on these nano-composite systems was investigated through both Eley - Rideal and Langmuir Hinshelwood mechanism. While, these clusters interact with O2 non-dissociatively with an elongation of the Osbnd O bond, further interaction with CO led to formation of CO2 spontaneously. On contrary, the CO2 evolution by co-adsorption of O2 and CO molecules has a transition state barrier. On the basis of the results it is inferred that nano-composite material of Alsbnd Au shows significant promise toward effective oxidative catalysis.

Advanced Electronic Technology.

DTIC Science & Technology

1978-11-15

nitride by band-to-band tunneling through the oxide, (2 ) pronounced field detrapping of charge in the nitride takes place , and (3) the VAP defect density...W/E operations - Charge carriers can escape from the fatigue state by back tunneling so that as IN~fl — (NI ) and LN~~J — [N~~J the short-term...in Vinyl Chloride 4843 Infrared Laser Photochem- T. F. Deutach Accepted by J. Cheni. Phys. istry of Silane 4852 Transve rse Modes in Gap- S. A

Quantum many-body intermetallics: Phase stability of Fe3Al and small-gap formation in Fe2VAl

NASA Astrophysics Data System (ADS)

Kristanovski, Oleg; Richter, Raphael; Krivenko, Igor; Lichtenstein, Alexander I.; Lechermann, Frank

2017-01-01

Various intermetallic compounds harbor subtle electronic correlation effects. To elucidate this fact for the Fe-Al system, we perform a realistic many-body investigation based on a combination of density functional theory with dynamical mean-field theory in a charge self-consistent manner. A better characterization and understanding of the phase stability of bcc-based D 03-Fe3Al through an improved description of the correlated charge density and the magnetic energy is achieved. Upon replacement of one Fe sublattice with V, the Heusler compound Fe2VAl is realized, known to display bad-metal behavior and increased specific heat. Here we document a charge-gap opening at low temperatures in line with previous experimental work. The gap structure does not match conventional band theory and is reminiscent of (pseudo)gap characteristics in correlated oxides.

Disorder induced semiconductor to metal transition and modifications of grain boundaries in nanocrystalline zinc oxide thin film

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

Singh, Fouran; Kumar, Vinod; Chaudhary, Babloo

2012-10-01

This paper report on the disorder induced semiconductor to metal transition (SMT) and modifications of grain boundaries in nanocrystalline zinc oxide thin film. Disorder is induced using energetic ion irradiation. It eliminates the possibility of impurities induced transition. However, it is revealed that some critical concentration of defects is needed for inducing such kind of SMT at certain critical temperature. Above room temperature, the current-voltage characteristics in reverse bias attributes some interesting phenomenon, such as electric field induced charge transfer, charge trapping, and diffusion of defects. The transition is explained by the defects induced disorder and strain in ZnO crystallitesmore » created by high density of electronic excitations.« less

Inorganic nanostructured materials for high performance electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Sheng; Sun, Shouheng; You, Xiao-Zeng

2014-01-01

Electrochemical supercapacitors (ES) are a well-known energy storage system that has high power density, long life-cycle and fast charge-discharge kinetics. Nanostructured materials are a new generation of electrode materials with large surface area and short transport/diffusion path for ions and electrons to achieve high specific capacitance in ES. This mini review highlights recent developments of inorganic nanostructure materials, including carbon nanomaterials, metal oxide nanoparticles, and metal oxide nanowires/nanotubes, for high performance ES applications.

Inorganic nanostructured materials for high performance electrochemical supercapacitors.

PubMed

Liu, Sheng; Sun, Shouheng; You, Xiao-Zeng

2014-02-21

Electrochemical supercapacitors (ES) are a well-known energy storage system that has high power density, long life-cycle and fast charge-discharge kinetics. Nanostructured materials are a new generation of electrode materials with large surface area and short transport/diffusion path for ions and electrons to achieve high specific capacitance in ES. This mini review highlights recent developments of inorganic nanostructure materials, including carbon nanomaterials, metal oxide nanoparticles, and metal oxide nanowires/nanotubes, for high performance ES applications.

Electrochemical investigations of ionic liquids with vinylene carbonate for applications in rechargeable lithium ion batteries

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

Sun, Xiao-Guang; Dai, Sheng

2010-01-01

Ionic liquids based on methylpropylpyrrolidinium (MPPY) and methylpropylpiperidinium (MPPI) cations and bis(trifluoromethanesulfionyl)imide (TFSI) anion have been synthesized and characterized by thermal analysis, cyclic voltammetry, impedance spectroscopy as well as gavanostatic charge/discharge tests. 10 wt% of vinylene carbonate (VC) was added to the electrolytes of 0.5 M LiTFSI/MPPY.TFSI and 0.5 M LiTFSI/MPPI.TFSI, which were evaluated in Li || natural graphite (NG) half cells at 25 oC and 50 oC under different current densities. At 25 oC, due to their intrinsic high viscosities, the charge/discharge capacities under the current density of 80 A cm-2 were much lower than those under the currentmore » density of 40 A cm-2. At 50 oC, with reduced viscosities, the charge/discharge capacities under both current densities were almost indistinguishable, which were also close to the typical values obtained using conventional carbonate electrolytes. In addition, the discharge capacities of the half cells were very stable with cycling, due to the effective formation of solid electrolyte interphase (SEI) on the graphite electrode. On the contrary, the charge/discharge capacities of the Li || LiCoO2 cells using both ionic liquid electrolytes under the current density of 40 A cm-2 decreased continually with cycling, which were primarily due to the low oxidative stability of VC on the surface of LiCoO2.« less

One-step electroplating porous graphene oxide electrodes of supercapacitors for ultrahigh capacitance and energy density.

PubMed

Wang, Yongjie; Zhu, Jiaqi

2015-02-06

An electroplating method was used for the first time to synthesize 3D porous graphene oxide (PGO) architectures, exhibiting ultrahigh capacitance and energy density as electrodes of supercapacitors. Scanning electron microscopy illustrated the porous structures which promoted the stability and alleviated the stacking of the graphene oxide layers. As investigated in a three-electrode supercapacitor cell, PGO electrodes exhibited the maximum capacitance and energy of 973 F · g(-1) and 98.4 Wh · Kg(-1), which are better than current reports and comparable to batteries. At 4 A · g(-1) for high-power applications, PGO electrodes reached a capacitance, energy, and power density of 493 F · g(-1), 49.9 Wh · Kg(-1), and 1700 W · Kg(-1), and they retained ∼97.83% of capacitance after 10 000 charge/discharge processes. Furthermore, when the PGO was bent exaggeratedly, it still displayed identical properties, which is of important significance for supporting wearable devices.

Density functional theory study of defect energies and space charge distribution at a solid-oxide electrolyte surface

NASA Astrophysics Data System (ADS)

Han, Chu; Bongiorno, Angelo

2014-03-01

Yttrium-doped barium zirconate (BZY) is a proton conducting electrolyte forming a class of novel materials for new generation of solid oxide fuel cells, for hydrogen separation and purification, and for electrolysis of water. Here we use density functional theory calculations to compute the energy of protons and oxygen vacancies at the surface and in the bulk of lightly Y-doped BZY materials. We found that protons are energetically more stable at the surface termination than in the bulk of BZY by about 1 eV. In contrast, doubly-positively charged oxygen vacancies are found to form iso-energetic defects at both the terminal surface layer and in the bulk of BZY, while in the sub-surface region the defect energy raises by about 1 eV with respect to the value in the bulk. The energetic behavior of protons and oxygen vacancies in the near surface region of BZY is attributed to the competition of strain and electrostatic effects. Lattice model representations of BZY surfaces are then used in combination with Monte Carlo simulations to solve the Poisson-Boltzmann equation and investigate the implication of the results above on the structure of the space charge region at the surface of BZY materials.

Charge versus orbital-occupancy ordering in manganites

NASA Astrophysics Data System (ADS)

Luo, Weidong; Varela, Maria; Tao, Jing; Pennycook, Stephen J.; Pantelides, Sokrates T.

2006-03-01

It is generally assumed that density-functional theory (DFT) in the local-spin-density approximation (LSDA) or the generalized- gradient approximation (GGA) is not adequate to describe mixed- valence manganites. Here we report benchmark DFT/GGA calculations for the ground-state structural, electronic and magnetic properties for both undoped and doped CaMnO3 and find the results to be in excellent agreement with available data, including new atomic-resolution Z-contrast imaging and electron-energy loss spectra. More specifically, we found that the DFT results predict two inequivalent Mn atoms in both 0.33 and 0.5 electron-doped CaMnO3, in agreement with experimental evidence of Mn^+3/Mn^+4 oxidation state ordering. The inequivalent Mn atoms are marked by their distinctive orbital occupancies, dissimilar local Jahn-Teller distortion and different magnetic moments from DFT calculations. We also show that the spherically integrated charges associated with the two inequivalent Mn atoms are the same, and they are actually the same as in the Mn metal. This charge neutrality with different orbital occupancies is the result of self-consistency and atomic relaxations in the crystal. We conclude that DFT without additional correlations can account for the observed properties of oxidation-state ordering in this system. The impact of the results on other mixed-valence systems will be discussed.

Adaptation of plastic surfaces for tissue culture by glow discharge.

PubMed Central

Amstein, C F; Hartman, P A

1975-01-01

Plastic petri dishes and microtitration plates were electrically charged by a glow discharge unit installed in a vacuum evaporator. Charged and uncharged plates, as well as plates commercially treated for tissue culture, were inoculated with Vero and BHK-21 cell lines; secondary cultures of monkey kidney, chicken lung, canine kidney, and embryonic bovine kidney; and primary chicken embryo fibroblasts and chicken lung cells. All cell cultures grew normally on petri plates charged with the covers open. Growth rate and cell density compared favorably with growth on the commercial tissue culture plates; cell growth was somewhat less dense, however, on plates charged with the covers closed. Charged plates could be sterilized by ultraviolet light and ethylene oxide with no adverse effects on cell growth. Cells inoculated onto plates charged up to 7 months before inoculation grew as well as on freshly charged plates. Images PMID:818106

Capacitance-voltage characteristics of sub-nanometric Al2O3 / TiO2 laminates: dielectric and interface charge densities.

PubMed

Kahouli, Abdelkader; Elbahri, Marwa Ben; Lebedev, Oleg; Lüders, Ulrike

2017-07-12

Advanced amorphous sub-nanometric laminates based on TiO 2 and Al 2 O 3 were deposited by atomic layer deposition at low temperature. Low densities of 'slow' and 'fast' interface states are achieved with values of 3.96 · 10 10 cm -2 and 4.85 · 10 -9 eV -1 cm -2 , respectively, by using a 40 nm laminate constituted of 0.7 nm TiO 2 and 0.8 nm Al 2 O 3 . The sub-nanometric laminate shows a low hysteresis width of 20 mV due to the low oxide charge density of about 3.72 · 10 11 cm -2 . Interestingly, such properties are required for stable and reliable performance of MOS capacitors and transistor operation. Thus, decreasing the individual layer thickness to the sub-nanometric range and combining two dielectric materials with oppositely charged defects may play a major role in the electrical response, highly promising for the application in future micro and nano-electronics applications.

B-Site Cation-Ordered Double-Perovskite Oxide as an Outstanding Electrode Material for Supercapacitive Energy Storage Based on the Anion Intercalation Mechanism.

PubMed

Xu, Zhenye; Liu, Yu; Zhou, Wei; Tade, Moses O; Shao, Zongping

2018-03-21

Perovskite oxides are highly promising electrodes for oxygen-ion-intercalation-type supercapacitors owing to their high oxygen vacancy concentration, oxygen diffusion rate, and tap density. Based on the anion intercalation mechanism, the capacitance is contributed by surface redox reactions and oxygen ion intercalation in the bulk materials. A high concentration of oxygen vacancies is needed because it is the main charge carrier. In this study, we propose a B-site cation-ordered Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ as an electrode material with an extremely high oxygen vacancy concentration and oxygen diffusion rate. A maximum capacitance of 1050 F g -1 was achieved, and a high capacitance of 780 F g -1 was maintained even after 3000 charge-discharge cycles at a current density of 1 A g -1 with an aqueous alkaline solution (6 M KOH) electrolyte, indicating an excellent cycling stability. In addition, the specific volumetric capacitance of Ba 2 Bi 0.1 Sc 0.2 Co 1.7 O 6-δ reaches up to 2549.4 F cm -3 based on the dense construction and high tap density (3.2 g cm -3 ). In addition, an asymmetric supercapacitor was constructed using activated carbon as a negative electrode, and it displayed the highest specific energy density of 70 Wh kg -1 at the power density of 787 W kg -1 in this study.

Development of high energy density supercapacitor through hydrothermal synthesis of RGO/nano-structured cobalt sulphide composites

NASA Astrophysics Data System (ADS)

Jana, Milan; Saha, Sanjit; Samanta, Pranab; Murmu, Naresh Chandra; Kim, Nam Hoon; Kuila, Tapas; Lee, Joong Hee

2015-02-01

Co9S8/reduced graphene oxide (RGO) composites were prepared on nickel foam substrate through hydrothermal reaction and used directly as supercapacitor electrode. The field emission scanning electron microscopy analysis of the composites showed the formation of Co9S8 nano-rods on the RGO surfaces. The average crystal size of the Co9S8 nano rods grown on the RGO sheets were ˜25-36 nm as calculated from x-ray diffraction analysis. The reduction of graphene oxide (GO) was confirmed by Raman and x-ray photoelectron spectroscopy analysis. The electrical conductivity of the Co9S8/RGO composite was recorded as 1690 S m-1 at room temperature, which is much higher than that of pure GO further confirming the hydrothermal reduction of GO. Cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy were investigated to check the electrochemical performances of the Co9S8/RGO composites. The Co9S8/RGO composites supported on nickel foam showed very high specific capacitance (Sc)(1349 F g-1 at a current density of 2.2 A g-1), energy density (68.6 W h kg-1) and power density (1319 W kg-1) in 6 M KOH electrolyte. The retention in Sc of the composite electrode was found to be ˜96% after 1000 charge-discharge cycles.

Efficiency Enhancement of Nanotextured Black Silicon Solar Cells Using Al2O3/TiO2 Dual-Layer Passivation Stack Prepared by Atomic Layer Deposition.

PubMed

Wang, Wei-Cheng; Tsai, Meng-Chen; Yang, Jason; Hsu, Chuck; Chen, Miin-Jang

2015-05-20

In this study, efficient nanotextured black silicon (NBSi) solar cells composed of silicon nanowire arrays and an Al2O3/TiO2 dual-layer passivation stack on the n(+) emitter were fabricated. The highly conformal Al2O3 and TiO2 surface passivation layers were deposited on the high-aspect-ratio surface of the NBSi wafers using atomic layer deposition. Instead of the single Al2O3 passivation layer with a negative oxide charge density, the Al2O3/TiO2 dual-layer passivation stack treated with forming gas annealing provides a high positive oxide charge density and a low interfacial state density, which are essential for the effective field-effect and chemical passivation of the n(+) emitter. In addition, the Al2O3/TiO2 dual-layer passivation stack suppresses the total reflectance over a broad range of wavelengths (400-1000 nm). Therefore, with the Al2O3/TiO2 dual-layer passivation stack, the short-circuit current density and efficiency of the NBSi solar cell were increased by 11% and 20%, respectively. In conclusion, a high efficiency of 18.5% was achieved with the NBSi solar cells by using the n(+)-emitter/p-base structure passivated with the Al2O3/TiO2 stack.

Porous Ni-Co-Mn oxides prisms for high performance electrochemical energy storage

NASA Astrophysics Data System (ADS)

Zhao, Jianbo; Li, Man; Li, Junru; Wei, Chengzhen; He, Yuyue; Huang, Yixuan; Li, Qiaoling

2017-12-01

Porous Ni-Co-Mn oxides prisms have been successfully synthesized via a facile route. The process involves the preparation of nickel-cobalt-manganese acetate hydroxide by a simple co-precipitation method and subsequently the thermal treatment. The as-synthesized Ni-Co-Mn oxides prisms had a large surface area (96.53 m2 g-1) and porous structure. As electrode materials for supercapacitors, porous Ni-Co-Mn oxides prisms showed a high specific capacitance of 1623.5 F g-1 at 1.0 A g-1. Moreover, the porous Ni-Co-Mn oxides prisms were also employed as positive electrode materials to assemble flexible solid-state asymmetric supercapacitors. The resulting flexible device had a maximum volumetric energy density (0.885 mW h cm-3) and power density (48.9 mW cm-3). Encouragingly, the flexible device exhibited good cycling stability with only about 2.2% loss after 5000 charge-discharge cycles and excellent mechanical stability. These results indicate that porous Ni-Co-Mn oxides prisms have the promising application in high performance electrochemical energy storage.

Paramagnetic defects and charge trapping behavior of ZrO2 films deposited on germanium by plasma-enhanced CVD

NASA Astrophysics Data System (ADS)

Mahata, C.; Bera, M. K.; Bose, P. K.; Maiti, C. K.

2009-02-01

Internal photoemission and magnetic resonance studies have been performed to investigate the charge trapping behavior and chemical nature of defects in ultrathin (~14 nm) high-k ZrO2 dielectric films deposited on p-Ge (1 0 0) substrates at low temperature (<200 °C) by plasma-enhanced chemical vapor deposition (PECVD) in a microwave (700 W, 2.45 GHz) plasma at a pressure of ~65 Pa. Both the band and defect-related electron states have been characterized using electron paramagnetic resonance, internal photoemission, capacitance-voltage and current-voltage measurements under UV illumination. Capacitance-voltage and photocurrent-voltage measurements were used to determine the centroid of oxide charge within the high-k gate stack. The observed shifts in photocurrent response of the Al/ZrO2/GeO2/p-Ge metal-insulator-semiconductor (MIS) capacitors indicate the location of the centroids to be within the ZrO2 dielectric near to the gate electrode. Moreover, the measured flat band voltage and photocurrent shifts also indicate a large density of traps in the dielectric. The impact of plasma nitridation on the interfacial quality of the oxides has been investigated. Different N sources, such as NO and NH3, have been used for nitrogen engineering. Oxynitride samples show a lower defect density and trapping over the non-nitrided samples. The charge trapping and detrapping properties of MIS capacitors under stressing in constant current and voltage modes have been investigated in detail.

Impact of low-dose electron irradiation on $$n^{+}p$$ silicon strip sensors

DOE PAGES

Adam, W.

2015-08-28

The response of n +p silicon strip sensors to electrons from a 90Sr source was measured using a multi-channel read-out system with 25 ns sampling time. The measurements were performed over a period of several weeks, during which the operating conditions were varied. The sensors were fabricated by Hamamatsu Photonics on 200 μm thick float-zone and magnetic-Czochralski silicon. Their pitch was 80 μm, and both p-stop and p-spray isolation of the n + strips were studied. The electrons from the 90Sr source were collimated to a spot with a full-width-at-half-maximum of 2 mm at the sensor surface, and the dosemore » rate in the SiO 2 at the maximum was about 50 Gy(SiO 2)/d. After only a few hours of making measurements, significant changes in charge collection and charge sharing were observed. Annealing studies, with temperatures up to 80 °C and annealing times of 18 h showed that the changes can only be partially annealed. The observations can be qualitatively explained by the increase of the positive oxide-charge density due to the ionization of the SiO 2 by the radiation from the β source. TCAD simulations of the electric field in the sensor for different oxide-charge densities and different boundary conditions at the sensor surface support this explanation. As a result, the relevance of the measurements for the design of n +p strip sensors is discussed.« less

Characterization of plasma processing induced charging damage to MOS devices

NASA Astrophysics Data System (ADS)

Ma, Shawming

1997-12-01

Plasma processing has become an integral part of the fabrication of integrated circuits and takes at least 30% of whole process steps since it offers advantages in terms of directionality, low temperature and process convenience. However, wafer charging during plasma processes is a significant concern for both thin oxide damage and profile distortion. In this work, the factors affecting this damage will be explained by plasma issues, device structure and oxide quality. The SPORT (Stanford Plasma On-wafer Real Time) charging probe was developed to investigate the charging mechanism of different plasma processes including poly-Si etching, resist ashing and PECVD. The basic idea of this probe is that it simulates a real device structure in the plasma environment and allows measurement of plasma induced charging voltages and currents directly in real time. This measurement is fully compatible with other charging voltage measurement but it is the only one to do in real-time. Effect of magnetic field induced plasma nonuniformity on spatial dependent charging is well understood by this measurement. In addition, the plasma parameters including ion current density and electron temperature can also be extracted from the probe's plasma I-V characteristics using a dc Langmuir probe like theory. It will be shown that the MOS device tunneling current from charging, the dependence on antenna ratio and the etch uniformity can all be predicted by using this measurement. Moreover, the real-time measurement reveals transient and electrode edge effect during processing. Furthermore, high aspect ratio pattern induced electron shading effects can also be characterized by the probe. On the oxide quality issue, wafer temperature during plasma processing has been experimentally shown to be critical to charging damage. Finally, different MOS capacitor testing methods including breakdown voltage, charge-to-breakdown, gate leakage current and voltage-time at constant current bias were compared to find the optimum method for charging device reliability testing.

Charge states of ions, and mechanisms of charge ordering transitions

NASA Astrophysics Data System (ADS)

Pickett, Warren E.; Quan, Yundi; Pardo, Victor

2014-07-01

To gain insight into the mechanism of charge ordering transitions, which conventionally are pictured as a disproportionation of an ion M as 2Mn+→M(n+1)+ + M(n-1)+, we (1) review and reconsider the charge state (or oxidation number) picture itself, (2) introduce new results for the putative charge ordering compound AgNiO2 and the dual charge state insulator AgO, and (3) analyze the cationic occupations of the actual (not formal) charge, and work to reconcile the conundrums that arise. We establish that several of the clearest cases of charge ordering transitions involve no disproportion (no charge transfer between the cations, and hence no charge ordering), and that the experimental data used to support charge ordering can be accounted for within density functional-based calculations that contain no charge transfer between cations. We propose that the charge state picture retains meaning and importance, at least in many cases, if one focuses on Wannier functions rather than atomic orbitals. The challenge of modeling charge ordering transitions with model Hamiltonians isdiscussed.

Tuning charge–discharge induced unit cell breathing in layer-structured cathode materials for lithium-ion batteries

DOE PAGES

Zhou, Yong-Ning; Ma, Jun; Hu, Enyuan; ...

2014-11-18

Through a systematic study of lithium molybdenum trioxide (Li 2MoO 3), a new ‘unit cell breathing’ mechanism is introduced based on both crystal and electronic structural changes of transition metal oxide cathode materials during charge–discharge: For widely used LiMO 2 (M = Co, Ni, Mn), lattice parameters, a and b, contracts during charge. However, for Li 2MoO 3, such changes are in opposite directions. Metal–metal bonding is used to explain such ‘abnormal’ behaviour and a generalized hypothesis is developed. The expansion of M–M bond becomes the controlling factor for a(b) evolution during charge, in contrast to the shrinking M–O asmore » controlling factor in ‘normal’ materials. The cation mixing caused by migration of Mo ions at higher oxidation state provides the benefits of reducing the c expansion range in early stage of charging and suppressing the structure collapse at high voltage charge. These results open a new strategy for designing and engineering layered cathode materials for high energy density lithium-ion batteries.« less

Interpreting anomalies observed in oxide semiconductor TFTs under negative and positive bias stress

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

Jin, Jong Woo; Nathan, Arokia, E-mail: an299@cam.ac.uk; Barquinha, Pedro

2016-08-15

Oxide semiconductor thin-film transistors can show anomalous behavior under bias stress. Two types of anomalies are discussed in this paper. The first is the shift in threshold voltage (V{sub TH}) in a direction opposite to the applied bias stress, and highly dependent on gate dielectric material. We attribute this to charge trapping/detrapping and charge migration within the gate dielectric. We emphasize the fundamental difference between trapping/detrapping events occurring at the semiconductor/dielectric interface and those occurring at gate/dielectric interface, and show that charge migration is essential to explain the first anomaly. We model charge migration in terms of the non-instantaneous polarizationmore » density. The second type of anomaly is negative V{sub TH} shift under high positive bias stress, with logarithmic evolution in time. This can be argued as electron-donating reactions involving H{sub 2}O molecules or derived species, with a reaction rate exponentially accelerated by positive gate bias and exponentially decreased by the number of reactions already occurred.« less

Final Technical Report for DE-SC0001878 [Theory and Simulation of Defects in Oxide Materials

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

Chelikowsky, James R.

2014-04-14

We explored a wide variety of oxide materials and related problems, including materials at the nanoscale and generic problems associated with oxide materials such as the development of more efficient computational tools to examine these materials. We developed and implemented methods to understand the optical and structural properties of oxides. For ground state properties, our work is predominantly based on pseudopotentials and density functional theory (DFT), including new functionals and going beyond the local density approximation (LDA): LDA+U. To study excited state properties (quasiparticle and optical excitations), we use time dependent density functional theory, the GW approach, and GW plusmore » Bethe-Salpeter equation (GW-BSE) methods based on a many-body Green function approaches. Our work focused on the structural, electronic, optical and magnetic properties of defects (such as oxygen vacancies) in hafnium oxide, titanium oxide (both bulk and clusters) and related materials. We calculated the quasiparticle defect states and charge transition levels of oxygen vacancies in monoclinic hafnia. we presented a milestone G0W0 study of two of the crystalline phases of dye-sensitized TiO{sub 2} clusters. We employed hybrid density functional theory to examine the electronic structure of sexithiophene/ZnO interfaces. To identify the possible effect of epitaxial strain on stabilization of the ferromagnetic state of LaCoO{sub 3} (LCO), we compare the total energy of the magnetic and nonmagnetic states of the strained theoretical bulk structure.« less

Ultrasmall iron oxide nanoparticles for biomedical applications: improving the colloidal and magnetic properties.

PubMed

Costo, Rocio; Bello, Valentina; Robic, Caroline; Port, Marc; Marco, Jose F; Puerto Morales, M; Veintemillas-Verdaguer, Sabino

2012-01-10

A considerable increase in the saturation magnetization, M(s) (40%), and initial susceptibility of ultrasmall (<5 nm) iron oxide nanoparticles prepared by laser pyrolysis was obtained through an optimized acid treatment. Moreover, a significant enhancement in the colloidal properties, such as smaller aggregate sizes in aqueous media and increased surface charge densities, was found after this chemical protocol. The results are consistent with a reduction in nanoparticle surface disorder induced by a dissolution-recrystallization mechanism.

Environment-Modulated Crystallization of Cu2O and CuO Nanowires by Electrospinning and Their Charge Storage Properties.

PubMed

Harilal, Midhun; G Krishnan, Syam; Pal, Bhupender; Reddy, M Venkatashamy; Ab Rahim, Mohd Hasbi; Yusoff, Mashitah Mohd; Jose, Rajan

2018-02-06

This article reports the synthesis of cuprous oxide (Cu 2 O) and cupric oxide (CuO) nanowires by controlling the calcination environment of electrospun polymeric nanowires and their charge storage properties. The Cu 2 O nanowires showed higher surface area (86 m 2 g -1 ) and pore size than the CuO nanowires (36 m 2 g -1 ). Electrochemical analysis was carried out in 6 M KOH, and both the electrodes showed battery-type charge storage mechanism. The electrospun Cu 2 O electrodes delivered high discharge capacity (126 mA h g -1 ) than CuO (72 mA h g -1 ) at a current density of 2.4 mA cm -2 . Electrochemical impedance spectroscopy measurements show almost similar charge-transfer resistance in Cu 2 O (1.2 Ω) and CuO (1.6 Ω); however, Cu 2 O showed an order of magnitude higher ion diffusion. The difference in charge storage between these electrodes is attributed to the difference in surface properties and charge kinetics at the electrode. The electrode also shows superior cyclic stability (98%) and Coulombic efficiency (98%) after 5000 cycles. Therefore, these materials could be acceptable choices as a battery-type or pseudocapacitive electrode in asymmetric supercapacitors.

Adsorption contributions of graphene to sodium ion storage performance

NASA Astrophysics Data System (ADS)

Fu, Hao; Xu, Zhanwei; Guan, Weiwei; Shen, Xuetao; Cao, Liyun; Huang, Jianfeng

2018-05-01

Graphene derivates, including graphite, graphene oxide (GO), and reduced graphene oxide (rGO), are employed as sodium ion battery anodes to investigate the effect of adsorption reactions on their electrochemical performance. GO and rGO exhibit the reversible capacity of 230, 192 mAh g‑1 at a low current density of 100 mA g‑1. However, when tested at higher current densities of 200, 500, and 1000 mA g‑1, the GO electrodes deliver 136, 76, and 38 mAh g‑1, respectively. As a comparison, rGO exhibits capacity as high as 168, 133, and 117 mAh g‑1 at the same conditions—23.5%, 75.0%, and 207.9% higher, respectively, than the capacities of GO. These analyses, based on the cyclic voltammetry curves, discharge/charge voltage profiles, rate and cycle performance, as well as infrared spectroscopy analysis, show the contributions of the capacity from reversible physical and chemical adsorption. The main behavior type of rGO is physical adsorption, which meets the requirements of the fast charge/discharge process, while the predominant behavior of GO is chemical adsorption.

Physical Theory of Voltage Fade in Lithium- and Manganese-Rich Transition Metal Oxides

DOE PAGES

Rinaldo, Steven G.; Gallagher, Kevin G.; Long, Brandon R.; ...

2015-03-04

Lithium- and manganese-rich (LMR) transition metal oxide cathodes are of interest for lithium-ion battery applications due to their increased energy density and decreased cost. However, the advantages in energy density and cost are offset, in part, due to the phenomena of voltage fade. Specifically, the voltage profiles (voltage as a function of capacity) of LMR cathodes transform from a high energy configuration to a lower energy configuration as they are repeatedly charged (Li removed) and discharged (Li inserted). Here, we propose a physical model of voltage fade that accounts for the emergence of a low voltage Li phase due tomore » the introduction of transition metal ion defects within a parent Li phase. The phenomenological model was re-cast in a general form and experimental LMR charge profiles were de-convoluted to extract the evolutionary behavior of various components of LMR capacitance profiles. Evolution of the voltage fade component was found to follow a universal growth curve with a maximal voltage fade capacity of ≈ 20% of the initial total capacity.« less

All-solid-state asymmetric supercapacitors based on Fe-doped mesoporous Co3O4 and three-dimensional reduced graphene oxide electrodes with high energy and power densities.

PubMed

Zhang, Cheng; Wei, Jun; Chen, Leiyi; Tang, Shaolong; Deng, Mingsen; Du, Youwei

2017-10-19

An asymmetric supercapacitor offers opportunities to effectively utilize the full potential of the different potential windows of the two electrodes for a higher operating voltage, resulting in an enhanced specific capacitance and significantly improved energy without sacrificing the power delivery and cycle life. To achieve high energy and power densities, we have synthesized an all-solid-state asymmetric supercapacitor with a wider voltage range using Fe-doped Co 3 O 4 and three-dimensional reduced graphene oxide (3DrGO) as the positive and negative electrodes, respectively. In contrast to undoped Co 3 O 4 , the increased density of states and modified charge spatial separation endow the Fe-doped Co 3 O 4 electrode with greatly improved electrochemical capacitive performance, including high specific capacitance (1997 F g -1 and 1757 F g -1 at current densities of 1 and 20 A g -1 , respectively), excellent rate capability, and superior cycling stability. Remarkably, the optimized all-solid-state asymmetric supercapacitor can be cycled reversibly in a wide range of 0-1.8 V, thus delivering a high energy density (270.3 W h kg -1 ), high power density (9.0 kW kg -1 at 224.2 W h kg -1 ), and excellent cycling stability (91.8% capacitance retention after 10 000 charge-discharge cycles at a constant current density of 10 A g -1 ). The superior capacitive performance suggests that such an all-solid-state asymmetric supercapacitor shows great potential for developing energy storage systems with high levels of energy and power delivery.

Tunable one-dimensional electron gas carrier densities at nanostructured oxide interfaces

DOE PAGES

Zhang, Lipeng; Xu, Haixuan; Kent, Paul R. C.; ...

2016-05-06

The emergence of two-dimensional metallic states at the LaAlO 3/SrTiO 3 (LAO/STO) heterostructure interface is known to occur at a critical thickness of four LAO over layers. This insulator-to-metal transition can be explained through the polar catastrophe mechanism arising from the divergence of the electrostatic potential at the LAO surface. Here, we demonstrate that nanostructuring can be effective in reducing or eliminating this critical thickness. Employing a modified polar catastrophe" model, we demonstrate that the nanowire heterostructure electrostatic potential diverges more rapidly as a function of layer thickness than in a regular heterostructure. Our first principles calculations indicate that formore » nanowire heterostructure geometries a one-dimensional electron gas (1DEG) can be induced, consistent with recent experimental observations of 1D conductivity in LAO/STO steps. Similar to LAO/STO 2DEGs, we predict that the 1D charge density will decay laterally within a few unit cells away from the nanowire; thus providing a mechanism for tuning the carrier behavior between 1D and 2D conductivity. Furthermore, our work provides insight into the creation and manipulation of charge density at an oxide heterostructure interface and therefore may be beneficial for future nanoelectronic devices and for the engineering of novel quantum phases.« less

Interfacial characteristics and leakage current transfer mechanisms in organometal trihalide perovskite gate-controlled devices via doping of PCBM

NASA Astrophysics Data System (ADS)

Wang, Yucheng; Zhang, Yuming; Liu, Yintao; Pang, Tiqiang; Hu, Ziyang; Zhu, Yuejin; Luan, Suzhen; Jia, Renxu

2017-11-01

Two types of perovskite (with and without doping of PCBM) based metal-oxide-semiconductor (MOS) gate-controlled devices were fabricated and characterized. The study of the interfacial characteristics and charge transfer mechanisms by doping of PCBM were analyzed by material and electrical measurements. Doping of PCBM does not affect the size and crystallinity of perovskite films, but has an impact on carrier extraction in perovskite MOS devices. The electrical hysteresis observed in capacitance-voltage and current-voltage measurements can be alleviated by doping of PCBM. Experimental results demonstrate that extremely low trap densities are found for the perovskite device without doping, while the doped sample leads to higher density of interface state. Three mechanisms including Ohm’s law, trap-filled-limit (TFL) emission, and child’s law were used to analyze possible charge transfer mechanisms. Ohm’s law mechanism is well suitable for charge transfer of both the perovskite MOS devices under light condition at large voltage, while TFL emission well addresses the behavior of charge transfer under dark at small voltage. This change of charge transfer mechanism is attributed to the impact of the ion drift within perovskites.

In situ fabrication of nickel based oxide on nitrogen-doped graphene for high electrochemical performance supercapacitors

NASA Astrophysics Data System (ADS)

Pan, Denghui; Zhang, Mingmei; Wang, Ying; Yan, Zaoxue; Jing, Junjie; Xie, Jimin

2017-10-01

In this article, we synthesize Ni(OH)2 homogeneous grown on nitrogen-doped graphene (Ni(OH)2/NG), subsequently, small and uniform nickel oxide nanoparticle (NiO/NG) is also successfully obtained through tube furnace calcination method. The high specific capacitance of the NiO/NG electrode can reach to 1314.1 F/g at a charge and discharge current density of 2 A/g, meanwhile the specific capacitance of Ni(OH)2/NG electrode is also 1350 F/g. The capacitance of NiO/NG can remain 93.7% of the maximum value after 1000 cycles, while the Ni(OH)2/NG electrode losses 16.9% of the initial capacitance after 1000 cycles. It can be attributed to nickel hydroxide instability during charge-discharge cycles.

Metal Adatoms and Clusters on Ultrathin Zirconia Films

PubMed Central

2016-01-01

Nucleation and growth of transition metals on zirconia has been studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Since STM requires electrical conductivity, ultrathin ZrO2 films grown by oxidation of Pt3Zr(0001) and Pd3Zr(0001) were used as model systems. DFT studies were performed for single metal adatoms on supported ZrO2 films as well as the (1̅11) surface of monoclinic ZrO2. STM shows decreasing cluster size, indicative of increasing metal–oxide interaction, in the sequence Ag < Pd ≈ Au < Ni ≈ Fe. Ag and Pd nucleate mostly at steps and domain boundaries of ZrO2/Pt3Zr(0001) and form three-dimensional clusters. Deposition of low coverages of Ni and Fe at room temperature leads to a high density of few-atom clusters on the oxide terraces. Weak bonding of Ag to the oxide is demonstrated by removing Ag clusters with the STM tip. DFT calculations for single adatoms show that the metal–oxide interaction strength increases in the sequence Ag < Au < Pd < Ni on monoclinic ZrO2, and Ag ≈ Au < Pd < Ni on the supported ultrathin ZrO2 film. With the exception of Au, metal nucleation and growth on ultrathin zirconia films follow the usual rules: More reactive (more electropositive) metals result in a higher cluster density and wet the surface more strongly than more noble metals. These bind mainly to the oxygen anions of the oxide. Au is an exception because it can bind strongly to the Zr cations. Au diffusion may be impeded by changing its charge state between −1 and +1. We discuss differences between the supported ultrathin zirconia films and the surfaces of bulk ZrO2, such as the possibility of charge transfer to the substrate of the films. Due to their large in-plane lattice constant and the variety of adsorption sites, ZrO2{111} surfaces are more reactive than many other oxygen-terminated oxide surfaces. PMID:27213024

Renewable cathode materials from biopolymer/conjugated polymer interpenetrating networks.

PubMed

Milczarek, Grzegorz; Inganäs, Olle

2012-03-23

Renewable and cheap materials in electrodes could meet the need for low-cost, intermittent electrical energy storage in a renewable energy system if sufficient charge density is obtained. Brown liquor, the waste product from paper processing, contains lignin derivatives. Polymer cathodes can be prepared by electrochemical oxidation of pyrrole to polypyrrole in solutions of lignin derivatives. The quinone group in lignin is used for electron and proton storage and exchange during redox cycling, thus combining charge storage in lignin and polypyrrole in an interpenetrating polypyrrole/lignin composite.

Dual path mechanism in the thermal reduction of graphene oxide.

PubMed

Larciprete, Rosanna; Fabris, Stefano; Sun, Tao; Lacovig, Paolo; Baraldi, Alessandro; Lizzit, Silvano

2011-11-02

Graphene is easily produced by thermally reducing graphene oxide. However, defect formation in the C network during deoxygenation compromises the charge carrier mobility in the reduced material. Understanding the mechanisms of the thermal reactions is essential for defining alternative routes able to limit the density of defects generated by carbon evolution. Here, we identify a dual path mechanism in the thermal reduction of graphene oxide driven by the oxygen coverage: at low surface density, the O atoms adsorbed as epoxy groups evolve as O(2) leaving the C network unmodified. At higher coverage, the formation of other O-containing species opens competing reaction channels, which consume the C backbone. We combined spectroscopic tools and ab initio calculations to probe the species residing on the surface and those released in the gas phase during heating and to identify reaction pathways and rate-limiting steps. Our results illuminate the current puzzling scenario of the low temperature gasification of graphene oxide.

Dependence of Grain Size on the Performance of a Polysilicon Channel TFT for 3D NAND Flash Memory.

PubMed

Kim, Seung-Yoon; Park, Jong Kyung; Hwang, Wan Sik; Lee, Seung-Jun; Lee, Ki-Hong; Pyi, Seung Ho; Cho, Byung Jin

2016-05-01

We investigated the dependence of grain size on the performance of a polycrystalline silicon (poly-Si) channel TFT for application to 3D NAND Flash memory devices. It has been found that the device performance and memory characteristics are strongly affected by the grain size of the poly-Si channel. Higher on-state current, faster program speed, and poor endurance/reliability properties are observed when the poly-Si grain size is large. These are mainly attributed to the different local electric field induced by an oxide valley at the interface between the poly-Si channel and the gate oxide. In addition, the trap density at the gate oxide interface was successfully measured using a charge pumping method by the separation between the gate oxide interface traps and traps at the grain boundaries in the poly-Si channel. The poly-Si channel with larger grain size has lower interface trap density.

Observation of interface defects in thermally oxidized SiC using positron annihilation

NASA Astrophysics Data System (ADS)

Dekker, James; Saarinen, Kimmo; Ólafsson, Halldór; Sveinbjörnsson, Einar Ö.

2003-03-01

Positron annihilation has been applied to study thermally oxidized 4H- and 6H-SiC. The SiC/SiO2 interface is found to contain a high density of open-volume defects. The positron trapping at the interface defects correlates with the charge of the interface determined by capacitance-voltage experiments. For oxides grown on n-SiC substrates, the positron annihilation characteristics at these defects are nearly indistinguishable from those of a silicon/oxide interface, with no discernable contribution from C-related bonds or carbon clusters. These results indicate that those defects at the SiC/oxide interface, which are visible to positrons, are similar to those at the Si/oxide interface. The positron annihilation characteristics suggest that these defects are vacancies surrounded by oxygen atoms.

Electronic Structure Calculations of Ammonia Adsorption on Graphene and Graphene Oxide with Epoxide and Hydroxyl Groups

NASA Astrophysics Data System (ADS)

Nancy Anna Anasthasiya, A.; Khaneja, Mamta; Jeyaprakash, B. G.

2017-10-01

Ammonia adsorption on graphene (G) and graphene oxide (GO) was investigated through density functional theory calculations. In the GO system, the obtained binding energy, band gap, charge transfer and electronic structure revealed that the epoxide (GO-O) and hydroxyl groups (GO-OH) in GO enhance the NH3 adsorption, which leads to the chemisorption of NH3 on GO. The dissociation of NH3 to NH2 and formation of OH was also observed when the O and H atoms were separated at 0.985 Å, 1.019 Å, 1.035 Å, and 1.044 Å for various GO systems. The maximum charge transfer value was found to be 0.054 |e| with the binding energy of 1.143 eV for GO with a single epoxide (GO-1O) group. The charge transfer from NH3 to G or GO and the bond formation in this study agree with the reported experimental results.

Digital modulation of the nickel valence state in a cuprate-nickelate heterostructure

NASA Astrophysics Data System (ADS)

Wrobel, F.; Geisler, B.; Wang, Y.; Christiani, G.; Logvenov, G.; Bluschke, M.; Schierle, E.; van Aken, P. A.; Keimer, B.; Pentcheva, R.; Benckiser, E.

2018-03-01

Layer-by-layer oxide molecular-beam epitaxy has been used to synthesize cuprate-nickelate multilayer structures of composition (La2CuO4)m/LaO /(LaNiO3)n . In a combined experimental and theoretical study, we show that these structures allow a clean separation of dopant and doped layers. Specifically, the LaO layer separating cuprate and nickelate blocks provides an additional charge that, according to density-functional theory calculations, is predominantly accommodated in the interfacial nickelate layers. This is reflected in an elongation of bond distances and changes in valence state, as observed by scanning transmission electron microscopy and x-ray absorption spectroscopy. Moreover, the predicted charge disproportionation in the nickelate interface layers leads to a metal-to-insulator transition when the thickness is reduced to n =2 , as observed in electrical transport measurements. The results exemplify the perspectives of charge transfer in metal-oxide multilayers to induce doping without introducing chemical and structural disorder.

Giant oscillating thermopower at oxide interfaces

PubMed Central

Pallecchi, Ilaria; Telesio, Francesca; Li, Danfeng; Fête, Alexandre; Gariglio, Stefano; Triscone, Jean-Marc; Filippetti, Alessio; Delugas, Pietro; Fiorentini, Vincenzo; Marré, Daniele

2015-01-01

Understanding the nature of charge carriers at the LaAlO3/SrTiO3 interface is one of the major open issues in the full comprehension of the charge confinement phenomenon in oxide heterostructures. Here, we investigate thermopower to study the electronic structure in LaAlO3/SrTiO3 at low temperature as a function of gate field. In particular, under large negative gate voltage, corresponding to the strongly depleted charge density regime, thermopower displays high negative values of the order of 104–105μVK−1, oscillating at regular intervals as a function of the gate voltage. The huge thermopower magnitude can be attributed to the phonon-drag contribution, while the oscillations map the progressive depletion and the Fermi level descent across a dense array of localized states lying at the bottom of the Ti 3d conduction band. This study provides direct evidence of a localized Anderson tail in the two-dimensional electron liquid at the LaAlO3/SrTiO3 interface. PMID:25813265

Proton trapping in SiO 2 layers thermally grown on Si and SiC

NASA Astrophysics Data System (ADS)

Afanas'ev, V. V.; Ciobanu, F.; Pensl, G.; Stesmans, A.

2002-11-01

Positive charging of thermal SiO 2 layers on (1 0 0)Si and (0 0 0 1)6H-, 4H-SiC related to trapping of protons is studied using low-energy proton implantation into the oxide, and compared to the trapping of holes generated by 10-eV photons. Proton trapping has an initial probability close to 100% and shows little sensitivity to the annealing-induced oxygen deficiency of SiO 2. In contrast to protons, hole trapping in as-grown SiO 2 shows a much lower efficiency which increases upon oxide annealing, in qualitative correlation with the higher density of O 3Si• defects (E' centers) detected by electron spin resonance after hole injection. Despite these differences, the neutralization of positive charges induced by holes and protons has the same cross-section, and in both cases is accompanied by liberation of atomic H suggesting that protons account for positive charge in both cases. The rupture of Si-O bonds in the oxide observed upon proton injection suggests, as a first basic step, the bonding of a proton to a bridging oxygen atom in SiO 2 network.

Calcium and lithium ion production for laser ion source

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

Okamura, M.; Palm, K.; Stifler, C.

2015-08-23

Calcium and lithium ion beams are required by NASA Space Radiation Laboratory (NSRL) at Brookhaven National Laboratory (BNL) to simulate the effects of cosmic radiation. To find out difficulties to provide such high reactive material as laser targets, the both species were experimentally tested. Plate-shaped lithium and calcium targets were fabricated to create ablation plasmas with a 6ns, 1064nm Nd:YAG laser. We found significant oxygen contamination in both the Ca and Li high-charge-state beams due to the rapid oxidation of the surfaces. A large-spot-size, low-power-density laser was then used to analyze the low-charge-state beams without scanning the targets. The low-charge-statemore » Ca beam did not have any apparent oxygen contamination, showing the potential to clean the target entirely with a low-power beam once in the chamber. The Li target was clearly still oxidizing in the chamber after each low-power shot. To measure the rate of oxidation, we shot the low-power laser at the target repeatedly at 10sec, 30sec, 60sec, and 120sec interval lengths, showing a linear relation between the interval time and the amount of oxygen in the beam.« less

Local charge-density change and superconductivity: A positron study

NASA Astrophysics Data System (ADS)

Jean, Y. C.; Sundar, C. S.; Bharathi, A.; Kyle, J.; Nakanishi, H.; Tseng, P. K.; Hor, P. H.; Meng, R. L.; Huang, Z. J.; Chu, C. W.; Wang, Z. Z.; Turchi, P. E. A.; Howell, R. H.; Wachs, A. L.; Fluss, M. J.

1990-03-01

The temperature dependence between 10 and 300 K of the positron lifetime was measured in the high-temperature superconductors YBA2(Cu1-xMx)3O6+δ, where M=Zn and Ga with x=0.0 to 0.07 and δ>0.8. In the undoped and Ga-doped samples, the positron lifetime in the Bloch state, τb, was observed to decrease below Tc. In the Zn-doped samples, a dramatic x-dependent temperature variation of τb was observed: from a decrease of Tb below Tc for x=0.01 to an increase of τb for x>0.02. These new experimental results are interpreted in terms of a change in the local charge density of high-Tc oxides associated with the superconducting transition.

Influence of the spatially inhomogeneous gap distribution on the quasiparticle current in c-axis junctions involving d-wave superconductors with charge density waves.

PubMed

Ekino, T; Gabovich, A M; Suan Li, Mai; Szymczak, H; Voitenko, A I

2016-11-09

The quasiparticle tunnel current J(V) between the superconducting ab-planes along the c-axis and the corresponding conductance [Formula: see text] were calculated for symmetric junctions composed of disordered d-wave layered superconductors partially gapped by charge density waves (CDWs). Here, V is the voltage. Both the checkerboard and unidirectional CDWs were considered. It was shown that the spatial spread of the CDW-pairing strength substantially smears the peculiarities of G(V) appropriate to uniform superconductors. The resulting curves G(V) become very similar to those observed for a number of cuprates in intrinsic junctions, e.g. mesas. In particular, the influence of CDWs may explain the peak-dip-hump structures frequently found for high-T c oxides.

Pseudocapacitive and hierarchically ordered porous electrode materials supercapacitors

NASA Astrophysics Data System (ADS)

Saruhan, B.; Gönüllü, Y.; Arndt, B.

2013-05-01

Commercially available double layer capacitors store energy in an electrostatic field. This forms in the form of a double layer by charged particles arranged on two electrodes consisting mostly of active carbon. Such double layer capacitors exhibit a low energy density, so that components with large capacity according to large electrode areas are required. Our research focuses on the development of new electrode materials to realize the production of electrical energy storage systems with high energy density and high power density. Metal oxide based electrodes increase the energy density and the capacitance by addition of pseudo capacitance to the static capacitance present by the double layer super-capacitor electrodes. The so-called hybrid asymmetric cell capacitors combine both types of energy storage in a single component. In this work, the production routes followed in our laboratories for synthesis of nano-porous and aligned metal oxide electrodes using the electrochemical and sputter deposition as well as anodization methods will be described. Our characterisation studies concentrate on electrodes having redox metal-oxides (e.g. MnOx and WOx) and hierarchically aligned nano-porous Li-doped TiO2-NTs. The material specific and electrochemical properties achieved with these electrodes will be presented.

Effect of NO annealing on charge traps in oxide insulator and transition layer for 4H-SiC metal-oxide-semiconductor devices

NASA Astrophysics Data System (ADS)

Jia, Yifan; Lv, Hongliang; Niu, Yingxi; Li, Ling; Song, Qingwen; Tang, Xiaoyan; Li, Chengzhan; Zhao, Yanli; Xiao, Li; Wang, Liangyong; Tang, Guangming; Zhang, Yimen; Zhang, Yuming

2016-09-01

The effect of nitric oxide (NO) annealing on charge traps in the oxide insulator and transition layer in n-type 4H-SiC metal-oxide-semiconductor (MOS) devices has been investigated using the time-dependent bias stress (TDBS), capacitance-voltage (C-V), and secondary ion mass spectroscopy (SIMS). It is revealed that two main categories of charge traps, near interface oxide traps (Nniot) and oxide traps (Not), have different responses to the TDBS and C-V characteristics in NO-annealed and Ar-annealed samples. The Nniot are mainly responsible for the hysteresis occurring in the bidirectional C-V characteristics, which are very close to the semiconductor interface and can readily exchange charges with the inner semiconductor. However, Not is mainly responsible for the TDBS induced C-V shifts. Electrons tunneling into the Not are hardly released quickly when suffering TDBS, resulting in the problem of the threshold voltage stability. Compared with the Ar-annealed sample, Nniot can be significantly suppressed by the NO annealing, but there is little improvement of Not. SIMS results demonstrate that the Nniot are distributed within the transition layer, which correlated with the existence of the excess silicon. During the NO annealing process, the excess Si atoms incorporate into nitrogen in the transition layer, allowing better relaxation of the interface strain and effectively reducing the width of the transition layer and the density of Nniot. Project supported by the National Natural Science Foundation of China (Grant Nos. 61404098 and 61274079), the Doctoral Fund of Ministry of Education of China (Grant No. 20130203120017), the National Key Basic Research Program of China (Grant No. 2015CB759600), the National Grid Science & Technology Project, China (Grant No. SGRI-WD-71-14-018), and the Key Specific Project in the National Science & Technology Program, China (Grant Nos. 2013ZX02305002-002 and 2015CB759600).

An all-solid-state lithium/polyaniline rechargeable cell

NASA Astrophysics Data System (ADS)

Li, Changzhi; Peng, Xinsheng; Zhang, Borong; Wang, Baochen

1992-07-01

The performance of an all-solid-state cell having a lithium negative electrode, a modified polyethylene oxide (PEO)-epoxy resin (ER) electrolyte, and a polyaniline (PAn) positive electrode has been studied using cyclic voltammetry, charge/discharge cycling, and polarization curves at various temperatures. The redox reaction of the PAn electrode at the PAn/modified PEO-ER interface exhibits good reversibility. At 50-80 C, the Li/PEO-ER-LiClO4/PAn cell shows more than 40 charge/discharge cycles, 90 percent charge/discharge efficiency, and 54 W h kg discharge energy density (on PAn weight basis) at 50 micro-A between 2 and 4 V. The polarization performance of the battery improves steadily with increase in temperature.

Computational insights into charge transfer across functionalized semiconductor surfaces

NASA Astrophysics Data System (ADS)

Kearney, Kara; Rockett, Angus; Ertekin, Elif

2017-12-01

Photoelectrochemical water-splitting is a promising carbon-free fuel production method for producing H2 and O2 gas from liquid water. These cells are typically composed of at least one semiconductor photoelectrode which is prone to degradation and/or oxidation. Various surface modifications are known for stabilizing semiconductor photoelectrodes, yet stabilization techniques are often accompanied by a decrease in photoelectrode performance. However, the impact of surface modification on charge transport and its consequence on performance is still lacking, creating a roadblock for further improvements. In this review, we discuss how density functional theory and finite-element device simulations are reliable tools for providing insight into charge transport across modified photoelectrodes.

Electrokinetic Supercapacitor for Simultaneous Harvesting and Storage of Mechanical Energy.

PubMed

Yang, Peihua; Qu, Xiaopeng; Liu, Kang; Duan, Jiangjiang; Li, Jia; Chen, Qian; Xue, Guobin; Xie, Wenke; Xu, Zhimou; Zhou, Jun

2018-03-07

Energy harvesting and storage are two distinct processes that are generally achieved using two separated parts based on different physical and chemical principles. Here we report a self-charging electrokinetic supercapacitor that directly couples the energy harvesting and storage processes into one device. The device consists of two identical carbon nanotube/titanium electrodes, separated by a piece of anodic aluminum oxide nanochannels membrane. Pressure-driven electrolyte flow through the nanochannels generates streaming potential, which can be used to charge the capacitive electrodes, accomplishing simultaneous energy generation and storage. The device stores electric charge density of 0.4 mC cm -2 after fully charging under pressure of 2.5 bar. This work may offer a train of thought for the development of a new type of energy unit for self-powered systems.

Quantifying charge carrier concentration in ZnO thin films by Scanning Kelvin Probe Microscopy

PubMed Central

Maragliano, C.; Lilliu, S.; Dahlem, M. S.; Chiesa, M.; Souier, T.; Stefancich, M.

2014-01-01

In the last years there has been a renewed interest for zinc oxide semiconductor, mainly triggered by its prospects in optoelectronic applications. In particular, zinc oxide thin films are being widely used for photovoltaic applications, in which the determination of the electrical conductivity is of great importance. Being an intrinsically doped material, the quantification of its doping concentration has always been challenging. Here we show how to probe the charge carrier density of zinc oxide thin films by Scanning Kelvin Probe Microscopy, a technique that allows measuring the contact potential difference between the tip and the sample surface with high spatial resolution. A simple electronic energy model is used for correlating the contact potential difference with the doping concentration in the material. Limitations of this technique are discussed in details and some experimental solutions are proposed. Two-dimensional doping concentration images acquired on radio frequency-sputtered intrinsic zinc oxide thin films with different thickness and deposited under different conditions are reported. We show that results inferred with this technique are in accordance with carrier concentration expected for zinc oxide thin films deposited under different conditions and obtained from resistivity and mobility measurements. PMID:24569599

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

An, Ho-Myoung; Kim, Hee-Dong; Kim, Tae Geun, E-mail: tgkim1@korea.ac.kr

Graphical abstract: The degradation tendency extracted by CP technique was almost the same in both the bulk-type and TFT-type cells. - Highlights: • D{sub it} is directly investigated from bulk-type and TFT-type CTF memory. • Charge pumping technique was employed to analyze the D{sub it} information. • To apply the CP technique to monitor the reliability of the 3D NAND flash. - Abstract: The energy distribution and density of interface traps (D{sub it}) are directly investigated from bulk-type and thin-film transistor (TFT)-type charge trap flash memory cells with tunnel oxide degradation, under program/erase (P/E) cycling using a charge pumping (CP)more » technique, in view of application in a 3-demension stackable NAND flash memory cell. After P/E cycling in bulk-type devices, the interface trap density gradually increased from 1.55 × 10{sup 12} cm{sup −2} eV{sup −1} to 3.66 × 10{sup 13} cm{sup −2} eV{sup −1} due to tunnel oxide damage, which was consistent with the subthreshold swing and transconductance degradation after P/E cycling. Its distribution moved toward shallow energy levels with increasing cycling numbers, which coincided with the decay rate degradation with short-term retention time. The tendency extracted with the CP technique for D{sub it} of the TFT-type cells was similar to those of bulk-type cells.« less

Graphene oxide-MnO2 nanocomposite for supercapacitor application

NASA Astrophysics Data System (ADS)

Muhammed Shafi, P.; Vishal, Jose K.; Chandra Bose, A.

2016-09-01

Increased depletion of fossil fuels along with global warming and climate change made the society to think about alternate green and sustainable energy sources and better energy storage devices. Extensive research has been performed on the development of solar cells, fuel cells, Lithium- ion battery and supercapacitors to combat the green house effect and its consequences, and to meet the increased energy crisis. Supercapacitors, also known as electrochemical capacitors are gained a great attention because of their pulse power supply, long cycle life (>100,000), simple principle and high dynamic of charge propagation. Its greater power density than lithium- ion battery and much larger energy density than conventional capacitors brought super capacitors to a promising energy storage device to meet the increased energy demands. Here we demonstrate supercapacitor electrode materials with graphene oxide (electric double layer capacitor) and α-MnO2 nanomaterial (pseudo-capacitor), as well as composite of these materials, which means that the bulk of the material undergoes a fast redox reaction to provide the capacitive response and they exhibit superior specific energies in addition to the carbon-based supercapacitors (double-layer capacitors). A simple soft chemical route is utilized to synthesize graphene oxide, α-MnO2 and graphene oxide-MnO2 composite. The phase and the structure of the synthesized materials are studied using X-ray diffractometry (XRD). The functional group and the presence of impurities are understood from Fourier transform infrared (FTIR) spectra. The capacitive properties of the graphene oxide, graphene oxide - MnO2 nanocomposite and α-MnO2 are tested with the help of cyclic voltammetry (CV) and galvanostatic charge - discharge techniques using 1 M Na2SO4 in aqueous solution as electrolyte. It was found that graphene oxide - MnO2 nanocomposite shows better electrochemical behaviour compared to individual graphene oxide and α-MnO2 nanomaterial.

Self-Assembled Heteroepitaxial Oxide Nanocomposite for Photoelectrochemical Solar Water Oxidation

PubMed Central

2016-01-01

We report on spontaneously phase ordered heteroepitaxial SrTiO3 (STO):ZnFe2O4 (ZFO) nanocomposite films that give rise to strongly enhanced photoelectrochemical solar water oxidation, consistent with enhanced photoinduced charge separation. The STO:ZFO nanocomposite yielded an enhanced photocurrent density of 0.188 mA/cm2 at 1.23 V vs a reversible hydrogen electrode, which was 7.9- and 2.6-fold higher than that of the plain STO film and ZFO film cases under 1-sun illumination, respectively. The photoelectrode also produced stable photocurrent and Faradaic efficiencies of H2 and O2 formation that were more than 90%. Incident-photon-to-current-conversion efficiency measurements, Tauc plots, Mott–Schottky plots, and electrochemical impedance spectroscopy measurements proved that the strongly enhanced photogenerated charge separation resulted from vertically aligned pseudosingle crystalline components, epitaxial heterojunctions, and a staggered band alignment of the components of the nanocomposite films. This study presents a completely new avenue for efficient solar energy conversion applications. PMID:27212792

CO oxidation on Ru-Pt bimetallic nanoclusters supported on TiO2(101): The effect of charge polarization

NASA Astrophysics Data System (ADS)

Jia, Chuanyi; Zhong, Wenhui; Deng, Mingsen; Jiang, Jun

2018-03-01

Pt-based catalyst is widely used in CO oxidation, while its catalytic activity is often undermined because of the CO poisoning effect. Here, using density functional theory, we propose the use of a Ru-Pt bimetallic cluster supported on TiO2 for CO oxidation, to achieve both high activity and low CO poisoning effect. Excellent catalytic activity is obtained in a Ru1Pt7/TiO2(101) system, which is ascribed to strong electric fields induced by charge polarization between one Ru atom and its neighboring Pt atoms. Because of its lower electronegativity, the Ru atom donates electrons to neighboring Pt. This induces strong electric fields around the top-layered Ru, substantially promoting the adsorption of O2/CO + O2 and eliminating the CO poisoning effect. In addition, the charge polarization also drives the d-band center of the Ru1Pt7 cluster to up-shift to the Fermi level. For surface O2 activation/CO oxidation, the strong electric field and d-band center close to the Fermi level can promote the adsorption of O2 and CO as well as reduce the reaction barrier of the rate-determining step. Meanwhile, since O2 easily dissociates on Ru1Pt7/TiO2(101) resulting in unwanted oxidation of Ru and Pt, a CO-rich condition is necessary to protect the catalyst at high temperature.

Thermally oxidized titania nanotubes enhance the corrosion resistance of Ti6Al4V.

PubMed

Grotberg, John; Hamlekhan, Azhang; Butt, Arman; Patel, Sweetu; Royhman, Dmitry; Shokuhfar, Tolou; Sukotjo, Cortino; Takoudis, Christos; Mathew, Mathew T

2016-02-01

The negative impact of in vivo corrosion of metallic biomedical implants remains a complex problem in the medical field. We aimed to determine the effects of electrochemical anodization (60V, 2h) and thermal oxidation (600°C) on the corrosive behavior of Ti-6Al-4V, with serum proteins, at physiological temperature. Anodization produced a mixture of anatase and amorphous TiO2 nanopores and nanotubes, while the annealing process yielded an anatase/rutile mixture of TiO2 nanopores and nanotubes. The surface area was analyzed by the Brunauer-Emmett-Teller method and was estimated to be 3 orders of magnitude higher than that of polished control samples. Corrosion resistance was evaluated on the parameters of open circuit potential, corrosion potential, corrosion current density, passivation current density, polarization resistance and equivalent circuit modeling. Samples both anodized and thermally oxidized exhibited shifts of open circuit potential and corrosion potential in the noble direction, indicating a more stable nanoporous/nanotube layer, as well as lower corrosion current densities and passivation current densities than the smooth control. They also showed increased polarization resistance and diffusion limited charge transfer within the bulk oxide layer. The treatment groups studied can be ordered from greatest corrosion resistance to least as Anodized+Thermally Oxidized > Anodized > Smooth > Thermally Oxidized for the conditions investigated. This study concludes that anodized surface has a potential to prevent long term implant failure due to corrosion in a complex in-vivo environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Oxygen vacancy diffusion in bulk SrTiO3 from density functional theory calculations

DOE PAGES

Zhang, Lipeng; Liu, Bin; Zhuang, Houlong; ...

2016-04-01

Point defects and point defect diffusion contribute significantly to the properties of perovskite materials. However, even for the prototypical case of oxygen vacancies in SrTiO 3 (STO), predictions vary widely. Here we present a comprehensive and systematic study of the diffusion barriers for this material. We use density functional theory (DFT) and assess the role of different cell sizes, density functionals, and charge states. Our results show that vacancy-induced octahedral rotations, which are limited by the boundary conditions of the supercell, can significantly affect the computed oxygen vacancy diffusion energy barrier. The diffusion energy barrier of a charged oxygen vacancymore » is lower than that of a neutral one. Unexpectedly, we find that with increasing supercell size, the effects of the oxygen vacancy charge state, the type of DFT exchange and correlation functional on the energy barrier diminish, and the different DFT predictions asymptote to a value in the range of 0.39-0.49 eV. This work provides important insight and guidance that should be considered for investigations of point defect diffusion in other perovskite materials and in oxide superlattices.« less

Impact of GaN cap on charges in Al₂O₃/(GaN/)AlGaN/GaN metal-oxide-semiconductor heterostructures analyzed by means of capacitance measurements and simulations

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

Ťapajna, M., E-mail: milan.tapajna@savba.sk; Jurkovič, M.; Válik, L.

2014-09-14

Oxide/semiconductor interface trap density (D{sub it}) and net charge of Al₂O₃/(GaN)/AlGaN/GaN metal-oxide-semiconductor high-electron mobility transistor (MOS-HEMT) structures with and without GaN cap were comparatively analyzed using comprehensive capacitance measurements and simulations. D{sub it} distribution was determined in full band gap of the barrier using combination of three complementary capacitance techniques. A remarkably higher D{sub it} (∼5–8 × 10¹²eV⁻¹ cm⁻²) was found at trap energies ranging from E C-0.5 to 1 eV for structure with GaN cap compared to that (D{sub it} ∼ 2–3 × 10¹²eV⁻¹ cm⁻²) where the GaN cap was selectively etched away. D{sub it} distributions were then used for simulation of capacitance-voltage characteristics. A good agreement betweenmore » experimental and simulated capacitance-voltage characteristics affected by interface traps suggests (i) that very high D{sub it} (>10¹³eV⁻¹ cm⁻²) close to the barrier conduction band edge hampers accumulation of free electron in the barrier layer and (ii) the higher D{sub it} centered about E C-0.6 eV can solely account for the increased C-V hysteresis observed for MOS-HEMT structure with GaN cap. Analysis of the threshold voltage dependence on Al₂O₃ thickness for both MOS-HEMT structures suggests that (i) positive charge, which compensates the surface polarization, is not necessarily formed during the growth of III-N heterostructure, and (ii) its density is similar to the total surface polarization charge of the GaN/AlGaN barrier, rather than surface polarization of the top GaN layer only. Some constraints for the positive surface compensating charge are discussed.« less

Catalytic behavior of ‘Pt-atomic chain encapsulated gold nanotube’: A density functional study

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

Nigam, Sandeep, E-mail: snigam@barc.gov.in; Majumder, Chiranjib

2016-05-23

With an aim to design novel material and explore its catalytic performance towards CO oxidation, Pt atomic chain was introduced inside gold nanotube (Au-NT). Theoretical calculations at the level of first principles formalism was carried out to investigate the atomic and electronic properties of the composite. Geometrically Pt atoms prefer to align in zig-zag fashion. Significant electronic charge transfer from inside Pt atoms to the outer wall Au atoms is observed. Interaction of O{sub 2} with Au-NT wall follows by injection of additional electronic charge in the anti-bonding orbital of oxygen molecule leading to activation of the O-O bond. Furthermore » interaction of CO molecule with the activated oxygen molecule leads to spontaneous oxidation reaction and formation of CO{sub 2}.« less

Mobile charge, soft breakdown, and self-healing in hydrogen silsesquioxane based intermetal dielectric

NASA Astrophysics Data System (ADS)

Devine, R. A. B.

2002-09-01

The electrical characteristics of hydrogen silsesquioxane based flowable oxide (FOxregistered) films proposed for interconnect isolation applications have been studied. It is demonstrated that negative and positive charges exist in the as-made, cured films with densities of 0.95 x1012 and 1.5 x1012 cm-2, respectively for thicknesses of 114 nm. The negative charges can be removed from the films by application of modest electric fields (positive or negative, approx1.75 MV cm-1). The positive charge can be similarly displaced but not removed from the film; this results in time dependent relaxation and redistribution of the positive charge if the films are left unbiased. Time dependent irreversible evolution of the leakage current under positive and negative bias (approx3 MV cm-1) shows a slow breakdown phenomena. An unusual self-healing effect is evidenced in these films.

Trap densities and transport properties of pentacene metal-oxide-semiconductor transistors: II—Numerical modeling of dc characteristics

NASA Astrophysics Data System (ADS)

Basile, A. F.; Kyndiah, A.; Biscarini, F.; Fraboni, B.

2014-06-01

A numerical procedure to calculate the drain-current (ID) vs. gate-voltage (VG) characteristics from numerical solutions of the Poisson equation for organic Thin-Film Transistors (TFTs) is presented. Polaron transport is modeled as two-dimensional charge transport in a semiconductor having free-carrier density of states proportional to the density of molecules and traps with energy equal to the polaron-hopping barrier. The simulated ID-VG curves are proportional to the product of the density of free carriers, calculated as a function of VG, and the intrinsic mobility, assumed to be a constant independent of temperature. The presence of traps in the oxide was also taken into account in the model, which was applied to a TFT made with six monolayers of pentacene grown on an oxide substrate. The polaron-hopping barrier determines the temperature dependence of the simulated ID-VG curves, trapping in the oxide is responsible for current reduction at high bias and the slope of the characteristics near threshold is related to the metal-semiconductor work-function difference. The values of the model parameters yielding the best match between calculations and experiments are consistent with previous experimental results and theoretical predictions. Therefore, this model enables to extract both physical and technological properties of thin-film devices from the temperature-dependent dc characteristics.

Quantum-well charge and voltage distribution in a metal–insulator–semiconductor structure upon resonant electron Tunneling

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

Vexler, M. I., E-mail: vexler@mail.ioffe.ru; Illarionov, Yu. Yu.; Grekhov, I. V.

The prerequisites for electron storage in the quantum well of a metal–oxide–p{sup +}-Si resonant-tunneling structure and the effect of the stored charge on the voltage distribution are theoretically investigated. Systems with SiO{sub 2}, HfO{sub 2}, and TiO{sub 2} insulators are studied. It is demonstrated that the occurrence of a charge in the well in the case of resonant transport can be expected in structures on substrates with an acceptor concentration from (5–6) × 10{sup 18} to (2–3) × 10{sup 19} cm{sup –3} in the range of oxide thicknesses dependent on this concentration. In particular, the oxide layer thickness in themore » structures with SiO{sub 2}/p{sup +}-Si(10{sup 19} cm{sup –3}) should exceed ~3 nm. The electron density in the well can reach ~10{sup 12} cm{sup –2} and higher. However, the effect of this charge on the electrostatics of the structure becomes noticeable only at relatively high voltages far above the activation of resonant transport through the first subband.« less

Polyacetal Carboxylic Acids: a New Group of Antiviral Polyanions

PubMed Central

Claes, P.; Billiau, A.; De Clercq, E.; Desmyter, J.; Schonne, E.; Vanderhaeghe, H.; De Somer, P.

1970-01-01

Chlorite-oxidized oxypolysaccharides are polyacetal carboxylic acids. They inhibited the cytopathic effect of vesicular stomatitis virus in mouse embryo cell cultures challenged at low input multiplicity. After intraperitoneal injection of these compounds in mice, interferon appeared in the circulation. The compounds also protected mice against lethal mengovirus infection and against the development of experimental pox lesions on the tail. Chlorite-oxidized oxyamylose was antiviral only when at least 64% of the glucopyranose units were oxidized, an observation which suggested a correlation between charge density and antiviral effect. The antiviral activity was also influenced by the molecular weight, as demonstrated by the fact that chlorite-oxidized dextrans which had a high intrinsic viscosity were more active than those with low intrinsic viscosity. PMID:4314553

Electron density distribution in BaPb{sub 1-x}Sb{sub x}O{sub 3} superconducting oxides studied by double nuclear magnetic resonance methods

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

Piskunov, Yu. V., E-mail: piskunov@imp.uran.ru; Ogloblichev, V. V.; Arapova, I. Yu.

2011-11-15

The effect of charge disorder on the formation of an inhomogeneous state of the electron system in the conduction band in BaPb{sub 1-x}Sb{sub x}O{sub 3} superconducting oxides is investigated experimentally by NMR methods. The NMR spectra of {sup 17}O are measured systematically, and the contributions from {sup 17}O atoms with different cation nearest surroundings are identified. It is found that microscopic regions with an elevated spin density of charge carriers are formed within two coordination spheres near antimony ions. Nuclei of the superconducting phase of the oxide (regions with an elevated antimony concentration) microscopically distributed over the sample are detectedmore » in compounds with x = 0.25 and 0.33. Experiments in which a double resonance signal of the spin echo of {sup 17}O-{sup 207}Pb and {sup 17}O-{sup 121}Sb are measured in the metal phase of BaPb{sub 1-x}Sb{sub x}O{sub 3} oxides are carried out for the first time. The constants of indirect heteronuclear spin-spin {sup 17}O-{sup 207}Pb interaction are determined as functions of the local Knight shift {sub 207}Ks. The estimates of the constants of the indirect interaction between the nuclei of the nearest neighbors (O-Pb and Pb-Pb atoms) and analysis of evolution of the NMR spectra of {sup 17}O upon a change in the antimony concentration are convincing evidence in favor of the development of a microscopically inhomogeneous state of the electron system in the metal phase of BaPb{sub 1-x}Sb{sub x}O{sub 3} oxides.« less

Ion-gel-gating-induced oxygen vacancy formation in epitaxial L a0.5S r0.5Co O3 -δ films from in operando x-ray and neutron scattering

NASA Astrophysics Data System (ADS)

Walter, Jeff; Yu, Guichuan; Yu, Biqiong; Grutter, Alexander; Kirby, Brian; Borchers, Julie; Zhang, Zhan; Zhou, Hua; Birol, Turan; Greven, Martin; Leighton, Chris

2017-12-01

Ionic-liquid/gel-based transistors have emerged as a potentially ideal means to accumulate high charge-carrier densities at the surfaces of materials such as oxides, enabling control over electronic phase transitions. Substantial gaps remain in the understanding of gating mechanisms, however, particularly with respect to charge carrier vs oxygen defect creation, one contributing factor being the dearth of experimental probes beyond electronic transport. Here we demonstrate the use of synchrotron hard x-ray diffraction and polarized neutron reflectometry as in operando probes of ion-gel transistors based on ferromagnetic L a0.5S r0.5Co O3 -δ . An asymmetric gate-bias response is confirmed to derive from electrostatic hole accumulation at negative gate bias vs oxygen vacancy formation at positive bias. The latter is detected via a large gate-induced lattice expansion (up to 1%), complementary bulk measurements and density functional calculations enabling quantification of the bias-dependent oxygen vacancy density. Remarkably, the gate-induced oxygen vacancies proliferate through the entire thickness of 30-40-unit-cell-thick films, quantitatively accounting for changes in the magnetization depth profile. These results directly elucidate the issue of electrostatic vs redox-based response in electrolyte-gated oxides, also demonstrating powerful approaches to their in operando investigation.

Charge-density-wave partial gap opening in quasi-2D KMo 6O 17 purple bronze studied by angle resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Valbuena, M. A.; Avila, J.; Pantin, V.; Drouard, S.; Guyot, H.; Asensio, M. C.

2006-05-01

Low dimensional (LD) metallic oxides have been a subject of continuous interest in the last two decades, mainly due to the electronic instabilities that they present at low temperatures. In particular, charge density waves (CDW) instabilities associated with a strong electron-phonon interaction have been found in Molybdenum metallic oxides such as KMo 6O 17 purple bronze. We report an angle resolved photoemission (ARPES) study from room temperature (RT) to T ˜40 K well below the Peierls transition temperature for this material, with CDW transition temperature TCDW ˜120 K. We have focused on photoemission spectra along ΓM high symmetry direction as well as photoemission measurements were taken as a function of temperature at one representative kF point in the Brillouin zone in order to look for the characteristic gap opening after the phase transition. We found out a pseudogap opening and a decrease in the density of states near the Fermi energy, EF, consistent with the partial removal of the nested portions of the Fermi surface (FS) at temperature below the CDW transition. In order to elucidate possible Fermi liquid (FL) or non-Fermi liquid (NFL) behaviour we have compared the ARPES data with that one reported on quasi-1D K 0.3MoO 3 blue bronze.

Structural and electrical properties of AlN layers grown on silicon by reactive RF magnetron sputtering

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

Bazlov, N., E-mail: n.bazlov@spbu.ru; Pilipenko, N., E-mail: nelly.pilipenko@gmail.com; Vyvenko, O.

2016-06-17

AlN films of different thicknesses were deposited on n-Si (100) substrates by reactive radio frequency (rf) magnetron sputtering. Dependences of structure and electrical properties on thickness of deposited films were researched. The structures of the films were analyzed with scanning electron microscopy (SEM) and with transmitting electron microscopy (TEM). Electrical properties of the films were investigated on Au-AlN-(n-Si) structures by means of current-voltage (I-V), capacitance-voltage (C-V) and deep level transient spectroscopy (DLTS) techniques. Electron microscopy investigations had shown that structure and chemical composition of the films were thickness stratified. Near silicon surface layer was amorphous aluminum oxide one contained trapsmore » of positive charges with concentration of about 4 × 10{sup 18} cm{sup −3}. Upper layers were nanocrystalline ones consisted of both wurzite AlN and cubic AlON nanocrystals. They contained traps both positive and negative charges which were situated within 30 nm distance from silicon surface. Surface densities of these traps were about 10{sup 12} cm{sup −2}. Electron traps with activation energies of (0.2 ÷ 0.4) eV and densities of about 10{sup 10} cm{sup −2} were revealed on interface between aluminum oxide layer and silicon substrate. Their densities varied weakly with the film thickness.« less

Reactivities of Substituted α-Phenyl-N-tert-butyl Nitrones

PubMed Central

2015-01-01

In this work, a series of α-phenyl-N-tert-butyl nitrones bearing one, two, or three substituents on the tert-butyl group was synthesized. Cyclic voltammetry (CV) was used to investigate their electrochemical properties and showed a more pronounced substituent effect for oxidation than for reduction. Rate constants of superoxide radical (O2•–) reactions with nitrones were determined using a UV–vis stopped-flow method, and phenyl radical (Ph•) trapping rate constants were measured by EPR spectroscopy. The effect of N-tert-butyl substitution on the charge density and electron density localization of the nitronyl carbon as well as on the free energies of nitrone reactivity with O2•– and HO2• were computationally rationalized at the PCM/B3LYP/6-31+G**//B3LYP/6-31G* level of theory. Theoretical and experimental data showed that the rates of the reaction correlate with the nitronyl carbon charge density, suggesting a nucleophilic nature of O2•– and Ph• addition to the nitronyl carbon atom. Finally, the substituent effect was investigated in cell cultures exposed to hydrogen peroxide and a correlation between the cell viability and the oxidation potential of the nitrones was observed. Through a combination of computational methodologies and experimental methods, new insights into the reactivity of free radicals with nitrone derivatives have been proposed. PMID:24968285

Fabrication and characterization of AlN metal-insulator-semiconductor grown Si substrate

NASA Astrophysics Data System (ADS)

Mahyuddin, A.; Azrina, A.; Mohd Yusoff, M. Z.; Hassan, Z.

2017-11-01

An experimental investigation was conducted to explore the effect of inserting a single AlGaN interlayer between AlN epilayer and GaN/AlN heterostructures on Si (111) grown by molecular beam epitaxy (MBE). It is confirmed from the scanning electron microscopy (SEM) that the AlGaN interlayer has a remarkable effect on reducing the tensile stress and dislocation density in AlN top layer. Capacitance-voltage (C-V) measurements were conducted to study the electrical properties of AlN/GaN heterostructures. While deriving the findings through the calculation it is suggested that the AlGaN interlayer can significantly reduce the value of effective oxide charge density and total effective number of charges per unit area which are 1.37 × 10-6C/cm2 and 8.55 × 1012cm-2, respectively.

Local Charge Injection and Extraction on Surface-Modified Al2O3 Nanoparticles in LDPE.

PubMed

Borgani, Riccardo; Pallon, Love K H; Hedenqvist, Mikael S; Gedde, Ulf W; Haviland, David B

2016-09-14

We use a recently developed scanning probe technique to image with high spatial resolution the injection and extraction of charge around individual surface-modified aluminum oxide nanoparticles embedded in a low-density polyethylene (LDPE) matrix. We find that the experimental results are consistent with a simple band structure model where localized electronic states are available in the band gap (trap states) in the vicinity of the nanoparticles. This work offers experimental support to a previously proposed mechanism for enhanced insulating properties of nanocomposite LDPE and provides a powerful experimental tool to further investigate such properties.

Inducing and manipulating magnetization in 2D zinc–oxide by strain and external voltage

NASA Astrophysics Data System (ADS)

Taivansaikhan, P.; Tsevelmaa, T.; Rhim, S. H.; Hong, S. C.; Odkhuu, D.

2018-04-01

Two-dimensional (2D) structures that exhibit intriguing magnetic phenomena such as perpendicular magnetic anisotropy and its switchable feature are of great interests in spintronics research. Herein, the density functional theory studies reveal the critical impacts of strain and external gating on vacancy-induced magnetism and its spin direction in a graphene-like single layer of zinc oxide (ZnO). In contrast to the pristine and defective ZnO with an O-vacancy, the presence of a Zn-vacancy induces significant magnetic moments to its first neighboring O and Zn atoms due to the charge deficit. We further predict that the direction of magnetization easy axis reverses from an in-plane to perpendicular orientation under a practically achievable biaxial compressive strain of only ~1–2% or applying an electric field by means of the charge density modulation. This magnetization reversal is mainly driven by the strain- and electric-field-induced changes in the spin–orbit coupled d states of the first-neighbor Zn atom to a Zn-vacancy. These findings open interesting prospects for exploiting strain and electric field engineering to manipulate magnetism and magnetization orientation of 2D materials.

In-situ probing of coupled atomic restructuring and metallicity of oxide heterointerfaces induced by polar adsorbates

NASA Astrophysics Data System (ADS)

Ryu, S.; Zhou, H.; Paudel, T. R.; Irwin, J.; Podkaminer, J. P.; Bark, C. W.; Lee, D.; Kim, T. H.; Fong, D. D.; Rzchowski, M. S.; Tsymbal, E. Y.; Eom, C. B.

2017-10-01

Microscopic understanding of the surface-controlled conductivity of the two dimensional electron gas at complex oxide interfaces is crucial for developing functional interfaces. We observe conductivity and structural modification using in-situ synchrotron surface x-ray diffraction as the surface of a model LaAlO3/SrTiO3 (001) heterostructure is changed by polar adsorbates. We find that polar adsorbate-induced interfacial metallicity reduces polar distortions in the LaAlO3 layer. First-principles density functional theory calculations show that surface dipoles introduced by polar adsorbates lead to additional charge transfer and the reduction of polar displacements in the LaAlO3 layer, consistent with the experimental observations. Our study supports that internal structural deformations controlling functionalities can be driven without the application of direct electrical or thermal bias and offers a route to tuning interfacial properties. These results also highlight the important role of in-situ x-ray scattering with atomic resolution in capturing and exploring structural distortions and charge density changes caused by external perturbations such as chemical adsorption, redox reaction, and generation and/or annihilation of surface defects.

Tantalum oxide/silicon nitride: A negatively charged surface passivation stack for silicon solar cells

NASA Astrophysics Data System (ADS)

Wan, Yimao; Bullock, James; Cuevas, Andres

2015-05-01

This letter reports effective passivation of crystalline silicon (c-Si) surfaces by thermal atomic layer deposited tantalum oxide (Ta2O5) underneath plasma enhanced chemical vapour deposited silicon nitride (SiNx). Cross-sectional transmission electron microscopy imaging shows an approximately 2 nm thick interfacial layer between Ta2O5 and c-Si. Surface recombination velocities as low as 5.0 cm/s and 3.2 cm/s are attained on p-type 0.8 Ω.cm and n-type 1.0 Ω.cm c-Si wafers, respectively. Recombination current densities of 25 fA/cm2 and 68 fA/cm2 are measured on 150 Ω/sq boron-diffused p+ and 120 Ω/sq phosphorus-diffused n+ c-Si, respectively. Capacitance-voltage measurements reveal a negative fixed insulator charge density of -1.8 × 1012 cm-2 for the Ta2O5 film and -1.0 × 1012 cm-2 for the Ta2O5/SiNx stack. The Ta2O5/SiNx stack is demonstrated to be an excellent candidate for surface passivation of high efficiency silicon solar cells.

In-situ probing of coupled atomic restructuring and metallicity of oxide heterointerfaces induced by polar adsorbates

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

Ryu, S.; Zhou, H.; Paudel, T. R.

Microscopic understanding of the surface-controlled conductivity of the two dimensional electron gas at complex oxide interfaces is crucial for developing functional interfaces. We observe conductivity and structural modification using in-situ synchrotron surface x-ray diffraction as the surface of a model LaAlO3/SrTiO3 (001) heterostructure is changed by polar adsorbates. We find that polar adsorbate-induced interfacial metallicity reduces polar distortions in the LaAlO3 layer. First-principles density functional theory calculations show that surface dipoles introduced by polar adsorbates lead to additional charge transfer and the reduction of polar displacements in the LaAlO3 layer, consistent with the experimental observations. Our study supports that internalmore » structural deformations controlling functionalities can be driven without the application of direct electrical or thermal bias and offers a route to tuning interfacial properties. These results also highlight the important role of in-situ x-ray scattering with atomic resolution in capturing and exploring structural distortions and charge density changes caused by external perturbations such as chemical adsorption, redox reaction, and generation and/or annihilation of surface defects.« less

Adsorption and oxidation of oxalic acid on anatase TiO2 (001) surface: A density functional theory study.

PubMed

Sun, Tao; Wang, Yun; Zhang, Haimin; Liu, Porun; Zhao, Huijun

2015-09-15

Anatase TiO2 (001) surfaces have attracted great interest for photo-degradation of organic species recently due to their high reactivity. In this work, adsorption properties and oxidation mechanisms of oxalic acid on the anatase TiO2 (001) surface have been theoretically investigated using the first-principles density functional theory. Various possible adsorption configurations are considered by diversifying the connectivity of carboxylic groups with the surface. It is found that the adsorption of oxalic acid on the anatase (001) surface prefer the dissociative states. A novel double-bidentate configuration has been found due to the structural match between oxalic acid and the (001) surface. More charge is transferred from the adsorbed oxalic acid to the surface with the double-bidentate configuration when comparing with other adsorption structures. Thus, there is a positive correlation relationship between the transferred charge amount and the interfacial bond numbers when oxalic acid adsorbs on the anatase TiO2 (001) surface. The adsorption energies with dispersion corrections have demonstrated that the van der Waals interactions play an important role in the adsorption, especially when adsorbates are close to the surface. Copyright © 2015 Elsevier Inc. All rights reserved.

Mesoporous nanocrystalline film architecture for capacitive storage devices

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

Dunn, Bruce S.; Tolbert, Sarah H.; Wang, John

A mesoporous, nanocrystalline, metal oxide construct particularly suited for capacitive energy storage that has an architecture with short diffusion path lengths and large surface areas and a method for production are provided. Energy density is substantially increased without compromising the capacitive charge storage kinetics and electrode demonstrates long term cycling stability. Charge storage devices with electrodes using the construct can use three different charge storage mechanisms immersed in an electrolyte: (1) cations can be stored in a thin double layer at the electrode/electrolyte interface (non-faradaic mechanism); (2) cations can interact with the bulk of an electroactive material which then undergoesmore » a redox reaction or phase change, as in conventional batteries (faradaic mechanism); or (3) cations can electrochemically adsorb onto the surface of a material through charge transfer processes (faradaic mechanism).« less

Metal Doped Manganese Oxide Thin Films for Supercapacitor Application.

PubMed

Tung, Mai Thanh; Thuy, Hoang Thi Bich; Hang, Le Thi Thu

2015-09-01

Co and Fe doped manganese oxide thin films were prepared by anodic deposition at current density of 50 mA cm(-2) using the electrolyte containing manganese sulfate and either cobalt sulfate or ferrous sulfate. Surface morphology and crystal structure of oxides were studied by scanning electron microscope (SEM) and X-ray diffraction (XRD). Chemical composition of materials was analyzed by X-ray energy dispersive spectroscope (EDS), iodometric titration method and complexometric titration method, respectively. Supercapacitive behavior of Co and Fe doped manganese oxide films were characterized by cyclic voltammetry (CV) and impedance spectroscopy (EIS). The results show that the doped manganese oxides are composed of nano fiber-like structure with radius of 5-20 nm and remain amorphous structure after heat treatment at 100 degrees C for 2 hours. The average valence of manganese increases from +3.808 to +3.867 after doping Co and from +3.808 to +3.846 after doping Fe. The doped manganese oxide film electrodes exhibited preferably ideal pseudo-capacitive behavior. The specific capacitance value of deposited manganese oxide reaches a maximum of 175.3 F/g for doping Co and 244.6 F/g for doping Fe. The thin films retained about 84% of the initial capacity even after 500 cycles of charge-discharge test. Doping Co and Fe decreases diffusion and charge transfer resistance of the films. The electric double layer capacitance and capacitor response frequency are increased after doping.

An all-solid-state lithium/polyaniline rechargeable cell

NASA Astrophysics Data System (ADS)

Changzhi, Li; Xinsheng, Peng; Borong, Zhang; Baochen, Wang

The performance of an all-solid-state cell having a lithium negative electrode, a modified polyethylene oxide (PEO)—epoxy resin (ER) electrolyte, and a polyaniline (PAn) positive electrode has been studied using cyclic voltammetry, charge/discharge cycling, and polarization curves at various temperatures. The redox reaction of the PAn electrode at the PAn/modifed PEOER interface exhibits good reversibility. At 50-80 °C, the Li/PEOERLiClO 4/PAn cell shows more than 40 charge/discharge cycles, 90% charge/discharge efficiency, and 54 W h kg -1 discharge energy density (on PAn weight basis) at 50 μA between 2 and 4 V. The polarization performance of the battery improves steadily with increase in temperature.

Investigation of multi-state charge-storage properties of redox-active organic molecules in silicon-molecular hybrid devices for DRAM and Flash applications

NASA Astrophysics Data System (ADS)

Gowda, Srivardhan Shivappa

Molecular electronics has recently spawned a considerable amount of interest with several molecules possessing charge-conduction and charge-storage properties proposed for use in electronic devices. Hybrid silicon-molecular technology has the promise of augmenting the current silicon technology and provide for a transitional path to future molecule-only technology. The focus of this dissertation work has been on developing a class of hybrid silicon-molecular electronic devices for DRAM and Flash memory applications utilizing redox-active molecules. This work exploits the ability of molecules to store charges with single-electron precision at room temperature. The hybrid devices are fabricated by forming self-assembled monolayers of redox-active molecules on Si and oxide (SiO2 and HfO2) surfaces via formation of covalent linkages. The molecules possess discrete quantum states from which electrons can tunnel to the Si substrate at discrete applied voltages (oxidation process, cell write), leaving behind a positively charged layer of molecules. The reduction (erase) process, which is the process of electrons tunneling back from Si to the molecules, neutralizes the positively charged molecular monolayer. Hybrid silicon-molecular capacitor test structures were electrically characterized with an electrolyte gate using cyclic voltammetry (CyV) and impedance spectroscopy (CV) techniques. The redox voltages, kinetics (write/erase speeds) and charge-retention characteristics were found to be strongly dependent on the Si doping type and densities, and ambient light. It was also determined that the redox energy states in the molecules communicate with the valence band of the Si substrate. This allows tuning of write and read states by modulating minority carriers in n- and p-Si substrates. Ultra-thin dielectric tunnel barriers (SiO2, HfO2) were placed between the molecules and the Si substrate to augment charge-retention for Flash memory applications. The redox response was studied as a function of tunnel oxide thickness, dielectric permittivity and energy barrier, and modified Butler-Volmer expressions were postulated to describe the redox kinetics. The speed vs. retention performance of the devices was improved via asymmetric layered tunnel barriers. The properties of molecules can be tailored by molecular design and synthetic chemistry. In this work, it was demonstrated that an alternate route to tune/enhance the properties of the hybrid device is to engineer the substrate (silicon) component. The molecules were attached to diode surfaces to tune redox voltages and improve charge-retention characteristics. N+ pockets embedded in P-Si well were utilized to obtain multiple states from a two-state molecule. The structure was also employed as a characterization tool in investigating the intrinsic properties of the molecules such as lateral conductivity within the monolayer. Redox molecules were also incorporated on an ultra thin gate-oxide of Si MOSFETs with the intent of studying the interaction of redox states with Si MOSFETs. The discrete molecular states were manifested in the drain current and threshold voltage characteristics of the device. This work demonstrates the multi-state modulation of Si-MOSFETs' drain current via redox-active molecular monolayers. Polymeric films of redox-active molecules were incorporated to improve the charge-density (ON/OFF ratio) and these structures may be employed for multi-state, low-voltage Flash memory applications. The most critical aspect of this research effort is to build a reliable and high density solid state memory technology. To this end, efforts were directed towards replacement of the electrolytic gate, which forms an extremely thin insulating double layer (˜10 nm) at the electrolyte-molecule interface, with a combination of an ultra-thin high-K dielectric layer and a metal gate. Several interesting observations were made in the research approaches towards integration and provided valuable insights into the electrolyte-redox systems. In summary, this work provides fundamental insights into the interaction of redox-energy states with silicon substrate and realistic approaches for exploiting the unique properties of the molecules that may enable solutions for nanoscale high density, low-voltage, long retention and multiple bit memory applications.

95 MeV oxygen ion irradiation effects on N-channel MOSFETs

NASA Astrophysics Data System (ADS)

Prakash, A. P. G.; Ke, S. C.; Siddappa, K.

2003-09-01

The N-channel metal oxide semiconductor field effect transistors (MOSFETs) were exposed to 95 MeV oxygen ions, in the fluence range of 5 x 10(10) to 5 x 10(13) ions/cm(2). The influence of ion irradiation on threshold voltage (V-TH), linear drain current (I-DLin), leakage current (I-L), drain conductance (g(D)), transconductance (g(m)), mobility (mu) and drain saturation current (I-DSat) of MOSFETs was studied systematically for various fluence. The V-TH of the irradiated MOSFET was found to decrease significantly after irradiation. The interface (N-it) and oxide trapped charge (N-ot) were estimated from the subthreshold measurements and were found to increase after irradiation. The densities of oxide-trapped (DeltaN(it)) charge in irradiated MOSFETs were found to he higher than those of the interface trapped charge (DeltaN(ot)). The I-DLin and I-Dsat of MOSFETs were also found to decrease significantly after irradiation. Studies on effects of 95 MeV oxygen ion irradiation on g(m), g(D) and mu show a degradation varying front 70 to 75% after irradiation. The mobility degradation coefficients for N-it(alpha(it)) and N-ot(alpha(it)) were estimated. The results of these studies are presented and discussed.

Nonstoichiometric Titanium Oxides via Pulsed Laser Ablation in Water.

PubMed

Huang, Chang-Ning; Bow, Jong-Shing; Zheng, Yuyuan; Chen, Shuei-Yuan; Ho, Newjin; Shen, Pouyan

2010-04-13

Titanium oxide compounds TiO,Ti2O3, and TiO2 with a considerable extent of nonstoichiometry were fabricated by pulsed laser ablation in water and characterized by X-ray/electron diffraction, X-ray photoelectron spectroscopy and electron energy loss spectroscopy. The titanium oxides were found to occur as nanoparticle aggregates with a predominant 3+ charge and amorphous microtubes when fabricated under an average power density of ca. 1 × 108W/cm2 and 1011W/cm2, respectively followed by dwelling in water. The crystalline colloidal particles have a relatively high content of Ti2+ and hence a lower minimum band gap of 3.4 eV in comparison with 5.2 eV for the amorphous state. The protonation on both crystalline and amorphous phase caused defects, mainly titanium rather than oxygen vacancies and charge and/or volume-compensating defects. The hydrophilic nature and presumably varied extent of undercoordination at the free surface of the amorphous lamellae accounts for their rolling as tubes at water/air and water/glass interfaces. The nonstoichiometric titania thus fabricated have potential optoelectronic and catalytic applications in UV-visible range and shed light on the Ti charge and phase behavior of titania-water binary in natural shock occurrence.

Nonstoichiometric Titanium Oxides via Pulsed Laser Ablation in Water

PubMed Central

2010-01-01

Titanium oxide compounds TiO,Ti2O3, and TiO2 with a considerable extent of nonstoichiometry were fabricated by pulsed laser ablation in water and characterized by X-ray/electron diffraction, X-ray photoelectron spectroscopy and electron energy loss spectroscopy. The titanium oxides were found to occur as nanoparticle aggregates with a predominant 3+ charge and amorphous microtubes when fabricated under an average power density of ca. 1 × 108W/cm2 and 1011W/cm2, respectively followed by dwelling in water. The crystalline colloidal particles have a relatively high content of Ti2+ and hence a lower minimum band gap of 3.4 eV in comparison with 5.2 eV for the amorphous state. The protonation on both crystalline and amorphous phase caused defects, mainly titanium rather than oxygen vacancies and charge and/or volume-compensating defects. The hydrophilic nature and presumably varied extent of undercoordination at the free surface of the amorphous lamellae accounts for their rolling as tubes at water/air and water/glass interfaces. The nonstoichiometric titania thus fabricated have potential optoelectronic and catalytic applications in UV–visible range and shed light on the Ti charge and phase behavior of titania-water binary in natural shock occurrence. PMID:20672115

Preliminary study on zinc-air battery using zinc regeneration electrolysis with propanol oxidation as a counter electrode reaction

NASA Astrophysics Data System (ADS)

Wen, Yue-Hua; Cheng, Jie; Ning, Shang-Qi; Yang, Yu-Sheng

A zinc-air battery using zinc regeneration electrolysis with propanol oxidation as a counter electrode reaction is reported in this paper. It possesses functions of both zincate reduction and electrochemical preparation, showing the potential for increasing the electronic energy utilization. Charge/discharge tests and scanning electron microscopy (SEM) micrographs reveal that when a nickel sheet plated with the high-H 2-overpotential metal, cadmium, was used as the negative substrate electrode, the dendritic formation and hydrogen evolution are suppressed effectively, and granular zinc deposits become larger but relatively dense with the increase of charge time. The performance of batteries is favorable even if the charge time is as long as 5 h at the current density of 20 mA cm -2. Better discharge performance is achieved using a 'cavity-opening' configuration for the discharge cell rather than a 'gas-introducing' configuration. The highest energy efficiency is up to 59.2%. That is, the energy consumed by organic electro-synthesis can be recovered by 59.2%. Cyclic voltammograms show that the sintered nickel electrode exhibits a good electro-catalysis activity for the propanol oxidation. The increase of propanol concentration conduces to an enhancement in the organic electro-synthesis efficiency. The organic electro-synthesis current efficiency of 82% can be obtained.

Explicit continuous charge-based compact model for long channel heavily doped surrounding-gate MOSFETs incorporating interface traps and quantum effects

NASA Astrophysics Data System (ADS)

Hamzah, Afiq; Hamid, Fatimah A.; Ismail, Razali

2016-12-01

An explicit solution for long-channel surrounding-gate (SRG) MOSFETs is presented from intrinsic to heavily doped body including the effects of interface traps and fixed oxide charges. The solution is based on the core SRGMOSFETs model of the Unified Charge Control Model (UCCM) for heavily doped conditions. The UCCM model of highly doped SRGMOSFETs is derived to obtain the exact equivalent expression as in the undoped case. Taking advantage of the undoped explicit charge-based expression, the asymptotic limits for below threshold and above threshold have been redefined to include the effect of trap states for heavily doped cases. After solving the asymptotic limits, an explicit mobile charge expression is obtained which includes the trap state effects. The explicit mobile charge model shows very good agreement with respect to numerical simulation over practical terminal voltages, doping concentration, geometry effects, and trap state effects due to the fixed oxide charges and interface traps. Then, the drain current is obtained using the Pao-Sah's dual integral, which is expressed as a function of inversion charge densities at the source/drain ends. The drain current agreed well with the implicit solution and numerical simulation for all regions of operation without employing any empirical parameters. A comparison with previous explicit models has been conducted to verify the competency of the proposed model with the doping concentration of 1× {10}19 {{cm}}-3, as the proposed model has better advantages in terms of its simplicity and accuracy at a higher doping concentration.

Symmetrical solid oxide fuel cells with impregnated SrFe0.75Mo0.25O3-δ electrodes

NASA Astrophysics Data System (ADS)

Meng, Xie; Liu, Xuejiao; Han, Da; Wu, Hao; Li, Junliang; Zhan, Zhongliang

2014-04-01

Here we report nominally symmetrical solid oxide fuel cells that feature thin La0.9Sr0.1Ga0.8Mg0.2O3-δ (LSGM) electrolytes and impregnated SrFe0.75Mo0.25O3-δ (SFMO)-LSGM composite electrodes. Operation on hydrogen fuels and air oxidants can produce maximum power densities of 0.39 W cm-2 at 650 °C and 0.97 W cm-2 at 800 °C. Impedance measurements indicate that the anode and the cathode polarizations are 0.22 and 0.04 Ω cm2 at 800 °C, respectively. Hydrogen partial pressure and temperature dependence of impedance data in humidified hydrogen shows that hydrogen oxidation kinetics is largely determined by hydrogen adsorption on the SFMO catalysts at high temperatures and charge transfer reactions along the SFMO|LSGM interfaces at low temperatures. Carbon tolerance of the present fuel cells is also examined in iso-octane fuels balanced by nitrogen at 800 °C that yields stable maximum power densities of 0.39 W cm-2.

Graphene Oxide/Poly(3-hexylthiophene) Nanocomposite Thin-Film Phototransistor for Logic Circuit Applications

NASA Astrophysics Data System (ADS)

Mansouri, S.; Coskun, B.; El Mir, L.; Al-Sehemi, Abdullah G.; Al-Ghamdi, Ahmed; Yakuphanoglu, F.

2018-04-01

Graphene is a sheet-structured material that lacks a forbidden band, being a good candidate for use in radiofrequency applications. We have elaborated graphene-oxide-doped poly(3-hexylthiophene) nanocomposite to increase the interlayer distance and thereby open a large bandgap for use in the field of logic circuits. Graphene oxide/poly(3-hexylthiophene) (GO/P3HT) nanocomposite thin-film transistors (TFTs) were fabricated on silicon oxide substrate by spin coating method. The current-voltage ( I- V) characteristics of TFTs with various P3HT compositions were studied in the dark and under light illumination. The photocurrent, charge carrier mobility, subthreshold voltage, density of interface states, density of occupied states, and I ON/ I OFF ratio of the devices strongly depended on the P3HT weight ratio in the composite. The effects of white-light illumination on the electrical parameters of the transistors were investigated. The results indicated that GO/P3HT nanocomposite thin-film transistors have high potential for use in radiofrequency applications, and their feasibility for use in digital applications has been demonstrated.

Electrical properties of radio-frequency sputtered HfO2 thin films for advanced CMOS technology

NASA Astrophysics Data System (ADS)

Sarkar, Pranab Kumar; Roy, Asim

2015-08-01

The Hafnium oxide (HfO2) high-k thin films have been deposited by radio frequency (rf) sputtering technique on p-type Si (100) substrate. The thickness, composition and phases of films in relation to annealing temperatures have been investigated by using cross sectional FE-SEM (Field Emission Scanning Electron Microscope) and grazing incidence x-ray diffraction (GI-XRD), respectively. GI-XRD analysis revealed that at annealing temperatures of 350°C, films phases change to crystalline from amorphous. The capacitance-voltage (C-V) and current-voltage (I-V) characteristics of the annealed HfO2 film have been studied employing Al/HfO2/p-Si metal-oxide-semiconductor (MOS) structures. The electrical properties such as dielectric constant, interface trap density and leakage current density have been also extracted from C-V and I-V Measurements. The value of dielectric constant, interface trap density and leakage current density of annealed HfO2 film is obtained as 23,7.57×1011eV-1 cm-2 and 2.7×10-5 Acm-2, respectively. In this work we also reported the influence of post deposition annealing onto the trapping properties of hafnium oxide and optimized conditions under which no charge trapping is observed into the dielectric stack.

Quantum Corrections to the 'Atomistic' MOSFET Simulations

NASA Technical Reports Server (NTRS)

Asenov, Asen; Slavcheva, G.; Kaya, S.; Balasubramaniam, R.

2000-01-01

We have introduced in a simple and efficient manner quantum mechanical corrections in our 3D 'atomistic' MOSFET simulator using the density gradient formalism. We have studied in comparison with classical simulations the effect of the quantum mechanical corrections on the simulation of random dopant induced threshold voltage fluctuations, the effect of the single charge trapping on interface states and the effect of the oxide thickness fluctuations in decanano MOSFETs with ultrathin gate oxides. The introduction of quantum corrections enhances the threshold voltage fluctuations but does not affect significantly the amplitude of the random telegraph noise associated with single carrier trapping. The importance of the quantum corrections for proper simulation of oxide thickness fluctuation effects has also been demonstrated.

Insulators obtained by electron cyclotron resonance plasmas on Si or GaAs

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

Diniz, J.A.; Doi, I.; Swart, J.W

2003-03-15

Silicon oxynitride (SiO{sub x}N{sub y}) and nitride (SiN{sub x}) insulators have been deposited or grown (with or without silane in the gas mixture, respectively) by electron cyclotron resonance (ECR) plasmas on Si and/or GaAs substrates at room temperature (20 deg. C) and low pressures (up to 10 mTorr). Chemical bonding characteristics of the SiO{sub x}N{sub y} and SiN{sub x} films were evaluated using Fourier transform infrared spectrometry (FTIR). The profile measurements determined the film thickness, the deposition (or oxidation) rate and the etch rates in buffered HF (BHF). The refractive indexes and the thicknesses were determined by ellipsometry. The effectivemore » interface charge densities were determined by capacitance-voltage (C-V) measurements. With these processes and analyses, different films were obtained and optimized. Suitable gate insulators for metal-insulator-semiconductor (MIS) devices with low interface charge densities were developed: (a) SiN{sub x} films deposited by ECR-chemical vapor deposition (ECR-PECVD) on GaAs substrates; (b) SiO{sub x}N{sub y} insulators obtained by low-energy molecular nitrogen ion ({sup 28}N{sub 2}{sup +}) implantation (energy of 5 keV and dose of 1x10{sup 15}/cm{sup 2}) in Si substrates prior to high-density O{sub 2} ECR plasma oxidation; and (c) SiO{sub x}N{sub y} insulators grown (without silane in the gas mixture) by O{sub 2}/N{sub 2}/Ar ECR plasma 'oxynitridation'. Furthermore, some SiN{sub x} films also present very good masking characteristics for local oxidation of silicon process.« less

Partial oxidation of step-bound water leads to anomalous pH effects on metal electrode step-edges

DOE PAGES

Schwarz, Kathleen; Xu, Bingjun; Yan, Yushan; ...

2016-05-26

The design of better heterogeneous catalysts for applications such as fuel cells and electrolyzers requires a mechanistic understanding of electrocatalytic reactions and the dependence of their activity on operating conditions such as pH. A satisfactory explanation for the unexpected pH dependence of electrochemical properties of platinum surfaces has so far remained elusive, with previous explanations resorting to complex co-adsorption of multiple species and resulting in limited predictive power. This knowledge gap suggests that the fundamental properties of these catalysts are not yet understood, limiting systematic improvement. In this paper, we analyze the change in charge and free energies upon adsorptionmore » using density-functional theory (DFT) to establish that water adsorbs on platinum step edges across a wide voltage range, including the double-layer region, with a loss of approximately 0.2 electrons upon adsorption. We show how this as-yet unreported change in net surface charge due to this water explains the anomalous pH variations of the hydrogen underpotential deposition (H upd) and the potentials of zero total charge (PZTC) observed in published experimental data. This partial oxidation of water is not limited to platinum metal step edges, and we report the charge of the water on metal step edges of commonly used catalytic metals, including copper, silver, iridium, and palladium, illustrating that this partial oxidation of water broadly influences the reactivity of metal electrodes.« less

Non-metallic dopant modulation of conductivity in substoichiometric tantalum pentoxide: A first-principles study

NASA Astrophysics Data System (ADS)

Bondi, Robert J.; Fox, Brian P.; Marinella, Matthew J.

2017-06-01

We apply density-functional theory calculations to predict dopant modulation of electrical conductivity (σo) for seven dopants (C, Si, Ge, H, F, N, and B) sampled at 18 quantum molecular dynamics configurations of five independent insertion sites into two (high/low) baseline references of σo in amorphous Ta2O5, where each reference contains a single, neutral O vacancy center (VO0). From this statistical population (n = 1260), we analyze defect levels, physical structure, and valence charge distributions to characterize nanoscale modification of the atomistic structure in local dopant neighborhoods. C is the most effective dopant at lowering Ta2Ox σo, while also exhibiting an amphoteric doping behavior by either donating or accepting charge depending on the host oxide matrix. Both B and F robustly increase Ta2Ox σo, although F does so through elimination of Ta high charge outliers, while B insertion conversely creates high charge O outliers through favorable BO3 group formation, especially in the low σo reference. While N applications to dope and passivate oxides are prevalent, we found that N exacerbates the stochasticity of σo we sought to mitigate; sensitivity to the N insertion site and some propensity to form N-O bond chemistries appear responsible. We use direct first-principles predictions of σo to explore feasible Ta2O5 dopants to engineer improved oxides with lower variance and greater repeatability to advance the manufacturability of resistive memory technologies.

Interactions of hydrogen with amorphous hafnium oxide

NASA Astrophysics Data System (ADS)

Kaviani, Moloud; Afanas'ev, Valeri V.; Shluger, Alexander L.

2017-02-01

We used density functional theory (DFT) calculations to study the interaction of hydrogen with amorphous hafnia (a -HfO2 ) using a hybrid exchange-correlation functional. Injection of atomic hydrogen, its diffusion towards electrodes, and ionization can be seen as key processes underlying charge instability of high-permittivity amorphous hafnia layers in many applications. Hydrogen in many wide band gap crystalline oxides exhibits negative-U behavior (+1 and -1 charged states are thermodynamically more stable than the neutral state) . Our results show that in a -HfO2 hydrogen is also negative-U, with charged states being the most thermodynamically stable at all Fermi level positions. However, metastable atomic hydrogen can share an electron with intrinsic electron trapping precursor sites [Phys. Rev. B 94, 020103 (2016)., 10.1103/PhysRevB.94.020103] forming a [etr -+O -H ] center, which is lower in energy on average by about 0.2 eV. These electron trapping sites can affect both the dynamics and thermodynamics of the interaction of hydrogen with a -HfO2 and the electrical behavior of amorphous hafnia films in CMOS devices.

Intercalating graphene with clusters of Fe3O4 nanocrystals for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Ke, Qingqing; Tang, Chunhua; Liu, Yanqiong; Liu, Huajun; Wang, John

2014-04-01

A hierarchical nanostructure consisting of graphene sheets intercalated by clusters of Fe3O4 nanocystals is developed for high-performance supercapacitor electrode. Here we show that the negatively charged graphene oxide (GO) and positively charged Fe3O4 clusters enable a strong electrostatic interaction, generating a hierarchical 3D nanostructure, which gives rise to the intercalated composites through a rational hydrothermal process. The electrocapacitive behavior of the resultant composites is systematically investigated by cyclic voltammeter and galvanostatic charge-discharge techniques, where a positive synergistic effect between graphene and Fe3O4 clusters is identified. A maximum specific capacitance of 169 F g-1 is achieved in the Fe3O4 clusters decorated with effectively reduced graphene oxide (Fe3O4-rGO-12h), which is much higher than those of rGO (101 F g-1) and Fe3O4 (68 F g-1) at the current density of 1 Ag-1. Moreover, this intercalated hierarchical nanostructure demonstrates a good capacitance retention, retaining over 88% of the initial capacity after 1000 cycles.

From two-dimensional graphene oxide to three-dimensional honeycomb-like Ni3S2@graphene oxide composite: insight into structure and electrocatalytic properties

NASA Astrophysics Data System (ADS)

Wei, Xinting; Li, Yueqiang; Xu, Wenli; Zhang, Kaixuan; Yin, Jie; Shi, Shaozhen; Wei, Jiazhen; Di, Fangfang; Guo, Junxue; Wang, Can; Chu, Chaofan; Sui, Ning; Chen, Baoli; Zhang, Yingtian; Hao, Hongguo; Zhang, Xianxi; Zhao, Jinsheng; Zhou, Huawei; Wang, Shuhao

2017-12-01

Three-dimensional (3D) graphene composites have drawn increasing attention in energy storage/conversion applications due to their unique structures and properties. Herein, we synthesized 3D honeycomb-like Ni3S2@graphene oxide composite (3D honeycomb-like Ni3S2@GO) by a one-pot hydrothermal method. We found that positive charges of Ni2+ and negative charges of NO_{3^{- in Ni(NO3)2 induced a transformation of graphene oxide with smooth surface into graphene oxide with wrinkled surface (w-GO). The w-GO in the mixing solution of Ni(NO3)2/thioacetamide/H2O evolved into 3D honeycomb-like Ni3S2@GO in solvothermal process. The GO effectively inhibited the aggregation of Ni3S2 nanoparticles. Photoelectrochemical cells based on 3D Ni3S2@GO synthesized at 60 mM l-1 Ni(NO3)2 exhibited the best energy conversion efficiency. 3D Ni3S2@GO had smaller charge transfer resistance and larger exchange current density than pure Ni3S2 for iodine reduction reaction. The cyclic stability of 3D honeycomb-like Ni3S2@GO was good in the iodine electrolyte. Results are of great interest for fundamental research and practical applications of 3D GO and its composites in solar water-splitting, artificial photoelectrochemical cells, electrocatalysts and Li-S or Na-S batteries.}}

Electrochemical behaviour of manganese & ruthenium mixed oxide@ reduced graphene oxide nanoribbon composite in symmetric and asymmetric supercapacitor

NASA Astrophysics Data System (ADS)

Ahuja, Preety; Ujjain, Sanjeev Kumar; Kanojia, Rajni

2018-01-01

This paper reports the interaction of 3d-4d transition metal mixed oxide as simultaneous existence of M(3d) and M(4d) expectedly enhance the electrochemical performance of the resulting composite. Electrochemical performance of MnO2-RuO2 nanoflakes reduced graphene oxide nanoribbon composite (MnO2-RuO2@GNR) is intensively explored in symmetric and asymmetric supercapacitor assembly. In situ incorporation of graphene oxide nanoribbon (GONR) during synthesis provides efficient binding sites for growth of MnO2-RuO2 nanoflakes via their surface functionalities. The interconnected MnO2-RuO2 nanoflakes via GNR form a network with enhanced diffusion kinetics leading to efficient supercapacitor performance. Fabricated asymmetric supercapacitor reveals energy density 60 Wh kg-1 at power density 14 kW kg-1. Based on the analysis of impedance data in terms of complex power, quick response time of supercapacitor reveals excellent power delivery of the device. Improved cycling stability after 7000 charge discharge cycles for symmetric and asymmetric supercapacitor highlights the buffering action of GNR and can be generalized for next generation high performance supercapacitor.

New insights into the opening band gap of graphene oxides

NASA Astrophysics Data System (ADS)

Tran, Ngoc Thanh Thuy; Lin, Shih-Yang; Lin, Ming-Fa

Electronic properties of oxygen absorbed few-layer graphenes are investigated using first-principle calculations. They are very sensitive to the changes in the oxygen concentration, number of graphene layer, and stacking configuration. The feature-rich band structures exhibit the destruction or distortion of the Dirac cone, opening of band gap, anisotropic energy dispersions, O- and (C,O)-dominated energy dispersions, and extra critical points. The band decomposed charge distributions reveal the π-bonding dominated energy gap. The orbital-projected density of states (DOS) have many special structures mainly coming from a composite energy band, the parabolic and partially flat ones. The DOS and spatial charge distributions clearly indicate the critical orbital hybridizations in O-O, C-O and C-C bonds, being responsible for the diversified properties. All of the few-layer graphene oxides are semi-metals except for the semiconducting monolayer ones.

Impact of the Valence Charge of Transition Metals on the Cobalt- and Rhodium-Catalyzed Synthesis of Indenamines, Indenols, and Isoquinolinium Salts: A Catalytic Cycle Involving MIII/MV [M = Co, Rh] for [4+2] Annulation.

PubMed

Chiou, Mong-Feng; Jayakumar, Jayachandran; Cheng, Chien-Hong; Chuang, Shih-Ching

2018-06-13

Reaction mechanisms for the synthesis of indenamines, indenols, and isoquinolinium salts through cobalt- and rhodium-catalysis were investigated using density functional theory calculations. We found that the valence charge of transition metals dramatically influences the reaction pathways. Catalytic reactions involving lower-oxidation-state transition metals (M I /M III , M = Co and Rh) generally favor a [3+2] cyclization pathway, whereas those involving higher oxidation states (M III /M V ) proceed through a [4+2] cyclization pathway. A catalytic cycle with novel M III /M V as a crucial species was successfully revealed for isoquinolinium salts synthesis, which highly valent M V was not only encountered in the [RhCp*]-catalysis but also in the [CoCp*]-catalysis.

Positron states and annihilation characteristics of surface-trapped positrons at the oxidized Cu(110) surface

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Olenga, Antoine; Weiss, A. H.

2013-03-01

The process by which oxide layers are formed on metal surfaces is still not well understood. In this work we present the results of theoretical studies of positron states and annihilation characteristics of surface-trapped positrons at the oxidized Cu(110) surface. An ab-initio investigation of stability and associated electronic properties of different adsorption phases of oxygen on Cu(110) has been performed on the basis of density functional theory and using DMOl3 code. The changes in the positron work function and the surface dipole moment when oxygen atoms occupy on-surface and sub-surface sites have been attributed to charge redistribution within the first two layers, buckling effects within each layer and interlayer expansion. The computed positron binding energy, positron surface state wave function, and annihilation probabilities of surface trapped positrons with relevant core electrons demonstrate their sensitivity to oxygen coverage, elemental content, atomic structure of the topmost layers of surfaces, and charge transfer effects. Theoretical results are compared with experimental data obtained from studies of oxidized transition metal surfaces using positron annihilation induced Auger electron spectroscopy. This work was supported in part by the National Science Foundation Grant DMR-0907679.

Lithium intercalation in sputter deposited antimony-doped tin oxide thin films: Evidence from electrochemical and optical measurements

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

Montero, J., E-mail: jose.montero@angstrom.uu.se; Granqvist, C. G.; Niklasson, G. A.

2014-04-21

Transparent conducting oxides are used as transparent electrical contacts in a variety of applications, including in electrochromic smart windows. In the present work, we performed a study of transparent conducting antimony-doped tin oxide (ATO) thin films by chronopotentiometry in a Li{sup +}-containing electrolyte. The open circuit potential vs. Li was used to investigate ATO band lineups, such as those of the Fermi level and the ionization potential, as well as the dependence of these lineups on the preparation conditions for ATO. Evidence was found for Li{sup +} intercalation when a current pulse was set in a way so as tomore » drive ions from the electrolyte into the ATO lattice. Galvanostatic intermittent titration was then applied to determine the lithium diffusion coefficient within the ATO lattice. The electrochemical density of states of the conducting oxide was studied by means of the transient voltage recorded during the chronopotentiometry experiments. These measurements were possible because, as Li{sup +} intercalation took place, charge compensating electrons filled the lowest part of the conduction band in ATO. Furthermore, the charge insertion modified the optical properties of ATO according to the Drude model.« less

Electro-oxidation of methanol on gold in alkaline media: Adsorption characteristics of reaction intermediates studied using time resolved electro-chemical impedance and surface plasmon resonance techniques

NASA Astrophysics Data System (ADS)

Assiongbon, K. A.; Roy, D.

2005-12-01

Electro-catalytic oxidation of methanol is the anode reaction in direct methanol fuel cells. We have studied the adsorption characteristics of the intermediate reactants of this multistep reaction on a gold film electrode in alkaline solutions by combining surface plasmon resonance (SPR) measurements with Fourier transform electro-chemical impedance spectroscopy (FT-EIS). Methanol oxidation in this system shows no significant effects of "site poisoning" by chemisorbed CO. Our results suggest that OH - chemisorbed onto Au acts as a stabilizing agent for the surface species of electro-active methanol. Double layer charging/discharging and adsorption/desorption of OH - show more pronounced effects than adsorption/oxidation of methanol in controlling the surface charge density of the Au substrate. These effects are manifested in both the EIS and the SPR data, and serve as key indicators of the surface reaction kinetics. The data presented here describe the important role of adsorbed OH - in electro-catalysis of methanol on Au, and demonstrate how SPR and FT-EIS can be combined for quantitative probing of catalytically active metal-solution interfaces.

Self-powered fluorescence display devices based on a fast self-charging/recharging battery (Mg/Prussian blue).

PubMed

Zhang, Hui; Yu, You; Zhang, Lingling; Zhai, Yiwen; Dong, Shaojun

2016-11-01

Stimuli-responsive (such as voltage and/or light) fluorescence display systems have attracted particular attention in their promising fields of application. However, there are few examples of self-powered fluorescence display devices. Here we designed and fabricated a self-powered fluorescence display device based on a fast-charging/recharging battery. The specially designed battery was composed of a Prussian blue (PB) cathode and a magnesium metal anode with a high theoretical redox potential difference (∼2.8 V). Moreover, smartly adding a trace amount of NaClO in the electrolyte could realize oxidizing PW to PB ∼480 times faster than when oxidizing without NaClO, leading to the fast self-charging and high power density (maximum power density of 13.34 mW cm -2 , about two to three orders of magnitude larger than previous bio-fuel cells) of the Mg/PB battery. Most importantly, PB was used as not only the cathodic catalyst but also as an electrochromic material, making it possible to construct a self-powered and rechargeable electrochromic fluorescence display with only two electrodes. Besides, fluorescent [Ru(bpy) 3 ] 2+ -doped silica nanoparticles (Ru@SiO 2 ), were selected as the fluorescence resonance energy transfer (FRET) donor to match PB (FRET acceptor). To the best of our knowledge, we demonstrated a self-powered and rechargeable electrochromic fluorescence display with only two electrodes for the first time.

TiO2 nanocrystals decorated Z-schemed core-shell CdS-CdO nanorod arrays as high efficiency anodes for photoelectrochemical hydrogen generation.

PubMed

Li, Chia-Hsun; Hsu, Chan-Wei; Lu, Shih-Yuan

2018-07-01

TiO 2 nanocrystals decorated core-shell CdS-CdO nanorod arrays, TiO 2 @CdO/CdS NR, were fabricated as high efficiency anodes for photoelctrochemical hydrogen generation. The novel sandwich heterostructure was constructed from first growth of CdS nanorod arrays on a fluorine doped tin oxide (FTO) substrate with a hydrothermal process, followed by in situ generation of CdO thin films of single digit nanometers from the CdS nanorod surfaces through thermal oxidation, and final decoration of TiO 2 nanocrystals of 10-20 nm via a successive ionic layer absorption and reaction process. The core-shell CdS-CdO heterostructure possesses a Z-scheme band structure to enhance interfacial charge transfer, facilitating effective charge separation to suppress electron-hole recombination within CdS for much improved current density generation. The final decoration of TiO 2 nanocrystals passivates surface defects and trap states of CdO, further suppressing surface charge recombination for even higher photovoltaic conversion efficiencies. The photoelectrochemical performances of the plain CdS nanorod array were significantly improved with the formation of the sandwich heterostructure, achieving a photo current density of 3.2 mA/cm 2 at 1.23 V (vs. RHE), a 141% improvement over the plain CdS nanorod array and a 32% improvement over the CdO/CdS nanorod array. Copyright © 2018 Elsevier Inc. All rights reserved.

High-efficiency p-n junction oxide photoelectrodes for photoelectrochemical water splitting.

PubMed

Liu, Zhifeng; Yan, Lu

2016-11-16

Development of all oxide p-n junctions makes a significant advancement in photoelectrode catalysis functional materials. In this article, we report the preparation of TiO 2 nanorod (NR)/Cu 2 O photoanodes via a simple hydrothermal method followed by an electrochemical deposition process. This facile synthesis route can simultaneously achieve uniform TiO 2 NR/Cu 2 O composite nanostructures and obtain varied amounts of Cu 2 O by controlling the deposition time. The photocurrent density of TiO 2 NR/Cu 2 O heterojunction photoanodes enhanced the photocatalytic activity with a photocurrent density of 5.25 mA cm -2 at 1.23 V versus RHE compared to pristine TiO 2 NR photoanodes under the same conditions. It is demonstrated that the presence of Cu 2 O has played an important role in expanding the spectral response region and reducing the photogenerated charge recombination rate. More importantly, the results provide new insights into the performance of all oxide p-n junctions as photoanodes for PEC water splitting.

Neutral beam and ICP etching of HKMG MOS capacitors: Observations and a plasma-induced damage model

NASA Astrophysics Data System (ADS)

Kuo, Tai-Chen; Shih, Tzu-Lang; Su, Yin-Hsien; Lee, Wen-Hsi; Current, Michael Ira; Samukawa, Seiji

2018-04-01

In this study, TiN/HfO2/Si metal-oxide-semiconductor (MOS) capacitors were etched by a neutral beam etching technique under two contrasting conditions. The configurations of neutral beam etching technique were specially designed to demonstrate a "damage-free" condition or to approximate "reactive-ion-etching-like" conditions to verify the effect of plasma-induced damage on electrical characteristics of MOS capacitors. The results show that by neutral beam etching (NBE), the interface state density (Dit) and the oxide trapped charge (Qot) were lower than routine plasma etching. Furthermore, the decrease in capacitor size does not lead to an increase in leakage current density, indicating less plasma induced side-wall damage. We present a plasma-induced gate stack damage model which we demonstrate by using these two different etching configurations. These results show that NBE is effective in preventing plasma-induced damage at the high-k/Si interface and on the high-k oxide sidewall and thus improve the electrical performance of the gate structure.

Synthesis of nanoporous CuO/TiO2/Pd-NiO composite catalysts by chemical dealloying and their performance for methanol and ethanol electro-oxidation

NASA Astrophysics Data System (ADS)

Niu, Mengying; Xu, Wence; Zhu, Shengli; Liang, Yanqin; Cui, Zhenduo; Yang, Xianjin; Inoue, Akihisa

2017-09-01

Nanoporous CuO/TiO2/Pd-NiO-x (x = 0, 1, 3, 5, 7 at%) catalysts have been synthesized by dealloying Cu-Ti-Pd-Ni alloy ribbons in acid solution. The nanoporous structure and chemical composition of the catalysts distribute uniformly. Based on the electrochemical active area (EASA), electrocatalytic activity and stability, the np-CuO/TiO2/Pd-NiO-3 catalyst possesses the best performance for methanol and ethanol electro-oxidation. For methanol and ethanol electro-oxidation, the anodic current densities in forward scan of the np-CuO/TiO2/Pd-NiO-3 catalyst are about 5.6 times and 2.1 times larger than that of the np-CuO/TiO2/Pd catalyst, respectively. The introduction of NiO provides more electrochemical active sites due to the improved geometrical and bifunctional mechanism. NiO promotes the adsorption of oxygen-containing species (OHads) on the catalyst surface, and electron effect between Pd and Ni is favorable for charge transfer. This accelerates the removal of intermediate products during the oxidation process. The electrocatalytic processes of methanol and ethanol oxidation in alkaline solution are controlled by both charge transfer and diffusion.

Analysis of amorphous indium-gallium-zinc-oxide thin-film transistor contact metal using Pilling-Bedworth theory and a variable capacitance diode model

NASA Astrophysics Data System (ADS)

Kiani, Ahmed; Hasko, David G.; Milne, William I.; Flewitt, Andrew J.

2013-04-01

It is widely reported that threshold voltage and on-state current of amorphous indium-gallium-zinc-oxide bottom-gate thin-film transistors are strongly influenced by the choice of source/drain contact metal. Electrical characterisation of thin-film transistors indicates that the electrical properties depend on the type and thickness of the metal(s) used. Electron transport mechanisms and possibilities for control of the defect state density are discussed. Pilling-Bedworth theory for metal oxidation explains the interaction between contact metal and amorphous indium-gallium-zinc-oxide, which leads to significant trap formation. Charge trapping within these states leads to variable capacitance diode-like behavior and is shown to explain the thin-film transistor operation.

Electrical properties of metal/Al2O3/In0.53Ga0.47As capacitors grown on InP

NASA Astrophysics Data System (ADS)

Ferrandis, Philippe; Billaud, Mathilde; Duvernay, Julien; Martin, Mickael; Arnoult, Alexandre; Grampeix, Helen; Cassé, Mikael; Boutry, Hervé; Baron, Thierry; Vinet, Maud; Reimbold, Gilles

2018-04-01

To overcome the Fermi-level pinning in III-V metal-oxide-semiconductor capacitors, attention is usually focused on the choice of dielectric and surface chemical treatments prior to oxide deposition. In this work, we examined the influence of the III-V material surface cleaning and the semiconductor growth technique on the electrical properties of metal/Al2O3/In0.53Ga0.47As capacitors grown on InP(100) substrates. By means of the capacitance-voltage measurements, we demonstrated that samples do not have the same total oxide charge density depending on the cleaning solution used [(NH4)2S or NH4OH] prior to oxide deposition. The determination of the interface trap density revealed that a Fermi-level pinning occurs for samples grown by metalorganic chemical vapor deposition but not for similar samples grown by molecular beam epitaxy. Deep level transient spectroscopy analysis explained the Fermi-level pinning by an additional signal for samples grown by metalorganic chemical vapor deposition, attributed to the tunneling effect of carriers trapped in oxide toward interface states. This work emphasizes that the choice of appropriate oxide and cleaning treatment is not enough to prevent a Fermi-level pinning in III-V metal-oxide-semiconductor capacitors. The semiconductor growth technique needs to be taken into account because it impacts the trapping properties of the oxide.

Pronounced photogating effect in atomically thin WSe2 with a self-limiting surface oxide layer

NASA Astrophysics Data System (ADS)

Yamamoto, Mahito; Ueno, Keiji; Tsukagoshi, Kazuhito

2018-04-01

The photogating effect is a photocurrent generation mechanism that leads to marked responsivity in two-dimensional (2D) semiconductor-based devices. A key step to promote the photogating effect in a 2D semiconductor is to integrate it with a high density of charge traps. Here, we show that self-limiting surface oxides on atomically thin WSe2 can serve as effective electron traps to facilitate p-type photogating. By examining the gate-bias-induced threshold voltage shift of a p-type transistor based on single-layer WSe2 with surface oxide, the electron trap density and the trap rate of the oxide are determined to be >1012 cm-2 and >1010 cm-2 s-1, respectively. White-light illumination on an oxide-covered 4-layer WSe2 transistor leads to the generation of photocurrent, the magnitude of which increases with the hole mobility. During illumination, the photocurrent evolves on a timescale of seconds, and a portion of the current persists even after illumination. These observations indicate that the photogenerated electrons are trapped deeply in the surface oxide and effectively gate the underlying WSe2. Owing to the pronounced photogating effect, the responsivity of the oxide-covered WSe2 transistor is observed to exceed 3000 A/W at an incident optical power of 1.1 nW, suggesting the effectiveness of surface oxidation in facilitating the photogating effect in 2D semiconductors.

Ordered Fe(II)Ti(IV)O3 Mixed Monolayer Oxide on Rutile TiO2(011).

PubMed

Halpegamage, Sandamali; Ding, Pan; Gong, Xue-Qing; Batzill, Matthias

2015-08-25

Oxide monolayers supported or intermixed with an oxide support are potential nanocatalysts whose properties are determined by the interplay with the support. For fundamental studies of monolayer oxides on metal oxide supports, well-defined systems are needed, but so far, the synthesis of monolayer oxides with long-range order on single-crystal oxide surfaces is rare. Here, we show by a combination of scanning tunneling microscopy, photoemission spectroscopy, and density functional theory (DFT)-based computational analysis that the rutile TiO2(011) surface supports the formation of an ordered mixed FeTiO3 monolayer. Deposition of iron in a slightly oxidizing atmosphere (10(-8) Torr O2) and annealing to 300 °C results in a well-ordered surface structure with Fe in a 2+ charge state and Ti in a 4+ charge states. Low-energy ion scattering suggests that the cation surface composition is close to half Fe and half Ti. This surface is stable in ultrahigh vacuum to annealing temperatures of 300 °C before the iron is reduced. DFT simulations confirm that a surface structure with coverage of 50% FeO units is stable and forms an ordered structure. Although distinct from known bulk phases of the iron-titanium oxide systems, the FeTiO3 monolayer exhibits some resemblance to the ilmenite structure, which may suggest that a variety of different mixed oxide phases (of systems that exist in a bulk ilmenite phase) may be synthesized in this way on the rutile TiO2(011) substrate.

Theoretical evidence for unexpected O-rich phases at corners of MgO surfaces

NASA Astrophysics Data System (ADS)

Bhattacharya, Saswata; Berger, Daniel; Reuter, Karsten; Ghiringhelli, Luca M.; Levchenko, Sergey V.

2017-12-01

Realistic oxide materials are often semiconductors, in particular at elevated temperatures, and their surfaces contain undercoordinated atoms at structural defects such as steps and corners. Using hybrid density-functional theory and ab initio atomistic thermodynamics, we investigate the interplay of bond-making, bond-breaking, and charge-carrier trapping at the corner defects at the (100) surface of a p -doped MgO in thermodynamic equilibrium with an O2 atmosphere. We show that by manipulating the coordination of surface atoms, one can drastically change and even reverse the order of stability of reduced versus oxidized surface sites.

Plasma electrolytic oxidation treatment mode influence on corrosion properties of coatings obtained on Zr-1Nb alloy in silicate-phosphate electrolyte

NASA Astrophysics Data System (ADS)

Farrakhov, R. G.; Mukaeva, V. R.; Fatkullin, A. R.; Gorbatkov, M. V.; Tarasov, P. V.; Lazarev, D. M.; Babu, N. Ramesh; Parfenov, E. V.

2018-01-01

This research is aimed at improvement of corrosion properties for Zr-1Nb alloy via plasma electrolytic oxidation (PEO). The coatings obtained in DC, pulsed unipolar and pulsed bipolar modes were assessed using SEM, XRD, PDP and EIS techniques. It was shown that pulsed unipolar mode provides the PEO coatings having promising combination of the coating thickness, surface roughness, porosity, corrosion potential and current density, and charge transfer resistance, all contributing to corrosion protection of the zirconium alloy for advanced fuel cladding applications.

Modeling of Sonos Memory Cell Erase Cycle

NASA Technical Reports Server (NTRS)

Phillips, Thomas A.; MacLeond, Todd C.; Ho, Fat D.

2010-01-01

Silicon-oxide-nitride-oxide-silicon (SONOS) nonvolatile semiconductor memories (NVSMS) have many advantages. These memories are electrically erasable programmable read-only memories (EEPROMs). They utilize low programming voltages, endure extended erase/write cycles, are inherently resistant to radiation, and are compatible with high-density scaled CMOS for low power, portable electronics. The SONOS memory cell erase cycle was investigated using a nonquasi-static (NQS) MOSFET model. The SONOS floating gate charge and voltage, tunneling current, threshold voltage, and drain current were characterized during an erase cycle. Comparisons were made between the model predictions and experimental device data.

First principles LDA + U and GGA + U study of protactinium and protactinium oxides: dependence on the effective U parameter

NASA Astrophysics Data System (ADS)

Obodo, K. O.; Chetty, N.

2013-04-01

The electronic structure and properties of protactinium and its oxides (PaO and PaO2) have been studied within the framework of the local density approximation (LDA), the Perdew-Burke-Ernzerhof generalized gradient approximation [GGA(PBE)], LDA + U and GGA(PBE) + U implementations of density functional theory. The dependence of selected observables of these materials on the effective U parameter has been investigated in detail. The examined properties include lattice constants, bulk moduli, the effect of charge density distributions, the hybridization of the 5f orbital and the energy of formation for PaO and PaO2. The LDA gives better agreement with experiment for the bulk modulus than the GGA for Pa but the GGA gives better structural properties. We found that PaO is metallic and PaO2 is a Mott-Hubbard insulator. This is consistent with observations for the other actinide oxides. We discover that GGA and LDA incorrectly give metallic behavior for PaO2. The GGA(PBE) + U calculated indirect band gap of 3.48 eV reported for PaO2 is a prediction and should stimulate further studies of this material.

Synthesis of three-dimensionally ordered macroporous manganese dioxide-carbon nanocomposites for supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Zhi; Tan, Xiuli; Gao, Xin; Song, Lihong

2014-12-01

In this article, we report a composite of MnO2 nanoparticles supported by three-dimensionally ordered macroporous carbon (MnO2/3DOM carbon nanocomposites) fabricated by means of a simple multi-component infiltration of three-dimensional templates. MnO2 nanoparticles of 2 nm-6 nm are observed to be highly dispersed on the 3DOM carbon scaffolds. Cyclic voltammetry, galvanostatic charge/discharge and electrochemical impedance spectroscopy techniques are employed to assess the properties of these nanocomposites for use in supercapacitors. The results demonstrate that MnO2 can be effectively utilized with assistance of the 3DOM carbon in the electrode. The specific capacitance of the nanocomposite electrode can reach as high as 347 F g-1 at a current density of 0.5 A g-1. Moreover, the electrode exhibit excellent charge/discharge rate and good cycling stability, retaining over 92% of its initial charge after 5500 cycles at a current density of 2.5 A g-1. Such MnO2/3DOM carbon nanocomposite represents a promising exploring direction for enhancing the device performance of metal oxide-based electrochemical supercapacitors.

Continuously controlled optical band gap in oxide semiconductor thin films

DOE PAGES

Herklotz, Andreas; Rus, Stefania Florina; Ward, Thomas Zac

2016-02-02

The optical band gap of the prototypical semiconducting oxide SnO 2 is shown to be continuously controlled through single axis lattice expansion of nanometric films induced by low-energy helium implantation. While traditional epitaxy-induced strain results in Poisson driven multidirectional lattice changes shown to only allow discrete increases in bandgap, we find that a downward shift in the band gap can be linearly dictated as a function of out-of-plane lattice expansion. Our experimental observations closely match density functional theory that demonstrates that uniaxial strain provides a fundamentally different effect on the band structure than traditional epitaxy-induced multiaxes strain effects. In conclusion,more » charge density calculations further support these findings and provide evidence that uniaxial strain can be used to drive orbital hybridization inaccessible with traditional strain engineering techniques.« less

Improvement of interfacial and electrical properties of Al2O3/ n-Ga0.47In0.53As for III-V impact ionization MOSFETs

NASA Astrophysics Data System (ADS)

Lechaux, Y.; Fadjie, A.; Bollaert, S.; Talbo, V.; Mateos, J.; González, T.; Vasallo, B. G.; Wichmann, N.

2015-10-01

In this work, Metal - Oxide - Semiconductor Capacitors (MOSCaps) based on Al2O3/ n-Ga0.47In0.53As interface have been studied. In order to have high MOSFETs performance, it is necessary to improve the semiconductor - oxide interface quality. It is observed that the (NH4)2S passivation shows lower interface trap density in the order of 6×1011cm-2.eV-1. Also, it is observed that O2 plasma densification after a passivation in a NH4OH solution improves the electrical behaviour of the charge control. Low interface trap density in the order of 1×1012cm-2.eV-1 was obtained for different treatments presented in this work.

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

Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.

Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn 2O 4) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn 2O 4 thin films in electrolytes containing Li +, Na +, K +, and Mg 2+ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn 2O 4 informed by screened hybrid density functional theory calculationsmore » is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn 2O 4. It is shown that the incorporation of Li + or other cations into the host manganese dioxide spinel structure (λ-MnO 2) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn 2O 4. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn 2O 4 arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.« less

Improved charge trapping properties by embedded graphene oxide quantum-dots for flash memory application

NASA Astrophysics Data System (ADS)

Jia, Xinlei; Yan, Xiaobing; Wang, Hong; Yang, Tao; Zhou, Zhenyu; Zhao, Jianhui

2018-06-01

In this work, we have investigated two kinds of charge trapping memory devices with Pd/Al2O3/ZnO/SiO2/p-Si and Pd/Al2O3/ZnO/graphene oxide quantum-dots (GOQDs)/ZnO/SiO2/p-Si structure. Compared with the single ZnO sample, the memory window of the ZnO-GOQDs-ZnO sample reaches a larger value (more than doubled) of 2.7 V under the sweeping gate voltage ± 7 V, indicating a better charge storage capability and the significant charge trapping effects by embedding the GOQDs trapping layer. The ZnO-GOQDs-ZnO devices have better date retention properties with the high and low capacitances loss of ˜ 1.1 and ˜ 6.9%, respectively, as well as planar density of the trapped charges of 1.48 × 1012 cm- 2. It is proposed that the GOQDs play an important role in the outstanding memory characteristics due to the deep quantum potential wells and the discrete distribution of the GOQDs. The long date retention time might have resulted from the high potential barrier which suppressed both the back tunneling and the leakage current. Intercalating GOQDs in the memory device is a promising method to realize large memory window, low-power consumption and excellent retention properties.

Flexoelectricity in ATiO3 (A = Sr, Ba, Pb) perovskite oxide superlattices from density functional theory

NASA Astrophysics Data System (ADS)

Plymill, Austin; Xu, Haixuan

2018-04-01

Flexoelectric coefficients for several bulk and superlattice perovskite systems are determined using a direct approach from first principles density functional theory calculations. A strong enhancement in the longitudinal flexoelectric coefficient has been observed in the 1SrTiO3/1PbTiO3 superlattice with alternating single atomic layers of SrTiO3 and PbTiO3. It was found that atomistic displacement, charge response under strain, and interfaces affect the flexoelectric properties of perovskite superlattice systems. These factors can be used to tune this effect in dielectrics. It was further found that the calculated Born effective charge for an ion under the influence of strain can differ significantly from the bulk value. These insights can be used to help search for more effective flexoelectric materials to be implemented in electromechanical devices.

Polyarene mediators for mediated redox flow battery

DOEpatents

Delnick, Frank M.; Ingersoll, David; Liang, Chengdu

2018-01-02

The fundamental charge storage mechanisms in a number of currently studied high energy redox couples are based on intercalation, conversion, or displacement reactions. With exception to certain metal-air chemistries, most often the active redox materials are stored physically in the electrochemical cell stack thereby lowering the practical gravimetric and volumetric energy density as a tradeoff to achieve reasonable power density. In a general embodiment, a mediated redox flow battery includes a series of secondary organic molecules that form highly reduced anionic radicals as reaction mediator pairs for the reduction and oxidation of primary high capacity redox species ex situ from the electrochemical cell stack. Arenes are reduced to stable anionic radicals that in turn reduce a primary anode to the charged state. The primary anode is then discharged using a second lower potential (more positive) arene. Compatible separators and solvents are also disclosed herein.

Ultrahigh-Power Pseudocapacitors Based on Ordered Porous Heterostructures of Electron-Correlated Oxides.

PubMed

Lang, Xing-You; Liu, Bo-Tian; Shi, Xiang-Mei; Li, Ying-Qi; Wen, Zi; Jiang, Qing

2016-05-01

Nanostructured transition-metal oxides can store high-density energy in fast surface redox reactions, but their poor conductivity causes remarkable reductions in the energy storage of most pseudocapacitors at high power delivery (fast charge/discharge rates). Here it is shown that electron-correlated oxide hybrid electrodes made of nanocrystalline vanadium sesquioxide and manganese dioxide with 3D and bicontinuous nanoporous architecture (NP V 2 O 3 /MnO 2 ) have enhanced conductivity because of metallization of electron-correlated V 2 O 3 skeleton via insulator-to-metal transition. The conductive V 2 O 3 skeleton at ambient temperature enables fast electron and ion transports in the entire electrode and facilitates charge transfer at abundant V 2 O 3 /MnO 2 interface. These merits significantly improve the pseudocapacitive behavior and rate capability of the constituent MnO 2 . Symmetric pseudocapacitors assembled with binder-free NP V 2 O 3 /MnO 2 electrodes deliver ultrahigh electrical powers (up to ≈422 W cm 23 ) while maintaining the high volumetric energy of thin-film lithium battery with excellent stability.

Capabilities of CdTe-Based Detectors With {mathrm {MoO}}_{x} Contacts for Detection of X- and gamma -Radiation

NASA Astrophysics Data System (ADS)

Maslyanchuk, O. L.; Solovan, M. M.; Brus, V. V.; Kulchynsky, V. V.; Maryanchuk, P. D.; Fodchuk, I. M.; Gnatyuk, V. A.; Aoki, T.; Potiriadis, C.; Kaissas, Y.

2017-05-01

The charge transport mechanism and spectrometric properties of the X-ray and γ-ray detectors, fabricated by the deposition of molybdenum oxide thin films onto semi-insulating p-CdTe crystals were studied. The current transport processes in the Mo-MoOx/p-CdTe/MoOx-Mo structure are well described in the scope of the carrier's generation in the space-charge region and the space-charge-limited current models. The lifetime of charge carriers, the energy of hole traps, and the density of discrete trapping centers were determined from the comparison of the experimental data and calculations. Spectrometric properties of Mo-MoOx/p-CdTe/MoOx-Mo structures were also investigated. It is shown that the investigated heterojunctions have demonstrated promising characteristics for practical application in X-ray and γ-ray detector fabrication.

Carbocations from Oxidized Metabolites of Benzo[a]anthracene. A Computational Study of Their Methylated and Fluorinated Derivatives and Guanine Adducts

PubMed Central

Borosky, Gabriela L.; Laali, Kenneth K.

2008-01-01

Structure-reactivity relationships and substituent effects on carbocation stability in benzo[a] anthracene (BA) derivatives have been studied computationally at the B3LYP/6-31G* and MP2/6-31G** levels. Bay-region carbocations are formed by O-protonation of the 1,2-epoxides in barrierless processes. This process is energetically more favored as compared to carbocation generation via zwitterion formation/O-protonation, via single electron oxidation to generate a radical cation, or via benzylic hydroxylation. Relative carbocation stabilities were determined in the gas phase and in water as solvent (PCM method). Charge delocalization mode in the BA carbocation framework was deduced from NPA-derived changes in charges, and substitution by methyl or fluorine was studied at different positions selected on basis of the carbocation charge density. A bay-region methyl group produces structural distortion with consequent deviation from planarity of the aromatic system, which destabilizes the epoxide, favoring ring opening. Whereas fluorine substitution at sites bearing significant positive charge leads to carbocation stabilization by fluorine p-π back-bonding, a fluorine atom at a ring position which presented negative charge density leads to inductive destabilization. Methylated derivatives are less sensitive to substituent effects as compared to the fluorinated analogues. Although the solvent decreases the exothermicity of the epoxide ring opening reactions due to greater stabilization of the reactants, it provokes no changes in relative reactivities. Relative energies in the resulting bay-region carbocations are examined taking into account the available biological activity data on these compounds. In selected cases, quenching of bay-region carbocations was investigated by analyzing relative energies (in the gas phase and in water) and geometries of their guanine adducts formed via covalent bond formation with the exocyclic amino group and with the N-7. PMID:16841957

Methods for passivating silicon devices at low temperature to achieve low interface state density and low recombination velocity while preserving carrier lifetime

DOEpatents

Chen, Zhizhang; Rohatgi, Ajeet

1995-01-01

A new process has been developed to achieve a very low SiO.sub.x /Si interface state density D.sub.it, low recombination velocity S (<2 cm/s), and high effective carrier lifetime T.sub.eff (>5 ms) for oxides deposited on silicon substrates at low temperature. The technique involves direct plasma-enhanced chemical vapor deposition (PECVD), with appropriate growth conditions, followed by a photo-assisted rapid thermal annealing (RTA) process. Approximately 500-A-thick SiO.sub.x layers are deposited on Si by PECVD at 250.degree. C. with 0.02 W/cm.sup.-2 rf power, then covered with SiN or an evaporated thin aluminum layer, and subjected to a photo-assisted anneal in forming gas ambient at 350.degree. C., resulting in an interface state density D.sub.it in the range of about 1-4.times.10.sup.10 cm.sup.-2 eV.sup.-1, which sets a record for the lowest interface state density D.sub.it for PECVD oxides fabricated to date. Detailed analysis shows that the PECVD deposition conditions, photo-assisted anneal, forming gas ambient, and the presence of an aluminum layer on top of the oxides during the anneal, all contributed to this low value of interface state density D.sub.it. Detailed metal-oxide semiconductor analysis and model calculations show that such a low recombination velocity S is the result of moderately high positive oxide charge (5.times.10.sup.11 -1.times.10.sup.12 cm.sup.-2) and relatively low midgap interface state density (1.times.10.sup.10 -4.times.10.sup.10 cm.sup.-2 eV.sup.-1). Photo-assisted anneal was found to be superior to furnace annealing, and a forming gas ambient was better than a nitrogen ambient for achieving a very low surface recombination velocity S.

Layered Lithium-Rich Oxide Nanoparticles Doped with Spinel Phase: Acidic Sucrose-Assistant Synthesis and Excellent Performance as Cathode of Lithium Ion Battery.

PubMed

Chen, Min; Chen, Dongrui; Liao, Youhao; Zhong, Xiaoxin; Li, Weishan; Zhang, Yuegang

2016-02-01

Nanolayered lithium-rich oxide doped with spinel phase is synthesized by acidic sucrose-assistant sol-gel combustion and evaluated as the cathode of a high-energy-density lithium ion battery. Physical characterizations indicate that the as-synthesized oxide (LR-SN) is composed of uniform and separated nanoparticles of about 200 nm, which are doped with about 7% spinel phase, compared to the large aggregated ones of the product (LR) synthesized under the same condition but without any assistance. Charge/discharge demonstrates that LR-SN exhibits excellent rate capability and cyclic stability: delivering an average discharge capacity of 246 mAh g(-1) at 0.2 C (1C = 250 mA g(-1)) and earning a capacity retention of 92% after 100 cycles at 4 C in the lithium anode-based half cell, compared to the 227 mA g(-1) and the 63% of LR, respectively. Even in the graphite anode-based full cell, LR-SN still delivers a capacity of as high as 253 mAh g(-1) at 0.1 C, corresponding to a specific energy density of 801 Wh kg(-1), which are the best among those that have been reported in the literature. The separated nanoparticles of the LR-SN provide large sites for charge transfer, while the spinel phase doped in the nanoparticles facilitates lithium ion diffusion and maintains the stability of the layered structure during cycling.

Cascade redox flow battery systems

DOEpatents

Horne, Craig R.; Kinoshita, Kim; Hickey, Darren B.; Sha, Jay E.; Bose, Deepak

2014-07-22

A reduction/oxidation ("redox") flow battery system includes a series of electrochemical cells arranged in a cascade, whereby liquid electrolyte reacts in a first electrochemical cell (or group of cells) before being directed into a second cell (or group of cells) where it reacts before being directed to subsequent cells. The cascade includes 2 to n stages, each stage having one or more electrochemical cells. During a charge reaction, electrolyte entering a first stage will have a lower state-of-charge than electrolyte entering the nth stage. In some embodiments, cell components and/or characteristics may be configured based on a state-of-charge of electrolytes expected at each cascade stage. Such engineered cascades provide redox flow battery systems with higher energy efficiency over a broader range of current density than prior art arrangements.

Nano-Ni induced surface modification relevant to the hydrogenation performances in La-Mg based alloys

NASA Astrophysics Data System (ADS)

Zhang, Huaiwei; Fu, Li; Xuan, Weidong; Li, Xingguo

2018-05-01

Nano-Ni drived modification in LaMg3/Ni composite is investigated. The new phases of LaMg2 and MgNi2 can be formed on the sample surface during the milling process. There is almost no electric charge transfer process between Ni and La element through XPS analyses. The amorphization structure can be found on the alloy surface with the increasing of reaction duration, and the capacity and cycle stability are also greatly promoted. On the other hand, the milled alloys show the lower charge transfer resistance, better anti-corrosion ability and higher oxidation current density.

(LaTiO3)n/(LaVO3)n as a model system for unconventional charge transfer and polar metallicity

NASA Astrophysics Data System (ADS)

Weng, Yakui; Zhang, Jun-Jie; Gao, Bin; Dong, Shuai

At interfaces between oxide materials, lattice and electronic reconstructions always play important roles in exotic phenomena. In this study, the density-functional theory and maximally localized Wannier functions are employed to investigate the (LaTiO3)n/(LaVO3)n magnetic superlattices. By considering lattice distortion and dimensional effect, many interesting interfacial physics have been found in the n = 1 superlattice, e.g. magnetic phase transition, unconventional charge transfer, and metal-insulator transition. In addition, the compatibility among the polar structure, ferrimagnetism, and metallicity is predicted in the n = 2 superlattice.

Examination of charge transfer in Au/YSZ for high-temperature optical gas sensing

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

Baltrus, John P.; Ohodnicki, Paul R.

2014-01-01

Au-nanoparticle incorporated oxide thin film materials demonstrate significant promise as functionalsensor materials for high temperature optical gas sensing in severe environments relevant for fossil andnuclear based power generation. The Au/yttria-stabilized zirconia (YSZ) system has been extensivelystudied in the literature and serves as a model system for fundamental investigations that seek to betterunderstand the mechanistic origin of the plasmonic gas sensing response. In this work, X-ray photoelec-tron spectroscopy techniques are applied to Au/YSZ films in an attempt to provide further experimentalevidence for a proposed sensing mechanism involving a change in free carrier density of Au nanoparticles due to charge transfer.

Quantum chemical calculations of Cr2O3/SnO2 using density functional theory method

NASA Astrophysics Data System (ADS)

Jawaher, K. Rackesh; Indirajith, R.; Krishnan, S.; Robert, R.; Das, S. Jerome

2018-03-01

Quantum chemical calculations have been employed to study the molecular effects produced by Cr2O3/SnO2 optimised structure. The theoretical parameters of the transparent conducting metal oxides were calculated using DFT / B3LYP / LANL2DZ method. The optimised bond parameters such as bond lengths, bond angles and dihedral angles were calculated using the same theory. The non-linear optical property of the title compound was calculated using first-order hyperpolarisability calculation. The calculated HOMO-LUMO analysis explains the charge transfer interaction between the molecule. In addition, MEP and Mulliken atomic charges were also calculated and analysed.

Objective Molecular Dynamics with Self-consistent Charge Density Functional Tight-Binding (SCC-DFTB) Method

NASA Astrophysics Data System (ADS)

Dumitrica, Traian; Hourahine, Ben; Aradi, Balint; Frauenheim, Thomas

We discus the coupling of the objective boundary conditions into the SCC density functional-based tight binding code DFTB+. The implementation is enabled by a generalization to the helical case of the classical Ewald method, specifically by Ewald-like formulas that do not rely on a unit cell with translational symmetry. The robustness of the method in addressing complex hetero-nuclear nano- and bio-fibrous systems is demonstrated with illustrative simulations on a helical boron nitride nanotube, a screw dislocated zinc oxide nanowire, and an ideal double-strand DNA. Work supported by NSF CMMI 1332228.

High temperature charging efficiency and degradation behavior of high capacity Ni-MH batteries

NASA Astrophysics Data System (ADS)

Choi, Jeon; Kim, Joong

2001-02-01

Recently the Ni/MH secondary battery has been studied extensively to achieve higher energy density, longer cycle life and faster charging-discharging rate for electric vehicles and portable computers, and etc. In this work, the charging efficiency of the Ni-MH battery which uses Ni electrode with addition of various compounds and the degradation behavior of the 90Ah battery were studied. The battery using the Ni electrode with Ca(OH)2 addition showed the charging efficiency and the utilization ratio significantly better than electrodes without added compounds. After 418 cycles, the residual capacities at the Ni electrode showed nearly the same values in the upper, middle and lower regions. In the case of the MH electrode, the residual capacity in the upper region appeared lower than that in other regions. As a result of ICP analysis, the amount of dissolved elements in the three regions appeared almost the same. The faster degradation in the upper region of the MH electrode was caused by the TiO2 oxide film formed at the electrode surface because of overcharging. The thickness of the oxide film increases with cycling, so it will form a layer that is not able to allow hydrogen to penetrate into the MH electrode.

Method of adhesion between an oxide layer and a metal layer

DOEpatents

Jennison, Dwight R.; Bogicevic, Alexander; Kelber, Jeffry A.; Chambers, Scott A.

2004-09-14

A method of controlling the wetting characteristics and increasing the adhesion between a metal and an oxide layer. By introducing a negatively-charged species to the surface of an oxide layer, layer-by-layer growth of metal deposited onto the oxide surface is promoted, increasing the adhesion strength of the metal-oxide interface. The negatively-charged species can either be deposited onto the oxide surface or a compound can be deposited that dissociates on, or reacts with, the surface to form the negatively-charged species. The deposited metal adatoms can thereby bond laterally to the negatively-charged species as well as vertically to the oxide surface as well as react with the negatively charged species, be oxidized, and incorporated on or into the surface of the oxide.

Changes in charge density vs changes in formal oxidation states: The case of Sn halide perovskites and their ordered vacancy analogues

NASA Astrophysics Data System (ADS)

Dalpian, Gustavo M.; Liu, Qihang; Stoumpos, Constantinos C.; Douvalis, Alexios P.; Balasubramanian, Mahalingam; Kanatzidis, Mercouri G.; Zunger, Alex

2017-07-01

Shifting the Fermi energy in solids by doping, defect formation, or gating generally results in changes in the charge density distribution, which reflect the ability of the bonding pattern in solids to adjust to such external perturbations. In the traditional chemistry textbook, such changes are often described by the formal oxidation states (FOS) whereby a single atom type is presumed to absorb the full burden of the perturbation (change in charge) of the whole compound. In the present paper, we analyze the changes in the position-dependence charge density due to shifts of the Fermi energy on a general physical basis, comparing with the view of the FOS picture. We use the halide perovskites CsSn X3 (X =F , Cl, Br, I) as examples for studying the general principle. When the solar absorber CsSn I3 (termed 113) loses 50 % of its Sn atoms, thereby forming the ordered vacancy compound C s2Sn I6 (termed 216), the Sn is said in the FOS picture to change from Sn(II) to Sn(IV). To understand the electronic properties of these two groups we studied the 113 and 216 compound pairs CsSnC l3 and C s2SnC l6 , CsSnB r3 and C s2SnB r6 , and CsSn I3 and C s2Sn I6 , complementing them by CsSn F3 and C s2Sn F6 in the hypothetical cubic structure for completing the chemical trends. These materials were also synthesized by chemical routes and characterized by x-ray diffraction, 119Sn-Mössbauer spectroscopy, and K -edge x-ray absorption spectroscopy. We find that indeed in going from 113 to 216 (equivalent to the introduction of two holes per unit) there is a decrease in the s charge on Sn, in agreement with the FOS picture. However, at the same time, we observe an increase of the p charge via downshift of the otherwise unoccupied p level, an effect that tends to replenish much of the lost s charge. At the end, the change in the charge on the Sn site as a result of adding two holes to the unit cell is rather small. This effect is theoretically explained as a "self-regulating response" [Raebiger, Lany, and Zunger, Nature (London) 453, 763 (2008), 10.1038/nature07009] whereby the system rehybridizes to minimize the effect of the charge perturbation created by vacancy formation. Rather than having a single preselected atom (here Sn) absorb the full brunt of the perturbation producing two holes, we find that the holes are distributed in a complex pattern throughout the octahedral systems of X6 ligands, forming hole orbitals with some specific symmetries. This clarifies the relation between FOS and charge transfer that can be applied to a wide variety of materials.

Changes in charge density vs changes in formal oxidation states: The case of Sn halide perovskites and their ordered vacancy analogues

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

Dalpian, Gustavo M.; Liu, Qihang; Stoumpos, Constantinos C.

Shifting the Fermi energy in solids by doping, defect formation, or gating generally results in changes in the charge density distribution, which reflect the ability of the bonding pattern in solids to adjust to such external perturbations. In the traditional chemistry textbook, such changes are often described by the formal oxidation states (FOS) whereby a single atom type is presumed to absorb the full burden of the perturbation (change in charge) of the whole compound. In the present paper, we analyze the changes in the position-dependence charge density due to shifts of the Fermi energy on a general physical basis,more » comparing with the view of the FOS picture. We use the halide perovskites CsSnX3 (X = F, Cl, Br, I) as examples for studying the general principle. When the solar absorber CsSnI3 (termed 113) loses 50% of its Sn atoms, thereby forming the ordered vacancy compound Cs2SnI6 (termed 216), the Sn is said in the FOS picture to change from Sn(II) to Sn(IV). To understand the electronic properties of these two groups we studied the 113 and 216 compound pairs CsSnCl3 and Cs2SnCl6, CsSnBr3 and Cs2SnBr6, and CsSnI3 and Cs2SnI6, complementing them by CsSnF3 and Cs2SnF6 in the hypothetical cubic structure for completing the chemical trends. These materials were also synthesized by chemical routes and characterized by x-ray diffraction, 119Sn-Mössbauer spectroscopy, and K-edge x-ray absorption spectroscopy. We find that indeed in going from 113 to 216 (equivalent to the introduction of two holes per unit) there is a decrease in the s charge on Sn, in agreement with the FOS picture. However, at the same time, we observe an increase of the p charge via downshift of the otherwise unoccupied p level, an effect that tends to replenish much of the lost s charge. At the end, the change in the charge on the Sn site as a result of adding two holes to the unit cell is rather small. This effect is theoretically explained as a “self-regulating response” [Raebiger, Lany, and Zunger, Nature (London) 453, 763 (2008)] whereby the system rehybridizes to minimize the effect of the charge perturbation created by vacancy formation. Rather than having a single preselected atom (here Sn) absorb the full brunt of the perturbation producing two holes, we find that the holes are distributed in a complex pattern throughout the octahedral systems of X6 ligands, forming hole orbitals with some specific symmetries. This clarifies the relation between FOS and charge transfer that can be applied to a wide variety of materials.« less

Conversion of spin current into charge current in a topological insulator: Role of the interface

NASA Astrophysics Data System (ADS)

Dey, Rik; Prasad, Nitin; Register, Leonard F.; Banerjee, Sanjay K.

2018-05-01

Three-dimensional spin current density injected onto the surface of a topological insulator (TI) produces a two-dimensional charge current density on the surface of the TI, which is the so-called inverse Edelstein effect (IEE). The ratio of the surface charge current density on the TI to the spin current density injected across the interface defined as the IEE length was shown to be exactly equal to the mean free path in the TI determined to be independent of the electron transmission rate across the interface [Phys. Rev. B 94, 184423 (2016), 10.1103/PhysRevB.94.184423]. However, we find that the transmission rate across the interface gives a nonzero contribution to the transport relaxation rate in the TI as well as to the effective IEE relaxation rate (over and above any surface hybridization effects), and the IEE length is always less than the original mean free path in the TI without the interface. We show that both the IEE relaxation time and the transport relaxation time in the TI are modified by the interface transmission time. The correction becomes significant when the transmission time across the interface becomes comparable to or less than the original momentum scattering time in the TI. This correction is similar to experimental results in Rashba electron systems in which the IEE relaxation time was found shorter in the case of direct interface with metal in which the interface transmission rate will be much higher, compared to interfaces incorporating insulating oxides. Our results indicate the continued importance of the interface to obtain a better spin-to-charge current conversion and a limitation to the conversion efficiency due to the quality of the interface.

Engineered cost-effective growth of Co-based nanoflakes as a sustainable water oxidation electrocatalyst

NASA Astrophysics Data System (ADS)

Pourreza, M.; Naseri, N.

2017-11-01

Developing low-cost, scalable and reproducible synthesis methods for water oxidation reaction (WOR) catalysts is highly desirable and also challenging in energy, environmental and industrial applications. In this context, electrochemical deposition is known as an easy and cost-effective technique in nanomaterial growth. Herein, cobalt-based nanoflakes were grown on a flexible and commercially available steel mesh substrate by electrodeposition approach with a crystalline structure as a mixture of oxide, hydroxide and oxyhydroxide phases. For the first time, the correlation between electrodeposition parameters, time and current density, and morphological characteristics of the grown nanoflakes (density and aspect ratio based on SEM results) has been derived. According to a comprehensive study of the flakes’ electrocatalytic performance in WOR, the optimized sample fabricated with a moderate electrodeposition current density (7 mA cm-2) and duration time (2000 s) revealed the highest density (7.6  ×  108 cm-2) and aspect ratio (7.1) as well as the lowest values for overpotential (OP  =  324 mV) and charge transfer resistance (14 Ω). This designed array of Co-based nanoflakes also showed the lowest value of overpotential for bare cobalt-based WOR electrocatalysts reported yet. High and low values for deposition current density and/or deposition time had a negative effect on the sample surface, leaving some areas without any flakes or with incomplete and inefficient formation of nanoflakes with low densities and aspect ratios. A similar effect was observed for annealed samples in the range of 200-400 °C. Based on recorded overpotentials and extracted surface morphological parameters, a linear and logarithmic behavior in overpotential-flake density dependency was proposed for current density and time controlled systems, respectively.

Layer by Layer Ex-Situ Deposited Cobalt-Manganese Oxide as Composite Electrode Material for Electrochemical Capacitor

PubMed Central

Rusi; Chan, P. Y.; Majid, S. R.

2015-01-01

The composite metal oxide electrode films were fabricated using ex situ electrodeposition method with further heating treatment at 300°C. The obtained composite metal oxide film had a spherical structure with mass loading from 0.13 to 0.21 mg cm-2. The structure and elements of the composite was investigated using X-ray diffraction (XRD) and energy dispersive X-ray (EDX). The electrochemical performance of different composite metal oxides was studied by cyclic voltammetry (CV) and galvanostatic charge-discharge (CD). As an active electrode material for a supercapacitor, the Co-Mn composite electrode exhibits a specific capacitance of 285 Fg-1 at current density of 1.85 Ag-1 in 0.5M Na2SO4 electrolyte. The best composite electrode, Co-Mn electrode was then further studied in various electrolytes (i.e., 0.5M KOH and 0.5M KOH/0.04M K3Fe(CN) 6 electrolytes). The pseudocapacitive nature of the material of Co-Mn lead to a high specific capacitance of 2.2 x 103 Fg-1 and an energy density of 309 Whkg-1 in a 0.5MKOH/0.04MK3Fe(CN) 6 electrolyte at a current density of 10 Ag-1. The specific capacitance retention obtained 67% of its initial value after 750 cycles. The results indicate that the ex situ deposited composite metal oxide nanoparticles have promising potential in future practical applications. PMID:26158447

Layer by Layer Ex-Situ Deposited Cobalt-Manganese Oxide as Composite Electrode Material for Electrochemical Capacitor.

PubMed

Rusi; Chan, P Y; Majid, S R

2015-01-01

The composite metal oxide electrode films were fabricated using ex situ electrodeposition method with further heating treatment at 300°C. The obtained composite metal oxide film had a spherical structure with mass loading from 0.13 to 0.21 mg cm(-2). The structure and elements of the composite was investigated using X-ray diffraction (XRD) and energy dispersive X-ray (EDX). The electrochemical performance of different composite metal oxides was studied by cyclic voltammetry (CV) and galvanostatic charge-discharge (CD). As an active electrode material for a supercapacitor, the Co-Mn composite electrode exhibits a specific capacitance of 285 Fg(-1) at current density of 1.85 Ag(-1) in 0.5 M Na2SO4 electrolyte. The best composite electrode, Co-Mn electrode was then further studied in various electrolytes (i.e., 0.5 M KOH and 0.5 M KOH/0.04 M K3Fe(CN) 6 electrolytes). The pseudocapacitive nature of the material of Co-Mn lead to a high specific capacitance of 2.2 x 10(3) Fg(-1) and an energy density of 309 Whkg(-1) in a 0.5 M KOH/0.04 M K3Fe(CN) 6 electrolyte at a current density of 10 Ag(-1). The specific capacitance retention obtained 67% of its initial value after 750 cycles. The results indicate that the ex situ deposited composite metal oxide nanoparticles have promising potential in future practical applications.

Exceptionally Active and Stable Spinel Nickel Manganese Oxide Electrocatalysts for Urea Oxidation Reaction.

PubMed

Periyasamy, Sivakumar; Subramanian, Palaniappan; Levi, Elena; Aurbach, Doron; Gedanken, Aharon; Schechter, Alex

2016-05-18

Spinel nickel manganese oxides, widely used materials in the lithium ion battery high voltage cathode, were studied in urea oxidation catalysis. NiMn2O4, Ni1.5Mn1.5O4, and MnNi2O4 were synthesized by a simple template-free hydrothermal route followed by a thermal treatment in air at 800 °C. Rietveld analysis performed on nonstoichiometric nickel manganese oxide-Ni1.5Mn1.5O4 revealed the presence of three mixed phases: two spinel phases with different lattice parameters and NiO unlike the other two spinels NiMn2O4 and MnNi2O4. The electroactivity of nickel manganese oxide materials toward the oxidation of urea in alkaline solution is evaluated using cyclic voltammetric measurements. Ni1.5Mn1.5O4 exhibits excellent redox characteristics and lower charge transfer resistances in comparison with other compositions of nickel manganese oxides and nickel oxide prepared under similar conditions.The Ni1.5Mn1.5O4modified electrode oxidizes urea at 0.29 V versus Ag/AgCl with a corresponding current density of 6.9 mA cm(-2). At a low catalyst loading of 50 μg cm(-2), the urea oxidation current density of Ni1.5Mn1.5O4 in alkaline solution is 7 times higher than that of nickel oxide and 4 times higher than that of NiMn2O4 and MnNi2O4, respectively.

Iron Oxide Films Prepared by Rapid Thermal Processing for Solar Energy Conversion

PubMed Central

Wickman, B.; Bastos Fanta, A.; Burrows, A.; Hellman, A.; Wagner, J. B.; Iandolo, B.

2017-01-01

Hematite is a promising and extensively investigated material for various photoelectrochemical (PEC) processes for energy conversion and storage, in particular for oxidation reactions. Thermal treatments during synthesis of hematite are found to affect the performance of hematite electrodes considerably. Herein, we present hematite thin films fabricated via one-step oxidation of Fe by rapid thermal processing (RTP). In particular, we investigate the effect of oxidation temperature on the PEC properties of hematite. Films prepared at 750 °C show the highest activity towards water oxidation. These films show the largest average grain size and the highest charge carrier density, as determined from electron microscopy and impedance spectroscopy analysis. We believe that the fast processing enabled by RTP makes this technique a preferred method for investigation of novel materials and architectures, potentially also on nanostructured electrodes, where retaining high surface area is crucial to maximize performance. PMID:28091573

Characterisation of Nd2O3 thick gate dielectric for silicon

NASA Astrophysics Data System (ADS)

Dakhel, A. A.

2004-03-01

Thin neodymium films were prepared by the reactive synthesis method on Si (P) substrates to form MOS devices. The oxide films were characterised by UV absorption spectroscopy, X-ray fluorescence (EDXRF) and X-ray diffraction (XRD). The ac conductance and capacitance of the devices were studied as a function of frequency in the range 100 Hz-100 kHz, of temperature in the range 293-473 K and of gate voltage. It was proved that a suitable formalism to explain the frequency dependence of the ac conductivity and capacitance of the insulator is controlled by a universal power law based on the relaxation processes of the hopping or tunnelling of the current carriers between equilibrium sites. The temperature dependence of the ac conductance at the accumulation state shows a small activation energy of about 0.07 eV for a MOS device with amorphous neodymium oxide. The temperature dependence of the accumulation capacitance for a MOS structure with crystalline neodymium oxide shows a maximum at about 390 K; such a maximum was not observed for the structure with amorphous neodymium oxide. The method of capacitance-gate voltage (C-Vg) measurements was used to investigate the effect of annealing in air and in vacuum on the surface density of states (Nss) at the insulator/semiconductor (I/S) interface. It was concluded that the density of surface states in the mid-gap increases by about five times while the density of the trapped charges in the oxide layer decreases by about eight times when the oxide crystallises into a polycrystalline structure.

Highly crumpled solar reduced graphene oxide electrode for supercapacitor application

NASA Astrophysics Data System (ADS)

Mohanapriya, K.; Ahirrao, Dinesh J.; Jha, Neetu

2018-04-01

Highly crumpled solar reduced graphene oxide (CSRGO) was synthesized by simple and rapid method through freezing the solar reduced graphene oxide aqueous suspension using liquid nitrogen and used as electrode material for supercapacitor application. This electrode material was characterized by transmission electron microscope (TEM), X-Ray diffractometer (XRD) and Raman Spectroscopy techniques to understand the morphology and structure. The electrochemical performance was studied by cyclic voltammetry (CV), galvanostatic charge/discharge (CD) and electrochemical impedance spectroscopy (EIS) using 6M KOH electrolyte. The CSRGO exhibit high specifc capacitance of 210.1 F g-1 at the current density of 0.5 A g-1 and shows excellent rate capability. These features make the CSRGO material as promising electrode for high-performance supercapacitors.

Alkaline-stable nickel manganese oxides with ideal band gap for solar fuel photoanodes.

PubMed

Suram, Santosh K; Zhou, Lan; Shinde, Aniketa; Yan, Qimin; Yu, Jie; Umehara, Mitsutaro; Stein, Helge S; Neaton, Jeffrey B; Gregoire, John M

2018-05-01

Combinatorial (photo)electrochemical studies of the (Ni-Mn)Ox system reveal a range of promising materials for oxygen evolution photoanodes. X-ray diffraction, quantum efficiency, and optical spectroscopy mapping reveal stable photoactivity of NiMnO3 in alkaline conditions with photocurrent onset commensurate with its 1.9 eV direct band gap. The photoactivity increases upon mixture with 10-60% Ni6MnO8 providing an example of enhanced charge separation via heterojunction formation in mixed-phase thin film photoelectrodes. Density functional theory-based hybrid functional calculations of the band edge energies in this oxide reveal that a somewhat smaller than typical fraction of exact exchange is required to explain the favorable valence band alignment for water oxidation.

First principles investigation of heterogeneous catalysis on metal oxide surfaces

NASA Astrophysics Data System (ADS)

Ghoussoub, Mireille

Metal oxides possess unique electronic and structural properties that render them highly favourable for applications in heterogeneous catalysis. In this study, computational atomistic modelling based on Density Functional Theory was used to investigate the reduction of carbon dioxide over hydroxylated indium oxide nanoparticles, as well at the activation of methane over oxygen-covered bimetallic surfaces. The first study employed metadynamics-biased ab initio molecular dynamics to obtain the free energy surface of the various reaction steps at finite temperature. In the second study, the nudged elastic band method was used to probe the C-H activation mechanisms for different surface configurations. In both cases, activation energies, reaction energies, transition state structures, and charge analysis results are used to explain the underlying mechanistic pathways.

Formal Valence, 3 d Occupation, and Charge Ordering Transitions

NASA Astrophysics Data System (ADS)

Pickett, Warren

2014-03-01

The metal-insulator transition (MIT), discovered by Verwey in the late 1930s, has been thought to be one of the best understood of MITs, the other ones being named after Wigner, Peierls, Mott, and Anderson. Continuing work on these transitions finds in some cases less and less charge to order, raising the fundamental question of just where the entropy is coming from, and just what is ordering. To provide insight into the mechanism of charge-ordering transitions, which conventionally are pictured as a disproportionation, I will (1) review and reconsider the charge state (or oxidation number) picture itself, (2) introduce new theoretical results for the rare earth nickelates (viz. YNiO3), the putative charge ordering compound AgNiO2, and the dual charge state insulator AgO, and (3) analyze cationic occupations of actual (not formal) charge, and work to reconcile the conundrums that arise. Several of the clearest cases of charge ordering transitions involve no disproportion; moreover, the experimental data used to support charge ordering can be accounted for within density functional based calculations that contain no charge transfer The challenge of modeling charge ordering transitions with model Hamiltonians will be discussed. Acknowledgment: Y. Quan, V. Pardo. Supported by NSF award DMR-1207622-0.

Novel ultrathin Bi2O3 nanowires for supercapacitor electrode materials with high performance

NASA Astrophysics Data System (ADS)

Qiu, Yongfu; Fan, Hongbo; Chang, Xueyi; Dang, Haifeng; Luo, Qun; Cheng, Zhiyu

2018-03-01

In this paper, the ultrathin Bi2O3 nanowires are synthesized by an oxidative metal vapor transport deposition technique. Their diameters and length are about 10 nm and several tens of micrometers, the growth direction is along [101] and the specific surface area is about 7.34 m2 g-1. The galvanostatic charge-discharge measurement results show that the specific capacitances of the Bi2O3 nanowires-based electrodes increase with the decrease of the current densities. The maximum capacitance is 691.3 F g-1 at the current density of 2.0 A g-1. The Ragone plot shows that the Bi2O3 nanowires has excellent supercapacitive performance. Moreover, the cyclic stability is measured by the galvanostatic charge/discharge technique at a constant current density of 10.0 A g-1 in 6.0 M KOH electrolyte. The results show the excellent capacitance retention of 75.5% over 3000 cycles. In a word, the Bi2O3 nanowires should be the ideal potential electrode materials for low-costing and effective electrochemical supercapacitors.

Formation and stability of water-soluble, molecular polyelectrolyte complexes: effects of charge density, mixing ratio, and polyelectrolyte concentration.

PubMed

Shovsky, Alexander; Varga, Imre; Makuska, Ricardas; Claesson, Per M

2009-06-02

The formation of complexes with stoichiometric (1:1) as well as nonstoichiometric (2:1) and (1:2) compositions between oppositely charged synthetic polyelectrolytes carrying strong ionic groups and significantly different molecular weights is reported in this contribution. Poly(sodium styrenesulfonate) (NaPSS) was used as polyanion, and a range of copolymers with various molar ratios of the poly(methacryloxyethyltrimethylammonium) chloride, poly(METAC), and the nonionic poly(ethylene oxide) ether methacrylate, poly(PEO45MEMA), were used as polycations. Formation and stability of PECs have been investigated by dynamic and static light scattering (LS), turbidity, and electrophoretic mobility measurements as a function of polyelectrolyte solution concentration, charge density of the cationic polyelectrolyte, and mixing ratio. The data obtained demonstrate that in the absence of PEO45 side chains the 100% charged polymer (polyMETAC) formed insoluble PECs with PSS that precipitate from solution when exact stoichiometry is achieved. In nonstoichiometric complexes (1:2) and (2:1) large colloidally stable aggregates were formed. The presence of even a relatively small amount of PEO45 side chains (25%) in the cationic copolymer was sufficient for preventing precipitation of the formed stoichiometric and nonstoichiometric complexes. These PEC's are sterically stabilized by the PEO45 chains. By further increasing the PEO45 side-chain content (50 and 75%) of the cationic copolymer, small, water-soluble molecular complexes could be formed. The data suggest that PSS molecules and the charged backbone of the cationic brush form a compact core, and with sufficiently high PEO45 chain density (above 25%) molecular complexes are formed that are stable over prolonged times.

Cyclic Nanostructures of Tungsten Oxide (WO3) n   (n = 2-6) as NO x Gas Sensor: A Theoretical Study.

PubMed

Izadyar, Mohammad; Jamsaz, Azam

2014-01-01

Today's WO3-based gas sensors have received a lot of attention, because of important role as a sensitive layer for detection of the small quantities of  NO x . In this research, a theoretical study has been done on the sensing properties of different cyclic nanoclusters of (WO3) n   (n = 2-6) for NO x   (x = 1,2) gases. Based on the calculated adsorption energies by B3LYP and X3LYP functionals, from the different orientations of  NO x molecule on the tungsten oxide clusters, O-N⋯W was preferred. Different sizes of the mentioned clusters have been analyzed and W2O6 cluster was chosen as the best candidate for NO x detection from the energy viewpoint. Using the concepts of the chemical hardness and electronic charge transfer, some correlations between the energy of adsorption and interaction energy have been established. These analyses confirmed that the adsorption energy will be boosted with charge transfer enhancement. However, the chemical hardness relationship is reversed. Finally, obtained results from the natural bond orbital and electronic density of states analysis confirmed the electronic charge transfer from the adsorbates to WO3 clusters and Fermi level shifting after adsorption, respectively. The last parameter confirms that the cyclic clusters of tungsten oxide can be used as NO x gas sensors.

Cyclic Nanostructures of Tungsten Oxide (WO3)n  (n = 2–6) as NOx Gas Sensor: A Theoretical Study

PubMed Central

Izadyar, Mohammad; Jamsaz, Azam

2014-01-01

Today's WO3-based gas sensors have received a lot of attention, because of important role as a sensitive layer for detection of the small quantities of  NOx. In this research, a theoretical study has been done on the sensing properties of different cyclic nanoclusters of (WO3)n  (n = 2–6) for NOx  (x = 1,2) gases. Based on the calculated adsorption energies by B3LYP and X3LYP functionals, from the different orientations of  NOx molecule on the tungsten oxide clusters, O–N⋯W was preferred. Different sizes of the mentioned clusters have been analyzed and W2O6 cluster was chosen as the best candidate for NOx detection from the energy viewpoint. Using the concepts of the chemical hardness and electronic charge transfer, some correlations between the energy of adsorption and interaction energy have been established. These analyses confirmed that the adsorption energy will be boosted with charge transfer enhancement. However, the chemical hardness relationship is reversed. Finally, obtained results from the natural bond orbital and electronic density of states analysis confirmed the electronic charge transfer from the adsorbates to WO3 clusters and Fermi level shifting after adsorption, respectively. The last parameter confirms that the cyclic clusters of tungsten oxide can be used as NOx gas sensors. PMID:25544841

Synthesis, structural characterization and mobility measurement of electron accepting pyrazine derivatives

NASA Astrophysics Data System (ADS)

Lai, William W.

Several pyrazine based cyano aza derivatives have been synthesized and electronic devices made from them. Hole and electron mobilities were measured using a time of flight (TOF) method with silicon wafers as both the substrate and charge carrier generation layer. The high density of charge carriers generated from silicon allowed for film layers as thin as 100nm and up to 250nm. Two compounds, 2,3,6,7-tetracyano-1,4,5,8-tetraazanapthalene (TCNN) and 2,3,6,7-tetracyano-9,10-dioctyl-1,4,5,6,9,10-hexaazaanthracene (DOA) were shown to be good electron acceptors. The potentials at which TCNN and DOA are reduced was -0.03 and -1.5 volts respectively. Electron mobilities of both compounds were found to be 2x10-5 cm2V˙s . The previously unreported oxidation potential of 2,3,6,7-tetracyano-9,10-dioctyl 1,4,5,6,9,10-hexaazaanthracene was measured and the hole mobility was determined to be 2x10-5 cm2V˙s . In the case of DOA, the charge carrier density of the electron carriers was comparable to that of the charge carrier density of the hole carriers. In contrast, the electron TOF signal of TCNN, which does not exhibit an oxidation, is greater than the hole TOF signal by roughly 200 fold. The inability for TCNN to act as a hole carrier was remedied by combining it with tetrathiafulvalene (TTF) as an electron donor. Crystals of the 1:1 complex were grown and the solved structure revealed segregated stacking. Conductivity measurements, by both two and four point methods determined the range of conductivity ranging from 10-5 to 10-6 Scm . The electron and hole mobility of the material was determined to be 2x10-5 and 2x10-6 cm2V˙s respectively. With the complementary TTF:TCNN system, the electron V-s and hole TOF signals were comparable, indicating a material that can equally conduct electrons or holes.

Non-metallic dopant modulation of conductivity in substoichiometric tantalum pentoxide: A first-principles study

DOE PAGES

Bondi, Robert J.; Fox, Brian P.; Marinella, Matthew J.

2017-06-01

Here, we apply density-functional theory calculations to predict dopant modulation of electrical conductivity (σ o) for seven dopants (C, Si, Ge, H, F, N, and B) sampled at 18 quantum molecular dynamics configurations of five independent insertion sites into two (high/low) baseline references of σo in amorphous Ta 2O 5, where each reference contains a single, neutral O vacancy center (V O 0). From this statistical population (n = 1260), we analyze defect levels, physical structure, and valence charge distributions to characterize nanoscale modification of the atomistic structure in local dopant neighborhoods. C is the most effective dopant at loweringmore » Ta 2O x σ o, while also exhibiting an amphoteric doping behavior by either donating or accepting charge depending on the host oxide matrix. Both B and F robustly increase Ta 2O x σ o, although F does so through elimination of Ta high charge outliers, while B insertion conversely creates high charge O outliers through favorable BO 3 group formation, especially in the low σ o reference. While N applications to dope and passivate oxides are prevalent, we also found that N exacerbates the stochasticity of σ o we sought to mitigate; sensitivity to the N insertion site and some propensity to form N-O bond chemistries appear responsible. Finally, we use direct first-principles predictions of σ o to explore feasible Ta 2O 5 dopants to engineer improved oxides with lower variance and greater repeatability to advance the manufacturability of resistive memory technologies.« less

Surface Charge Transfer Doping via Transition Metal Oxides for Efficient p-Type Doping of II-VI Nanostructures.

PubMed

Xia, Feifei; Shao, Zhibin; He, Yuanyuan; Wang, Rongbin; Wu, Xiaofeng; Jiang, Tianhao; Duhm, Steffen; Zhao, Jianwei; Lee, Shuit-Tong; Jie, Jiansheng

2016-11-22

Wide band gap II-VI nanostructures are important building blocks for new-generation electronic and optoelectronic devices. However, the difficulty of realizing p-type conductivity in these materials via conventional doping methods has severely handicapped the fabrication of p-n homojunctions and complementary circuits, which are the fundamental components for high-performance devices. Herein, by using first-principles density functional theory calculations, we demonstrated a simple yet efficient way to achieve controlled p-type doping on II-VI nanostructures via surface charge transfer doping (SCTD) using high work function transition metal oxides such as MoO 3 , WO 3 , CrO 3 , and V 2 O 5 as dopants. Our calculations revealed that these oxides were capable of drawing electrons from II-VI nanostructures, leading to accumulation of positive charges (holes injection) in the II-VI nanostructures. As a result, Fermi levels of the II-VI nanostructures were shifted toward the valence band regions after surface modifications, along with the large enhancement of work functions. In situ ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy characterizations verified the significant interfacial charge transfer between II-VI nanostructures and surface dopants. Both theoretical calculations and electrical transfer measurements on the II-VI nanostructure-based field-effect transistors clearly showed the p-type conductivity of the nanostructures after surface modifications. Strikingly, II-VI nanowires could undergo semiconductor-to-metal transition by further increasing the SCTD level. SCTD offers the possibility to create a variety of electronic and optoelectronic devices from the II-VI nanostructures via realization of complementary doping.

Hierarchical Ni-Co layered double hydroxide nanosheets on functionalized 3D-RGO films for high energy density asymmetric supercapacitor

NASA Astrophysics Data System (ADS)

Jiang, Liyang; Sui, Yanwei; Qi, Jiqiu; Chang, Yuan; He, Yezeng; Meng, Qingkun; Wei, Fuxiang; Sun, Zhi; Jin, Yunxue

2017-12-01

In this paper, ultrathin reduced graphene oxide films on nickel foam were fabricated via a facile dip-coating method combined with thermal reduction. Hierarchical Ni-Co layered double hydroxide nanosheets with network structure were electrodeposited on the ultrathin reduced graphene oxide films in a simple three-electrode system. The thickness of Ni-Co layered double hydroxide nanosheets can be controlled through adjusting the deposition temperature. The as-prepared electrode exhibited excellent electrochemical performance with specific capacitance of 1454.2 F g-1 at a current density of 1 A g-1. An asymmetric supercapacitor device was designed with the as-prepared composites as positive electrode material and Nitrogen-doped reduced graphene oxide as negative electrode material. This device could be operated in a working voltage range of 0-1.8 V in 1 M KOH aqueous electrolyte, delivering a high energy density of 56.4 W h kg-1 at a power density of 882.5 W kg-1. One supercapacitor can power two LEDs with rated voltage of 1.8-2.0 V. After 10,000 consecutive charge-discharge tests at 10 A g-1, this asymmetric supercapacitor revealed an excellent cycle life with 98.3% specific capacitance retention. These excellent electrochemical performances make it become one of most promising candidates for high energy supercapacitor device.

Anomalous low strain induced by surface charge in nanoporous gold with low relative density.

PubMed

Liu, Feng; Ye, Xing-Long; Jin, Hai-Jun

2017-07-26

The surface stress induced axial strain in a fiber-like solid is larger than its radical strain, and is also greater than the radical strain in similar-sized spherical solids. It is thus envisaged that the surface-induced macroscopic dimension change (i.e., actuation strain) in nanoporous gold (NPG) increases with decreasing relative density, or alternatively, with an increasing ratio between volumes of fiber-like ligaments and sphere-like nodes. In this study, electrochemical actuations of NPG with similar structure sizes, same (oxide-covered) surface state but different relative densities were characterized in situ in response to surface charging/discharging. We found that the actuation strain amplitude did not increase, but decreased dramatically with decreasing relative density of NPG, in contrast to the above prediction. The actuation strain decreased abruptly when the relative density of NPG was decreased to below 0.25, when the Au content in the AuAg precursor was below 20 at%. Further studies indicate that this anomalous behavior cannot be explained by potential- or size-dependences of the elasticity, the structure difference arising from different dealloying rates, or additional strain induced by the external load during dilatometry experiments. In NPG with low relative density, mutual movements of nano-ligaments may occur in the pore space and disconnected regions, which may compensate the local strain in ligaments and account for the anomalous low actuation strain in macroscopic NPG samples.

CO adsorption on small Au{sub n} (n = 1–4) structures supported on hematite. I. Adsorption on iron terminated α-Fe{sub 2}O{sub 3} (0001) surface

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

Pabisiak, Tomasz; Kiejna, Adam, E-mail: kiejna@ifd.uni.wroc.pl; Winiarski, Maciej J.

2016-01-28

This is the first of two papers dealing with the adsorption of Au and formation of Au{sub n} nanostructures (n = 1–4) on hematite (0001) surface and adsorption of CO thereon. The stoichiometric Fe-terminated (0001) surface of hematite was investigated using density functional theory in the generalized gradient approximation of Perdew-Burke-Ernzerhof (PBE) form with Hubbard correction U, accounting for strong electron correlations (PBE+U). The structural, energetic, and electronic properties of the systems studied were examined for vertical and flattened configurations of Au{sub n} nanostructures adsorbed on the hematite surfaces. The flattened ones, which can be viewed as bilayer-like structures, weremore » found energetically more favored than vertical ones. For both classes of structures the adsorption binding energy increases with the number of Au atoms in a structure. The adsorption of Au{sub n} induces charge rearrangement at the Au{sub n}/oxide contact which is reflected in work function changes. In most considered cases Au{sub n} adsorption increases the work function. A detailed analysis of the bonding electron charge is presented and the corresponding electron charge rearrangements at the contacts were quantified by a Bader charge analyses. The interaction of a CO molecule with the Au{sub n} nanostructures supported on α-Fe{sub 2}O{sub 3} (0001) and the oxide support was studied. It is found that the CO adsorption binding to the hematite supported Au{sub n} structures is more than twice as strong as to the bare hematite surface. Analysis of the Bader charges on the atoms showed that in each case CO binds to the most positively charged (cationic) atom of the Au{sub n} structure. Changes in the electronic structure of the Au{sub n} species and of the oxide support, and their consequences for the interactions with CO, are discussed.« less

Intertwined nanocarbon and manganese oxide hybrid foam for high-energy supercapacitors.

PubMed

Wang, Wei; Guo, Shirui; Bozhilov, Krassimir N; Yan, Dong; Ozkan, Mihrimah; Ozkan, Cengiz S

2013-11-11

Rapid charging and discharging supercapacitors are promising alternative energy storage systems for applications such as portable electronics and electric vehicles. Integration of pseudocapacitive metal oxides with single-structured materials has received a lot of attention recently due to their superior electrochemical performance. In order to realize high energy-density supercapacitors, a simple and scalable method is developed to fabricate a graphene/MWNT/MnO2 nanowire (GMM) hybrid nanostructured foam, via a two-step process. The 3D few-layer graphene/MWNT (GM) architecture is grown on foamed metal foils (nickel foam) via ambient pressure chemical vapor deposition. Hydrothermally synthesized α-MnO2 nanowires are conformally coated onto the GM foam by a simple bath deposition. The as-prepared hierarchical GMM foam yields a monographical graphene foam conformally covered with an intertwined, densely packed CNT/MnO2 nanowire nanocomposite network. Symmetrical electrochemical capacitors (ECs) based on GMM foam electrodes show an extended operational voltage window of 1.6 V in aqueous electrolyte. A superior energy density of 391.7 Wh kg(-1) is obtained for the supercapacitor based on the GMM foam, which is much higher than ECs based on GM foam only (39.72 Wh kg(-1) ). A high specific capacitance (1108.79 F g(-1) ) and power density (799.84 kW kg(-1) ) are also achieved. Moreover, the great capacitance retention (97.94%) after 13 000 charge-discharge cycles and high current handability demonstrate the high stability of the electrodes of the supercapacitor. These excellent performances enable the innovative 3D hierarchical GMM foam to serve as EC electrodes, resulting in energy-storage devices with high stability and power density in neutral aqueous electrolyte. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrical characteristics of thin Ta2O5 films deposited by reactive pulsed direct-current magnetron sputtering

NASA Astrophysics Data System (ADS)

Kim, J.-Y.; Nielsen, M. C.; Rymaszewski, E. J.; Lu, T.-M.

2000-02-01

Room temperature deposition of tantalum oxide films on metallized silicon substrates was investigated by reactive pulsed magnetron sputtering of Ta in an Ar/O2 ambient. The dielectric constant of the tantalum oxide ranged from 19 to 31 depending on the oxygen percentage [P(%)=PO2/(PO2+PAr)] used during sputtering. The leakage current density was less than 10 nA/cm2 at 0.5 MV/cm electric field and the dielectric breakdown field was greater than 3.8 MV/cm for P=60%. A charge storage as high as 3.3 μF/cm2 was achieved for 70-Å-thick film. Pulse frequency variation (from 20 to 200 kHz) did not give a significant effect in the electrical properties (dielectric constant or leakage current density) of the Ta2O5 films.

Three-dimensional sulphur/nitrogen co-doped reduced graphene oxide as high-performance supercapacitor binder-free electrodes

NASA Astrophysics Data System (ADS)

Huo, Jinghao; Zheng, Peng; Wang, Xiaofei; Guo, Shouwu

2018-06-01

Sulphur/nitrogen co-doped reduced graphene oxide (SNG) aerogels were prepared by a simple solvothermal method with l-cysteine-assisted in ethylene glycol. The morphology and composition tests showed that the S/N heteroatoms were evenly distributed on SNG microsheets, and these microsheets were further composed of SNG aerogels with three-dimensional (3D) porous structure. The cyclic voltammetry and galvanostatic charge/discharge tests illustrated the SNG bind-free electrode possessed electric double-layer capacitance and pseudocapacitance, and had a capacitance of 254 F g-1 at a current density of 1 A g-1. After the 5000 cycles tests, the capacitance retained 83.54% at a current density of 2 A g-1. Meanwhile, the electrochemical impedance spectroscopy data shown the electrode materials had excellent capacity and good conductivity. Hence, the SNG aerogel prepared by l-cysteine-assisted solvothermal method is a great material for high-performance supercapacitors.

Two-Dimensional Metal Oxide Nanomaterials for Next-Generation Rechargeable Batteries.

PubMed

Mei, Jun; Liao, Ting; Kou, Liangzhi; Sun, Ziqi

2017-12-01

The exponential increase in research focused on two-dimensional (2D) metal oxides has offered an unprecedented opportunity for their use in energy conversion and storage devices, especially for promising next-generation rechargeable batteries, such as lithium-ion batteries (LIBs) and sodium-ion batteries (NIBs), as well as some post-lithium batteries, including lithium-sulfur batteries, lithium-air batteries, etc. The introduction of well-designed 2D metal oxide nanomaterials into next-generation rechargeable batteries has significantly enhanced the performance of these energy-storage devices by providing higher chemically active interfaces, shortened ion-diffusion lengths, and improved in-plane carrier-/charge-transport kinetics, which have greatly promoted the development of nanotechnology and the practical application of rechargeable batteries. Here, the recent progress in the application of 2D metal oxide nanomaterials in a series of rechargeable LIBs, NIBs, and other post lithium-ion batteries is reviewed relatively comprehensively. Current opportunities and future challenges for the application of 2D nanomaterials in energy-storage devices to achieve high energy density, high power density, stable cyclability, etc. are summarized and outlined. It is believed that the integration of 2D metal oxide nanomaterials in these clean energy devices offers great opportunities to address challenges driven by increasing global energy demands. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trap densities and transport properties of pentacene metal-oxide-semiconductor transistors. I. Analytical modeling of time-dependent characteristics

NASA Astrophysics Data System (ADS)

Basile, A. F.; Cramer, T.; Kyndiah, A.; Biscarini, F.; Fraboni, B.

2014-06-01

Metal-oxide-semiconductor (MOS) transistors fabricated with pentacene thin films were characterized by temperature-dependent current-voltage (I-V) characteristics, time-dependent current measurements, and admittance spectroscopy. The channel mobility shows almost linear variation with temperature, suggesting that only shallow traps are present in the semiconductor and at the oxide/semiconductor interface. The admittance spectra feature a broad peak, which can be modeled as the sum of a continuous distribution of relaxation times. The activation energy of this peak is comparable to the polaron binding energy in pentacene. The absence of trap signals in the admittance spectra confirmed that both the semiconductor and the oxide/semiconductor interface have negligible density of deep traps, likely owing to the passivation of SiO2 before pentacene growth. Nevertheless, current instabilities were observed in time-dependent current measurements following the application of gate-voltage pulses. The corresponding activation energy matches the energy of a hole trap in SiO2. We show that hole trapping in the oxide can explain both the temperature and the time dependences of the current instabilities observed in pentacene MOS transistors. The combination of these experimental techniques allows us to derive a comprehensive model for charge transport in hybrid architectures where trapping processes occur at various time and length scales.

Calculation of the spin-polarized electronic structure of an interstitial iron impurity in silicon

NASA Astrophysics Data System (ADS)

Katayama-Yoshida, H.; Zunger, Alex

1985-06-01

We apply our self-consistent, all-electron, spin-polarized Green's-function method within an impurity-centered, dynamic basis set to study the interstitial iron impurity in silicon. We use two different formulations of the interelectron interactions: the local-spin-density (LSD) formalism and the self-interaction-corrected (SIC) local-spin-density (SIC-LSD) formalism. We find that the SIC-LSD approach is needed to obtain the correct high-spin ground state of Si:Fe+. We propose a quantitative explanation to the observed donor ionization energy and the high-spin ground states for Si:Fe+ within the SIC-LSD approach. For both Si:Fe0 and Si:Fe+, this approach leads to a hyperfine field, contact spin density, and ionization energy in better agreement with experiments than the simple LSD approach. The apparent dichotomy between the covalently delocalized nature of Si:Fe as suggested on the one hand by its reduced hyperfine field (relative to the free atom) and extended spin density and by the occurrence of two closely spaced, stable charge states (within 0.4 eV) and on the other hand by the atomically localized picture (suggested, for example, by the stability of a high-spin, ground-state configuration) is resolved. We find a large reduction in the hyperfine field and contact spin density due to the covalent hybridization between the impurity 3d orbitals and the tails of the delocalized sp3 hybrid orbitals of the surrounding silicon atoms. Using the calculated results, we discuss (i) the underlying mechanism for the stability and plurality of charged states, (ii) the covalent reduction in the hyperfine field, (iii) the remarkable constancy of the impurity Mössbauer isomer shift for different charged states, (iv) comparison with the multiple charged states in ionic crystals, and (v) some related speculation about the mechanism of (Fe2+/Fe3+) oxidation-reduction ionizations in heme proteins and electron-transporting biological systems.

Full-range electrical characteristics of WS{sub 2} transistors

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

Kumar, Jatinder; Bellus, Matthew Z.; Chiu, Hsin-Ying, E-mail: chiu@ku.edu

We fabricated transistors formed by few layers to bulk single crystal WS{sub 2} to quantify the factors governing charge transport. We established a capacitor network to analyze the full-range electrical characteristics of the channel, highlighting the role of quantum capacitance and interface trap density. We find that the transfer characteristics are mainly determined by the interplay between quantum and oxide capacitances. In the OFF-state, the interface trap density (<10{sup 12} cm{sup –2}) is a limiting factor for the subthreshold swing. Furthermore, the superior crystalline quality and the low interface trap density enabled the subthreshold swing to approach the theoretical limit onmore » a back-gated device on SiO{sub 2}/Si substrate.« less

Mixed cerium-platinum oxides: Electronic structure of [CeO]Pt{sub n} (n = 1, 2) and [CeO{sub 2}]Pt complex anions and neutrals

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

Ray, Manisha; Kafader, Jared O.; Topolski, Josey E.

The electronic structures of several small Ce–Pt oxide complexes were explored using a combination of anion photoelectron (PE) spectroscopy and density functional theory calculations. Pt and Pt{sub 2} both accept electron density from CeO diatomic molecules, in which the cerium atom is in a lower-than-bulk oxidation state (+2 versus bulk +4). Neutral [CeO]Pt and [CeO]Pt{sub 2} complexes are therefore ionic, with electronic structures described qualitatively as [CeO{sup +2}]Pt{sup −2} and [CeO{sup +}]Pt{sub 2}{sup −}, respectively. The associated anions are described qualitatively as [CeO{sup +}]Pt{sup −2} and [CeO{sup +}]Pt{sub 2}{sup −2}, respectively. In both neutrals and anions, the most stable molecularmore » structures determined by calculations feature a distinct CeO moiety, with the positively charged Ce center pointing toward the electron rich Pt or Pt{sub 2} moiety. Spectral simulations based on calculated spectroscopic parameters are in fair agreement with the spectra, validating the computationally determined structures. In contrast, when Pt is coupled with CeO{sub 2}, which has no Ce-localized electrons that can readily be donated to Pt, the anion is described as [CeO{sub 2}]Pt{sup −}. The molecular structure predicted computationally suggests that it is governed by charge-dipole interactions. The neutral [CeO{sub 2}]Pt complex lacks charge-dipole stabilizing interactions, and is predicted to be structurally very different from the anion, featuring a single Pt–O–Ce bridge bond. The PE spectra of several of the complexes exhibit evidence of photodissociation with Pt{sup −} daughter ion formation. The electronic structures of these complexes are related to local interactions in Pt-ceria catalyst-support systems.« less

Solid-State Densification of Spun-Cast Self-Assembled Monolayers for Use in Ultra-Thin Hybrid Dielectrics.

PubMed

Hutchins, Daniel O; Acton, Orb; Weidner, Tobias; Cernetic, Nathan; Baio, Joe E; Castner, David G; Ma, Hong; Jen, Alex K-Y

2012-11-15

Ultra-thin self-assembled monolayer (SAM)-oxide hybrid dielectrics have gained significant interest for their application in low-voltage organic thin film transistors (OTFTs). A [8-(11-phenoxy-undecyloxy)-octyl]phosphonic acid (PhO-19-PA) SAM on ultrathin AlO x (2.5 nm) has been developed to significantly enhance the dielectric performance of inorganic oxides through reduction of leakage current while maintaining similar capacitance to the underlying oxide structure. Rapid processing of this SAM in ambient conditions is achieved by spin coating, however, as-cast monolayer density is not sufficient for dielectric applications. Thermal annealing of a bulk spun-cast PhO-19-PA molecular film is explored as a mechanism for SAM densification. SAM density, or surface coverage, and order are examined as a function of annealing temperature. These SAM characteristics are probed through atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure spectroscopy (NEXAFS). It is found that at temperatures sufficient to melt the as-cast bulk molecular film, SAM densification is achieved; leading to a rapid processing technique for high performance SAM-oxide hybrid dielectric systems utilizing a single wet processing step. To demonstrate low-voltage devices based on this hybrid dielectric (with leakage current density of 7.7×10 -8 A cm -2 and capacitance density of 0.62 µF cm -2 at 3 V), pentacene thin-film transistors (OTFTs) are fabricated and yield sub 2 V operation and charge carrier mobilites of up to 1.1 cm 2 V -1 s -1 .

Solid-State Densification of Spun-Cast Self-Assembled Monolayers for Use in Ultra-Thin Hybrid Dielectrics

PubMed Central

Hutchins, Daniel O.; Acton, Orb; Weidner, Tobias; Cernetic, Nathan; Baio, Joe E.; Castner, David G.; Ma, Hong; Jen, Alex K.-Y.

2013-01-01

Ultra-thin self-assembled monolayer (SAM)-oxide hybrid dielectrics have gained significant interest for their application in low-voltage organic thin film transistors (OTFTs). A [8-(11-phenoxy-undecyloxy)-octyl]phosphonic acid (PhO-19-PA) SAM on ultrathin AlOx (2.5 nm) has been developed to significantly enhance the dielectric performance of inorganic oxides through reduction of leakage current while maintaining similar capacitance to the underlying oxide structure. Rapid processing of this SAM in ambient conditions is achieved by spin coating, however, as-cast monolayer density is not sufficient for dielectric applications. Thermal annealing of a bulk spun-cast PhO-19-PA molecular film is explored as a mechanism for SAM densification. SAM density, or surface coverage, and order are examined as a function of annealing temperature. These SAM characteristics are probed through atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and near edge X-ray absorption fine structure spectroscopy (NEXAFS). It is found that at temperatures sufficient to melt the as-cast bulk molecular film, SAM densification is achieved; leading to a rapid processing technique for high performance SAM-oxide hybrid dielectric systems utilizing a single wet processing step. To demonstrate low-voltage devices based on this hybrid dielectric (with leakage current density of 7.7×10−8 A cm−2 and capacitance density of 0.62 µF cm−2 at 3 V), pentacene thin-film transistors (OTFTs) are fabricated and yield sub 2 V operation and charge carrier mobilites of up to 1.1 cm2 V−1 s−1. PMID:24288423

Thermoelectric Properties and Thermal Tolerance of Indium Tin Oxide Nanowires.

PubMed

Hernandez, Jose A; Carpena Nunez, Jennifer; Fonseca, Luis F; Pettes, Michael Thompson; Yacaman, Miguel Jose; Benitez, Alfredo

2018-06-14

Single-crystalline indium tin oxide (ITO) nanowires were grown via a vapor-liquid-solid (VLS) method, with thermal tolerance up to ~1300°C. We report the electric and thermoelectric properties of the ITO nanowires before and after heat treatments and draw conclusions about their applicability as thermoelectric building blocks in nanodevices that can operate in high temperature conditions. The Seebeck coefficient and the thermal and electrical conductivities were measured in each individual nanowire by means of specialized micro-bridge thermometry devices. Measured data was analyzed and explained in terms of changes in charge carrier density, impurities and vacancies due to the thermal treatments. © 2018 IOP Publishing Ltd.

Enhanced optical and electrochemical properties of polyaniline/cobalt oxide nano composite

NASA Astrophysics Data System (ADS)

Niranjana, M.; Yesappa, L.; Ashokkumar, S. P.; Vijeth, H.; Basappa, M.; Devendrappa, H.

2018-05-01

Polyaniline and its composites at different wt. % of Cobalt oxide nano (PDC1, PDC2 and PDC5) were prepared by in-situ chemical reaction method The optical property was carried out using UV-Vis. Absorption Spectroscopy. The electrochemical property like cyclic voltammetry and galvonostatic charging-discharging was carried out for PANI and PDC nanocomposite electrode materials. A specific capacitance of 212.08 F/g and 336.41 F/g with scan rates 100 and 200 mV/s at 0.4 A/g current density respectively. These results are suggesting PDC composite is a prominent candidate for supercapacitor properties applications.

Batteries used to Power Implantable Biomedical Devices

PubMed Central

Bock, David C.; Marschilok, Amy C.; Takeuchi, Kenneth J.; Takeuchi, Esther S.

2012-01-01

Battery systems have been developed that provide years of service for implantable medical devices. The primary systems utilize lithium metal anodes with cathode systems including iodine, manganese oxide, carbon monofluoride, silver vanadium oxide and hybrid cathodes. Secondary lithium ion batteries have also been developed for medical applications where the batteries are charged while remaining implanted. While the specific performance requirements of the devices vary, some general requirements are common. These include high safety, reliability and volumetric energy density, long service life, and state of discharge indication. Successful development and implementation of these battery types has helped enable implanted biomedical devices and their treatment of human disease. PMID:24179249

Batteries used to Power Implantable Biomedical Devices.

PubMed

Bock, David C; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2012-12-01

Battery systems have been developed that provide years of service for implantable medical devices. The primary systems utilize lithium metal anodes with cathode systems including iodine, manganese oxide, carbon monofluoride, silver vanadium oxide and hybrid cathodes. Secondary lithium ion batteries have also been developed for medical applications where the batteries are charged while remaining implanted. While the specific performance requirements of the devices vary, some general requirements are common. These include high safety, reliability and volumetric energy density, long service life, and state of discharge indication. Successful development and implementation of these battery types has helped enable implanted biomedical devices and their treatment of human disease.

Enhanced charge ordering transition in doped CaFeO3 through steric templating

NASA Astrophysics Data System (ADS)

Jiang, Lai; Saldana-Greco, Diomedes; Schick, Joseph T.; Rappe, Andrew M.

2014-06-01

We report a density functional theory investigation of B-site doped CaFeO3, a prototypical charge ordered perovskite. At 290 K, CaFeO3 undergoes a metal-insulator transition and a charge disproportionation reaction 2Fe4+→Fe5++Fe3+. We observe that when Zr dopants occupy a (001) layer, the band gap of the resulting solid solution increases to 0.93 eV due to a two-dimensional Jahn-Teller-type distortion, where FeO6 cages on the xy plane elongate along x and y alternatively between neighboring Fe sites. Furthermore, we show that the rock-salt ordering of the Fe5+ and Fe3+ cations can be enhanced when the B-site dopants are arranged in a (111) plane due to a collective steric effect that facilitates the size discrepancy between the Fe5+O6 and Fe3+O6 octahedra and therefore gives rise to a larger band gap. The enhanced charge disproportionation in these solid solutions is verified by rigorously calculating the oxidation states of the Fe cations with different octahedral cage sizes. We therefore predict that the corresponding transition temperature will increase due to the enhanced charge ordering and larger band gap. The compositional, structural, and electrical relationships exploited in this paper can be extended to a variety of perovskites and nonperovskite oxides, providing guidance in the structural manipulation of electrical properties of functional materials.

Charging/discharging stability of a metal hydride battery electrode

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

Geng, M.; Han, J.; Feng, F.

1999-07-01

The metal hydride (MH) alloy powder for the negative electrode of the Ni/MH battery was first pulverized and oxidized by electrochemically charging and discharging for a number of cycles. The plate of the negative electrode of an experimental cell in this study was made from a mixture of a multicomponent AB{sub 5}-based alloy powder, nickel powder, and polytetra fluoroethylene (PTFE). The characteristics of the negative electrode, including discharge capacity, exchange current density, and hydrogen diffusivity, were studied by means of the electrochemical experiments and analysis in an experimental cell. The exchange current density of a Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85}Co{sub 0.45}Mn{submore » 0.35}Al{sub 0.35} alloy electrode increases with increasing number of charge/discharge cycles and then remains almost constant after 20 cycles. A microcracking activation, resulting from an increase in reaction surface area and an improvement in the electrode surface activation, increases the hydrogen exchange current densities. Measurement of hydrogen diffusivities for Mm{sub 0.95}Ti{sub 0.05}Ni{sub 3.85}Co{sub 0.45}Mn{sub 0.35}Al{sub 0.35} alloy powder shows that the ratio of D/a{sup 2} (D = hydrogen diffusivity; a = sphere radius) increases with increasing number of cycles but remains constant after 20 cycles.« less

Facile and Scalable Synthesis Method for High-Quality Few-Layer Graphene through Solution-Based Exfoliation of Graphite.

PubMed

Wee, Boon-Hong; Wu, Tong-Fei; Hong, Jong-Dal

2017-02-08

Here we describe a facile and scalable method for preparing defect-free graphene sheets exfoliated from graphite using the positively charged polyelectrolyte precursor poly(p-phenylenevinylene) (PPV-pre) as a stabilizer in an aqueous solution. The graphene exfoliated by PPV-pre was apparently stabilized in the solution as a form of graphene/PPV-pre (denoted to GPPV-pre), which remains in a homogeneous dispersion over a year. The thickness values of 300 selected 76% GPPV-pre flakes ranged from 1 to 10 nm, corresponding to between one and a few layers of graphene in the lateral dimensions of 1 to 2 μm. Furthermore, this approach was expected to yield a marked decrease in the density of defects in the electronic conjugation of graphene compared to that of graphene oxide (GO) obtained by Hummers' method. The positively charged GPPV-pre was employed to fabricate a poly(ethylene terephthalate) (PET) electrode layer-by-layer with negatively charged GO, yielding (GPPV-pre/GO) n film electrode. The PPV-pre and GO in the (GPPV-pre/GO) n films were simultaneously converted using hydroiodic acid vapor to fully conjugated PPV and reduced graphene oxide (RGO), respectively. The electrical conductivity of (GPPV/RGO) 23 multilayer films was 483 S/cm, about three times greater than that of the (PPV/RGO) 23 multilayer films (166 S/cm) comprising RGO (prepared by Hummers method). Furthermore, the superior electrical properties of GPPV were made evident, when comparing the capacitive performances of two supercapacitor systems; (polyaniline PANi/RGO) 30 /(GPPV/RGO) 23 /PET (volumetric capacitance = 216 F/cm 3 ; energy density = 19 mWh/cm 3 ; maximum power density = 498 W/cm 3 ) and (PANi/RGO) 30 /(PPV/RGO) 23 /PET (152 F/cm 3 ; 9 mWh/cm 3 ; 80 W/cm 3 ).

Laser processing of thick Li(NiMnCo)O2 electrodes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Rakebrandt, J.-H.; Smyrek, P.; Zheng, Y.; Seifert, H. J.; Pfleging, W.

2017-02-01

Lithium-ion batteries became the most promising types of mobile energy storage devices due to their high gravimetric and volumetric capacity, high cycle life-time, and low self-discharge. Nowadays, the cathode material lithium nickel manganese cobalt oxide (NMC) is one of the most widely used cathode material in commercial lithium-ion batteries due to many advantages such as high energy density (>150 Wh kg-1) on cell level, high power density (650 W kg-1 @ 25 °C and 50 % Depth of Discharge) [1], high specific capacity (163 mAh g-1) [2], high rate capability and good thermal stability in the fully charged state. However, in order to meet the requirements for the increasing demand for rechargeable high energy batteries, nickel-rich NMC electrodes with specific capacities up to 210 mAh g-1 seem to be the next generation cathodes which can reach on cell level desired energy densities higher than 250 Wh kg-1 [3]. Laser-structuring now enables to combine both concepts, high power and high energy lithium-ion batteries. For this purpose, lithium nickel manganese cobalt oxide cathodes were produced via tape casting containing 85-90 wt% of active material with a film thickness of 50-260 μm. The specific capacities were measured using galvanostatic measurements for different types of NMC with varying nickel, manganese and cobalt content at different charging/discharging currents ("C-rates"). An improved lithium-ion diffusion kinetics due to an increased active surface area could be achieved by laser-assisted generating of three dimensional architectures. Cells with unstructured and structured cathodes were compared. Ultrafast laser ablation was used in order to avoid a thermal impact to the material. It was shown that laser structuring of electrode materials leads to a significant improvement in electrochemical performance, especially at high charging and discharging C-rates.

Polymer/metal oxide hybrid dielectrics for low voltage field-effect transistors with solution-processed, high-mobility semiconductors

NASA Astrophysics Data System (ADS)

Held, Martin; Schießl, Stefan P.; Miehler, Dominik; Gannott, Florentina; Zaumseil, Jana

2015-08-01

Transistors for future flexible organic light-emitting diode (OLED) display backplanes should operate at low voltages and be able to sustain high currents over long times without degradation. Hence, high capacitance dielectrics with low surface trap densities are required that are compatible with solution-processable high-mobility semiconductors. Here, we combine poly(methyl methacrylate) (PMMA) and atomic layer deposition hafnium oxide (HfOx) into a bilayer hybrid dielectric for field-effect transistors with a donor-acceptor polymer (DPPT-TT) or single-walled carbon nanotubes (SWNTs) as the semiconductor and demonstrate substantially improved device performances for both. The ultra-thin PMMA layer ensures a low density of trap states at the semiconductor-dielectric interface while the metal oxide layer provides high capacitance, low gate leakage and superior barrier properties. Transistors with these thin (≤70 nm), high capacitance (100-300 nF/cm2) hybrid dielectrics enable low operating voltages (<5 V), balanced charge carrier mobilities and low threshold voltages. Moreover, the hybrid layers substantially improve the bias stress stability of the transistors compared to those with pure PMMA and HfOx dielectrics.

Enhanced electrochemical performance of sandwich-structured polyaniline-wrapped silicon oxide/carbon nanotubes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Liu, Hui; Zou, Yongjin; Huang, Liyan; Yin, Hao; Xi, Chengqiao; Chen, Xin; Shentu, Hongwei; Li, Chao; Zhang, Jingjing; Lv, ChunJu; Fan, Meiqiang

2018-06-01

Sandwich-structured carbon nanotubes, silicon oxide, and polyaniline (hereafter denoted as CNTs/SiOx/PANI) were prepared by combining a sol-gel method, magnesiothermic reduction at 250 °C, and chemical oxidative polymerization. The CNTs, SiOx and PANI in the composite was 16 wt%, 51 wt% and 33 wt%, respectively. The CNTs/SiOx/PANI electrodes exhibited excellent cycle and high-rate performance as anodes in Li-ion batteries, including charge/discharge capacities of 1156/1178 mAh g-1 after 60 cycles at 0.2 A g-1 current density and 728/725 mAh g-1 at 8 A g-1 current density. The improvement was due to the synergy between CNTs and PANI. The SiOx scattered on the CNTs core and coated by PANI improved its conductivity and accommodated the volume change during repeated lithiation/delithiation cycles. This simple synthesis provided a scalable route for the large-scale production of CNTs/SiOx/PANI nanostructures, with various applications such as in Li-ion batteries.

Electrical Characterization of Semiconductor Materials and Devices

NASA Astrophysics Data System (ADS)

Deen, M.; Pascal, Fabien

Semiconductor materials and devices continue to occupy a preeminent technological position due to their importance when building integrated electronic systems used in a wide range of applications from computers, cell-phones, personal digital assistants, digital cameras and electronic entertainment systems, to electronic instrumentation for medical diagnositics and environmental monitoring. Key ingredients of this technological dominance have been the rapid advances made in the quality and processing of materials - semiconductors, conductors and dielectrics - which have given metal oxide semiconductor device technology its important characteristics of negligible standby power dissipation, good input-output isolation, surface potential control and reliable operation. However, when assessing material quality and device reliability, it is important to have fast, nondestructive, accurate and easy-to-use electrical characterization techniques available, so that important parameters such as carrier doping density, type and mobility of carriers, interface quality, oxide trap density, semiconductor bulk defect density, contact and other parasitic resistances and oxide electrical integrity can be determined. This chapter describes some of the more widely employed and popular techniques that are used to determine these important parameters. The techniques presented in this chapter range in both complexity and test structure requirements from simple current-voltage measurements to more sophisticated low-frequency noise, charge pumping and deep-level transient spectroscopy techniques.

Unconventional irreversible structural changes in a high-voltage Li–Mn-rich oxide for lithium-ion battery cathodes

DOE PAGES

Mohanty, Debasish; Sefat, Athena S.; Payzant, E. Andrew; ...

2015-02-19

Making all-electric vehicles (EVs) commonplace in transportation applications will require affordable high-power and high-energy-density lithium-ion batteries (LIBs). The quest for suitable cathode materials to meet this end has currently plateaued with the discovery of high-voltage (≥4.7 V vs. Li +), high capacity (~250 mAh/g) lithium–manganese-rich (LMR) layered composite oxides. In spite of the promise of LMR oxides in high-energy-density LIBs, an irreversible structural change has been identified in this work that is governed by the formation of a ‘permanent’ spin-glass type magnetically frustrated phase indicating a dominant AB 2O 4 (A = Li, B = Mn) type spinel after amore » short-term lithium deintercalation (charging) and intercalation (discharging) process. Furthermore, reduction of transition metal (Mn) ions from the 4+ state (pristine LMR) to 3+ (cycled LMR), which alters the intercalation redox chemistry and suggests the presence of ‘unfilled’ lithium vacancies and/or oxygen vacancies in the lattice after cycling, has presented a major stumbling block. Finally, these situations result in both loss of capacity and fading of the voltage profile, and these combined effects significantly reduce the high energy density over even short-term cycling.« less

TEMPO-Oxidized Nanofibrillated Cellulose as a High Density Carrier for Bioactive Molecules.

PubMed

Weishaupt, Ramon; Siqueira, Gilberto; Schubert, Mark; Tingaut, Philippe; Maniura-Weber, Katharina; Zimmermann, Tanja; Thöny-Meyer, Linda; Faccio, Greta; Ihssen, Julian

2015-11-09

Controlled and efficient immobilization of specific biomolecules is a key technology to introduce new, favorable functions to materials suitable for biomedical applications. Here, we describe an innovative and efficient, two-step methodology for the stable immobilization of various biomolecules, including small peptides and enzymes onto TEMPO oxidized nanofibrillated cellulose (TO-NFC). The introduction of carboxylate groups to NFC by TEMPO oxidation provided a high surface density of negative charges able to drive the adsorption of biomolecules and take part in covalent cross-linking reactions with 1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide (EDAC) and glutaraldehyde (Ga) chemistry. Up to 0.27 μmol of different biomolecules per mg of TO-NFC could be reversibly immobilized by electrostatic interaction. An additional chemical cross-linking step prevented desorption of more than 80% of these molecules. Using the cysteine-protease papain as model, a highly active papain-TO-NFC conjugate was achieved. Once papain was immobilized, 40% of the initial enzymatic activity was retained, with an increase in kcat from 213 to >700 s(-1) for the covalently immobilized enzymes. The methodology presented in this work expands the range of application for TO-NFC in the biomedical field by enabling well-defined hybrid biomaterials with a high density of functionalization.

Composite Manganese Oxide Percolating Networks As a Suspension Electrode for an Asymmetric Flow Capacitor

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

Hatzell, Kelsey B.; Fan, Lei; Beidaghi, Majid

2014-05-05

In this study, we examine the use of a percolating network of metal oxide (MnO2) as the active material in a suspension electrode as a way to increase the capacitance and energy density of an electrochemical flow capacitor. Amorphous manganese oxide was synthesized via a low-temperature hydrothermal approach and combined with carbon black to form composite flowable electrodes of different compositions. All suspension electrodes were tested in static configurations and consisted of an active solid material (MnO2 or activated carbon) immersed in aqueous neutral electrolyte (1 M Na2SO4). Increasing concentrations of carbon black led to better rate performance but atmore » the cost of capacitance and viscosity. Furthermore, it was shown that an expanded voltage window of 1.6 V could be achieved when combining a composite MnO2-carbon black (cathode) and an activated carbon suspension (anode) in a charge balanced asymmetric device. The expansion of the voltage window led to a significant increase in the energy density to ~11 Wh kg–1 at a power density of ~50 W kg–1. These values are ~3.5 times and ~2 times better than a symmetric suspension electrode based on activated carbon.« less

Electrochemical treatment of cork boiling wastewater with a boron-doped diamond anode.

PubMed

Fernandes, Annabel; Santos, Diana; Pacheco, Maria José; Ciríaco, Lurdes; Simões, Rogério; Gomes, Arlindo C; Lopes, Ana

2015-01-01

Anodic oxidation at a boron-doped diamond anode of cork boiling wastewater was successfully used for mineralization and biodegradability enhancement required for effluent discharge or subsequent biological treatment, respectively. The influence of the applied current density (30-70 mA/cm2) and the background electrolyte concentration (0-1.5 g/L Na2SO4) on the performance of the electrochemical oxidation was investigated. The supporting electrolyte was required to achieve conductivities that enabled anodic oxidation at the highest current intensities applied. The results indicated that pollutant removal increased with the applied current density, and after 8 h, reductions greater than 90% were achieved for COD, dissolved organic carbon, total phenols and colour. The biodegradability enhancement was from 0.13 to 0.59 and from 0.23 to 0.72 for the BOD/COD ratios with BOD of 5 and 20 days' incubation period, respectively. The tests without added electrolyte were performed at lower applied electrical charges (15 mA/cm2 or 30 V) with good organic load removal (up to 80%). For an applied current density of 30 mA/cm2, there was a minimum of electric conductivity of 1.9 mS/cm (corresponding to 0.75 g/L of Na2SO4), which minimized the specific energy consumption.

Defect engineering of two-dimensional WO3 nanosheets for enhanced electrochromism and photoeletrochemical performance

NASA Astrophysics Data System (ADS)

Zhou, Xiaofang; Zheng, Xiaoli; Yan, Bo; Xu, Tao; Xu, Qun

2017-04-01

The capability of introduction of oxygen vacancies in a controlled way has emerged as the heart of modern transition metal oxide semiconductor chemistry. As chemical defects, the oxygen vacancies have been proposed as electron donors, which are prone to increase carrier density and promote charge carrier separation. Herein, we have successfully prepared 2D WO3 ultrathin nanosheets with abundant surface oxygen vacancies by a combination of facile solvothermal reaction and hydrogenation method. The resultant hydrogenated WO3 ultrathin nanosheets exhibit remarkable electrochromism and photocatalytic performances compared with the non-hydrogenated samples, mainly due to their increased oxygen vacancies, narrowed band gap coupled with fast charge transfer and enhanced adsorption of visible light.

Charge generation layers for solution processed tandem organic light emitting diodes with regular device architecture.

PubMed

Höfle, Stefan; Bernhard, Christoph; Bruns, Michael; Kübel, Christian; Scherer, Torsten; Lemmer, Uli; Colsmann, Alexander

2015-04-22

Tandem organic light emitting diodes (OLEDs) utilizing fluorescent polymers in both sub-OLEDs and a regular device architecture were fabricated from solution, and their structure and performance characterized. The charge carrier generation layer comprised a zinc oxide layer, modified by a polyethylenimine interface dipole, for electron injection and either MoO3, WO3, or VOx for hole injection into the adjacent sub-OLEDs. ToF-SIMS investigations and STEM-EDX mapping verified the distinct functional layers throughout the layer stack. At a given device current density, the current efficiencies of both sub-OLEDs add up to a maximum of 25 cd/A, indicating a properly working tandem OLED.

Modeling of Optical Waveguide Poling and Thermally Stimulated Discharge (TSD) Charge and Current Densities for Guest/Host Electro Optic Polymers

NASA Technical Reports Server (NTRS)

Watson, Michael D.; Ashley, Paul R.; Abushagur, Mustafa

2004-01-01

A charge density and current density model of a waveguide system has been developed to explore the effects of electric field electrode poling. An optical waveguide may be modeled during poling by considering the dielectric charge distribution, polarization charge distribution, and conduction charge generated by the poling field. These charge distributions are the source of poling current densities. The model shows that boundary charge current density and polarization current density are the major source of currents measured during poling and thermally stimulated discharge These charge distributions provide insight into the poling mechanisms and are directly related to E(sub A), and, alpha(sub r). Initial comparisons with experimental data show excellent correlation to the model results.

Peculiarities of electron density distribution in bismuth chalcogenides, iron pnictides, cuprates and related unconventional superconductors

NASA Astrophysics Data System (ADS)

Orlov, V. G.; Sergeev, G. S.

2018-05-01

With the aim to reveal the origin of instabilities in the electron subsystem of unconventional superconductors, such as stripes or nematic symmetry breaking, electron band structure calculations were performed for a number of bismuth chalcogenides, bismuth oxide, iron pnictides, as well as for Bi2Sr2CaCu2O8, YBa2Cu3O7 and La2CuO4. It was found that bond critical points in the electron density distribution ρ(r) of all the studied compounds were characterized by positive sign of electron density Laplacian evidencing on depletion of electron charge from the area of bond critical points. A correlation was found between the Tc and the value of electron density Laplacian in the strongest bond critical points of superconductors and related substances.

Fabrication of TiO2/CuO photoelectrode with enhanced solar water splitting activity

NASA Astrophysics Data System (ADS)

Atabaev, Timur Sh.; Lee, Dae Hun; Hong, Nguyen Hoa

A bilayered TiO2/CuO photoelectrode was fabricated on a fluorine-doped tin oxide FTO substrate by spin-coating and pulsed laser deposition methods. The prepared bilayered system was assessed as a photoelectrode for solar water splitting. The fabricated TiO2/CuO photoelectrode exhibited a higher photocurrent density (0.022mA/cm2 at 1.23V vs. RHE) compared to bare TiO2 photoelectrode (0.013mA/cm2 at 1.23V vs. RHE). This photocurrent density enhancement was attributed to the improved charge separation combined with the improved sunlight harvesting efficiency of a bilayered structure.

DNA@Mn3(PO4)2 Nanoparticles Supported with Graphene Oxide as Photoelectrodes for Photoeletrocatalysis

NASA Astrophysics Data System (ADS)

Gao, Lixia; Xie, Jiale; Ma, Xiaoqing; Li, Man; Yu, Ling

2017-01-01

A novel deoxyribose nucleic acid (DNA)-based photoelectrode consisting of DNA@Mn3(PO4)2 nanoparticles on graphene oxide (GO) sheets was successfully fabricated for photoelectrocatalysis. DNA served as a soft template to guide the nucleation and growth of Mn3(PO4)2 nanoparticles in the synthesis of Mn3(PO4)2 nanoparticles. More importantly, the DNA also serves as semiconductor materials to adjust charge transport. Under UV light irradiation (180-420 nm, 15 mW/cm2), the photocurrent density of DNA@ Mn3(PO4)2/GO electrodes reached 9 μA/cm2 at 0.7 V bias (vs. SCE). An applied bias photon-to-current efficiency (ABPE) of 0.18% can be achieved, which was much higher than that of other control electrodes (<0.04%). In this DNA-based photoelectrode, well-matched energy levels can efficiently improve charge transfer and reduce the recombination of photogenerated electron-hole pairs.

Atomic-layer-deposited Al2O3 and HfO2 on InAlAs: A comparative study of interfacial and electrical characteristics

NASA Astrophysics Data System (ADS)

Wu, Li-Fan; Zhang, Yu-Ming; Lv, Hong-Liang; Zhang, Yi-Men

2016-10-01

Al2O3 and HfO2 thin films are separately deposited on n-type InAlAs epitaxial layers by using atomic layer deposition (ALD). The interfacial properties are revealed by angle-resolved x-ray photoelectron spectroscopy (AR-XPS). It is demonstrated that the Al2O3 layer can reduce interfacial oxidation and trap charge formation. The gate leakage current densities are 1.37 × 10-6 A/cm2 and 3.22 × 10-6 A/cm2 at +1 V for the Al2O3/InAlAs and HfO2/InAlAs MOS capacitors respectively. Compared with the HfO2/InAlAs metal-oxide-semiconductor (MOS) capacitor, the Al2O3/InAlAs MOS capacitor exhibits good electrical properties in reducing gate leakage current, narrowing down the hysteresis loop, shrinking stretch-out of the C-V characteristics, and significantly reducing the oxide trapped charge (Q ot) value and the interface state density (D it). Project supported by the National Basic Research Program of China (Grant No. 2010CB327505), the Advanced Research Foundation of China (Grant No. 914xxx803-051xxx111), the National Defense Advance Research Project, China (Grant No. 513xxxxx306), the National Natural Science Foundation of China (Grant No. 51302215), the Scientific Research Program Funded by Shaanxi Provincial Education Department, China (Grant No. 14JK1656), and the Science and Technology Project of Shaanxi Province, China (Grant No. 2016KRM029).

Vanadium Pentoxide Nanobelt-Reduced Graphene Oxide Nanosheet Composites as High-Performance Pseudocapacitive Electrodes: ac Impedance Spectroscopy Data Modeling and Theoretical Calculations

PubMed Central

Gupta, Sanju; Aberg, Bryce; Carrizosa, Sara B.; Dimakis, Nicholas

2016-01-01

Graphene nanosheets and graphene nanoribbons, G combined with vanadium pentoxide (VO) nanobelts (VNBs) and VNBs forming GVNB composites with varying compositions were synthesized via a one-step low temperature facile hydrothermal decomposition method as high-performance electrochemical pseudocapacitive electrodes. VNBs from vanadium pentoxides (VO) are formed in the presence of graphene oxide (GO), a mild oxidant, which transforms into reduced GO (rGOHT), assisting in enhancing the electronic conductivity coupled with the mechanical robustness of VNBs. From electron microscopy, surface sensitive spectroscopy and other complementary structural characterization, hydrothermally-produced rGO nanosheets/nanoribbons are decorated with and inserted within the VNBs’ layered crystal structure, which further confirmed the enhanced electronic conductivity of VNBs. Following the electrochemical properties of GVNBs being investigated, the specific capacitance Csp is determined from cyclic voltammetry (CV) with a varying scan rate and galvanostatic charging-discharging (V–t) profiles with varying current density. The rGO-rich composite V1G3 (i.e., VO/GO = 1:3) showed superior specific capacitance followed by VO-rich composite V3G1 (VO/GO = 3:1), as compared to V1G1 (VO/GO = 1:1) composite, besides the constituents, i.e., rGO, rGOHT and VNBs. Composites V1G3 and V3G1 also showed excellent cyclic stability and a capacitance retention of >80% after 500 cycles at the highest specific current density. Furthermore, by performing extensive simulations and modeling of electrochemical impedance spectroscopy data, we determined various circuit parameters, including charge transfer and solution resistance, double layer and low frequency capacitance, Warburg impedance and the constant phase element. The detailed analyses provided greater insights into physical-chemical processes occurring at the electrode-electrolyte interface and highlighted the comparative performance of thin heterogeneous composite electrodes. We attribute the superior performance to the open graphene topological network being beneficial to available ion diffusion sites and the faster transport kinetics having a larger accessible geometric surface area and synergistic integration with optimal nanostructured VO loading. Computational simulations via periodic density functional theory (DFT) with and without V2O5 adatoms on graphene sheets are also performed. These calculations determine the total and partial electronic density of state (DOS) in the vicinity of the Fermi level (i.e., higher electroactive sites), in turn complementing the experimental results toward surface/interfacial charge transfer on heterogeneous electrodes. PMID:28773738

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

Schwarz, Kathleen; Xu, Bingjun; Yan, Yushan

The design of better heterogeneous catalysts for applications such as fuel cells and electrolyzers requires a mechanistic understanding of electrocatalytic reactions and the dependence of their activity on operating conditions such as pH. A satisfactory explanation for the unexpected pH dependence of electrochemical properties of platinum surfaces has so far remained elusive, with previous explanations resorting to complex co-adsorption of multiple species and resulting in limited predictive power. This knowledge gap suggests that the fundamental properties of these catalysts are not yet understood, limiting systematic improvement. In this paper, we analyze the change in charge and free energies upon adsorptionmore » using density-functional theory (DFT) to establish that water adsorbs on platinum step edges across a wide voltage range, including the double-layer region, with a loss of approximately 0.2 electrons upon adsorption. We show how this as-yet unreported change in net surface charge due to this water explains the anomalous pH variations of the hydrogen underpotential deposition (H upd) and the potentials of zero total charge (PZTC) observed in published experimental data. This partial oxidation of water is not limited to platinum metal step edges, and we report the charge of the water on metal step edges of commonly used catalytic metals, including copper, silver, iridium, and palladium, illustrating that this partial oxidation of water broadly influences the reactivity of metal electrodes.« less

Excitons in strongly correlated oxide nanocrystals NicMg1-cO

NASA Astrophysics Data System (ADS)

Sokolov, V. I.; Churmanov, V. N.; Pustovarov, V. A.; Gruzdev, N. B.; Uimin, M. A.; Byzov, I. V.; Zatsepin, A. F.; Kuznetsova, J. A.

2018-05-01

This paper reports about excitons in strongly correlated oxide nanocrystals NicMg1-cO (c = 0.008 and c = 1). At 8 K two weak peaks were firstly observed in the optical density spectrum of NiO nanocrystals at the energies of 3.510 eV and 3.543 eV. The intensity of the peaks subsides with an increase of temperature and a decrease of nanoparticle sizes from 25 nm to 10 nm. The peaks were attributed to the formation of p-d charge transfer excitons {d9h}. A tunneling annihilation for {d9h} excitons diminishes their lifetime drastically, even at low temperatures. This fact is considered as an inherent feature in the p-d charge transfer excitons {d9h}, which makes them significantly different from the Wannier-Mott excitons for semiconductors with direct allowed transitions. We believe that energy shift between two peaks originates due to the spin-orbit splitting of the top of the valence band, equals 33 meV. In p-d charge transfer photoluminescence excitation spectrum of NicMg1-cO (c = 0.008), we have revealed two [d9h] exciton lines near the charge transfer band edge. Energy shift of these lines (equals 25 meV) is due to the spin-orbit splitting of MgO valence band top.

O3-type layered transition metal oxide Na(NiCoFeTi) 1/4O 2 as a high rate and long cycle life cathode material for sodium ion batteries

DOE PAGES

Yue, Ji -Li; Yang, Xiao -Qing; Zhou, Yong -Ning; ...

2015-10-09

High rate capability and long cycle life are challenging goals for the development of room temperature sodium-ion batteries. Here we report a new single phase quaternary O3-type layer-structured transition metal oxide Na(NiCoFeTi) 1/4O 2 synthesized by a simple solid-state reaction as a new cathode material for sodium-ion batteries. It can deliver a reversible capacity of 90.6 mA h g –1 at a rate as high as 20C. At 5C, 75.0% of the initial specific capacity can be retained after 400 cycles with a capacity-decay rate of 0.07% per cycle, demonstrating a superior long-term cyclability at high current density. X-ray diffractionmore » and absorption characterization revealed reversible phase transformations and electronic structural changes during the Na + deintercalation/intercalation process. Ni, Co and Fe ions contribute to charge compensation during charge and discharge. Although Ti ions do not contribute to the charge transfer, they play a very important role in stabilizing the structure during charge and discharge by suppressing the Fe migration. Additionally, Ti substitution can also smooth the charge–discharge plateaus effectively, which provides a potential advantage for the commercialization of this material for room temperature sodium-ion batteries.« less

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

Gürel, Hikmet Hakan, E-mail: hhakan.gurel@kocaeli.edu.tr; Salmankurt, Bahadır

Graphene as a 2D material has unique chemical and electronic properties. Because of its unique physical, chemical, and electronic properties, its interesting shape and size make it a promising nanomaterial in many biological applications. However, the lower water-solubility and the irreversible aggregation due to the strong π-π stacking hinder the wide application of graphene nanosheets in biomedical field. Thus, graphene oxide (GO), one derivative of graphene, has been used more frequently in the biological system owing to its relatively higher water solubility and biocompatibility. Recently, it has been demonstrated that nanomaterials with different functional groups on the surface can bemore » used to bind the drug molecules with high affinity. GO has different functional groups such as H, OH and O on its surface; it can be a potential candidate as a drug carrier. The interactions of biomolecules and graphene like structures are long-ranged and very weak. Development of new techniques is very desirable for design of bioelectronics sensors and devices. In this work, we present first-principles spin polarized calculations within density functional theory to calculate effects of charging on DNA/RNA nucleobases on graphene oxide. It is shown that how modify structural and electronic properties of nucleobases on graphene oxide by applied charging.« less

Hierarchically assembled 3D nanoflowers and 0D nanoparticles of nickel sulfides on reduced graphene oxide with excellent lithium storage performances

NASA Astrophysics Data System (ADS)

Tronganh, Nguyen; Gao, Yang; Jiang, Wei; Tao, Haihua; Wang, Shanshan; Zhao, Bing; Jiang, Yong; Chen, Zhiwen; Jiao, Zheng

2018-05-01

Constructing heterostructure can endow composites with many novel physical and electrochemical properties due to the built-in specific charge transfer dynamics. However, controllable fabrication route to heterostructures is still a great challenge up to now. In this work, a SiO2-assisted hydrothermal method is developed to fabricate heterostructured nickel sulfides/reduced graphene oxide (NiSx/rGO) composite. The SiO2 particles hydrolyzed from tetraethyl orthosilicate could assist the surface controllable co-growth of 3D nanoflowers and 0D nanoparticles of Ni3S2/NiS decorated on reduced graphene oxide, and the possible co-growth mechanism is discussed in detail. In this composite, the heterostructured nanocomposite with different morphologies, chemical compositions and crystal structures, along with varied electronic states and band structure, can promote the interface charge transfer kinetics and lead to excellent lithium storage performances. Electrochemical measurements reveal that the NiSx/rGO composite presents 1187.0 mA h g-1 at 100 mA g-1 and achieves a highly stable capacity of 561.2 mA h g-1 even when the current density is up to 5 A g-1.

Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

DOEpatents

Doeff, Marca M.; Peng, Marcus Y.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard C.

1996-01-01

An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

A facile synthesis of high quality nanostructured CeO2 and Gd2O3-doped CeO2 solid electrolytes for improved electrochemical performance.

PubMed

Kuo, Yu-Lin; Su, Yu-Ming; Chou, Hung-Lung

2015-06-07

This study describes the use of a composite nitrate salt solution as a precursor to synthesize CeO2 and Gd2O3-doped CeO2 (GDC) nanoparticles (NPs) using an atmospheric pressure plasma jet (APPJ). The microstructures of CeO2 and GDC NPs were found to be cubical and spherical shaped nanocrystallites with average particle sizes of 10.5 and 6.7 nm, respectively. Reactive oxygen species, detected by optical emission spectroscopy (OES), are believed to be the major oxidative agents for the formation of oxide materials in the APPJ process. Based on the material characterization and OES observations, the study effectively demonstrated the feasibility of preparing well-crystallized GDC NPs by the APPJ system as well as the gas-to-particle mechanism. Notably, the Bader charge of CeO2 and Ce0.9Gd0.1O2 characterized by density function theory (DFT) simulation and AC impedance measurements shows that Gd helps in increasing the charge on Ce0.9Gd0.1O2 NPs, thus improving their conductivity and making them candidate materials for electrolytes in solid oxide fuel cells.

Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

DOEpatents

Doeff, M.M.; Peng, M.Y.; Ma, Y.; Visco, S.J.; DeJonghe, L.C.

1996-09-24

An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M{sub x}Z{sub y}Mn{sub (1{minus}y)}O{sub 2}, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell. 11 figs.

Electrodeposition of Polypyrrole and Reduced Graphene Oxide onto Carbon Bundle Fibre as Electrode for Supercapacitor.

PubMed

Abdul Bashid, Hamra Assyaima; Lim, Hong Ngee; Kamaruzaman, Sazlinda; Abdul Rashid, Suraya; Yunus, Robiah; Huang, Nay Ming; Yin, Chun Yang; Rahman, Mohammad Mahbubur; Altarawneh, Mohammednoor; Jiang, Zhong Tao; Alagarsamy, Pandikumar

2017-12-01

A nanocomposite comprising of polypyrrole and reduced graphene oxide was electrodeposited onto a carbon bundle fibre (CBF) through a two-step approach (CBF/PPy-rGO-2). The CBF/PPy-rGO-2 had a highly porous structure compared to a nanocomposite of polypyrrole and reduced graphene oxide that was electrodeposited onto a CBF in a one-step approach (CBF/PPy-rGO), as observed through a field emission scanning electron microscope. An X-ray photoelectron spectroscopic analysis revealed the presence of hydrogen bond between the oxide functional groups of rGO and the amine groups of PPy in PPy-rGO-2 nanocomposite. The fabricated CBF/PPy-rGO-2 nanocomposite material was used as an electrode material in a symmetrical solid-state supercapacitor, and the device yielded a specific capacitance, energy density and power density of 96.16 F g - 1 , 13.35 Wh kg - 1 and of 322.85 W kg - 1 , respectively. Moreover, the CBF/PPy-rGO-2 showed the capacitance retention of 71% after 500 consecutive charge/discharge cycles at a current density of 1 A g - 1 . The existence of a high degree of porosity in CBF/PPy-rGO-2 significantly improved the conductivity and facilitated the ionic penetration. The CBF/PPy-rGO-2-based symmetrical solid-state supercapacitor device demonstrated outstanding pliability because the cyclic voltammetric curves remained the same upon bending at various angles. Carbon bundle fibre modified with porous polypyrrole/reduced graphene oxide nanocomposite for flexible miniature solid-state supercapacitor.

Synergic mechanism of adsorption and metal-free catalysis for phenol degradation by N-doped graphene aerogel.

PubMed

Ren, Xiaohua; Guo, Huanhuan; Feng, Jinkui; Si, Pengchao; Zhang, Lin; Ci, Lijie

2018-01-01

3D porous N-doped reduced graphene oxide (N-rGO) aerogels were synthesized by a hydrothermal reduction of graphene oxide (GO) with urea and following freeze-drying process. N-rGO aerogels have a high BET surface of 499.70 m 2 /g and a high N doping content (5.93-7.46 at%) including three kinds of N (graphitic, pyridinic and pyrrolic). Their high catalytic performance for phenol oxidation in aqueous solution was investigated by catalytic activation of persulfate (PS). We have demonstrated that N-rGO aerogels are promising metal-free catalysts for phenol removal. Kinetics studies indicate that phenol degradation follows first-order reaction kinetics with the reaction rate constant of 0.16799 min -1 for N-rGO-A(1:30). Interestingly, the comparison of direct catalytic oxidation with adsorption-catalytic oxidation experiments indicates that adsorption plays an important role in the catalytic oxidation of phenol by decreasing the phenol degradation time. Spin density and adsorption modeling demonstrates that graphitic N in N-rGO plays the most important role for the catalytic performance by inducing high positive charge densities to adjacent carbon atoms and facilitating phenol adsorption on these carbon sites. Furthermore, the activation mechanism of persulfate (PS) on N-rGO was first investigated by DFT method and PS can be activated to generate strongly oxidative radical (SO 4 · - ) by transferring electrons to N-rGO. Copyright © 2017 Elsevier Ltd. All rights reserved.

Spin transport in oxygen adsorbed graphene nanoribbon

NASA Astrophysics Data System (ADS)

Kumar, Vipin

2018-04-01

The spin transport properties of pristine graphene nanoribbons (GNRs) have been most widely studied using theoretical and experimental tools. The possibilities of oxidation of fabricated graphene based nano electronic devices may change the device characteristics, which motivates to further explore the properties of graphene oxide nanoribbons (GONRs). Therefore, we present a systematic computational study on the spin polarized transport in surface oxidized GNR in antiferromagnetic (AFM) spin configuration using density functional theory combined with non-equilibrium Green's function (NEGF) method. It is found that the conductance in oxidized GNRs is significantly suppressed in the valance band and the conduction band. A further reduction in the conductance profile is seen in presence of two oxygen atoms on the ribbon plane. This change in the conductance may be attributed to change in the surface topology of the ribbon basal plane due to presence of the oxygen adatoms, where the charge transfer take place between the ribbon basal plane and the oxygen atoms.

A nanoporous metal recuperated MnO2 anode for lithium ion batteries.

PubMed

Guo, Xianwei; Han, Jiuhui; Zhang, Ling; Liu, Pan; Hirata, Akihiko; Chen, Luyang; Fujita, Takeshi; Chen, Mingwei

2015-10-07

Lithium-ion batteries (LIBs) have been intensively studied to meet the increased demands for the high energy density of portable electronics and electric vehicles. The low specific capacity of the conventional graphite based anodes is one of the key factors that limit the capacity of LIBs. Transition metal oxides, such as NiO, MnO2 and Fe3O4, are known to be promising anode materials that are expected to improve the specific capacities of LIBs for several times. However, the poor electrical conductivity of these oxides significantly restricts the lithium ion storage and charge/discharge rate. Here we report that dealloyed nanoporous metals can realize the intrinsic lithium storage performance of the oxides by forming oxide/metal composites. Without any organic binder, conductive additive and additional current collector, the hybrid electrodes can be directly used as anodes and show highly reversible specific capacity with high-rate capability and long cyclic stability.

Streaming potential method for characterizing interaction of electrical double layers between rice roots and Fe/Al oxide-coated quartz in situ.

PubMed

Liu, Zhao-Dong; Wang, Hai-Cui; Li, Jiu-Yu; Xu, Ren-Kou

2017-10-01

The interaction between rice roots and Fe/Al oxide-coated quartz was investigated through zeta potential measurements and column leaching experiments in present study. The zeta potentials of rice roots, Fe/Al oxide-coated quartz, and the binary systems containing rice roots and Fe/Al oxide-coated quartz were measured by a specially constructed streaming potential apparatus. The interactions between rice roots and Fe/Al oxide-coated quartz particles were evaluated/deduced based on the differences of zeta potentials between the binary systems and the single system of rice roots. The zeta potentials of the binary systems moved in positive directions compared with that of rice roots, suggesting that there were overlapping of diffuse layers of electric double layers on positively charged Fe/Al oxide-coated quartz and negatively charged rice roots and neutralization of positive charge on Fe/Al oxide-coated quartz with negative charge on rice roots. The greater amount of positive charges on Al oxide led to the stronger interaction of Al oxide-coated quartz with rice roots and the more shift of zeta potential compared with Fe oxide. The overlapping of diffuse layers on Fe/Al oxide-coated quartz and rice roots was confirmed by column leaching experiments. The greater overlapping of diffuse layers on Al oxide and rice roots led to more simultaneous adsorptions of K + and NO 3 - and greater reduction in leachate electric conductivity when the column containing Al oxide-coated quartz and rice roots was leached with KNO 3 solution, compared with the columns containing rice roots and Fe oxide-coated quartz or quartz. When the KNO 3 solution was replaced with deionized water to flush the columns, more K + and NO 3 - were desorbed from the binary system containing Al oxide-coated quartz and rice roots than from other two binary systems, suggesting that the stronger electrostatic interaction between Al oxide and rice roots promoted the desorption of K + and NO 3 - from the binary system and enhanced overlapping of diffuse layers on these oppositely charged surfaces compared with other two binary systems. In conclusion, the overlapping of diffuse layers occurred between positively charged Fe/Al oxides and rice roots, which led to neutralization of opposite charge and affected adsorption and desorption of ions onto and from the charged surfaces of Fe/Al oxides and rice roots.

Hexagonal CeO2 nanostructures: an efficient electrode material for supercapacitors.

PubMed

Maheswari, Nallappan; Muralidharan, Gopalan

2016-09-28

Cerium oxide (CeO2) has emerged as a new and promising pseudocapacitive material due to its prominent valance states and extensive applications in various fields. In the present study, hexagonal CeO2 nanostructures have been prepared via the hydrothermal method employing cationic surfactant cetyl trimethyl ammonium bromide (CTAB). CTAB ensures a slow rate of hydrolysis to form small sized CeO2 nanostructures. The role of calcination temperature on the morphological, structural, electrochemical properties and cyclic stability has been assessed for supercapacitor applications. The mesoscopic hexagonal architecture endows the CeO2 with not only a higher specific capacity, but also with an excellent rate capability and cyclability. When the charge/discharge current density is increased from 2 to 10 A g(-1) the reversible charge capacity decreased from 927 F g(-1) to 475 F g(-1) while 100% capacity retention at a high current density of 20 A g(-1) even after 1500 cycles could be achieved. Furthermore, the asymmetric supercapacitor based on CeO2 exhibited a significantly higher energy density of 45.6 W h kg(-1) at a power density of 187.5 W kg(-1) with good cyclic stability. The electrochemical richness of the CeO2 nanostructure makes it a suitable electrode material for supercapacitor applications.

Investigation on porous MnO microsphere anode for lithium ion batteries

NASA Astrophysics Data System (ADS)

Zhong, Kaifu; Zhang, Bin; Luo, Shihai; Wen, Wen; Li, Hong; Huang, Xuejie; Chen, Liquan

MnO microspheres with and without carbon coating are prepared as anode materials for lithium ion batteries. The MnO microsphere material shows a reversible capacity of 800 mAh g -1 and an initial efficiency of 71%. It can deliver 600 mAh g -1 at a rate of 400 mA g -1. Results of Mn K-edge X-ray absorption near-edge structure (XANES) spectra and extended X-ray absorption fine structure (EXAFS) confirm further the conversion reaction mechanism, indicate that pristine MnO is reduced to Mn 0 after discharging to 0 V and part of reduced Mn 0 is not oxidized to Mn 2+ after charging to 3 V. This explains the origin of the initial irreversible capacity loss partially. The quasi open circuit voltage and the relationship between the current density and the overpotential are investigated. Both indicate that there is a significant voltage difference between the charging and discharging profiles even when the current density decreases to zero.

A model study of tunneling conductance spectra of ferromagnetically ordered manganites

NASA Astrophysics Data System (ADS)

Panda, Saswati; Kar, J. K.; Rout, G. C.

2018-02-01

We report here the interplay of ferromagnetism (FM) and charge density wave (CDW) in manganese oxide systems through the study of tunneling conductance spectra. The model Hamiltonian consists of strong Heisenberg coupling in core t2g band electrons within mean-field approximation giving rise to ferromagnetism. Ferromagnetism is induced in the itinerant eg electrons due to Kubo-Ohata type double exchange (DE) interaction among the t2g and eg electrons. The charge ordering (CO) present in the eg band giving rise to CDW interaction is considered as the extra-mechanism to explain the colossal magnetoresistance (CMR) property of manganites. The magnetic and CDW order parameters are calculated using Zubarev's Green's function technique and solved self-consistently and numerically. The eg electron density of states (DOS) calculated from the imaginary part of the Green's function explains the experimentally observed tunneling conductance spectra. The DOS graph exhibits a parabolic gap near the Fermi energy as observed in tunneling conductance spectra experiments.

Extraction of sub-gap density of states via capacitance-voltage measurement for the erasing process in a TFT charge-trapping memory

NASA Astrophysics Data System (ADS)

Chiang, Yen-Chang; Hsiao, Yang-Hsuan; Li, Jeng-Ting; Chen, Jen-Sue

2018-02-01

Charge-trapping memories (CTMs) based on zinc tin oxide (ZTO) semiconductor thin-film transistors (TFTs) can be programmed by a positive gate voltage and erased by a negative gate voltage in conjunction with light illumination. To understand the mechanism involved, the sub-gap density of states associated with ionized oxygen vacancies in the ZTO active layer is extracted from optical response capacitance-voltage (C-V) measurements. The corresponding energy states of ionized oxygen vacancies are observed below the conduction band minimum at approximately 0.5-1.0 eV. From a comparison of the fitted oxygen vacancy concentration in the CTM-TFT after the light-bias erasing operation, it is found that the pristine-erased device contains more oxygen vacancies than the program-erased device because the trapped electrons in the programmed device are pulled into the active layer and neutralized by the oxygen vacancies that are present there.

First principle investigation of electronic structure, chemical bonding and optical properties of tetrabarium gallium trinitride oxide single crystal

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

Khan, Saleem Ayaz, E-mail: sayaz_usb@yahoo.com; Azam, Sikander

The electronic band structure, valence electron charge density and optical susceptibilities of tetrabarium gallium trinitride (TGT) were calculated via first principle study. The electronic band structure calculation describes TGT as semiconductor having direct band gap of 1.38 eV. The valence electronic charge density contour verified the non-polar covalent nature of the bond. The absorption edge and first peak of dielectric tensor components showed electrons transition from N-p state to Ba-d state. The calculated uniaxial anisotropy (0.4842) and birefringence (−0.0061) of present paper is prearranged as follow the spectral components of the dielectric tensor. The first peak in energy loss functionmore » (ELOS) shows the energy loss of fast traveling electrons in the material. The first sharp peak produced in ELOS around 10.5 eV show plasmon loss having plasma frequencies 0.1536, 0.004 and 0.066 of dielectric tensor components. This plasmon loss also cause decrease in reflectivity spectra.« less

Non-classical behaviour of higher valence dopants in chromium (III) oxide by a Cr vacancy compensation mechanism

NASA Astrophysics Data System (ADS)

Carey, John J.; Nolan, Michael

2017-10-01

Modification of metal oxides with dopants that have a stable oxidation in their parent oxides which is higher than the host system is expected to introduce extra electrons into the material to improve carrier mobility. This is essential for applications in catalysis, SOFCs and solar energy materials. Density functional theory calculations are used to investigate the change in electronic and geometric structure of chromium (III) oxide by higher valence dopants, namely; Ce, Ti, V and Zr. For single metal doping, we find that the dopants with variable oxidation states, Ce, Ti and V, adopt a valence state of  +3, while Zr dopant has a  +4 oxidation state and reduces a neighbouring Cr cation. Chromium vacancy formation is greatly enhanced for all dopants, and favoured over oxygen vacancy formation. The Cr vacancies generate holes which oxidise Ce, Ti and V from  +3 to  +4, while also oxidising lattice oxygen sites. For Zr doping, the generated holes oxidise the reduced Cr2+ cation back to Cr3+ and also two lattice oxygen atoms. Three metal atoms in the bulk lattice facilitate spontaneous Cr vacancy from charge compensation. A non-classical compensation mechanism is observed for Ce, Ti and V; all three metals are oxidised from  +3 to  +4, which explains experimental observations that these metals have a  +4 oxidation state in Cr2O3. Charge compensation of the three Zr metals proceeds by a classical higher valence doping mechanism; the three dopants reduce three Cr cations, which are subsequently charge compensated by a Cr vacancy oxidising three Cr2+ to Cr3+. The compensated structures are the correct ground state electronic structure for these doped systems, and used as a platform to investigate cation/anion vacancy formation. Unlike the single metal doped bulks, preference is now given for oxygen vacancy formation over Cr vacancy formation, indicating that the dopants increase the reducibility of Cr2O3 with Ce doping showing the strongest enhancement. The importance of the correct ground state in determining the formation of defects is emphasised.

Effect of native oxide layers on copper thin-film tensile properties: A reactive molecular dynamics study

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

Skarlinski, Michael D., E-mail: michael.skarlinski@rochester.edu; Quesnel, David J.; Department of Mechanical Engineering, University of Rochester, Rochester, New York 14627

2015-12-21

Metal-oxide layers are likely to be present on metallic nano-structures due to either environmental exposure during use, or high temperature processing techniques such as annealing. It is well known that nano-structured metals have vastly different mechanical properties from bulk metals; however, difficulties in modeling the transition between metallic and ionic bonding have prevented the computational investigation of the effects of oxide surface layers. Newly developed charge-optimized many body [Liang et al., Mater. Sci. Eng., R 74, 255 (2013)] potentials are used to perform fully reactive molecular dynamics simulations which elucidate the effects that metal-oxide layers have on the mechanical propertiesmore » of a copper thin-film. Simulated tensile tests are performed on thin-films while using different strain-rates, temperatures, and oxide thicknesses to evaluate changes in yield stress, modulus, and failure mechanisms. Findings indicate that copper-thin film mechanical properties are strongly affected by native oxide layers. The formed oxide layers have an amorphous structure with lower Cu-O bond-densities than bulk CuO, and a mixture of Cu{sub 2}O and CuO charge character. It is found that oxidation will cause modifications to the strain response of the elastic modulii, producing a stiffened modulii at low temperatures (<75 K) and low strain values (<5%), and a softened modulii at higher temperatures. While under strain, structural reorganization within the oxide layers facilitates brittle yielding through nucleation of defects across the oxide/metal interface. The oxide-free copper thin-film yielding mechanism is found to be a tensile-axis reorientation and grain creation. The oxide layers change the observed yielding mechanism, allowing for the inner copper thin-film to sustain an FCC-to-BCC transition during yielding. The mechanical properties are fit to a thermodynamic model based on classical nucleation theory. The fit implies that the oxidation of the films reduces the activation volume for yielding.« less

Oxidation-labile subfraction of human plasma low density lipoprotein isolated by ion-exchange chromatography.

PubMed

Shimano, H; Yamada, N; Ishibashi, S; Mokuno, H; Mori, N; Gotoda, T; Harada, K; Akanuma, Y; Murase, T; Yazaki, Y

1991-05-01

We isolated subfractions of human plasma low density lipoprotein (LDL) using ion-exchange chromatography. Plasma LDL from normolipidemic subjects were applied to a DEAE Sepharose 6B column. After elution of the bulk of LDL at 150 mM NaCl (the major fraction), the residual LDL was eluted at 500 mM NaCl and designated as the minor fraction. The minor fraction, only less than 1% of total LDL, tended to be somewhat similar in certain properties to oxidized LDL, e.g., an increased negative charge, higher protein/cholesterol ratio, and a higher flotation density than native LDL. These results were consistent with data reported by Avogaro et al. (1988. Arteriosclerosis. 8: 79-87). However, assays of 125I-labeled LDL binding activity for LDL receptors equal to that of the major fraction. Incorporation of [14C]oleate into cholesteryl ester [acyl-CoA:cholesterol acyltransferase (ACAT) activity] in mouse peritoneal macrophages incubated with the minor fraction was only slightly greater than that with the major fraction. Incubation of the minor fraction with 0.5 microM Cu2+ caused a remarkable stimulation of ACAT activity, while stimulation by the major fraction required incubation with 5 microM Cu2+, suggesting that the minor fraction was relatively labile to oxidation. The minor but definite presence of a plasma LDL subfraction more negative and susceptible to oxidation implicates the possibility of its association with atherogenesis.

Work Function of Oxide Ultrathin Films on the Ag(100) Surface.

PubMed

Sementa, Luca; Barcaro, Giovanni; Negreiros, Fabio R; Thomas, Iorwerth O; Netzer, Falko P; Ferrari, Anna Maria; Fortunelli, Alessandro

2012-02-14

Theoretical calculations of the work function of monolayer (ML) and bilayer (BL) oxide films on the Ag(100) surface are reported and analyzed as a function of the nature of the oxide for first-row transition metals. The contributions due to charge compression, charge transfer and rumpling are singled out. It is found that the presence of empty d-orbitals in the oxide metal can entail a charge flow from the Ag(100) surface to the oxide film which counteracts the decrease in the work function due to charge compression. This flow can also depend on the thickness of the film and be reduced in passing from ML to BL systems. A regular trend is observed along first-row transition metals, exhibiting a maximum for CuO, in which the charge flow to the oxide is so strong as to reverse the direction of rumpling. A simple protocol to estimate separately the contribution due to charge compression is discussed, and the difference between the work function of the bare metal surface and a Pauling-like electronegativity of the free oxide slabs is used as a descriptor quantity to predict the direction of charge transfer.

Instability analysis of charges trapped in the oxide of metal-ultra thin oxide-semiconductor structures

NASA Astrophysics Data System (ADS)

Aziz, A.; Kassmi, K.; Maimouni, R.; Olivié, F.; Sarrabayrouse, G.; Martinez, A.

2005-09-01

In this paper, we present the theoretical and experimental results of the influence of a charge trapped in ultra-thin oxide of metal/ultra-thin oxide/semiconductor structures (MOS) on the I(Vg) current-voltage characteristics when the conduction is of the Fowler-Nordheim (FN) tunneling type. The charge, which is negative, is trapped near the cathode (metal/oxide interface) after constant current injection by the metal (Vg<0). Of particular interest is the influence on the Δ Vg(Vg) shift over the whole I(Vg) characteristic at high field (greater than the injection field (>12.5 MV/cm)). It is shown that the charge centroid varies linearly with respect to the voltage Vg. The behavior at low field (<12.5 MV/cm) is analyzed in référence A. Aziz, K. Kassmi, Ka. Kassmi, F. Olivié, Semicond. Sci. Technol. 19, 877 (2004) and considers that the trapped charge centroid is fixed. The results obtained make it possible to analyze the influence of the injected charge and the applied field on the centroid position of the trapped charge, and to highlight the charge instability in the ultra-thin oxide of MOS structures.

Current-voltage characteristics influenced by the nanochannel diameter and surface charge density in a fluidic field-effect-transistor.

PubMed

Singh, Kunwar Pal; Guo, Chunlei

2017-06-21

The nanochannel diameter and surface charge density have a significant impact on current-voltage characteristics in a nanofluidic transistor. We have simulated the effect of the channel diameter and surface charge density on current-voltage characteristics of a fluidic nanochannel with positive surface charge on its walls and a gate electrode on its surface. Anion depletion/enrichment leads to a decrease/increase in ion current with gate potential. The ion current tends to increase linearly with gate potential for narrow channels at high surface charge densities and narrow channels are more effective to control the ion current at high surface charge densities. The current-voltage characteristics are highly nonlinear for wide channels at low surface charge densities and they show different regions of current change with gate potential. The ion current decreases with gate potential after attaining a peak value for wide channels at low values of surface charge densities. At low surface charge densities, the ion current can be controlled by a narrow range of gate potentials for wide channels. The current change with source drain voltage shows ohmic, limiting and overlimiting regions.

Controlling the formation of rodlike V2O5 nanocrystals on reduced graphene oxide for high-performance supercapacitors.

PubMed

Li, Meili; Sun, Guoying; Yin, Pingping; Ruan, Changping; Ai, Kelong

2013-11-13

Vanadium pentoxide (V2O5) has attracted much attention for energy storage application because of its high Faradaic activity and stable crystal structure, which make it a promising electrode material for supercapacitors. However, the low electronic conductivity and small lithium-ion diffusion coefficient of V2O5 limit its practical applications. To overcome these limitations, a facile and efficient method is here demonstrated for the fabrication of V2O5/reduced graphene oxide (rGO) nanocomposites as electrode materials for supercapacitors. With this method, the reduction of graphene oxide can be achieved in a cost-effective and environmentally friendly solvent, without the addition of any other toxic reducing agent. Importantly, this solvent can control the formation of the uniform rodlike V2O5 nanocrystals on the surface of rGO. Compared to pure V2O5 microspheres, the V2O5/rGO nanocomposites exhibited a higher specific capacitance of 537 F g(-1) at a current density of 1 A g(-1) in neutral aqueous electrolytes, a higher energy density of 74.58 Wh kg(-1) at a power density of 500 W kg(-1), and better stability even after 1000 charge/discharge cycles. Their excellent performances can be attributed to the synergistic effect of rGO and rodlike V2O5 nanocrystals. Such impressive results may promote new opportunities for these electrode materials in high-energy-density storage systems.

Low-temperature direct synthesis of mesoporous vanadium nitrides for electrochemical capacitors

NASA Astrophysics Data System (ADS)

Lee, Hae-Min; Jeong, Gyoung Hwa; Kim, Sang-Wook; Kim, Chang-Koo

2017-04-01

Mesoporous vanadium nitrides are directly synthesized by a one-step chemical precipitation method at a low temperature (70 °C). Structural and morphological analyses reveal that vanadium nitride consist of long and slender nanowhiskers, and mesopores with diameters of 2-5 nm. Compositional analysis confirms the presence of vanadium in the VN structure, along with oxidized vanadium. The cyclic voltammetry and charge-discharge tests indicate that the obtained material stores charges via a combination of electric double-layer capacitance and pseudocapacitance mechanisms. The vanadium nitride electrode exhibits a specific capacitance of 598 F/g at a current density of 4 A/g. After 5000 charge-discharge cycles, the electrode has an equivalent series resistance of 1.42 Ω and retains 83% of its initial specific capacitance. This direct low-temperature synthesis of mesoporous vanadium nitrides is a simple and promising method to achieve high specific capacitance and low equivalent series resistance for electrochemical capacitor applications.

Cellulose Nanofibers from Softwood, Hardwood, and Tunicate: Preparation-Structure-Film Performance Interrelation.

PubMed

Zhao, Yadong; Moser, Carl; Lindström, Mikael E; Henriksson, Gunnar; Li, Jiebing

2017-04-19

This work reveals the structural variations of cellulose nanofibers (CNF) prepared from different cellulose sources, including softwood (Picea abies), hardwood (Eucalyptus grandis × E. urophylla), and tunicate (Ciona intestinalis), using different preparation processes and their correlations to the formation and performance of the films prepared from the CNF. Here, the CNF are prepared from wood chemical pulps and tunicate isolated cellulose by an identical homogenization treatment subsequent to either an enzymatic hydrolysis or a 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-mediated oxidation. They show a large structural diversity in terms of chemical, morphological, and crystalline structure. Among others, the tunicate CNF consist of purer cellulose and have a degree of polymerization higher than that of wood CNF. Introduction of surface charges via the TEMPO-mediated oxidation is found to have significant impacts on the structure, morphology, optical, mechanical, thermal, and hydrophobic properties of the prepared films. For example, the film density is closely related to the charge density of the used CNF, and the tensile stress of the films is correlated to the crystallinity index of the CNF. In turn, the CNF structure is determined by the cellulose sources and the preparation processes. This study provides useful information and knowledge for understanding the importance of the raw material for the quality of CNF for various types of applications.

Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction

NASA Astrophysics Data System (ADS)

Yang, Yang; Xu, Di; Wu, Qingyong; Diao, Peng

2016-10-01

Solar powered hydrogen evolution reaction (HER) is one of the key reactions in solar-to-chemical energy conversion. It is desirable to develop photocathodic materials that exhibit high activity toward photoelectrochemical (PEC) HER at more positive potentials because a higher potential means a lower overpotential for HER. In this work, the Cu2O/CuO bilayered composites were prepared by a facile method that involved an electrodeposition and a subsequent thermal oxidation. The resulting Cu2O/CuO bilayered composites exhibited a surprisingly high activity and good stability toward PEC HER, expecially at high potentials in alkaline solution. The photocurrent density for HER was 3.15 mA·cm-2 at the potential of 0.40 V vs. RHE, which was one of the two highest reported at the same potential on copper-oxide-based photocathode. The high photoactivity of the bilayered composite was ascribed to the following three advantages of the Cu2O/CuO heterojunction: (1) the broadened light absorption band that made more efficient use of solar energy, (2) the large space-charge-region potential that enabled a high efficiency for electron-hole separation, and (3) the high majority carrier density that ensured a faster charge transportation rate. This work reveals the potential of the Cu2O/CuO bilayered composite as a promising photocathodic material for solar water splitting.

Red Phosphorus Nanodots on Reduced Graphene Oxide as a Flexible and Ultra-Fast Anode for Sodium-Ion Batteries.

PubMed

Liu, Yihang; Zhang, Anyi; Shen, Chenfei; Liu, Qingzhou; Cao, Xuan; Ma, Yuqiang; Chen, Liang; Lau, Christian; Chen, Tian-Chi; Wei, Fei; Zhou, Chongwu

2017-06-27

Sodium-ion batteries offer an attractive option for potential low cost and large scale energy storage due to the earth abundance of sodium. Red phosphorus is considered as a high capacity anode for sodium-ion batteries with a theoretical capacity of 2596 mAh/g. However, similar to silicon in lithium-ion batteries, several limitations, such as large volume expansion upon sodiation/desodiation and low electronic conductance, have severely limited the performance of red phosphorus anodes. In order to address the above challenges, we have developed a method to deposit red phosphorus nanodots densely and uniformly onto reduced graphene oxide sheets (P@RGO) to minimize the sodium ion diffusion length and the sodiation/desodiation stresses, and the RGO network also serves as electron pathway and creates free space to accommodate the volume variation of phosphorus particles. The resulted P@RGO flexible anode achieved 1165.4, 510.6, and 135.3 mAh/g specific charge capacity at 159.4, 31878.9, and 47818.3 mA/g charge/discharge current density in rate capability test, and a 914 mAh/g capacity after 300 deep cycles in cycling stability test at 1593.9 mA/g current density, which marks a significant performance improvement for red phosphorus anodes for sodium-ion chemistry and flexible power sources for wearable electronics.

Another Strategy, Detouring Potential Decay by Fast Completion of Cation Mixing

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

Liu, Shuai; Feng, Xin; Wang, Xuelong

The Li-rich layer-structured oxides are regarded one of the most promising candidates of cathode materials for high energy-density Li-ion batteries. However, the uninterrupted migration of the transition metal (TM) ions during cycling and the resultant continuous fading of their discharge potentials bring challenges to the battery design and impede their commercial applications. Various efforts have been taken to suppress the migration of the TM ions such as surface modification and elemental substitution, but no success has been achieved to date. Another strategy hereby is proposed to address these issues, in which the TM migration is promoted and the layered materialmore » is transformed to a rocksalt in the first few charge/discharge cycles by specially designing a novel Li-rich layer-structured Li 1.2Mo 0.6Fe 0.2O 2 on the basis of density functional theory calculations. With such, the continuous falling of the discharge potential is detoured due to enhanced completion of the cation mixing. In-depth studies such as aberration-corrected scanning transmission electron microscopy confirm the drastic structural change at the atomic scale, and in situ X-ray absorption spectroscopy and Mössbauer spectroscopy clarify its charge compensation mechanism. In conclusion, this new strategy provides revelation for the development of the Li-rich layered oxides with mitigated potential decay and a longer lifespan.« less

Another Strategy, Detouring Potential Decay by Fast Completion of Cation Mixing

DOE PAGES

Liu, Shuai; Feng, Xin; Wang, Xuelong; ...

2018-02-12

The Li-rich layer-structured oxides are regarded one of the most promising candidates of cathode materials for high energy-density Li-ion batteries. However, the uninterrupted migration of the transition metal (TM) ions during cycling and the resultant continuous fading of their discharge potentials bring challenges to the battery design and impede their commercial applications. Various efforts have been taken to suppress the migration of the TM ions such as surface modification and elemental substitution, but no success has been achieved to date. Another strategy hereby is proposed to address these issues, in which the TM migration is promoted and the layered materialmore » is transformed to a rocksalt in the first few charge/discharge cycles by specially designing a novel Li-rich layer-structured Li 1.2Mo 0.6Fe 0.2O 2 on the basis of density functional theory calculations. With such, the continuous falling of the discharge potential is detoured due to enhanced completion of the cation mixing. In-depth studies such as aberration-corrected scanning transmission electron microscopy confirm the drastic structural change at the atomic scale, and in situ X-ray absorption spectroscopy and Mössbauer spectroscopy clarify its charge compensation mechanism. In conclusion, this new strategy provides revelation for the development of the Li-rich layered oxides with mitigated potential decay and a longer lifespan.« less

Wall-like hierarchical metal oxide nanosheet arrays grown on carbon cloth for excellent supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Huang, Zongyu; Zhang, Zhen; Qi, Xiang; Ren, Xiaohui; Xu, Guanghua; Wan, Pengbo; Sun, Xiaoming; Zhang, Han

2016-07-01

Recently, considerable efforts have been made to satisfy the future requirements of electrochemical energy storage using novel functional electrode materials. Binary transition metal oxides (BTMOs) possess multiple oxidation states that enable multiple redox reactions, showing higher supercapacitive properties than single component metal oxides. In this work, a facile hydrothermal method is provided for the synthesis of wall-like hierarchical metal oxide MMoO4 (M = Ni, Co) nanosheet arrays, which are directly grown on flexible carbon cloth for use as advanced binder-free electrodes for supercapacitors. By virtue of their intriguing structure, the resulted active material nanosheets with a high specific surface area can provide a large electroactive region, which could facilitate easy accession of electrolyte ions and fast charge transport, resulting in an enhanced electrochemical performance. Separately, the as-synthesized MMoO4 (M = Ni, Co) samples have exhibited superior specific capacitances (1483 F g-1 of NiMoO4 and 452 F g-1 of CoMoO4 at a current density of 2 A g-1), as well as excellent cycling stability (93.1% capacitance retention of NiMoO4 and 95.9% capacitance retention of CoMoO4 after 2000 cycles). The results show that the binder-free electrodes constructed by deposition of MMoO4 (M = Ni, Co) nanosheets on carbon cloth are promising candidates for the application of supercapacitors.Recently, considerable efforts have been made to satisfy the future requirements of electrochemical energy storage using novel functional electrode materials. Binary transition metal oxides (BTMOs) possess multiple oxidation states that enable multiple redox reactions, showing higher supercapacitive properties than single component metal oxides. In this work, a facile hydrothermal method is provided for the synthesis of wall-like hierarchical metal oxide MMoO4 (M = Ni, Co) nanosheet arrays, which are directly grown on flexible carbon cloth for use as advanced binder-free electrodes for supercapacitors. By virtue of their intriguing structure, the resulted active material nanosheets with a high specific surface area can provide a large electroactive region, which could facilitate easy accession of electrolyte ions and fast charge transport, resulting in an enhanced electrochemical performance. Separately, the as-synthesized MMoO4 (M = Ni, Co) samples have exhibited superior specific capacitances (1483 F g-1 of NiMoO4 and 452 F g-1 of CoMoO4 at a current density of 2 A g-1), as well as excellent cycling stability (93.1% capacitance retention of NiMoO4 and 95.9% capacitance retention of CoMoO4 after 2000 cycles). The results show that the binder-free electrodes constructed by deposition of MMoO4 (M = Ni, Co) nanosheets on carbon cloth are promising candidates for the application of supercapacitors. Electronic supplementary information (ESI) available: XRD pattern and charge-discharge plots. See DOI: 10.1039/c6nr04020a

Nano Copper Oxide-Modified Carbon Cloth as Cathode for a Two-Chamber Microbial Fuel Cell

PubMed Central

Dong, Feng; Zhang, Peng; Li, Kexun; Liu, Xianhua; Zhang, Pingping

2016-01-01

In this work, Cu2O nanoparticles were deposited on a carbon cloth cathode using a facile electrochemical method. The morphology of the modified cathode, which was characterized by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) tests, showed that the porosity and specific surface area of the cathode improved with longer deposition times. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) results showed that cupric oxide and cuprous oxide coexisted on the carbon cloth, which improved the electrochemical activity of cathode. The cathode with a deposition time of 100 s showed the best performance, with a power density twice that of bare carbon cloth. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) results revealed that moderate deposition of nano copper oxide on carbon cloth could dramatically reduce the charge transfer resistance, which contributed to the enhanced electrochemical performance. The mediation mechanism of copper oxide nanocatalyst was illustrated by the fact that the recycled conversion between cupric oxide and cuprous oxide accelerated the electron transfer efficiency on the cathode. PMID:28335366

Nano Copper Oxide-Modified Carbon Cloth as Cathode for a Two-Chamber Microbial Fuel Cell.

PubMed

Dong, Feng; Zhang, Peng; Li, Kexun; Liu, Xianhua; Zhang, Pingping

2016-12-09

In this work, Cu₂O nanoparticles were deposited on a carbon cloth cathode using a facile electrochemical method. The morphology of the modified cathode, which was characterized by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) tests, showed that the porosity and specific surface area of the cathode improved with longer deposition times. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) results showed that cupric oxide and cuprous oxide coexisted on the carbon cloth, which improved the electrochemical activity of cathode. The cathode with a deposition time of 100 s showed the best performance, with a power density twice that of bare carbon cloth. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) results revealed that moderate deposition of nano copper oxide on carbon cloth could dramatically reduce the charge transfer resistance, which contributed to the enhanced electrochemical performance. The mediation mechanism of copper oxide nanocatalyst was illustrated by the fact that the recycled conversion between cupric oxide and cuprous oxide accelerated the electron transfer efficiency on the cathode.

Spontaneous symmetry breaking and electronic and dielectric properties in commensurate La7 /4Sr1 /4CuO4 and La5 /3Sr1 /3NiO4

NASA Astrophysics Data System (ADS)

Petersen, J.; Bechstedt, F.; Furthmüller, J.; Scolfaro, L. M.

2018-05-01

Complex ordered phases involving spin and charge degrees of freedom in condensed matter, such as layered cuprates and nickelates, are exciting but not well understood solid-state phenomena. The rich underlying physics of the overdoped high-temperature superconductor L a7 /4S r1 /4Cu O4 and colossal dielectric constant insulator L a5 /3S r1 /3Ni O4 is studied from first principles within density functional (perturbation) theory, including an effective Hubbard potential U for the exchange and correlation of d orbitals. Charge density wave (CDW) and spin density wave (SDW) orders are found in both materials, where the stripes are commensurate with the lattice. The SDWs are accompanied by complex antiferromagnetic spin arrangements along the stripes. The first series of conduction bands related to the pseudogap observed in the cuprate are found to be directly related to CDW order, while the colossal dielectric constant in the nickelate is demonstrated to be a result of vibronic coupling with CDW order. Differences between the two oxides are related to how the stripes fill with carriers.

High-rate in-plane micro-supercapacitors scribed onto photo paper using in situ femtolaser-reduced graphene oxide/Au nanoparticle microelectrodes

DOE PAGES

Li, Ruozhou; Peng, Rui; Tumuluri, Uma; ...

2016-02-11

Direct laser-reduction of graphene oxide (GO), as a lithography-free approach, has been proven effective in manufacturing in-plane micro-supercapacitors (MSCs) with fast ion diffusion. However, the power density and the charge/discharge rate are still limited by the relatively low conductivity of electrodes. Here, we report a facile approach by exploiting femtolaser in situ reduction of the hydrated GO and chloroauric acid (HAuCl 4) nanocomposite simultaneously, which incorporates both the patterning of rGO electrodes and the fabrication of Au current collectors in a single step. These flexible MSCs boast achievements of one-hundred fold increase in electrode conductivities of up to 1.1 ×more » 10 6 S m –1, which provide superior rate capability (50% for the charging rate increase from 0.1 V s –1 to 100 V s –1), sufficiently high frequency responses (362 Hz, 2.76 ms time constant), and large specific capacitances of 0.77 mF cm –2 (17.2 F cm –3 for volumetric capacitance) at 1 V s –1, and 0.46 mF cm –2 (10.2 F cm –3) at 100 V s –1. The use of photo paper substrates enables the flexibility of this fabrication protocol. Moreover, proof-of-concept 3D MSCs are demonstrated with enhanced areal capacitance (up to 3.84 mF cm –2 at 1 V s –1) while keeping high rate capabilities. As a result, this prototype of all solid-state MSCs demonstrates the broad range of potentials of thin-film based energy storage device applications for flexible, portable, and wearable electronic devices that require a fast charge/discharge rate and high power density.« less

High-rate in-plane micro-supercapacitors scribed onto photo paper using in situ femtolaser-reduced graphene oxide/Au nanoparticle microelectrodes

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

Li, Ruozhou; Peng, Rui; Tumuluri, Uma

Direct laser-reduction of graphene oxide (GO), as a lithography-free approach, has been proven effective in manufacturing in-plane micro-supercapacitors (MSCs) with fast ion diffusion. However, the power density and the charge/discharge rate are still limited by the relatively low conductivity of electrodes. Here, we report a facile approach by exploiting femtolaser in situ reduction of the hydrated GO and chloroauric acid (HAuCl 4) nanocomposite simultaneously, which incorporates both the patterning of rGO electrodes and the fabrication of Au current collectors in a single step. These flexible MSCs boast achievements of one-hundred fold increase in electrode conductivities of up to 1.1 ×more » 10 6 S m –1, which provide superior rate capability (50% for the charging rate increase from 0.1 V s –1 to 100 V s –1), sufficiently high frequency responses (362 Hz, 2.76 ms time constant), and large specific capacitances of 0.77 mF cm –2 (17.2 F cm –3 for volumetric capacitance) at 1 V s –1, and 0.46 mF cm –2 (10.2 F cm –3) at 100 V s –1. The use of photo paper substrates enables the flexibility of this fabrication protocol. Moreover, proof-of-concept 3D MSCs are demonstrated with enhanced areal capacitance (up to 3.84 mF cm –2 at 1 V s –1) while keeping high rate capabilities. As a result, this prototype of all solid-state MSCs demonstrates the broad range of potentials of thin-film based energy storage device applications for flexible, portable, and wearable electronic devices that require a fast charge/discharge rate and high power density.« less

Electric field changes on Au nanoparticles on semiconductor supports--the molecular voltmeter and other methods to observe adsorbate-induced charge-transfer effects in Au/TiO2 nanocatalysts.

PubMed

McEntee, Monica; Stevanovic, Ana; Tang, Wenjie; Neurock, Matthew; Yates, John T

2015-02-11

Infrared (IR) studies of Au/TiO2 catalyst particles indicate that charge transfer from van der Waals-bound donor or acceptor molecules on TiO2 to or from Au occurs via transport of charge carriers in the semiconductor TiO2 support. The ΔνCO on Au is shown to be proportional to the polarizability of the TiO2 support fully covered with donor or acceptor molecules, producing a proportional frequency shift in νCO. Charge transfer through TiO2 is associated with the population of electron trap sites in the bandgap of TiO2 and can be independently followed by changes in photoluminescence intensity and by shifts in the broad IR absorbance region for electron trap sites, which is also proportional to the polarizability of donors by IR excitation. Density functional theory calculations show that electron transfer from the donor molecules to TiO2 and to supported Au particles produces a negative charge on the Au, whereas the transfer from the Au particles to the TiO2 support into acceptor molecules results in a positive charge on the Au. These changes along with the magnitudes of the shifts are consistent with the Stark effect. A number of experiments show that the ∼3 nm Au particles act as "molecular voltmeters" in influencing ΔνCO. Insulator particles, such as SiO2, do not display electron-transfer effects to Au particles on their surface. These studies are preliminary to doping studies of semiconductor-oxide particles by metal ions which modify Lewis acid/base oxide properties and possibly strongly modify the electron-transfer and catalytic activity of supported metal catalyst particles.

High-capacity electrode materials for rechargeable lithium batteries: Li3NbO4-based system with cation-disordered rocksalt structure.

PubMed

Yabuuchi, Naoaki; Takeuchi, Mitsue; Nakayama, Masanobu; Shiiba, Hiromasa; Ogawa, Masahiro; Nakayama, Keisuke; Ohta, Toshiaki; Endo, Daisuke; Ozaki, Tetsuya; Inamasu, Tokuo; Sato, Kei; Komaba, Shinichi

2015-06-23

Rechargeable lithium batteries have rapidly risen to prominence as fundamental devices for green and sustainable energy development. Lithium batteries are now used as power sources for electric vehicles. However, materials innovations are still needed to satisfy the growing demand for increasing energy density of lithium batteries. In the past decade, lithium-excess compounds, Li2MeO3 (Me = Mn(4+), Ru(4+), etc.), have been extensively studied as high-capacity positive electrode materials. Although the origin as the high reversible capacity has been a debatable subject for a long time, recently it has been confirmed that charge compensation is partly achieved by solid-state redox of nonmetal anions (i.e., oxide ions), coupled with solid-state redox of transition metals, which is the basic theory used for classic lithium insertion materials, such as LiMeO2 (Me = Co(3+), Ni(3+), etc.). Herein, as a compound with further excess lithium contents, a cation-ordered rocksalt phase with lithium and pentavalent niobium ions, Li3NbO4, is first examined as the host structure of a new series of high-capacity positive electrode materials for rechargeable lithium batteries. Approximately 300 mAh ⋅ g(-1) of high-reversible capacity at 50 °C is experimentally observed, which partly originates from charge compensation by solid-state redox of oxide ions. It is proposed that such a charge compensation process by oxide ions is effectively stabilized by the presence of electrochemically inactive niobium ions. These results will contribute to the development of a new class of high-capacity electrode materials, potentially with further lithium enrichment (and fewer transition metals) in the close-packed framework structure with oxide ions.

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

Babadi, A. S., E-mail: aein.shiri-babadi@eit.lth.se; Lind, E.; Wernersson, L. E.

A qualitative analysis on capacitance-voltage and conductance data for high-κ/InAs capacitors is presented. Our measured data were evaluated with a full equivalent circuit model, including both majority and minority carriers, as well as interface and border traps, formulated for narrow band gap metal-oxide-semiconductor capacitors. By careful determination of interface trap densities, distribution of border traps across the oxide thickness, and taking into account the bulk semiconductor response, it is shown that the trap response has a strong effect on the measured capacitances. Due to the narrow bandgap of InAs, there can be a large surface concentration of electrons and holesmore » even in depletion, so a full charge treatment is necessary.« less

Adsorption of the diazo dye Direct Red 23 onto a zinc oxide surface: A spectroscopic study

NASA Astrophysics Data System (ADS)

Lucilha, Adriana Campano; Bonancêa, Carlos Eduardo; Barreto, Wagner José; Takashima, Keiko

2010-01-01

The adsorption of the diazo dye Direct Red 23 onto a zinc oxide surface at 30 °C in the dark was investigated. The color reduction was monitored by spectrophotometry at 503 nm. The FTIR and Raman spectra of the Direct Red 23 adsorption as a function of ZnO concentration were registered. From the PM3 semi-empirical calculations of the atomic charge density and dipole moment of the Direct Red 23 molecule, it was demonstrated that the azo dye molecule may be adsorbed onto the ZnO surface through molecule geometry modifications, enhancing the interfacial area causing a variation in the bonding frequencies.

Electrospun Polyaniline/Polyethylene Oxide Nanofiber Field Effect Transistor

NASA Technical Reports Server (NTRS)

Pinto, N. J.; Johnson, A. T.; MacDiarmid, A. G.; Mueller, C. H.; Theofylaktos, N.; Robinson, D. C.; Miranda, F. A.

2003-01-01

We report on the observation of field effect transistor (FET) behavior in electrospun camphorsulfonic acid doped polyaniline(PANi)/polyethylene oxide(PE0) nanofibers. Saturation channel currents are observed at surprisingly low source/drain voltages. The hole mobility in the depletion regime is 1.4 x 10(exp -4) sq cm/V s while the 1-D charge density (at zero gate bias) is calculated to be approximately 1 hole per 50 two-ring repeat units of polyaniline, consistent with the rather high channel conductivity (approx. 10(exp -3) S/cm). Reducing or eliminating the PEO content in the fiber is expected to enhance device parameters. Electrospinning is thus proposed as a simple method of fabricating 1-D polymer FET's.

A Theoretical Investigation on CO Oxidation by Single-Atom Catalysts M1/γ-Al2O3 (M=Pd, Fe, Co, and Ni).

PubMed

Yang, Tao; Fukuda, Ryoichi; Hosokawa, Saburo; Tanaka, Tsunehiro; Sakaki, Shigeyoshi; Ehara, Masahiro

2017-04-07

Single-atom catalysts have attracted much interest recently because of their excellent stability, high catalytic activity, and remarkable atom efficiency. Inspired by the recent experimental discovery of a highly efficient single-atom catalyst Pd 1 /γ-Al 2 O 3 , we conducted a comprehensive DFT study on geometries, stabilities and CO oxidation catalytic activities of M 1 /γ-Al 2 O 3 (M=Pd, Fe, Co, and Ni) by using slab-model. One of the most important results here is that Ni 1 /Al 2 O 3 catalyst exhibits higher activity in CO oxidation than Pd 1 /Al 2 O 3 . The CO oxidation occurs through the Mars van Krevelen mechanism, the rate-determining step of which is the generation of CO 2 from CO through abstraction of surface oxygen. The projected density of states (PDOS) of 2 p orbitals of the surface O, the structure of CO-adsorbed surface, charge polarization of CO and charge transfer from CO to surface are important factors for these catalysts. Although the binding energies of Fe and Co with Al 2 O 3 are very large, those of Pd and Ni are small, indicating that the neighboring O atom is not strongly bound to Pd and Ni, which leads to an enhancement of the reactivity of the O atom toward CO. The metal oxidation state is suggested to be one of the crucial factors for the observed catalytic activity.

In situ Ni-doping during cathodic electrodeposition of hematite for excellent photoelectrochemical performance of nanostructured nickel oxide-hematite p-n junction photoanode

NASA Astrophysics Data System (ADS)

Phuan, Yi Wen; Ibrahim, Elyas; Chong, Meng Nan; Zhu, Tao; Lee, Byeong-Kyu; Ocon, Joey D.; Chan, Eng Seng

2017-01-01

Nanostructured nickel oxide-hematite (NiO/α-Fe2O3) p-n junction photoanodes synthesized from in situ doping of nickel (Ni) during cathodic electrodeposition of hematite were successfully demonstrated. A postulation model was proposed to explain the fundamental mechanism of Ni2+ ions involved, and the eventual formation of NiO on the subsurface region of hematite that enhanced the potential photoelectrochemical water oxidation process. Through this study, it was found that the measured photocurrent densities of the Ni-doped hematite photoanodes were highly dependent on the concentrations of Ni dopant used. The optimum Ni dopant at 25 M% demonstrated an excellent photoelectrochemical performance of 7-folds enhancement as compared to bare hematite photoanode. This was attributed to the increased electron donor density through the p-n junction and thus lowering the energetic barrier for water oxidation activity at the optimum Ni dopant concentration. Concurrently, the in situ Ni-doping of hematite has also lowered the photogenerated charge carrier transfer resistance as measured using the electrochemical impedance spectroscopy. It is expected that the fundamental understanding gained through this study is helpful for the rational design and construction of highly efficient photoanodes for application in photoelectrochemical process.

Band diagram and rate analysis of thin film spinel LiMn 2O 4 formed by electrochemical conversion of ALD-grown MnO

DOE PAGES

Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.; ...

2016-09-22

Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn 2O 4) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn 2O 4 thin films in electrolytes containing Li +, Na +, K +, and Mg 2+ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn 2O 4 informed by screened hybrid density functional theory calculationsmore » is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn 2O 4. It is shown that the incorporation of Li + or other cations into the host manganese dioxide spinel structure (λ-MnO 2) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn 2O 4. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn 2O 4 arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.« less

Modulating the fixed charge density in silicon nitride films while monitoring the surface recombination velocity by photoluminescence imaging

NASA Astrophysics Data System (ADS)

Bazilchuk, Molly; Haug, Halvard; Marstein, Erik Stensrud

2015-04-01

Several important semiconductor devices such as solar cells and photodetectors may be fabricated based on surface inversion layer junctions induced by fixed charge in a dielectric layer. Inversion layer junctions can easily be fabricated by depositing layers with a high density of fixed charge on a semiconducting substrate. Increasing the fixed charge improves such devices; for instance, the efficiency of a solar cell can be substantially increased by reducing the surface recombination velocity, which is a function of the fixed charge density. Methods for increasing the charge density are therefore of interest. In this work, the fixed charge density in silicon nitride layers deposited by plasma enhanced chemical vapor deposition is increased to very high values above 1 × 1013 cm-2 after the application of an external voltage to a gate electrode. The effect of the fixed charge density on the surface recombination velocity was experimentally observed using the combination of capacitance-voltage characterization and photoluminescence imaging, showing a significant reduction in the surface recombination velocity for increasing charge density. The surface recombination velocity vs. charge density data was analyzed using a numerical device model, which indicated the presence of a sub-surface damage region formed during deposition of the layers. Finally, we have demonstrated that the aluminum electrodes used for charge injection may be chemically removed in phosphoric acid without loss of the underlying charge. The injected charge was shown to be stable for a prolonged time period, leading us to propose charge injection in silicon nitride films by application of soaking voltage as a viable method for fabricating inversion layer devices.

A reliable and controllable graphene doping method compatible with current CMOS technology and the demonstration of its device applications

NASA Astrophysics Data System (ADS)

Kim, Seonyeong; Shin, Somyeong; Kim, Taekwang; Du, Hyewon; Song, Minho; Kim, Ki Soo; Cho, Seungmin; Lee, Sang Wook; Seo, Sunae

2017-04-01

The modulation of charge carrier concentration allows us to tune the Fermi level (E F) of graphene thanks to the low electronic density of states near the E F. The introduced metal oxide thin films as well as the modified transfer process can elaborately maneuver the amounts of charge carrier concentration in graphene. The self-encapsulation provides a solution to overcome the stability issues of metal oxide hole dopants. We have manipulated systematic graphene p-n junction structures for electronic or photonic application-compatible doping methods with current semiconducting process technology. We have demonstrated the anticipated transport properties on the designed heterojunction devices with non-destructive doping methods. This mitigates the device architecture limitation imposed in previously known doping methods. Furthermore, we employed E F-modulated graphene source/drain (S/D) electrodes in a low dimensional transition metal dichalcogenide field effect transistor (TMDFET). We have succeeded in fulfilling n-type, ambipolar, or p-type field effect transistors (FETs) by moving around only the graphene work function. Besides, the graphene/transition metal dichalcogenide (TMD) junction in either both p- and n-type transistor reveals linear voltage dependence with the enhanced contact resistance. We accomplished the complete conversion of p-/n-channel transistors with S/D tunable electrodes. The E F modulation using metal oxide facilitates graphene to access state-of-the-art complimentary-metal-oxide-semiconductor (CMOS) technology.

Treatment of reverse-osmosis concentrate of printing and dyeing wastewater by electro-oxidation process with controlled oxidation-reduction potential (ORP).

PubMed

Wang, Jiade; Zhang, Tian; Mei, Yu; Pan, Bingjun

2018-06-01

Reverse osmosis concentrate (ROC) of printing and dyeing wastewater remains as a daunting environmental issue, which is characterized by high salinity, chemical oxygen demand (COD), chroma and low biodegradability. In this study electro-oxidation process (PbO 2 /Ti electrode) coupled with oxidation-reduction potential (ORP) online monitor was applied to treat such a ROC effluent. The results show that with the increase of specific electrical charge (Q sp ), the removal efficiencies of COD, TN and chroma increased significantly at the incipience and then reached a gentle stage; the optimal total current efficiency (12.04 kWh m -3 ) was obtained with the current density of 10 mA cm -2 (Q sp , 3.0 Ah L -1 ). Meanwhile, some inorganic ions can be simultaneously removed to varying degrees. FTIR analyses indicated that the macromolecular organics were decomposed into smaller molecules. A multi-parameter linear relationship between ORP and Q sp , COD and Cl - concentration was established, which can quantitatively reflect the effect of current density, chloride ion concentration, pollutants and reaction time on the performance of the electro-oxidation system. As compared to a traditional constant-current system, the constant-ORP system developed in this study (through the back-propagation neural network [BPN] model with ORP monitoring) approximately reduced the energy cost by 24-29%. The present work is expected to provide a potential alternative in optimizing the electro-oxidation process. Copyright © 2018 Elsevier Ltd. All rights reserved.

Direct modeling of the electrochemistry in the three-phase boundary of solid oxide fuel cell anodes by density functional theory: a critical overview.

PubMed

Shishkin, M; Ziegler, T

2014-02-07

The first principles modeling of electrochemical reactions has proven useful for the development of efficient, durable and low cost solid oxide full cells (SOFCs). In this account we focus on recent advances in modeling of structural, electronic and catalytic properties of the SOFC anodes based on density functional theory (DFT) first principle calculations. As a starting point, we highlight that the adequate analysis of cell electrochemistry generally requires modeling of chemical reactions at the metal/oxide interface rather than on individual metal or oxide surfaces. The atomic models of Ni/YSZ and Ni/CeO2 interfaces, required for DFT simulations of reactions on SOFC anodes are discussed next, together with the analysis of the electronic structure of these interfaces. Then we proceed to DFT-based findings on charge transfer mechanisms during redox reactions on these two anodes. We provide a comparison of the electronic properties of Ni/YSZ and Ni/CeO2 interfaces and present an interpretation of their different chemical performances. Subsequently we discuss the computed energy pathways of fuel oxidation mechanisms, obtained by various groups to date. We also discuss the results of DFT studies combined with microkinetic modeling as well as the results of kinetic Monte Carlo simulations. In conclusion we summarize the key findings of DFT modeling of metal/oxide interfaces to date and highlight possible directions in the future modeling of SOFC anodes.

Method for Estimating the Charge Density Distribution on a Dielectric Surface.

PubMed

Nakashima, Takuya; Suhara, Hiroyuki; Murata, Hidekazu; Shimoyama, Hiroshi

2017-06-01

High-quality color output from digital photocopiers and laser printers is in strong demand, motivating attempts to achieve fine dot reproducibility and stability. The resolution of a digital photocopier depends on the charge density distribution on the organic photoconductor surface; however, directly measuring the charge density distribution is impossible. In this study, we propose a new electron optical instrument that can rapidly measure the electrostatic latent image on an organic photoconductor surface, which is a dielectric surface, as well as a novel method to quantitatively estimate the charge density distribution on a dielectric surface by combining experimental data obtained from the apparatus via a computer simulation. In the computer simulation, an improved three-dimensional boundary charge density method (BCM) is used for electric field analysis in the vicinity of the dielectric material with a charge density distribution. This method enables us to estimate the profile and quantity of the charge density distribution on a dielectric surface with a resolution of the order of microns. Furthermore, the surface potential on the dielectric surface can be immediately calculated using the obtained charge density. This method enables the relation between the charge pattern on the organic photoconductor surface and toner particle behavior to be studied; an understanding regarding the same may lead to the development of a new generation of higher resolution photocopiers.

Inductive crystal field control in layered metal oxides with correlated electrons

DOE PAGES

Balachandran, P. V.; Cammarata, A.; Nelson-Cheeseman, B. B.; ...

2014-07-25

Here, we show that the NiO 6 crystal field energies can be tailored indirectly via heterovalent A cation ordering in layered (La,A) NiO 4 Ruddlesden-Popper (RP) oxides, where A = Sr, Ca, or Ba, using density functional calculations. We leverage as a driving force the electrostatic interactions between charged [LaO] 1+ and neutral [AO] 0 planes to inductively tune the Ni-O bond distortions, without intentional doping or epitaxial strain, altering the correlated d-orbital energies. We use this strategy to design cation ordered LaCaNiO 4 and LaBaNiO 4 with distortions favoring enhanced Ni e g orbital polarization, and find local electronicmore » structure signatures analogous to those in RP La-cuprates, i.e., parent phases of the high-temperature superconducting oxides.« less

Peroxide induced tin oxide coating of graphene oxide at room temperature and its application for lithium ion batteries.

PubMed

Sladkevich, S; Gun, J; Prikhodchenko, P V; Gutkin, V; Mikhaylov, A A; Novotortsev, V M; Zhu, J X; Yang, D; Hng, H H; Tay, Y Y; Tsakadze, Z; Lev, O

2012-12-07

We describe a new, simple and low-temperature method for ultra-thin coating of graphene oxide (GO) by peroxostannate, tin oxide or a mixture of tin and tin oxide crystallites by different treatments. The technique is environmentally friendly and does not require complicated infrastructure, an autoclave or a microwave. The supported peroxostannate phase is partially converted after drying to crystalline tin oxide with average, 2.5 nm cassiterite crystals. Mild heat treatment yielded full coverage of the reduced graphene oxide by crystalline tin oxide. Extensive heat treatment in vacuum at >500 °C yielded a mixture of elemental tin and cassiterite tin oxide nanoparticles supported on reduced graphene oxide (rGO). The usefulness of the new approach was demonstrated by the preparation of two types of lithium ion anodes: tin oxide-rGO and a mixture of tin oxide and tin coated rGO composites (SnO(2)-Sn-rGO). The electrodes exhibited stable charge/discharge cyclability and high charging capacity due to the intimate contact between the conductive graphene and the very small tin oxide crystallites. The charging/discharging capacity of the anodes exceeded the theoretical capacity predicted based on tin lithiation. The tin oxide coated rGO exhibited higher charging capacity but somewhat lower stability upon extended charge/discharge cycling compared to SnO(2)-Sn-rGO.

A charge-density-wave oscillator based on an integrated tantalum disulfide-boron nitride-graphene device operating at room temperature.

PubMed

Liu, Guanxiong; Debnath, Bishwajit; Pope, Timothy R; Salguero, Tina T; Lake, Roger K; Balandin, Alexander A

2016-10-01

The charge-density-wave (CDW) phase is a macroscopic quantum state consisting of a periodic modulation of the electronic charge density accompanied by a periodic distortion of the atomic lattice in quasi-1D or layered 2D metallic crystals. Several layered transition metal dichalcogenides, including 1T-TaSe 2 , 1T-TaS 2 and 1T-TiSe 2 exhibit unusually high transition temperatures to different CDW symmetry-reducing phases. These transitions can be affected by the environmental conditions, film thickness and applied electric bias. However, device applications of these intriguing systems at room temperature or their integration with other 2D materials have not been explored. Here, we demonstrate room-temperature current switching driven by a voltage-controlled phase transition between CDW states in films of 1T-TaS 2 less than 10 nm thick. We exploit the transition between the nearly commensurate and the incommensurate CDW phases, which has a transition temperature of 350 K and gives an abrupt change in current accompanied by hysteresis. An integrated graphene transistor provides a voltage-tunable, matched, low-resistance load enabling precise voltage control of the circuit. The 1T-TaS 2 film is capped with hexagonal boron nitride to provide protection from oxidation. The integration of these three disparate 2D materials in a way that exploits the unique properties of each yields a simple, miniaturized, voltage-controlled oscillator suitable for a variety of practical applications.

The role of charge transfer in the oxidation state change of Ce atoms in the TM13-CeO2(111) systems (TM = Pd, Ag, Pt, Au): a DFT + U investigation.

PubMed

Tereshchuk, Polina; Freire, Rafael L H; Ungureanu, Crina G; Seminovski, Yohanna; Kiejna, Adam; Da Silva, Juarez L F

2015-05-28

Despite extensive studies of transition metal (TM) clusters supported on ceria (CeO2), fundamental issues such as the role of the TM atoms in the change in the oxidation state of Ce atoms are still not well understood. In this work, we report a theoretical investigation based on static and ab initio molecular dynamics density functional theory calculations of the interaction of 13-atom TM clusters (TM = Pd, Ag, Pt, Au) with the unreduced CeO2(111) surface represented by a large surface unit cell and employing Hubbard corrections for the strong on-site Coulomb correlation in the Ce f-electrons. We found that the TM13 clusters form pyramidal-like structures on CeO2(111) in the lowest energy configurations with the following stacking sequence, TM/TM4/TM8/CeO2(111), while TM13 adopts two-dimensional structures at high energy structures. TM13 induces a change in the oxidation state of few Ce atoms (3 of 16) located in the topmost Ce layer from Ce(IV) (itinerant Ce f-states) to Ce(III) (localized Ce f-states). There is a charge flow from the TM atoms to the CeO2(111) surface, which can be explained by the electronegativity difference between the TM (Pd, Ag, Pt, Au) and O atoms, however, the charge is not uniformly distributed on the topmost O layer due to the pressure induced by the TM13 clusters on the underlying O ions, which yields a decrease in the ionic charge of the O ions located below the cluster and an increase in the remaining O ions. Due to the charge flow mainly from the TM8-layer to the topmost O-layer, the charge cannot flow from the Ce(IV) atoms to the O atoms with the same magnitude as in the clean CeO2(111) surface. Consequently, the effective cationic charge decreases mainly for the Ce atoms that have a bond with the O atoms not located below the cluster, and hence, those Ce atoms change their oxidation state from IV to III. This increases the size of the Ce(III) compared with the Ce(IV) cations, which builds-in a strain within the topmost Ce layer, and hence, also affecting the location of the Ce(III) cations and the structure of the TM13 clusters.

Charge Transport Properties in Disordered Organic Semiconductor as a Function of Charge Density: Monte Carlo Simulation

NASA Astrophysics Data System (ADS)

Shukri, Seyfan Kelil

2017-01-01

We have done Kinetic Monte Carlo (KMC) simulations to investigate the effect of charge carrier density on the electrical conductivity and carrier mobility in disordered organic semiconductors using a lattice model. The density of state (DOS) of the system are considered to be Gaussian and exponential. Our simulations reveal that the mobility of the charge carrier increases with charge carrier density for both DOSs. In contrast, the mobility of charge carriers decreases as the disorder increases. In addition the shape of the DOS has a significance effect on the charge transport properties as a function of density which are clearly seen. On the other hand, for the same distribution width and at low carrier density, the change occurred on the conductivity and mobility for a Gaussian DOS is more pronounced than that for the exponential DOS.

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

Duan, Guo Xing; Hatchtel, Jordan; Shen, Xiao

Here, we investigate negative-bias temperature instabilities in SiGe pMOSFETs with SiO 2/HfO 2 gate dielectrics. The activation energies we measured for interface-trap charge buildup during negative-bias temperature stress were lower for SiGe channel pMOSFETs with SiO 2/HfO 2 gate dielectrics and Si capping layers than for conventional Si channel pMOSFETs with SiO 2 gate dielectrics. Electron energy loss spectroscopy and scanning transmission electron microscopy images demonstrate that Ge atoms can diffuse from the SiGe layer into the Si capping layer, which is adjacent to the SiO 2/HfO 2 gate dielectric. Density functional calculations show that these Ge atoms reduce themore » strength of nearby Si-H bonds and that Ge-H bond energies are still lower, thereby reducing the activation energy for interface-trap generation for the SiGe devices. Moreover, activation energies for oxide-trap charge buildup during negative-bias temperature stress are similarly small for SiGe pMOSFETs with SiO 2/HfO 2 gate dielectrics and Si pMOSFETs with SiO 2 gate dielectrics, suggesting that, in both cases, the oxide-trap charge buildup likely is rate-limited by hole tunneling into the near-interfacial SiO 2.« less

A method to estimate statistical errors of properties derived from charge-density modelling

PubMed Central

Lecomte, Claude

2018-01-01

Estimating uncertainties of property values derived from a charge-density model is not straightforward. A methodology, based on calculation of sample standard deviations (SSD) of properties using randomly deviating charge-density models, is proposed with the MoPro software. The parameter shifts applied in the deviating models are generated in order to respect the variance–covariance matrix issued from the least-squares refinement. This ‘SSD methodology’ procedure can be applied to estimate uncertainties of any property related to a charge-density model obtained by least-squares fitting. This includes topological properties such as critical point coordinates, electron density, Laplacian and ellipticity at critical points and charges integrated over atomic basins. Errors on electrostatic potentials and interaction energies are also available now through this procedure. The method is exemplified with the charge density of compound (E)-5-phenylpent-1-enylboronic acid, refined at 0.45 Å resolution. The procedure is implemented in the freely available MoPro program dedicated to charge-density refinement and modelling. PMID:29724964

Photoelectron Spectroscopy of Doubly and Singly Charged Group VIB Dimetalate Anions: M2O72-, MM'072-, and M207- (M, M'=Cr, Mo, W)

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

Zhai, Hua Jin; Huang, Xin; Waters, Tom

2005-11-24

We produced both doubly and singly charged Group VIB dimetalate species-M2O7 2-, MM'O72-, and M2O7 - (M, M'=) Cr, Mo, W)susing two different experimental techniques (electrospray ionization for the doubly charged anions and laser vaporization for the singly charged anions) and investigated their electronic and geometric structures using photoelectron spectroscopy and density functional calculations. Distinct changes in the electronic and geometric structures were observed as a function of the metal and charge state. The electron binding energies of the heteronuclear dianions MM'O7 2- were observed to be roughly the average of those of their homonuclear counterparts (M2O7 2- and M'2O7more » 2-). Density functional calculations indicated that W2O7 2-, W2O7-, and W2O7 possess different ground-state structures: the dianion is highly symmetric (D3d,1A1g) with a single bridging oxo ligand, the monoanion is a doublet (C1, 2A) with two bridging oxo ligands and a radical terminal oxo ligand, whereas the neutral is a singlet (C1, 1A) with two bridging oxo ligands and a terminal peroxo ligand. The combined experimental and theoretical study provides insights into the evolution of geometric and electronic structures as a function of charge state. The clusters identified might provide insights into the possible structures of reactive species present in early transition-metal oxide catalysts that are relevant to their reactivity and catalytic function.« less

Enhancing the mechanical and biological performance of a metallic biomaterial for orthopedic applications through changes in the surface oxide layer by nanocrystalline surface modification.

PubMed

Bahl, Sumit; Shreyas, P; Trishul, M A; Suwas, Satyam; Chatterjee, Kaushik

2015-05-07

Nanostructured metals are a promising class of biomaterials for application in orthopedics to improve the mechanical performance and biological response for increasing the life of biomedical implants. Surface mechanical attrition treatment (SMAT) is an efficient way of engineering nanocrystalline surfaces on metal substrates. In this work, 316L stainless steel (SS), a widely used orthopedic biomaterial, was subjected to SMAT to generate a nanocrystalline surface. Surface nanocrystallization modified the nature of the oxide layer present on the surface. It increased the corrosion-fatigue strength in saline by 50%. This increase in strength is attributed to a thicker oxide layer, residual compressive stresses, high strength of the surface layer, and lower propensity for intergranular corrosion in the nanocrystalline layer. Nanocrystallization also enhanced osteoblast attachment and proliferation. Intriguingly, wettability and surface roughness, the key parameters widely acknowledged for controlling the cellular response remained unchanged after nanocrystallization. The observed cellular behavior is explained in terms of the changes in electronic properties of the semiconducting passive oxide film present on the surface of 316L SS. Nanocrystallization increased the charge carrier density of the n-type oxide film likely preventing denaturation of the adsorbed cell-adhesive proteins such as fibronectin. In addition, a net positive charge developed on the otherwise neutral oxide layer, which is known to facilitate cellular adhesion. The role of changes in the electronic properties of the oxide films on metal substrates is thus highlighted in this work. This study demonstrates the advantages of nanocrystalline surface modification by SMAT for processing metallic biomaterials used in orthopedic implants.

p-Type Transparent Conducting Oxide/n-Type Semiconductor Heterojunctions for Efficient and Stable Solar Water Oxidation.

PubMed

Chen, Le; Yang, Jinhui; Klaus, Shannon; Lee, Lyman J; Woods-Robinson, Rachel; Ma, Jie; Lum, Yanwei; Cooper, Jason K; Toma, Francesca M; Wang, Lin-Wang; Sharp, Ian D; Bell, Alexis T; Ager, Joel W

2015-08-05

Achieving stable operation of photoanodes used as components of solar water splitting devices is critical to realizing the promise of this renewable energy technology. It is shown that p-type transparent conducting oxides (p-TCOs) can function both as a selective hole contact and corrosion protection layer for photoanodes used in light-driven water oxidation. Using NiCo2O4 as the p-TCO and n-type Si as a prototypical light absorber, a rectifying heterojunction capable of light driven water oxidation was created. By placing the charge separating junction in the Si using a np(+) structure and by incorporating a highly active heterogeneous Ni-Fe oxygen evolution catalyst, efficient light-driven water oxidation can be achieved. In this structure, oxygen evolution under AM1.5G illumination occurs at 0.95 V vs RHE, and the current density at the reversible potential for water oxidation (1.23 V vs RHE) is >25 mA cm(-2). Stable operation was confirmed by observing a constant current density over 72 h and by sensitive measurements of corrosion products in the electrolyte. In situ Raman spectroscopy was employed to investigate structural transformation of NiCo2O4 during electrochemical oxidation. The interface between the light absorber and p-TCO is crucial to produce selective hole conduction to the surface under illumination. For example, annealing to produce more crystalline NiCo2O4 produces only small changes in its hole conductivity, while a thicker SiOx layer is formed at the n-Si/p-NiCo2O4 interface, greatly reducing the PEC performance. The generality of the p-TCO protection approach is demonstrated by multihour, stable, water oxidation with n-InP/p-NiCo2O4 heterojunction photoanodes.

Influence of the charge trap density distribution in a gate insulator on the positive-bias stress instability of amorphous indium-gallium-zinc oxide thin-film transistors

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

Kim, Eungtaek; Kim, Choong-Ki; Lee, Myung Keun

We investigated the positive-bias stress (PBS) instability of thin film transistors (TFTs) composed of different types of first-gate insulators, which serve as a protection layer of the active surface. Two different deposition methods, i.e., the thermal atomic layer deposition (THALD) and plasma-enhanced ALD (PEALD) of Al{sub 2}O{sub 3}, were applied for the deposition of the first GI. When THALD was used to deposit the GI, amorphous indium-gallium-zinc oxide (a-IGZO) TFTs showed superior stability characteristics under PBS. For example, the threshold voltage shift (ΔV{sub th}) was 0 V even after a PBS time (t{sub stress}) of 3000 s under a gate voltage (V{submore » G}) condition of 5 V (with an electrical field of 1.25 MV/cm). On the other hand, when the first GI was deposited by PEALD, the ΔV{sub th} value of a-IGZO TFTs was 0.82 V after undergoing an identical amount of PBS. In order to interpret the disparate ΔV{sub th} values resulting from PBS quantitatively, the average oxide charge trap density (N{sub T}) in the GI and its spatial distribution were investigated through low-frequency noise characterizations. A higher N{sub T} resulted during in the PEALD type GI than in the THALD case. Specifically, the PEALD process on a-IGZO layer surface led to an increasing trend of N{sub T} near the GI/a-IGZO interface compared to bulk GI owing to oxygen plasma damage on the a-IGZO surface.« less

Surface reactivity of mercury on the oxygen-terminated hematite(0001) surface: a first-principle study

NASA Astrophysics Data System (ADS)

Jung, J. E.; Wilcox, J.

2016-12-01

Hematite (α-Fe2O3) is a common mineral found in Earth's near-surface environment. Due to its nontoxicity, corrosion-resistance, and high thermal stability, α-Fe2O3 has attracted attentions as materials for various applications such as photocatalysts, gas sensors, as well as for the removal of heavy metals. In this study, α-Fe2O3 is chosen for potential mercury (Hg) sorbent in order to remove Hg from coal-fired power plants. Specifically, theoretical approaches using density functional theory (DFT) is used to understand surface reactivity of Hg on oxygen (O) terminated α-Fe2O3(0001) surface. The most probable adsorption sites of Hg, chlorine (Cl), and mercury chloride (HgCl) on the α-Fe2O3 surface are found based on adsorption energy calculations, and the oxidation states of the adsorbates are determined by Bader charge analysis. Additionally, projected density of states (PDOS) analysis characterizes the surface-adsorbate bonding mechanism. The results of adsorption energy calculation proposes that Hg physisorbs to the α-Fe2O3(0001) surface with adsorption energy of -0.278 eV, and the subsequent Bader charge analysis confirms that Hg is slightly oxidized. In addition, Cl introduced to the Hg-adsorbed surface strengthens Hg stability on the α-Fe2O3(0001) surface as evidenced by a shortened Hg-surface equilibrium distance. The PDOS analysis also suggests that Cl enhances the chemical bonding between the surface and the adsorbate, thereby increasing adsorption strength. In summary, α-Fe2O3 has ability to adsorb and oxidize Hg, and this reactivity is enhanced in the presence of Cl.

Density functional plus dynamical mean-field theory of the metal-insulator transition in early transition-metal oxides

NASA Astrophysics Data System (ADS)

Dang, Hung T.; Ai, Xinyuan; Millis, Andrew J.; Marianetti, Chris A.

2014-09-01

The combination of density functional theory and single-site dynamical mean-field theory, using both Hartree and full continuous-time quantum Monte Carlo impurity solvers, is used to study the metal-insulator phase diagram of perovskite transition-metal oxides of the form ABO3 with a rare-earth ion A =Sr, La, Y and transition metal B =Ti, V, Cr. The correlated subspace is constructed from atomiclike d orbitals defined using maximally localized Wannier functions derived from the full p-d manifold; for comparison, results obtained using a projector method are also given. Paramagnetic DFT + DMFT computations using full charge self-consistency along with the standard "fully localized limit" (FLL) double counting are shown to incorrectly predict that LaTiO3, YTiO3, LaVO3, and SrMnO3 are metals. A more general examination of the dependence of physical properties on the mean p-d energy splitting, the occupancy of the correlated d states, the double-counting correction, and the lattice structure demonstrates the importance of charge-transfer physics even in the early transition-metal oxides and elucidates the factors underlying the failure of the standard approximations. If the double counting is chosen to produce a p-d splitting consistent with experimental spectra, single-site dynamical mean-field theory provides a reasonable account of the materials properties. The relation of the results to those obtained from "d-only" models in which the correlation problem is based on the frontier orbital p-d antibonding bands is determined. It is found that if an effective interaction U is properly chosen the d-only model provides a good account of the physics of the d1 and d2 materials.

Self-templated Synthesis of Nickel Silicate Hydroxide/Reduced Graphene Oxide Composite Hollow Microspheres as Highly Stable Supercapacitor Electrode Material

NASA Astrophysics Data System (ADS)

Zhang, Yanhua; Zhou, Wenjie; Yu, Hong; Feng, Tong; Pu, Yong; Liu, Hongdong; Xiao, Wei; Tian, Liangliang

2017-05-01

Nickel silicate hydroxide/reduced graphene oxide (Ni3Si2O5(OH)4/RGO) composite hollow microspheres were one-pot hydrothermally synthesized by employing graphene oxide (GO)-wrapped SiO2 microspheres as the template and silicon source, which were prepared through sonication-assisted interfacial self-assembly of tiny GO sheets on positively charged SiO2 substrate microspheres. The composition, morphology, structure, and phase of Ni3Si2O5(OH)4/RGO microspheres as well as their electrochemical properties were carefully studied. It was found that Ni3Si2O5(OH)4/RGO microspheres featured distinct hierarchical porous morphology with hollow architecture and a large specific surface area as high as 67.6 m2 g-1. When utilized as a supercapacitor electrode material, Ni3Si2O5(OH)4/RGO hollow microspheres released a maximum specific capacitance of 178.9 F g-1 at the current density of 1 A g-1, which was much higher than that of the contrastive bare Ni3Si2O5(OH)4 hollow microspheres and bare RGO material developed in this work, displaying enhanced supercapacitive behavior. Impressively, the Ni3Si2O5(OH)4/RGO microsphere electrode exhibited outstanding rate capability and long-term cycling stability and durability with 97.6% retention of the initial capacitance after continuous charging/discharging for up to 5000 cycles at the current density of 6 A g-1, which is superior or comparable to that of most of other reported nickel-based electrode materials, hence showing promising application potential in the energy storage area.

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

Kleinlein, Claudia; Zheng, Shao-Liang; Betley, Theodore A.

Three ferric dipyrromethene complexes featuring different ancillary ligands were synthesized by one electron oxidation of ferrous precursors. Four-coordinate iron complexes of the type ( ArL)FeX 2 [ ArL = 1,9-(2,4,6-Ph 3C 6H 2) 2-5-mesityldipyrromethene] with X = Cl or tBuO were prepared and found to be high-spin (S = 5/2), as determined by superconducting quantum interference device magnetometry, electron paramagnetic resonance, and 57Fe Mössbauer spectroscopy. The ancillary ligand substitution was found to affect both ground state and excited properties of the ferric complexes examined. While each ferric complex displays reversible reduction and oxidation events, each alkoxide for chloride substitution resultsmore » in a nearly 600 mV cathodic shift of the Fe III/II couple. The oxidation event remains largely unaffected by the ancillary ligand substitution and is likely dipyrrin-centered. While the alkoxide substituted ferric species largely retain the color of their ferrous precursors, characteristic of dipyrrin-based ligand-to-ligand charge transfer (LLCT), the dichloride ferric complex loses the prominent dipyrrin chromophore, taking on a deep green color. Time-dependent density functional theory analyses indicate the weaker-field chloride ligands allow substantial configuration mixing of ligand-to-metal charge transfer into the LLCT bands, giving rise to the color changes observed. Furthermore, the higher degree of covalency between the alkoxide ferric centers is manifest in the observed reactivity. Delocalization of spin density onto the tert-butoxide ligand in ( ArL)FeCl(O tBu) is evidenced by hydrogen atom abstraction to yield ( ArL)FeCl and HOtBu in the presence of substrates containing weak C–H bonds, whereas the chloride ( ArL)FeCl 2 analogue does not react under these conditions.« less

Self-templated Synthesis of Nickel Silicate Hydroxide/Reduced Graphene Oxide Composite Hollow Microspheres as Highly Stable Supercapacitor Electrode Material.

PubMed

Zhang, Yanhua; Zhou, Wenjie; Yu, Hong; Feng, Tong; Pu, Yong; Liu, Hongdong; Xiao, Wei; Tian, Liangliang

2017-12-01

Nickel silicate hydroxide/reduced graphene oxide (Ni 3 Si 2 O 5 (OH) 4 /RGO) composite hollow microspheres were one-pot hydrothermally synthesized by employing graphene oxide (GO)-wrapped SiO 2 microspheres as the template and silicon source, which were prepared through sonication-assisted interfacial self-assembly of tiny GO sheets on positively charged SiO 2 substrate microspheres. The composition, morphology, structure, and phase of Ni 3 Si 2 O 5 (OH) 4 /RGO microspheres as well as their electrochemical properties were carefully studied. It was found that Ni 3 Si 2 O 5 (OH) 4 /RGO microspheres featured distinct hierarchical porous morphology with hollow architecture and a large specific surface area as high as 67.6 m 2  g -1 . When utilized as a supercapacitor electrode material, Ni 3 Si 2 O 5 (OH) 4 /RGO hollow microspheres released a maximum specific capacitance of 178.9 F g -1 at the current density of 1 A g -1 , which was much higher than that of the contrastive bare Ni 3 Si 2 O 5 (OH) 4 hollow microspheres and bare RGO material developed in this work, displaying enhanced supercapacitive behavior. Impressively, the Ni 3 Si 2 O 5 (OH) 4 /RGO microsphere electrode exhibited outstanding rate capability and long-term cycling stability and durability with 97.6% retention of the initial capacitance after continuous charging/discharging for up to 5000 cycles at the current density of 6 A g -1 , which is superior or comparable to that of most of other reported nickel-based electrode materials, hence showing promising application potential in the energy storage area.

Zirconium oxide surface passivation of crystalline silicon

NASA Astrophysics Data System (ADS)

Wan, Yimao; Bullock, James; Hettick, Mark; Xu, Zhaoran; Yan, Di; Peng, Jun; Javey, Ali; Cuevas, Andres

2018-05-01

This letter reports effective passivation of crystalline silicon (c-Si) surfaces by thermal atomic layer deposited zirconium oxide (ZrOx). The optimum layer thickness and activation annealing conditions are determined to be 20 nm and 300 °C for 20 min. Cross-sectional transmission electron microscopy imaging shows an approximately 1.6 nm thick SiOx interfacial layer underneath an 18 nm ZrOx layer, consistent with ellipsometry measurements (˜20 nm). Capacitance-voltage measurements show that the annealed ZrOx film features a low interface defect density of 1.0 × 1011 cm-2 eV-1 and a low negative film charge density of -6 × 1010 cm-2. Effective lifetimes of 673 μs and 1.1 ms are achieved on p-type and n-type 1 Ω cm undiffused c-Si wafers, respectively, corresponding to an implied open circuit voltage above 720 mV in both cases. The results demonstrate that surface passivation quality provided by ALD ZrOx is consistent with the requirements of high efficiency silicon solar cells.

Effect of Nanoparticles on the Morphology, Thermal, and Electrical Properties of Low-Density Polyethylene after Thermal Aging

PubMed Central

Wang, Youyuan; Zhang, Zhanxi; Xiao, Kun

2017-01-01

This paper investigates the morphology, thermal, and electrical properties of LDPE (low-density polyethylene)-based nanocomposites after thermal aging. The FTIR (Fourier transform infrared spectroscopy) spectra results show that thermo-oxidative reactions occur in neat LDPE and LDPE/SiO2 nanocomposites when the aging time is 35 days and in LDPE/MgO nanocomposites when the aging time is 77 days. Specifically, LDPE/MgO nanocomposites delay the appearance of thermo-oxidative reactions, showing anti-thermal aging ability. Furthermore, nanocomposites present lower onset degradation temperature than neat LDPE, showing better thermal stabilization. With regard to the electrical properties, nanocomposites maintain the ability to suppress space charge accumulation after thermal aging. Additionally, in comparison with SiO2 nanocomposites and neat LDPE, the permittivity of LDPE/MgO nanocomposites changes slightly after thermal aging. It is concluded that LDPE/MgO nanocomposites have better insulation properties than neat LDPE after thermal aging, which may be caused by the interface introduced by the nanoparticles. PMID:29023428

Electrochromic Properties of Tungsten Oxide Films Prepared by Reactive Sputtering

NASA Astrophysics Data System (ADS)

Kim, Min Hong; Kang, Tai Young; Jung, Yu Sup; Kim, Kyung Hwan

2013-05-01

WO3-x thin films were deposited on induim tin oxide (ITO) glass substrates with various oxygen flow ratios from 0.55 to 0.7 by the reactive facing-target sputtering method, at a power density of 4 W/cm2 and room temperature. The structural properties of the WO3-x thin films were measured by X-ray diffractometry and Raman spectral analysis. As-deposited WO3-x thin films had an amorphous structure. In the Raman spectra, WO3-x thin films exhibited two strong peaks at 770 and 950 cm-1 attributed to the vibrations of W6+-O and W6+=O bonds, respectively. The electrochemical and optical properties of WO3-x thin films were measured by cyclic voltammetry and UV/vis spectrometry. The results showed the highest charge density at an oxygen flow ratio of 0.7 and the highest transmittance in the visible range. The maximum coloration efficiency was 30.82 cm2/C at an oxygen flow ratio of 0.7.

Effect of Nanoparticles on the Morphology, Thermal, and Electrical Properties of Low-Density Polyethylene after Thermal Aging.

PubMed

Wang, Youyuan; Wang, Can; Zhang, Zhanxi; Xiao, Kun

2017-10-12

This paper investigates the morphology, thermal, and electrical properties of LDPE (low-density polyethylene)-based nanocomposites after thermal aging. The FTIR (Fourier transform infrared spectroscopy) spectra results show that thermo-oxidative reactions occur in neat LDPE and LDPE/SiO₂ nanocomposites when the aging time is 35 days and in LDPE/MgO nanocomposites when the aging time is 77 days. Specifically, LDPE/MgO nanocomposites delay the appearance of thermo-oxidative reactions, showing anti-thermal aging ability. Furthermore, nanocomposites present lower onset degradation temperature than neat LDPE, showing better thermal stabilization. With regard to the electrical properties, nanocomposites maintain the ability to suppress space charge accumulation after thermal aging. Additionally, in comparison with SiO₂ nanocomposites and neat LDPE, the permittivity of LDPE/MgO nanocomposites changes slightly after thermal aging. It is concluded that LDPE/MgO nanocomposites have better insulation properties than neat LDPE after thermal aging, which may be caused by the interface introduced by the nanoparticles.

Recent Advances in Metal Chalcogenides (MX; X = S, Se) Nanostructures for Electrochemical Supercapacitor Applications: A Brief Review

PubMed Central

Theerthagiri, Jayaraman; Durai, Govindarajan; Rana, Abu ul Hassan Sarwar; Sangeetha, Kirubanandam; Kuppusami, Parasuraman; Kim, Hyun-Seok

2018-01-01

Supercapacitors (SCs) have received a great deal of attention and play an important role for future self-powered devices, mainly owing to their higher power density. Among all types of electrical energy storage devices, electrochemical supercapacitors are considered to be the most promising because of their superior performance characteristics, including short charging time, high power density, safety, easy fabrication procedures, and long operational life. An SC consists of two foremost components, namely electrode materials, and electrolyte. The selection of appropriate electrode materials with rational nanostructured designs has resulted in improved electrochemical properties for high performance and has reduced the cost of SCs. In this review, we mainly spotlight the non-metallic oxide, especially metal chalcogenides (MX; X = S, Se) based nanostructured electrode materials for electrochemical SCs. Different non-metallic oxide materials are highlighted in various categories, such as transition metal sulfides and selenides materials. Finally, the designing strategy and future improvements on metal chalcogenide materials for the application of electrochemical SCs are also discussed. PMID:29671823

Suppression in the electrical hysteresis by using CaF2 dielectric layer for p-GaN MIS capacitors

NASA Astrophysics Data System (ADS)

Sang, Liwen; Ren, Bing; Liao, Meiyong; Koide, Yasuo; Sumiya, Masatomo

2018-04-01

The capacitance-voltage (C-V) hysteresis in the bidirectional measurements of the p-GaN metal-insulator-semiconductor (MIS) capacitor is suppressed by using a CaF2 dielectric layer and a post annealing treatment. The density of trapped charge states at the CaF2/p-GaN interface is dramatically reduced from 1.3 × 1013 cm2 to 1.1 × 1011/cm2 compared to that of the Al2O3/p-GaN interface with a large C-V hysteresis. It is observed that the disordered oxidized interfacial layer can be avoided by using the CaF2 dielectric. The downward band bending of p-GaN is decreased from 1.51 to 0.85 eV as a result of the low-density oxides-related trap states. Our work indicates that the CaF2 can be used as a promising dielectric layer for the p-GaN MIS structures.

Nano ZnO-activated carbon composite electrodes for supercapacitors

NASA Astrophysics Data System (ADS)

Selvakumar, M.; Krishna Bhat, D.; Manish Aggarwal, A.; Prahladh Iyer, S.; Sravani, G.

2010-05-01

A symmetrical (p/p) supercapacitor has been fabricated by making use of nanostructured zinc oxide (ZnO)-activated carbon (AC) composite electrodes for the first time. The composites have been characterized by field emission scanning electron microscopy (FESEM) and X-ray diffraction analysis (XRD). Electrochemical properties of the prepared nanocomposite electrodes and the supercapacitor have been studied using cyclic voltammetry (CV) and AC impedance spectroscopy in 0.1 M Na 2SO 4 as electrolyte. The ZnO-AC nanocomposite electrode showed a specific capacitance of 160 F/g for 1:1 composition. The specific capacitance of the electrodes decreased with increase in zinc oxide content. Galvanostatic charge-discharge measurements have been done at various current densities, namely 2, 4, 6 and 7 mA/cm 2. It has been found that the cells have excellent electrochemical reversibility and capacitive characteristics in 0.1 M Na 2SO 4 electrolyte. It has also been observed that the specific capacitance is constant up to 500 cycles at all current densities.

Enhanced and continuous electrostatic carrier doping on the SrTiO3 surface

PubMed Central

Eyvazov, A. B.; Inoue, I. H.; Stoliar, P.; Rozenberg, M. J.; Panagopoulos, C.

2013-01-01

Paraelectrical tuning of a charge carrier density as high as 1013 cm−2 in the presence of a high electronic carrier mobility on the delicate surfaces of correlated oxides, is a key to the technological breakthrough of a field effect transistor (FET) utilising the metal-nonmetal transition. Here we introduce the Parylene-C/Ta2O5 hybrid gate insulator and fabricate FET devices on single-crystalline SrTiO3, which has been regarded as a bedrock material for oxide electronics. The gate insulator accumulates up to ~1013cm−2 carriers, while the field-effect mobility is kept at 10 cm2/Vs even at room temperature. Further to the exceptional performance of our devices, the enhanced compatibility of high carrier density and high mobility revealed the mechanism for the long standing puzzle of the distribution of electrostatically doped carriers on the surface of SrTiO3. Namely, the formation and continuous evolution of field domains and current filaments.

Flexible and Self-Healing Aqueous Supercapacitors for Low Temperature Applications: Polyampholyte Gel Electrolytes with Biochar Electrodes.

PubMed

Li, Xinda; Liu, Li; Wang, Xianzong; Ok, Yong Sik; Elliott, Janet A W; Chang, Scott X; Chung, Hyun-Joong

2017-05-10

A flexible and self-healing supercapacitor with high energy density in low temperature operation was fabricated using a combination of biochar-based composite electrodes and a polyampholyte hydrogel electrolyte. Polyampholytes, a novel class of tough hydrogel, provide self-healing ability and mechanical flexibility, as well as low temperature operation for the aqueous electrolyte. Biochar is a carbon material produced from the low-temperature pyrolysis of biological wastes; the incorporation of reduced graphene oxide conferred mechanical integrity and electrical conductivity and hence the electrodes are called biochar-reduced-graphene-oxide (BC-RGO) electrodes. The fabricated supercapacitor showed high energy density of 30 Wh/kg with ~90% capacitance retention after 5000 charge-discharge cycles at room temperature at a power density of 50 W/kg. At -30 °C, the supercapacitor exhibited an energy density of 10.5 Wh/kg at a power density of 500 W/kg. The mechanism of the low-temperature performance excellence is likely to be associated with the concept of non-freezable water near the hydrophilic polymer chains, which can motivate future researches on the phase behaviour of water near polyampholyte chains. We conclude that the combination of the BC-RGO electrode and the polyampholyte hydrogel electrolyte is promising for supercapacitors for flexible electronics and for low temperature environments.

Single-molecule interfacial electron transfer dynamics in solar energy conversion

NASA Astrophysics Data System (ADS)

Dhital, Bharat

This dissertation work investigated the parameters affecting the interfacial electron transfer (ET) dynamics in dye-semiconductor nanoparticles (NPs) system by using single-molecule fluorescence spectroscopy and imaging combined with electrochemistry. The influence of the molecule-substrate electronic coupling, the molecular structure, binding geometry on the surface and the molecule-attachment surface chemistry on interfacial charge transfer processes was studied on zinc porphyrin-TiO2 NP systems. The fluorescence blinking measurement on TiO2 NP demonstrated that electronic coupling regulates dynamics of charge transfer processes at the interface depending on the conformation of molecule on the surface. Moreover, semiconductor surface charge induced electronic coupling of molecule which is electrostatically adsorbed on the semiconductor surface also predominantly alters the ET dynamics. Furthermore, interfacial electric field and electron accepting state density dependent ET dynamics has been dissected in zinc porphyrin-TiO2 NP system by observing the single-molecule fluorescence blinking dynamics and fluorescence lifetime with and without applied bias. The significant difference in fluorescence fluctuation and lifetime suggested the modulation of charge transfer dynamics at the interface with external electric field perturbation. Quasi-continuous distribution of fluorescence intensity with applied negative potential was attributed to the faster charge recombination due to reduced density of electron accepting states. The driving force and electron accepting state density ET dependent dynamics has also been probed in zinc porphyrin-TiO2 NP and zinc porphyrin-indium tin oxide (ITO) systems. Study of a molecule adsorbed on two different semiconductors (ITO and TiO2), with large difference in electron densities and distinct driving forces, allows us to observe the changes in rates of back electron transfer process reflected by the suppressed fluorescence blinking of molecule on ITO surface. Finally, the electric field effect on the interface properties has been probed by using surface-enhanced Raman spectroscopy and supported by density functional theory calculations in alizarin-TiO2 system. The perturbation, created by the external potential, has been observed to cause a shift and/or splitting interfacial bond vibrational mode, typical indicator of the coupling energy changes between alizarin and TiO2. Such splitting provides evidence for electric field-dependent electronic coupling changes that have a significant impact on the interfacial electron transfer dynamics.

Simulation study of signal formation in position sensitive planar p-on-n silicon detectors after short range charge injection

NASA Astrophysics Data System (ADS)

Peltola, T.; Eremin, V.; Verbitskaya, E.; Härkönen, J.

2017-09-01

Segmented silicon detectors (micropixel and microstrip) are the main type of detectors used in the inner trackers of Large Hadron Collider (LHC) experiments at CERN. Due to the high luminosity and eventual high fluence of energetic particles, detectors with fast response to fit the short shaping time of 20-25 ns and sufficient radiation hardness are required. Charge collection measurements carried out at the Ioffe Institute have shown a reversal of the pulse polarity in the detector response to short-range charge injection. Since the measured negative signal is about 30-60% of the peak positive signal, the effect strongly reduces the CCE even in non-irradiated detectors. For further investigation of the phenomenon the measurements have been reproduced by TCAD simulations. As for the measurements, the simulation study was applied for the p-on-n strip detectors similar in geometry to those developed for the ATLAS experiment and for the Ioffe Institute designed p-on-n strip detectors with each strip having a window in the metallization covering the p+ implant, allowing the generation of electron-hole pairs under the strip implant. Red laser scans across the strips and the interstrip gap with varying laser diameters and Si-SiO2 interface charge densities (Qf) were carried out. The results verify the experimentally observed negative response along the scan in the interstrip gap. When the laser spot is positioned on the strip p+ implant the negative response vanishes and the collected charge at the active strip increases respectively. The simulation results offer a further insight and understanding of the influence of the oxide charge density in the signal formation. The main result of the study is that a threshold value of Qf, that enables negligible losses of collected charges, is defined. The observed effects and details of the detector response for different charge injection positions are discussed in the context of Ramo's theorem.

Promethium-147 capacitor.

PubMed

Kavetskiy, A; Yakubova, G; Lin, Q; Chan, D; Yousaf, S M; Bower, K; Robertson, J D; Garnov, A; Meier, D

2009-06-01

Beta particle surface fluxes for tritium, Ni-63, Pm-147, and Sr-90 sources were calculated in this work. High current density was experimentally achieved from Pm-147 oxide in silica-titana glass. A 96 GBq (2.6 Ci) Pm-147 4pi-source with flux efficiency greater than 50% was used for constructing a direct charge capacitor with a polyimide coated collector and vacuum as electrical insulation. The capacitor connected to high resistance (TOmega) loads produced up to 35 kV. Overall conversion efficiency was over 10% (on optimal load).

QTAIM electron density study of natural chalcones

NASA Astrophysics Data System (ADS)

González Moa, María J.; Mandado, Marcos; Cordeiro, M. Natália D. S.; Mosquera, Ricardo A.

2007-09-01

QTAIM atomic and bond properties, ionization potential, and O-H bond dissociation energies calculated at the B3LYP/6-311++G(2d,2p) level indicate the natural chalcones bear a significant radical scavenging activity. However, their ionization potentials indicate they decrease the electron-transfer rate between antioxidant and oxygen that yields the pro-oxidative cations less than other natural antioxidants. Rings A and B display slight and similar positive charges, whereas ring B is involved in exocycle delocalization at a larger extension.

On the equilibrium charge density at tilt grain boundaries

NASA Astrophysics Data System (ADS)

Srikant, V.; Clarke, D. R.

1998-05-01

The equilibrium charge density and free energy of tilt grain boundaries as a function of their misorientation is computed using a Monte Carlo simulation that takes into account both the electrostatic and configurational energies associated with charges at the grain boundary. The computed equilibrium charge density increases with the grain-boundary angle and approaches a saturation value. The equilibrium charge density at large-angle grain boundaries compares well with experimental values for large-angle tilt boundaries in GaAs. The computed grain-boundary electrostatic energy is in agreement with the analytical solution to a one-dimensional Poisson equation at high donor densities but indicates that the analytical solution overestimates the electrostatic energy at lower donor densities.

Charging/discharging behavior and mechanism of silicon quantum dots embedded in amorphous silicon carbide films

NASA Astrophysics Data System (ADS)

Wen, Xixing; Zeng, Xiangbin; Zheng, Wenjun; Liao, Wugang; Feng, Feng

2015-01-01

The charging/discharging behavior of Si quantum dots (QDs) embedded in amorphous silicon carbide (a-SiCx) was investigated based on the Al/insulating layer/Si QDs embedded in a-SiCx/SiO2/p-Si (metal-insulator-quantum dots-oxide-silicon) multilayer structure by capacitance-voltage (C-V) and conductance-voltage (G-V) measurements. Transmission electron microscopy and Raman scattering spectroscopy measurements reveal the microstructure and distribution of Si QDs. The occurrence and shift of conductance peaks indicate the carrier transfer and the charging/discharging behavior of Si QDs. The multilayer structure shows a large memory window of 5.2 eV at ±8 V sweeping voltage. Analysis of the C-V and G-V results allows a quantification of the Coulomb charging energy and the trapped charge density associated with the charging/discharging behavior. It is found that the memory window is related to the size effect, and Si QDs with large size or low Coulomb charging energy can trap two or more electrons by changing the charging voltage. Meanwhile, the estimated lower potential barrier height between Si QD and a-SiCx, and the lower Coulomb charging energy of Si QDs could enhance the charging and discharging effect of Si QDs and lead to an enlarged memory window. Further studies of the charging/discharging mechanism of Si QDs embedded in a-SiCx can promote the application of Si QDs in low-power consumption semiconductor memory devices.

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

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

Xue, Meng; Nakayama, Miki; Liu, Ping

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Electrical characterization of doped strontium titanate thin films for semiconductor memories

NASA Astrophysics Data System (ADS)

Han, Jeong Hee

2002-08-01

Doped strontium titanate (ST) thin films were investigated for high-density memory applications. ST has become a promising candidate to replace conventional silicon oxide due to its high inherent dielectric constant, superior leakage characteristics, and good chemical stability. However, oxygen vacancies and the problems that arise as a result are one of the main drawbacks against this material. Resistance degradation is a serious reliability issue in perovskite titanate films and may be a result of oxygen vacancies. In this dissertation, an attempt to reduce the resistance degradation was made by doping the ST films with both niobium and lanthanum. Niobium is a B-site donor in the perovskite, whereas lanthanum is an A-site donor. Both have an extra valence charge than the atom which it replaces in the crystal structure. With a higher valence charge, the number of oxygen vacancies is hoped to be reduced and result in better electrical performance. Experimental results showed that the degradation rate is reduced by doping with either niobium or lanthanum. A bi-layer study was also performed to optimize the dielectric with the strengths of both doped and undoped strontium titanate and to distinguish the source of the oxygen vacancies. A study on the conduction mechanisms and dielectric dispersion was also performed. An additional study was made on the effect of iridium as a possible gate electrode for a MOS capacitor. Hafnium oxide was used as the high-permittivity oxide. The results observed showed that the capacitance was higher for iridium electrodes than those for platinum electrodes. However, both electrodes showed unacceptable frequency dispersion which may be caused by crude patterning techniques. A hysteresis review was also done for hafnium and zirconium oxides. It was observed that the hysteresis measured in the high-permittivity oxides are dependent on the accumulation sweep voltage due to the trapping and de-trapping of charge at the dielectric-silicon interface.

Electronic Interactions of Size-Selected Oxide Clusters on Metallic and Thin Film Oxide Supports

DOE PAGES

Xue, Meng; Nakayama, Miki; Liu, Ping; ...

2017-09-13

The interfacial electronic structure of various size-selected metal oxide nanoclusters (M 3O x; M = Mo, Nb, Ti) on Cu(111) and a thin film of Cu 2O supports were investigated in this paper by a combination of experimental methods and density functional theory (DFT). These systems explore electron transfer at the metal–metal oxide interface which can modify surface structure, metal oxidation states, and catalytic activity. Electron transfer was probed by measurements of surface dipoles derived from coverage dependent work function measurements using two-photon photoemission (2PPE) and metal core level binding energy spectra from X-ray photoelectron spectroscopy (XPS). The measured surfacemore » dipoles are negative for all clusters on Cu(111) and Cu 2O/Cu(111), but those on the Cu 2O surface are much larger in magnitude. In addition, sub-stoichiometric or “reduced” clusters exhibit smaller surface dipoles on both the Cu(111) and Cu 2O surfaces. Negative surface dipoles for clusters on Cu(111) suggest Cu → cluster electron transfer, which is generally supported by DFT-calculated Bader charge distributions. For Cu 2O/Cu(111), calculations of the surface electrostatic potentials show that the charge distributions associated with cluster adsorption structures or distortions at the cluster–Cu 2O–Cu(111) interface are largely responsible for the observed negative surface dipoles. Changes observed in the XPS spectra for the Mo 3d, Nb 3d, and Ti 2p core levels of the clusters on Cu(111) and Cu 2O/Cu(111) are interpreted with help from the calculated Bader charges and cluster adsorption structures, the latter providing information about the presence of inequivalent cation sites. Finally, the results presented in this work illustrate how the combined use of different experimental probes along with theoretical calculations can result in a more realistic picture of cluster–support interactions and bonding.« less

Surface Electrochemical Modification of a Nickel Substrate to Prepare a NiFe-based Electrode for Water Oxidation.

PubMed

Guo, Dingyi; Qi, Jing; Zhang, Wei; Cao, Rui

2017-01-20

The slow kinetics of water oxidation greatly jeopardizes the efficiency of water electrolysis for H 2 production. Developing highly active water oxidation electrodes with affordable fabrication costs is thus of great importance. Herein, a Ni II Fe III surface species on Ni metal substrate was generated by electrochemical modification of Ni in a ferrous solution by a fast, simple, and cost-effective procedure. In the prepared Ni II Fe III catalyst film, Fe III was incorporated uniformly through controlled oxidation of Fe II cations on the electrode surface. The catalytically active Ni II originated from the Ni foam substrate, which ensured the close contact between the catalyst and the support toward improved charge-transfer efficiency. The as-prepared electrode exhibited high activity and long-term stability for electrocatalytic water oxidation. The overpotentials required to reach water oxidation current densities of 50, 100, and 500 mA cm -2 are 276, 290, and 329 mV, respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The secret behind the success of doping nickel oxyhydroxide with iron.

PubMed

Fidelsky, Vicky; Toroker, Maytal Caspary

2017-03-15

Discovering better catalysts for water splitting is the holy grail of the renewable energy field. One of the most successful water oxidation catalysts is nickel oxyhydroxide (NiOOH), which is chemically active only as a result of doping with Fe. In order to shed light on how Fe improves efficiency, we perform Density Functional Theory +U (DFT+U) calculations of water oxidation reaction intermediates of Fe substitutional doped NiOOH. The results are analyzed while considering the presence of vacancies that we use as probes to test the effect of adding charge to the surface. We find that the smaller electronegativity of the Fe dopant relative to Ni allows the dopant to have several possible oxidation states with less energy penalty. As a result, the presence of vacancies which alters local oxidation states does not affect the low overpotential of Fe-doped NiOOH. We conclude that the secret to the success of doping NiOOH with iron is the ability of iron to easily change oxidation states, which is critical during the chemical reaction of water oxidation.

Thermal oxidation of Si/SiGe heterostructures for use in quantum dot qubits

NASA Astrophysics Data System (ADS)

Neyens, Samuel F.; Foote, Ryan H.; Knapp, T. J.; McJunkin, Thomas; Savage, D. E.; Lagally, M. G.; Coppersmith, S. N.; Eriksson, M. A.

Here we demonstrate dry thermal oxidation of a Si/SiGe heterostructure at 700°C and use a Hall bar device to measure the mobility after oxidation to be 43,000 cm2V-1s-1 at a carrier density of 4.1 ×1011 cm-2. Surprisingly, we find no significant reduction in mobility compared with an Al2O3 device made with atomic layer deposition on the same heterostructure, indicating thermal oxidation can be used to process Si/SiGe quantum dot devices. This result provides a path for investigating improvements to the gate oxide in Si/SiGe qubit devices, whose performance is believed to be limited by charge noise in the oxide layer. This work was supported in part by ARO (W911NF-12-0607) and NSF (DMR-1206915 and PHY-1104660). Development and maintenance of the growth facilities used for fabricating samples is supported by DOE (DE-FG02-03ER46028). This research utilized NSF-supported shared facilities at the University of Wisconsin-Madison.

Direct recognition of superparamagnetic nanocrystals by macrophage scavenger receptor SR-AI.

PubMed

Chao, Ying; Karmali, Priya P; Mukthavaram, Rajesh; Kesari, Santosh; Kouznetsova, Valentina L; Tsigelny, Igor F; Simberg, Dmitri

2013-05-28

Scavenger receptors (SRs) are molecular pattern recognition receptors that have been shown to mediate opsonin-independent uptake of therapeutic and imaging nanoparticles, underlying the importance of SRs in nanomedicine. Unlike pathogens, engineered nanomaterials offer great flexibility in control of surface properties, allowing addressing specific questions regarding the molecular mechanisms of nanoparticle recognition. Recently, we showed that SR-type AI/II mediates opsonin-independent internalization of dextran superparamagnetic iron oxide (SPIO) nanoparticles via positively charged extracellular collagen-like domain. To understand the mechanism of opsonin-independent SPIO recognition, we tested the binding and uptake of nanoparticles with different surface coatings by SR-AI. SPIO coated with 10 kDa dextran was efficiently recognized and taken up by SR-AI transfected cells and J774 macrophages, while SPIO with 20 kDa dextran coating or cross-linked dextran hydrogel avoided the binding and uptake. Nanoparticle negative charge density and zeta-potential did not correlate with SR-AI binding/uptake efficiency. Additional experiments and computer modeling revealed that recognition of the iron oxide crystalline core by the positively charged collagen-like domain of SR-AI is sterically hindered by surface polymer coating. Importantly, the modeling revealed a strong complementarity between the surface Fe-OH groups of the magnetite crystal and the charged lysines of the collagen-like domain of SR-AI, suggesting a specific recognition of SPIO crystalline surface. These data provide an insight into the molecular recognition of nanocrystals by innate immunity receptors and the mechanisms whereby polymer coatings promote immune evasion.

Protection of MOS capacitors during anodic bonding

NASA Astrophysics Data System (ADS)

Schjølberg-Henriksen, K.; Plaza, J. A.; Rafí, J. M.; Esteve, J.; Campabadal, F.; Santander, J.; Jensen, G. U.; Hanneborg, A.

2002-07-01

We have investigated the electrical damage by anodic bonding on CMOS-quality gate oxide and methods to prevent this damage. n-type and p-type MOS capacitors were characterized by quasi-static and high-frequency CV-curves before and after anodic bonding. Capacitors that were bonded to a Pyrex wafer with 10 μm deep cavities enclosing the capacitors exhibited increased leakage current and interface trap density after bonding. Two different methods were successful in protecting the capacitors from such damage. Our first approach was to increase the cavity depth from 10 μm to 50 μm, thus reducing the electric field across the gate oxide during bonding from approximately 2 × 105 V cm-1 to 4 × 104 V cm-1. The second protection method was to coat the inside of a 10 μm deep Pyrex glass cavity with aluminium, forming a Faraday cage that removed the electric field across the cavity during anodic bonding. Both methods resulted in capacitors with decreased interface trap density and unchanged leakage current after bonding. No change in effective oxide charge or mobile ion contamination was observed on any of the capacitors in the study.

Polymer/metal oxide hybrid dielectrics for low voltage field-effect transistors with solution-processed, high-mobility semiconductors

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

Held, Martin; Schießl, Stefan P.; Gannott, Florentina

Transistors for future flexible organic light-emitting diode (OLED) display backplanes should operate at low voltages and be able to sustain high currents over long times without degradation. Hence, high capacitance dielectrics with low surface trap densities are required that are compatible with solution-processable high-mobility semiconductors. Here, we combine poly(methyl methacrylate) (PMMA) and atomic layer deposition hafnium oxide (HfO{sub x}) into a bilayer hybrid dielectric for field-effect transistors with a donor-acceptor polymer (DPPT-TT) or single-walled carbon nanotubes (SWNTs) as the semiconductor and demonstrate substantially improved device performances for both. The ultra-thin PMMA layer ensures a low density of trap states atmore » the semiconductor-dielectric interface while the metal oxide layer provides high capacitance, low gate leakage and superior barrier properties. Transistors with these thin (≤70 nm), high capacitance (100–300 nF/cm{sup 2}) hybrid dielectrics enable low operating voltages (<5 V), balanced charge carrier mobilities and low threshold voltages. Moreover, the hybrid layers substantially improve the bias stress stability of the transistors compared to those with pure PMMA and HfO{sub x} dielectrics.« less

Molecular simulation insights on the in vacuo adsorption of amino acids on graphene oxide surfaces with varying surface oxygen densities

NASA Astrophysics Data System (ADS)

Rahmani, Farzin; Nouranian, Sasan; Mahdavi, Mina; Al-Ostaz, Ahmed

2016-11-01

In this fundamental study, a series of molecular dynamics simulations were performed in vacuo to investigate the energetics and select geometries of 20 standard amino acids (AAs) on pristine graphene (PG) and graphene oxide (GO) surfaces as a function of graphene surface oxygen density. These interactions are of key interest to graphene/biomolecular systems. Our results indicate that aromatic AAs exhibit the strongest total interactions with the PG surfaces due to π-π stacking. Tryptophan (Trp) has the highest aromaticity due to its indole side chain and, hence, has the strongest interaction among all AAs (-16.66 kcal/mol). Aliphatic, polar, and charged AAs show various levels of affinity to the PG sheets depending on the strength of their side chain hydrophobic interactions. For example, arginine (Arg) with its guanidinium side chain exhibits the strongest interaction with the PG sheets (-13.81 kcal/mol) following aromatic AAs. Also, glycine (Gly; a polar AA) has the weakest interaction with the PG sheets (-7.29 kcal/mol). When oxygen-containing functional groups are added to the graphene sheets, the π-π stacking in aromatic AAs becomes disrupted and perfect parallelism of the aromatic rings is lost. Moreover, hydrogen bonding and/or electrostatic interactions become more pronounced. Charged AAs exhibit the strongest interactions with the GO surfaces. In general, the AA-GO interactions increase with increasing surface oxygen density, and the effect is more pronounced at higher O/C ratios. This study provides a quantitative measure of AA-graphene interactions for the design and tuning of biomolecular systems suitable for biosensing, drug delivery, and gene delivery applications.

In vitro cytotoxicity of iron oxide nanoparticles: effects of chitosan and polyvinyl alcohol as stabilizing agents

NASA Astrophysics Data System (ADS)

Tran, Phong A.; Nguyen, Hiep T.; Fox, Kate; Tran, Nhiem

2018-03-01

Iron oxide magnetic nanoparticles have significant potential in biomedical applications such as in diagnosis, imaging and therapeutic agent delivery. The choice of stabilizers and surface functionalization is important as it is known to strongly influence the cytotoxicity of the nanoparticles. The present study aimed at investigating the effects of surface charges on the cytotoxicity of iron oxide nanoparticles. We used a co-precipitation method to synthesize iron oxide nanoparticles which were then stabilized with either chitosan (CS) or polyvinyl alcohol (PVA) which have net positive charge and zero charge at physiological pH, respectively. The nanoparticles were characterized in terms of size, charges and chemical oxidation state. Cytotoxicity of the nanoparticles was assessed using mouse fibroblast cells and was correlated with surface charges of the nanoparticles and their aggregation.

THERMOCHEMICAL HEAT STORAGE FOR CONCENTRATED SOLAR POWER

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

PROJECT STAFF

2011-10-31

Thermal energy storage (TES) is an integral part of a concentrated solar power (CSP) system. It enables plant operators to generate electricity beyond on sun hours and supply power to the grid to meet peak demand. Current CSP sensible heat storage systems employ molten salts as both the heat transfer fluid and the heat storage media. These systems have an upper operating temperature limit of around 400 C. Future TES systems are expected to operate at temperatures between 600 C to 1000 C for higher thermal efficiencies which should result in lower electricity cost. To meet future operating temperature andmore » electricity cost requirements, a TES concept utilizing thermochemical cycles (TCs) based on multivalent solid oxides was proposed. The system employs a pair of reduction and oxidation (REDOX) reactions to store and release heat. In the storage step, hot air from the solar receiver is used to reduce the oxidation state of an oxide cation, e.g. Fe3+ to Fe2+. Heat energy is thus stored as chemical bonds and the oxide is charged. To discharge the stored energy, the reduced oxide is re-oxidized in air and heat is released. Air is used as both the heat transfer fluid and reactant and no storage of fluid is needed. This project investigated the engineering and economic feasibility of this proposed TES concept. The DOE storage cost and LCOE targets are $15/kWh and $0.09/kWh respectively. Sixteen pure oxide cycles were identified through thermodynamic calculations and literature information. Data showed the kinetics of re-oxidation of the various oxides to be a key barrier to implementing the proposed concept. A down selection was carried out based on operating temperature, materials costs and preliminary laboratory measurements. Cobalt oxide, manganese oxide and barium oxide were selected for developmental studies to improve their REDOX reaction kinetics. A novel approach utilizing mixed oxides to improve the REDOX kinetics of the selected oxides was proposed. It partially replaces some of the primary oxide cations with selected secondary cations. This causes a lattice charge imbalance and increases the anion vacancy density. Such vacancies enhance the ionic mass transport and lead to faster re-oxidation. Reoxidation fractions of Mn3O4 to Mn2O3 and CoO to Co3O4 were improved by up to 16 fold through the addition of a secondary oxide. However, no improvement was obtained in barium based mixed oxides. In addition to enhancing the short term re-oxidation kinetics, it was found that the use of mixed oxides also help to stabilize or even improve the TES properties after long term thermal cycling. Part of this improvement could be attributed to a reduced grain size in the mixed oxides. Based on the measurement results, manganese-iron, cobalt-aluminum and cobalt iron mixed oxides have been proposed for future engineering scale demonstration. Using the cobalt and manganese mixed oxides, we were able to demonstrate charge and discharge of the TES media in both a bench top fixed bed and a rotary kiln-moving bed reactor. Operations of the fixed bed configuration are straight forward but require a large mass flow rate and higher fluid temperature for charging. The rotary kiln makes direct solar irradiation possible and provides significantly better heat transfer, but designs to transport the TES oxide in and out of the reactor will need to be defined. The final reactor and system design will have to be based on the economics of the CSP plant. A materials compatibility study was also conducted and it identified Inconel 625 as a suitable high temperature engineering material to construct a reactor holding either cobalt or manganese mixed oxides. To assess the economics of such a CSP plant, a packed bed reactor model was established as a baseline. Measured cobalt-aluminum oxide reaction kinetics were applied to the model and the influences of bed properties and process parameters on the overall system design were investigated. The optimal TES system design was found to be a network of eight fixed bed reactors at 18.75 MWth each with charge and discharge temperatures between 1200 C and 600 C, which provides a constant output temperature of 900 C. The charge and discharge time are 8 hours each respectively. This design was integrated into a process flowsheet of a CSP plant and the system's economics were determined using AspenPlus and NREL's Solar Advisory Model. Storage cost is very sensitive to materials cost and was calculated to be based around $40/kWh for cobalt based mixed oxide. It can potentially decrease to $10/kWh based on reduced materials cost on a bulk scale. The corresponding calculated LCOE was between $0.22 and 0.30/kW-h. The high LCOE is a result of the high charging temperature required in this first design and the cost of cobalt oxide. It is expected that a moving bed reactor using manganese oxide will significantly improve the economics of the proposed concept.« less

Extension of the self-consistent-charge density-functional tight-binding method: third-order expansion of the density functional theory total energy and introduction of a modified effective coulomb interaction.

PubMed

Yang, Yang; Yu, Haibo; York, Darrin; Cui, Qiang; Elstner, Marcus

2007-10-25

The standard self-consistent-charge density-functional-tight-binding (SCC-DFTB) method (Phys. Rev. B 1998, 58, 7260) is derived by a second-order expansion of the density functional theory total energy expression, followed by an approximation of the charge density fluctuations by charge monopoles and an effective damped Coulomb interaction between the atomic net charges. The central assumptions behind this effective charge-charge interaction are the inverse relation of atomic size and chemical hardness and the use of a fixed chemical hardness parameter independent of the atomic charge state. While these approximations seem to be unproblematic for many covalently bound systems, they are quantitatively insufficient for hydrogen-bonding interactions and (anionic) molecules with localized net charges. Here, we present an extension of the SCC-DFTB method to incorporate third-order terms in the charge density fluctuations, leading to chemical hardness parameters that are dependent on the atomic charge state and a modification of the Coulomb scaling to improve the electrostatic treatment within the second-order terms. These modifications lead to a significant improvement in the description of hydrogen-bonding interactions and proton affinities of biologically relevant molecules.

The influence of hydrogenation and oxygen vacancies on molybdenum oxides work function and gap states for application in organic optoelectronics.

PubMed

Vasilopoulou, Maria; Douvas, Antonios M; Georgiadou, Dimitra G; Palilis, Leonidas C; Kennou, Stella; Sygellou, Labrini; Soultati, Anastasia; Kostis, Ioannis; Papadimitropoulos, Giorgos; Davazoglou, Dimitris; Argitis, Panagiotis

2012-10-03

Molybdenum oxide is used as a low-resistance anode interfacial layer in applications such as organic light emitting diodes and organic photovoltaics. However, little is known about the correlation between its stoichiometry and electronic properties, such as work function and occupied gap states. In addition, despite the fact that the knowledge of the exact oxide stoichiometry is of paramount importance, few studies have appeared in the literature discussing how this stoichiometry can be controlled to permit the desirable modification of the oxide's electronic structure. This work aims to investigate the beneficial role of hydrogenation (the incorporation of hydrogen within the oxide lattice) versus oxygen vacancy formation in tuning the electronic structure of molybdenum oxides while maintaining their high work function. A large improvement in the operational characteristics of both polymer light emitting devices and bulk heterojunction solar cells incorporating hydrogenated Mo oxides as hole injection/extraction layers was achieved as a result of favorable energy level alignment at the metal oxide/organic interface and enhanced charge transport through the formation of a large density of gap states near the Fermi level.

Photolithographically Patterned TiO2 Films for Electrolyte-Gated Transistors.

PubMed

Valitova, Irina; Kumar, Prajwal; Meng, Xiang; Soavi, Francesca; Santato, Clara; Cicoira, Fabio

2016-06-15

Metal oxides constitute a class of materials whose properties cover the entire range from insulators to semiconductors to metals. Most metal oxides are abundant and accessible at moderate cost. Metal oxides are widely investigated as channel materials in transistors, including electrolyte-gated transistors, where the charge carrier density can be modulated by orders of magnitude upon application of relatively low electrical bias (2 V). Electrolyte gating offers the opportunity to envisage new applications in flexible and printed electronics as well as to improve our current understanding of fundamental processes in electronic materials, e.g. insulator/metal transitions. In this work, we employ photolithographically patterned TiO2 films as channels for electrolyte-gated transistors. TiO2 stands out for its biocompatibility and wide use in sensing, electrochromics, photovoltaics and photocatalysis. We fabricated TiO2 electrolyte-gated transistors using an original unconventional parylene-based patterning technique. By using a combination of electrochemical and charge carrier transport measurements we demonstrated that patterning improves the performance of electrolyte-gated TiO2 transistors with respect to their unpatterned counterparts. Patterned electrolyte-gated (EG) TiO2 transistors show threshold voltages of about 0.9 V, ON/OFF ratios as high as 1 × 10(5), and electron mobility above 1 cm(2)/(V s).

Electrochemical and Capacitive Properties of Carbon Dots/Reduced Graphene Oxide Supercapacitors.

PubMed

Dang, Yong-Qiang; Ren, Shao-Zhao; Liu, Guoyang; Cai, Jiangtao; Zhang, Yating; Qiu, Jieshan

2016-11-14

There is much recent interest in graphene-based composite electrode materials because of their excellent mechanical strengths, high electron mobilities, and large specific surface areas. These materials are good candidates for applications in supercapacitors. In this work, a new graphene-based electrode material for supercapacitors was fabricated by anchoring carbon dots (CDs) on reduced graphene oxide (rGO). The capacitive properties of electrodes in aqueous electrolytes were systematically studied by galvanostatic charge-discharge measurements, cyclic voltammetry, and electrochemical impedance spectroscopy. The capacitance of rGO was improved when an appropriate amount of CDs were added to the material. The CD/rGO electrode exhibited a good reversibility, excellent rate capability, fast charge transfer, and high specific capacitance in 1 M H₂SO₄. Its capacitance was as high as 211.9 F/g at a current density of 0.5 A/g. This capacitance was 74.3% higher than that of a pristine rGO electrode (121.6 F/g), and the capacitance of the CD/rGO electrode retained 92.8% of its original value after 1000 cycles at a CDs-to-rGO ratio of 5:1.

Conduction mechanism of leakage current due to the traps in ZrO2 thin film

NASA Astrophysics Data System (ADS)

Seo, Yohan; Lee, Sangyouk; An, Ilsin; Song, Chulgi; Jeong, Heejun

2009-11-01

In this work, a metal-oxide-semiconductor capacitor with zirconium oxide (ZrO2) gate dielectric was fabricated by an atomic layer deposition (ALD) technique and the leakage current characteristics under negative bias were studied. From the result of current-voltage curves there are two possible conduction mechanisms to explain the leakage current in the ZrO2 thin film. The dominant mechanism is the space charge limited conduction in the high-electric field region (1.5-5.0 MV cm-1) while the trap-assisted tunneling due to the existence of traps is prevailed in the low-electric field region (0.8-1.5 MV cm-1). Conduction caused by the trap-assisted tunneling is found from the experimental results of a weak temperature dependence of current, and the trap barrier height is obtained. The space charge limited conduction is evidenced, for different temperatures, by Child's law dependence of current density versus voltage. Child's law dependence can be explained by considering a single discrete trapping level and we can obtain the activation energy of 0.22 eV.

An investigation of manganese based electrode materials for use in lithium ion batteries

NASA Astrophysics Data System (ADS)

Sengupta, Surajit

Lithium-based batteries are potential candidates to provide maximum volumetric and gravimetric energy density. One of the most attractive candidates as a cathode material for secondary lithium ion battery systems is the spinel LiMn 2O4 because it is environmentally friendly, less expensive and is capable of providing high energy density as compared to other cathode materials that are currently available. One problem associated with the spinel structure is capacity fading during multiple cycles of charge and discharge operations. This behaviour is due in part to the structural distortion during deep charge and discharge where nearly 100% of the lithium is extracted and inserted inside the spinel structure. Capacity fading can also be caused by dissolution of manganese ions in the electrolyte phase. A solution based method has been adapted for the synthesis of lithium manganese oxide, and chromium and cobalt doped mixed oxide materials using polyvinyl alcohol (PVA) as a chelating agent. It has been found from TGA/DSC analysis that at around 220°C the synthesis reaction is completed. The precursor powders obtained were annealed at different temperatures and times in the range of 250°C to 600°C and from 2 to 8 hours respectively to obtain pure spinel oxides. From X-ray analysis it has been observed that the crystallite size can be controlled in the range of approximately 6 nm to 32 nm depending on the annealing time and the temperature. The morphology of the synthesized materials consisted of submicron sized particles agglomerated with micropores inside the network structure. To observe the effect of physical properties on battery performance cyclic chronopotentiometric evaluation was conducted. It has been found with these synthesized materials that there is an increase in the 1st discharge capacity with an increase in the annealing time and the temperature at both 1C and C/5 rates. This increase is more significant when the annealing temperature is 600°C as compared to that at 250°C. This implies that an increase in particle size may improve the initial discharge capacity. It was observed that at the discharge rate of 1C, the material annealed at 600°C for 8 hours showed the best performance with respect to an average initial discharge capacity, energy density and capacity retention. However, it was found that the initial discharge capacity, the energy density and the capacity retention are poor for highly crystalline, micron sized lithium manganese oxide cathode material. (Abstract shortened by UMI.)

Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer.

PubMed

Ghosh, Soumen; Sonnenberger, Andrew L; Hoyer, Chad E; Truhlar, Donald G; Gagliardi, Laura

2015-08-11

The correct description of charge transfer in ground and excited states is very important for molecular interactions, photochemistry, electrochemistry, and charge transport, but it is very challenging for Kohn-Sham (KS) density functional theory (DFT). KS-DFT exchange-correlation functionals without nonlocal exchange fail to describe both ground- and excited-state charge transfer properly. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory with a new type of density functional called an on-top density functional. Here we have used MC-PDFT to study challenging ground- and excited-state charge-transfer processes by using on-top density functionals obtained by translating KS exchange-correlation functionals. For ground-state charge transfer, MC-PDFT performs better than either the PBE exchange-correlation functional or CASPT2 wave function theory. For excited-state charge transfer, MC-PDFT (unlike KS-DFT) shows qualitatively correct behavior at long-range with great improvement in predicted excitation energies.

Interface investigation of solution processed high- κ ZrO2/Si MOS structure by DLTS

NASA Astrophysics Data System (ADS)

Kumar, Arvind; Mondal, Sandip; Rao, Ksr Koteswara

The interfacial region is dominating due to the continuous downscaling and integration of high- k oxides in CMOS applications. The accurate characterization of high- k oxides/semiconductor interface has the significant importance towards its usage in memory and thin film devices. The interface traps at the high - k /semiconductor interface can be quantified by deep level transient spectroscopy (DLTS) with better accuracy in contrast to capacitance-voltage (CV) and conductance technique. We report the fabrication of high- k ZrO2 films on p-Si substrate by a simple and inexpensive sol-gel spin-coating technique. Further, the ZrO2/Si interface is characterized through DLTS. The flat-band voltage (VFB) and the density of slow interface states (oxide trapped charges) extracted from CV characteristics are 0.37 V and 2x10- 11 C/cm2, respectively. The activation energy, interface state density and capture cross-section quantified by DLTS are EV + 0.42 eV, 3.4x1011 eV- 1 cm- 2 and 5.8x10- 18 cm2, respectively. The high quality ZrO2 films own high dielectric constant 15 with low leakage current density might be an appropriate insulating layer in future electronic application. The low value of interface state density and capture cross-section are the indication of high quality interface and the defect present at the interface may not affect the device performance to a great extent. The DLTS study provides a broad understanding about the traps present at the interface of spin-coated ZrO2/Si.

Broadband Light Absorption and Efficient Charge Separation Using a Light Scattering Layer with Mixed Cavities for High-Performance Perovskite Photovoltaic Cells with Stability.

PubMed

Moon, Byeong Cheul; Park, Jung Hyo; Lee, Dong Ki; Tsvetkov, Nikolai; Ock, Ilwoo; Choi, Kyung Min; Kang, Jeung Ku

2017-08-01

CH 3 NH 3 PbI 3 is one of the promising light sensitizers for perovskite photovoltaic cells, but a thick layer is required to enhance light absorption in the long-wavelength regime ranging from PbI 2 absorption edge (500 nm) to its optical band-gap edge (780 nm) in visible light. Meanwhile, the thick perovskite layer suppresses visible-light absorption in the short wavelengths below 500 nm and charge extraction capability of electron-hole pairs produced upon light absorption. Herein, we find that a new light scattering layer with the mixed cavities of sizes in 100 and 200 nm between transparent fluorine-doped tin oxide and mesoporous titanium dioxide electron transport layer enables full absorption of short-wavelength photons (λ < 500 nm) to the perovskite along with enhanced absorption of long-wavelength photons (500 nm < λ < 780 nm). Moreover, the light-driven electric field is proven to allow efficient charge extraction upon light absorption, thereby leading to the increased photocurrent density as well as the fill factor prompted by the slow recombination rate. Additionally, the photocurrent density of the cell with a light scattering layer of mixed cavities is stabilized due to suppressed charge accumulation. Consequently, this work provides a new route to realize broadband light harvesting of visible light for high-performance perovskite photovoltaic cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron Excess Doping and Effective Schottky Barrier Reduction on the MoS2/h-BN Heterostructure.

PubMed

Joo, Min-Kyu; Moon, Byoung Hee; Ji, Hyunjin; Han, Gang Hee; Kim, Hyun; Lee, Gwanmu; Lim, Seong Chu; Suh, Dongseok; Lee, Young Hee

2016-10-12

Layered hexagonal boron nitride (h-BN) thin film is a dielectric that surpasses carrier mobility by reducing charge scattering with silicon oxide in diverse electronics formed with graphene and transition metal dichalcogenides. However, the h-BN effect on electron doping concentration and Schottky barrier is little known. Here, we report that use of h-BN thin film as a substrate for monolayer MoS 2 can induce ∼6.5 × 10 11 cm -2 electron doping at room temperature which was determined using theoretical flat band model and interface trap density. The saturated excess electron concentration of MoS 2 on h-BN was found to be ∼5 × 10 13 cm -2 at high temperature and was significantly reduced at low temperature. Further, the inserted h-BN enables us to reduce the Coulombic charge scattering in MoS 2 /h-BN and lower the effective Schottky barrier height by a factor of 3, which gives rise to four times enhanced the field-effect carrier mobility and an emergence of metal-insulator transition at a much lower charge density of ∼1.0 × 10 12 cm -2 (T = 25 K). The reduced effective Schottky barrier height in MoS 2 /h-BN is attributed to the decreased effective work function of MoS 2 arisen from h-BN induced n-doping and the reduced effective metal work function due to dipole moments originated from fixed charges in SiO 2 .

Development and Application of a Wireless Sensor for Space Charge Density Measurement in an Ultra-High-Voltage, Direct-Current Environment

PubMed Central

Xin, Encheng; Ju, Yong; Yuan, Haiwen

2016-01-01

A space charge density wireless measurement system based on the idea of distributed measurement is proposed for collecting and monitoring the space charge density in an ultra-high-voltage direct-current (UHVDC) environment. The proposed system architecture is composed of a number of wireless nodes connected with space charge density sensors and a base station. The space charge density sensor based on atmospheric ion counter method is elaborated and developed, and the ARM microprocessor and Zigbee radio frequency module are applied. The wireless network communication quality and the relationship between energy consumption and transmission distance in the complicated electromagnetic environment is tested. Based on the experimental results, the proposed measurement system demonstrates that it can adapt to the complex electromagnetic environment under the UHVDC transmission lines and can accurately measure the space charge density. PMID:27775627

Development and Application of a Wireless Sensor for Space Charge Density Measurement in an Ultra-High-Voltage, Direct-Current Environment.

PubMed

Xin, Encheng; Ju, Yong; Yuan, Haiwen

2016-10-20

A space charge density wireless measurement system based on the idea of distributed measurement is proposed for collecting and monitoring the space charge density in an ultra-high-voltage direct-current (UHVDC) environment. The proposed system architecture is composed of a number of wireless nodes connected with space charge density sensors and a base station. The space charge density sensor based on atmospheric ion counter method is elaborated and developed, and the ARM microprocessor and Zigbee radio frequency module are applied. The wireless network communication quality and the relationship between energy consumption and transmission distance in the complicated electromagnetic environment is tested. Based on the experimental results, the proposed measurement system demonstrates that it can adapt to the complex electromagnetic environment under the UHVDC transmission lines and can accurately measure the space charge density.

Hybrid supercapacitor-battery materials for fast electrochemical charge storage

PubMed Central

Vlad, A.; Singh, N.; Rolland, J.; Melinte, S.; Ajayan, P. M.; Gohy, J.-F.

2014-01-01

High energy and high power electrochemical energy storage devices rely on different fundamental working principles - bulk vs. surface ion diffusion and electron conduction. Meeting both characteristics within a single or a pair of materials has been under intense investigations yet, severely hindered by intrinsic materials limitations. Here, we provide a solution to this issue and present an approach to design high energy and high power battery electrodes by hybridizing a nitroxide-polymer redox supercapacitor (PTMA) with a Li-ion battery material (LiFePO4). The PTMA constituent dominates the hybrid battery charge process and postpones the LiFePO4 voltage rise by virtue of its ultra-fast electrochemical response and higher working potential. We detail on a unique sequential charging mechanism in the hybrid electrode: PTMA undergoes oxidation to form high-potential redox species, which subsequently relax and charge the LiFePO4 by an internal charge transfer process. A rate capability equivalent to full battery recharge in less than 5 minutes is demonstrated. As a result of hybrid's components synergy, enhanced power and energy density as well as superior cycling stability are obtained, otherwise difficult to achieve from separate constituents. PMID:24603843

Coating polymeric carbon nitride photoanodes on conductive Y:ZnO nanorod arrays for overall water splitting.

PubMed

Fang, Yuanxing; Xu, Yuntao; Li, Xiaochun; Ma, Yiwen; Wang, Xinchen

2018-06-14

Solar-to-fuel conversion via photoelectrochemical (PEC) water splitting has the potential to ease current energy and environmental concerns. In pursuit of sustainability, polymeric carbon nitride (PCN) photosensitizers are receiving increasing attention as replacements for their inorganic counterparts. However, intense charge recombination, primarily because of the numerous surface defects, limits the use of PCN in PEC systems. Herein, photoanodes are designed by coating PCN films onto highly conductive yttrium (Y) doped zinc oxide (ZnO) nanorods (NRs) serving as charge collectors. The generation of charge carriers can therefore be promoted by this type II heterostructure. Accordingly, the charge collectors would be kept nearby for charge separation and transport to be used in the interfacial redox reactions. As such, the photocurrent density of the polymer electrode is improved to an exceptional value of 0.4 mA/cm2 at 1.23 V vs. reversible hydrogen electrode (RHE) in a Na2SO4 electrolyte solution under AM 1.5 illumination. The result reveals a more than 50-fold enhancement over the PCN films achieved by powder, and the efficiency can be preserved at ca. 95% for 160 minutes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simulation of Space Charge Dynamic in Polyethylene Under DC Continuous Electrical Stress

NASA Astrophysics Data System (ADS)

Boukhari, Hamed; Rogti, Fatiha

2016-10-01

The space charge dynamic plays a very important role in the aging and breakdown of polymeric insulation materials under high voltage. This is due to the intensification of the local electric field and the attendant chemical-mechanical effects in the vicinity around the trapped charge. In this paper, we have investigated the space charge dynamic in low-density polyethylene under high direct-current voltage, which is evaluated by experimental conditions. The evaluation is on the basis of simulation using a bipolar charge transport model consisting of charge injection, transports, trapping, detrapping, and recombination phenomena. The theoretical formulation of the physical problem is based on the Poisson, the continuity, and the transport equations. Numerical results provide temporal and local distributions of the electric field, the space charge density for the different kinds of charges (net charge density, mobile and trapped of electron density, mobile hole density), conduction and displacement current densities, and the external current. The result shows the appearance of the negative packet-like space charge with a large amount of the bulk under the dc electric field of 100 kV/mm, and the induced distortion of the electric field is largely near to the anode, about 39% higher than the initial electric field applied.

Effect of direct current sputtering power on the behavior of amorphous indium-gallium-zinc-oxide thin-film transistors under negative bias illumination stress: A combination of experimental analyses and device simulation

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

Jang, Jun Tae; Kim, Dong Myong; Choi, Sung-Jin

The effect of direct current sputtering power of indium-gallium-zinc-oxide (IGZO) on the performance and stability of the corresponding thin-film transistor devices was studied. The field effect mobility increases as the IGZO sputter power increases, at the expense of device reliability under negative bias illumination stress (NBIS). Device simulation based on the extracted sub-gap density of states indicates that the field effect mobility is improved as a result of the number of acceptor-like states decreasing. The degradation by NBIS is suggested to be induced by the formation of peroxides in IGZO rather than charge trapping.

Wedge-shaped potential and Airy-function electron localization in oxide superlattices.

PubMed

Popovic, Z S; Satpathy, S

2005-05-06

Oxide superlattices and microstructures hold the promise for creating a new class of devices with unprecedented functionalities. Density-functional studies of the recently fabricated, lattice-matched perovskite titanates (SrTiO3)n/(LaTiO3)m reveal a classic wedge-shaped potential well for the monolayer (m = 1) structure, originating from the Coulomb potential of a two-dimensional charged La sheet. The potential in turn confines the electrons in the Airy-function-localized states. Magnetism is suppressed for the monolayer structure, while in structures with a thicker LaTiO3 part, bulk antiferromagnetism is recovered, with a narrow transition region separating the magnetic LaTiO3 and the nonmagnetic SrTiO3.

Sputter deposition of indium tin oxide onto zinc pthalocyanine: Chemical and electronic properties of the interface studied by photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Gassmann, Jürgen; Brötz, Joachim; Klein, Andreas

2012-02-01

The interface chemistry and the energy band alignment at the interface formed during sputter deposition of transparent conducting indium tin oxide (ITO) onto the organic semiconductor zinc phtalocyanine (ZnPc), which is important for inverted, transparent, and stacked organic light emitting diodes, is studied by in situ photoelectron spectroscopy (XPS and UPS). ITO was sputtered at room temperature and a low power density with a face to face arrangement of the target and substrate. With these deposition conditions, no chemical reaction and a low barrier height for charge injection at this interface are observed. The barrier height is comparable to those observed for the reverse deposition sequence, which also confirms the absence of sputter damage.

Free volume dependence on electrical properties of Poly (styrene co-acrylonitrile)/Nickel oxide polymer nanocomposites

NASA Astrophysics Data System (ADS)

Ningaraju, S.; Hegde, Vinayakaprasanna N.; Prakash, A. P. Gnana; Ravikumar, H. B.

2018-04-01

Polymer nanocomposites of Poly (styrene co-acrylonitrile)/Nickel Oxide (PSAN/NiO) have been prepared. The increased free volume sizes up to 0.4 wt% of NiO loading indicates overall reduction in packing density of polymer network. The decreased o-Ps lifetime (τ3) at higher concentration of NiO indicates improved interfacial interaction between the surface of NiO nanoparticles and side chain of PSAN polymer matrix. The increased AC/DC conductivity at lower wt% of NiO loading demonstrates increased number of electric charge carriers/mobile ions and their mobility. The increased dielectric constant and dielectric loss up to 0.4 wt% of NiO loading suggests the increased dipoles polarization.

3D Aerogel of Graphitic Carbon Nitride Modified with Perylene Imide and Graphene Oxide for Highly Efficient Nitric Oxide Removal under Visible Light.

PubMed

Hu, Jundie; Chen, Dongyun; Li, Najun; Xu, Qingfeng; Li, Hua; He, Jinghui; Lu, Jianmei

2018-05-01

3D materials are considered promising for photocatalytic applications in air purification because of their large surface areas, controllability, and recyclability. Here, a series of aerogels consisting of graphitic-carbon nitride (g-C 3 N 4 ) modified with a perylene imide (PI) and graphene oxide (GO) are prepared for nitric oxide (NO) removal under visible-light irradiation. All of the photocatalysts exhibit excellent activity in NO removal because of the strong light absorption and good planarity of PI-g-C 3 N 4 coupled with the favorable charge transport properties of GO, which slow the recombination of electron-hole pairs. The aerogel containing thiophene displays the most efficient NO removal of the aerogel series, with a removal ratio of up to 66%. Density functional theory calculations are conducted to explain this result and recycling experiments are carried out to verify the stability and recyclability of these photocatalysts. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transparent conducting oxides: A δ-doped superlattice approach

PubMed Central

Cooper, Valentino R.; Seo, Sung S. Ambrose; Lee, Suyoun; Kim, Jun Sung; Choi, Woo Seok; Okamoto, Satoshi; Lee, Ho Nyung

2014-01-01

Metallic states appearing at interfaces between dissimilar insulating oxides exhibit intriguing phenomena such as superconductivity and magnetism. Despite tremendous progress in understanding their origins, very little is known about how to control the conduction pathways and the distribution of charge carriers. Using optical spectroscopic measurements and density-functional theory (DFT) simulations, we examine the effect of SrTiO3 (STO) spacer layer thickness on the optical transparency and carrier distribution in La δ-doped STO superlattices. We experimentally observe that these metallic superlattices remain highly transparent to visible light; a direct consequence of the appropriately large gap between the O 2p and Ti 3d states. In superlattices with relatively thin STO layers, we predict that three-dimensional conduction would occur due to appreciable overlap of quantum mechanical wavefunctions between neighboring δ-doped layers. These results highlight the potential for using oxide heterostructures in optoelectronic devices by providing a unique route for creating novel transparent conducting oxides. PMID:25109668

Direct imprinting of indium-tin-oxide precursor gel and simultaneous formation of channel and source/drain in thin-film transistor

NASA Astrophysics Data System (ADS)

Haga, Ken-ichi; Kamiya, Yuusuke; Tokumitsu, Eisuke

2018-02-01

We report on a new fabrication process for thin-film transistors (TFTs) with a new structure and a new operation principle. In this process, both the channel and electrode (source/drain) are formed simultaneously, using the same oxide material, using a single nano-rheology printing (n-RP) process, without any conventional lithography process. N-RP is a direct thermal imprint technique and deforms oxide precursor gel. To reduce the source/drain resistance, the material common to the channel and electrode is conductive indium-tin-oxide (ITO). The gate insulator is made of a ferroelectric material, whose high charge density can deplete the channel of the thin ITO film, which realizes the proposed operation principle. First, we have examined the n-RP conditions required for the channel and source/drain patterning, and found that the patterning properties are strongly affected by the cooling rate before separating the mold. Second, we have fabricated the TFTs as proposed and confirmed their TFT operation.

Quantification of surface charge density and its effect on boundary slip.

PubMed

Jing, Dalei; Bhushan, Bharat

2013-06-11

Reduction of fluid drag is important in the micro-/nanofluidic systems. Surface charge and boundary slip can affect the fluid drag, and surface charge is also believed to affect boundary slip. The quantification of surface charge and boundary slip at a solid-liquid interface has been widely studied, but there is a lack of understanding of the effect of surface charge on boundary slip. In this paper, the surface charge density of borosilicate glass and octadecyltrichlorosilane (OTS) surfaces immersed in saline solutions with two ionic concentrations and deionized (DI) water with different pH values and electric field values is quantified by fitting experimental atomic force microscopy (AFM) electrostatic force data using a theoretical model relating the surface charge density and electrostatic force. Results show that pH and electric field can affect the surface charge density of glass and OTS surfaces immersed in saline solutions and DI water. The mechanisms of the effect of pH and electric field on the surface charge density are discussed. The slip length of the OTS surface immersed in saline solutions with two ionic concentrations and DI water with different pH values and electric field values is measured, and their effects on the slip length are analyzed from the point of surface charge. Results show that a larger absolute value of surface charge density leads to a smaller slip length for the OTS surface.

Study of mechanism involved in synthesis of graphene oxide and reduced graphene oxide from graphene nanoplatelets

NASA Astrophysics Data System (ADS)

Sharma, Bhasha; Shekhar, Shashank; Malik, Parul; Jain, Purnima

2018-06-01

Graphene, a wonder material has inspired quest among researchers due to its numerous applications and exceptional properties. This paper highlights the mechanism and chemistry behind the fabrication of graphene oxide by using phosphoric acid. Chemical functionalization is of prime importance which avoids agglomeration of nanoparticles to attain inherent properties. As non-homogeneous dispersion limits its utilization due to interfacial interactions which restrict reactive sites to produce intercalated network. Thus, chemically functionalized graphene leads to stable dispersion and enhances thermal, mechanical and electrical properties of the resultant polymer composite materials. Solubility of graphene in aqueous solution is the major issue because graphene is hydrophobic, to rectify this oxygen containing hydrophilic groups must be introduced to make it compatible and this can be attained by covalent functionalization. Among all nanofiller GO has shown average particle size i.e. 95 nm and highest surface charge density. The characteristic changes were estimated using Raman spectra.

Structural “ δ Doping” to Control Local Magnetization in Isovalent Oxide Heterostructures

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

Moon, E. J.; He, Q.; Ghosh, S.

Modulation and δ-doping strategies, in which atomically thin layers of charged dopants are precisely deposited within a heterostructure, have played enabling roles in the discovery of new physical behavior in electronic materials. Here in this paper, we demonstrate a purely structural “δ-doping” strategy in complex oxide heterostructures, in which atomically thin manganite layers are inserted into an isovalent manganite host, thereby modifying the local rotations of corner-connected MnO 6 octahedra. Combining scanning transmission electron microscopy, polarized neutron reflectometry, and density functional theory, we reveal how local magnetic exchange interactions are enhanced within the spatially confined regions of suppressed octahedral rotations.more » Finally, the combined experimental and theoretical results illustrate the potential to utilize noncharge-based approaches to “doping” in order to enhance or suppress functional properties within spatially confined regions of oxide heterostructures.« less

High concentration effects of neutral-potential-well interface traps on recombination dc current-voltage lineshape in metal-oxide-silicon transistors

NASA Astrophysics Data System (ADS)

Chen, Zuhui; Jie, Bin B.; Sah, Chih-Tang

2008-11-01

Steady-state Shockley-Read-Hall kinetics is employed to explore the high concentration effect of neutral-potential-well interface traps on the electron-hole recombination direct-current current-voltage (R-DCIV) properties in metal-oxide-silicon field-effect transistors. Extensive calculations include device parameter variations in neutral-trapping-potential-well electron interface-trap density NET (charge states 0 and -1), dopant impurity concentration PIM, oxide thickness Xox, forward source/drain junction bias VPN, and transistor temperature T. It shows significant distortion of the R-DCIV lineshape by the high concentrations of the interface traps. The result suggests that the lineshape distortion observed in past experiments, previously attributed to spatial variation in surface impurity concentration and energy distribution of interface traps in the silicon energy gap, can also arise from interface-trap concentration along surface channel region.

Structural “ δ Doping” to Control Local Magnetization in Isovalent Oxide Heterostructures

DOE PAGES

Moon, E. J.; He, Q.; Ghosh, S.; ...

2017-11-08

Modulation and δ-doping strategies, in which atomically thin layers of charged dopants are precisely deposited within a heterostructure, have played enabling roles in the discovery of new physical behavior in electronic materials. Here in this paper, we demonstrate a purely structural “δ-doping” strategy in complex oxide heterostructures, in which atomically thin manganite layers are inserted into an isovalent manganite host, thereby modifying the local rotations of corner-connected MnO 6 octahedra. Combining scanning transmission electron microscopy, polarized neutron reflectometry, and density functional theory, we reveal how local magnetic exchange interactions are enhanced within the spatially confined regions of suppressed octahedral rotations.more » Finally, the combined experimental and theoretical results illustrate the potential to utilize noncharge-based approaches to “doping” in order to enhance or suppress functional properties within spatially confined regions of oxide heterostructures.« less

A Theoretical Investigation on CO Oxidation by Single‐Atom Catalysts M1/γ‐Al2O3 (M=Pd, Fe, Co, and Ni)

PubMed Central

Yang, Tao; Fukuda, Ryoichi; Hosokawa, Saburo; Tanaka, Tsunehiro

2017-01-01

Abstract Single‐atom catalysts have attracted much interest recently because of their excellent stability, high catalytic activity, and remarkable atom efficiency. Inspired by the recent experimental discovery of a highly efficient single‐atom catalyst Pd1/γ‐Al2O3, we conducted a comprehensive DFT study on geometries, stabilities and CO oxidation catalytic activities of M1/γ‐Al2O3 (M=Pd, Fe, Co, and Ni) by using slab‐model. One of the most important results here is that Ni1/Al2O3 catalyst exhibits higher activity in CO oxidation than Pd1/Al2O3. The CO oxidation occurs through the Mars van Krevelen mechanism, the rate‐determining step of which is the generation of CO2 from CO through abstraction of surface oxygen. The projected density of states (PDOS) of 2p orbitals of the surface O, the structure of CO‐adsorbed surface, charge polarization of CO and charge transfer from CO to surface are important factors for these catalysts. Although the binding energies of Fe and Co with Al2O3 are very large, those of Pd and Ni are small, indicating that the neighboring O atom is not strongly bound to Pd and Ni, which leads to an enhancement of the reactivity of the O atom toward CO. The metal oxidation state is suggested to be one of the crucial factors for the observed catalytic activity. PMID:28515795

Growth of a delta-doped silicon layer by molecular beam epitaxy on a charge-coupled device for reflection-limited ultraviolet quantum efficiency

NASA Technical Reports Server (NTRS)

Hoenk, Michael E.; Grunthaner, Paula J.; Grunthaner, Frank J.; Terhune, R. W.; Fattahi, Masoud; Tseng, Hsin-Fu

1992-01-01

Low-temperature silicon molecular beam epitaxy is used to grow a delta-doped silicon layer on a fully processed charge-coupled device (CCD). The measured quantum efficiency of the delta-doped backside-thinned CCD is in agreement with the reflection limit for light incident on the back surface in the spectral range of 260-600 nm. The 2.5 nm silicon layer, grown at 450 C, contained a boron delta-layer with surface density of about 2 x 10 exp 14/sq cm. Passivation of the surface was done by steam oxidation of a nominally undoped 1.5 nm Si cap layer. The UV quantum efficiency was found to be uniform and stable with respect to thermal cycling and illumination conditions.

Cu2O/CuO Bilayered Composite as a High-Efficiency Photocathode for Photoelectrochemical Hydrogen Evolution Reaction

PubMed Central

Yang, Yang; Xu, Di; Wu, Qingyong; Diao, Peng

2016-01-01

Solar powered hydrogen evolution reaction (HER) is one of the key reactions in solar-to-chemical energy conversion. It is desirable to develop photocathodic materials that exhibit high activity toward photoelectrochemical (PEC) HER at more positive potentials because a higher potential means a lower overpotential for HER. In this work, the Cu2O/CuO bilayered composites were prepared by a facile method that involved an electrodeposition and a subsequent thermal oxidation. The resulting Cu2O/CuO bilayered composites exhibited a surprisingly high activity and good stability toward PEC HER, expecially at high potentials in alkaline solution. The photocurrent density for HER was 3.15 mA·cm−2 at the potential of 0.40 V vs. RHE, which was one of the two highest reported at the same potential on copper-oxide-based photocathode. The high photoactivity of the bilayered composite was ascribed to the following three advantages of the Cu2O/CuO heterojunction: (1) the broadened light absorption band that made more efficient use of solar energy, (2) the large space-charge-region potential that enabled a high efficiency for electron-hole separation, and (3) the high majority carrier density that ensured a faster charge transportation rate. This work reveals the potential of the Cu2O/CuO bilayered composite as a promising photocathodic material for solar water splitting. PMID:27748380

Tantalum oxide/silicon nitride: A negatively charged surface passivation stack for silicon solar cells

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

Wan, Yimao, E-mail: yimao.wan@anu.edu.au; Bullock, James; Cuevas, Andres

2015-05-18

This letter reports effective passivation of crystalline silicon (c-Si) surfaces by thermal atomic layer deposited tantalum oxide (Ta{sub 2}O{sub 5}) underneath plasma enhanced chemical vapour deposited silicon nitride (SiN{sub x}). Cross-sectional transmission electron microscopy imaging shows an approximately 2 nm thick interfacial layer between Ta{sub 2}O{sub 5} and c-Si. Surface recombination velocities as low as 5.0 cm/s and 3.2 cm/s are attained on p-type 0.8 Ω·cm and n-type 1.0 Ω·cm c-Si wafers, respectively. Recombination current densities of 25 fA/cm{sup 2} and 68 fA/cm{sup 2} are measured on 150 Ω/sq boron-diffused p{sup +} and 120 Ω/sq phosphorus-diffused n{sup +} c-Si, respectively. Capacitance–voltage measurements reveal a negativemore » fixed insulator charge density of −1.8 × 10{sup 12 }cm{sup −2} for the Ta{sub 2}O{sub 5} film and −1.0 × 10{sup 12 }cm{sup −2} for the Ta{sub 2}O{sub 5}/SiN{sub x} stack. The Ta{sub 2}O{sub 5}/SiN{sub x} stack is demonstrated to be an excellent candidate for surface passivation of high efficiency silicon solar cells.« less

Charge induced enhancement of adsorption for hydrogen storage materials

NASA Astrophysics Data System (ADS)

Sun, Xiang

2009-12-01

The rising concerns about environmental pollution and global warming have facilitated research interest in hydrogen energy as an alternative energy source. To apply hydrogen for transportations, several issues have to be solved, within which hydrogen storage is the most critical problem. Lots of materials and devices have been developed; however, none is able to meet the DOE storage target. The primary issue for hydrogen physisorption is a weak interaction between hydrogen and the surface of solid materials, resulting negligible adsorption at room temperature. To solve this issue, there is a need to increase the interaction between the hydrogen molecules and adsorbent surface. In this study, intrinsic electric dipole is investigated to enhance the adsorption energy. The results from the computer simulation of single ionic compounds with hydrogen molecules to form hydrogen clusters showed that electrical charge of substances plays an important role in generation of attractive interaction with hydrogen molecules. In order to further examine the effects of static interaction on hydrogen adsorption, activated carbon with a large surface area was impregnated with various ionic salts including LiCl, NaCl, KCl, KBr, and NiCl2 and their performance for hydrogen storage was evaluated by using a volumetric method. Corresponding computer simulations have been carried out by using DFT (Density Functional Theory) method combined with point charge arrays. Both experimental and computational results prove that the adsorption capacity of hydrogen and its interaction with the solid materials increased with electrical dipole moment. Besides the intrinsic dipole, an externally applied electric field could be another means to enhance hydrogen adsorption. Hydrogen adsorption under an applied electric field was examined by using porous nickel foil as electrodes. Electrical signals showed that adsorption capacity increased with the increasing of gas pressure and external electric voltage. Direct measurement of the amount of hydrogen adsorption was also carried out with porous nickel oxides and magnesium oxides using the piezoelectric material PMN-PT as the charge supplier due to the pressure. The adsorption enhancement from the PMN-PT generated charges is obvious at hydrogen pressure between 0 and 60 bars, where the hydrogen uptake is increased at about 35% for nickel oxide and 25% for magnesium oxide. Computer simulation reveals that under the external electric field, the electron cloud of hydrogen molecules is pulled over to the adsorbent site and can overlap with the adsorbent electrons, which in turn enhances the adsorption energy. Experiments were also carried out to examine the effects of hydrogen spillover with charge induced enhancement. The results show that the overall storage capacity in nickel oxide increased remarkably by a factor of 4.

Oxidation-etching preparation of MnO2 tubular nanostructures for high-performance supercapacitors.

PubMed

Zhu, Jixin; Shi, Wenhui; Xiao, Ni; Rui, Xianhong; Tan, Huiteng; Lu, Xuehong; Hng, Huey Hoon; Ma, Jan; Yan, Qingyu

2012-05-01

1D hierarchical tubular MnO(2) nanostructures have been prepared through a facile hydrothermal method using carbon nanofibres (CNFs) as sacrificial template. The morphology of MnO(2) nanostructures can be adjusted by changing the reaction time or annealing process. Polycrystalline MnO(2) nanotubes are formed with a short reaction time (e.g., 10 min) while hierarchical tubular MnO(2) nanostructures composed of assembled nanosheets are obtained at longer reaction times (>45 min). The polycrystalline MnO(2) nanotubes can be further converted to porous nanobelts and sponge-like nanowires by annealing in air. Among all the types of MnO(2) nanostructures prepared, tubular MnO(2) nanostructures composed of assembled nanosheets show optimized charge storage performance when tested as supercapacitor electrodes, for example, delivering an power density of 13.33 kW·kg(-1) and a energy density of 21.1 Wh·kg(-1) with a long cycling life over 3000 cycles, which is mainly related to their features of large specific surface area and optimized charge transfer pathway.

Explosively driven low-density foams and powders

DOEpatents

Viecelli, James A [Orinda, CA; Wood, Lowell L [Simi Valley, CA; Ishikawa, Muriel Y [Livermore, CA; Nuckolls, John H [Danville, CA; Pagoria, Phillip F [Livermore, CA

2010-05-04

Hollow RX-08HD cylindrical charges were loaded with boron and PTFE, in the form of low-bulk density powders or powders dispersed in a rigid foam matrix. Each charge was initiated by a Comp B booster at one end, producing a detonation wave propagating down the length of the cylinder, crushing the foam or bulk powder and collapsing the void spaces. The PdV work done in crushing the material heated it to high temperatures, expelling it in a high velocity fluid jet. In the case of boron particles supported in foam, framing camera photos, temperature measurements, and aluminum witness plates suggest that the boron was completely vaporized by the crush wave and that the boron vapor turbulently mixed with and burned in the surrounding air. In the case of PTFE powder, X-ray photoelectron spectroscopy of residues recovered from fragments of a granite target slab suggest that heating was sufficient to dissociate the PTFE to carbon vapor and molecular fluorine which reacted with the quartz and aluminum silicates in the granite to form aluminum oxide and mineral fluoride compounds.

Functionalized organic semiconductor molecules to enhance charge carrier injection in electroluminescent cell

NASA Astrophysics Data System (ADS)

Yalcin, Eyyup; Kara, Duygu Akin; Karakaya, Caner; Yigit, Mesude Zeliha; Havare, Ali Kemal; Can, Mustafa; Tozlu, Cem; Demic, Serafettin; Kus, Mahmut; Aboulouard, Abdelkhalk

2017-07-01

Organic semiconductor (OSC) materials as a charge carrier interface play an important role to improve the device performance of organic electroluminescent cells. In this study, 4,4″-bis(diphenyl amino)-1,1':3‧,1″-terphenyl-5'-carboxylic acid (TPA) and 4,4″-di-9H-carbazol-9-yl-1,1':3‧,1″-terphenyl-5'-carboxylic acid (CAR) has been designed and synthesized to modify indium tin oxide (ITO) layer as interface. Bare ITO and PEDOT:PSS coated on ITO was used as reference anode electrodes for comparison. Furthermore, PEDOT:PSS coated over CAR/ITO and TPA/ITO to observe stability of OSC molecules and to completely cover the ITO surface. Electrical, optical and surface characterizations were performed for each device. Almost all modified devices showed around 36% decrease at the turn on voltage with respect to bare ITO. The current density of bare ITO, ITO/CAR and ITO/TPA were measured as 288, 1525 and 1869 A/m2, respectively. By increasing current density, luminance of modified devices showed much better performance with respect to unmodified devices.

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

Yoshimoto, Shinya, E-mail: yosshi@issp.u-tokyo.ac.jp; Shiozawa, Yuichiro; Koitaya, Takanori

Electronic states and electrical conductivity of the native oxide Si(111) surface adsorbed with an electron donor tetrakis(dimethylamino)ethylene (TDAE) were investigated using ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy (XPS), and independently driven four-probe conductivity measurements. The formation of positively charged TDAE species is confirmed by the downward shift of the vacuum level by 1.45 eV, the absence of HOMO level in the valence band, and observation of the positively charged state in the N 1s XPS spectra. Si 2p XPS spectra and four-probe conductivity measurements revealed that TDAE adsorption induces an increase in downward band bending and a reduction in electrical resistancemore » of the surface, respectively. The sheet conductivity and the electron density of the surface are 1.1 μS/◻ and 4.6 × 10{sup 9} cm{sup −2}, respectively, after TDAE adsorption, and they are as high as 350% of the original surface. These results demonstrate that the electron density of the semiconductor surface is successfully controlled by the electron donor molecule TDAE.« less

An Investigation of Quantum Dot Super Lattice Use in Nonvolatile Memory and Transistors

NASA Astrophysics Data System (ADS)

Mirdha, P.; Parthasarathy, B.; Kondo, J.; Chan, P.-Y.; Heller, E.; Jain, F. C.

2018-02-01

Site-specific self-assembled colloidal quantum dots (QDs) will deposit in two layers only on p-type substrate to form a QD superlattice (QDSL). The QDSL structure has been integrated into the floating gate of a nonvolatile memory component and has demonstrated promising results in multi-bit storage, ease of fabrication, and memory retention. Additionally, multi-valued logic devices and circuits have been created by using QDSL structures which demonstrated ternary and quaternary logic. With increasing use of site-specific self-assembled QDSLs, fundamental understanding of silicon and germanium QDSL charge storage capability, self-assembly on specific surfaces, uniform distribution, and mini-band formation has to be understood for successful implementation in devices. In this work, we investigate the differences in electron charge storage by building metal-oxide semiconductor (MOS) capacitors and using capacitance and voltage measurements to quantify the storage capabilities. The self-assembly process and distribution density of the QDSL is done by obtaining atomic force microscopy (AFM) results on line samples. Additionally, we present a summary of the theoretical density of states in each of the QDSLs.

Hybrid structure of polyaniline/ZnO nanograss and its application in dye-sensitized solar cell with performance improvement

NASA Astrophysics Data System (ADS)

Zhu, Shibu; Wei, Wei; Chen, Xiangnan; Jiang, Man; Zhou, Zuowan

2012-06-01

Polyaniline (PANI) hybridized ZnO photoanode for dye-sensitized solar cell (DSSC) was primarily prepared via a two-step process which involved hydrothermal growth of ZnO nanograss on the fluorine-doped tin oxide (FTO) substrate and subsequently chemisorption of PANI on the surfaces of the ZnO nanorods. The PANI hybridized ZnO nanograss films were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR), and the results indicated that there were chemical interactions between PANI and ZnO. Both pure ZnO nanograss and PANI hybridized ZnO nanograss were applied to DSSC. The results of photoelectrochemical measurement showed that the photocurrent density of PANI (100 mg/L) hybridized ZnO nanograss photoanode was significantly enhanced, and the overall light-conversion efficiency increased by 60%. The electrochemical impedance spectra (EIS) displayed that the electron densities in photoanodes of PANI hybridized ZnO nanograss were larger than that in pure ZnO nanograss. This is ascribed to more effective charge separation and faster interfacial charge transferring occurred in the hybrid photoanode.

Quantum Monte Carlo analysis of a charge ordered insulating antiferromagnet: The Ti 4O 7 Magneli phase

DOE PAGES

Benali, Anouar; Shulenburger, Luke; Krogel, Jaron T.; ...

2016-06-07

The Magneli phase Ti 4O 7 is an important transition metal oxide with a wide range of applications because of its interplay between charge, spin, and lattice degrees of freedom. At low temperatures, it has non-trivial magnetic states very close in energy, driven by electronic exchange and correlation interactions. We have examined three low- lying states, one ferromagnetic and two antiferromagnetic, and calculated their energies as well as Ti spin moment distributions using highly accurate Quantum Monte Carlo methods. We compare our results to those obtained from density functional theory- based methods that include approximate corrections for exchange and correlation.more » Our results confirm the nature of the states and their ordering in energy, as compared with density-functional theory methods. However, the energy differences and spin distributions differ. Here, a detailed analysis suggests that non-local exchange-correlation functionals, in addition to other approximations such as LDA+U to account for correlations, are needed to simultaneously obtain better estimates for spin moments, distributions, energy differences and energy gaps.« less

Model for thickness dependence of radiation charging in MOS structures

NASA Technical Reports Server (NTRS)

Viswanathan, C. R.; Maserjian, J.

1976-01-01

The model considers charge buildup in MOS structures due to hole trapping in the oxide and the creation of sheet charge at the silicon interface. The contribution of hole trapping causes the flatband voltage to increase with thickness in a manner in which square and cube dependences are limiting cases. Experimental measurements on samples covering a 200 - 1000 A range of oxide thickness are consistent with the model, using independently obtained values of hole-trapping parameters. An important finding of our experimental results is that a negative interface charge contribution due to surface states created during irradiation compensates most of the positive charge in the oxide at flatband. The tendency of the surface states to 'track' the positive charge buildup in the oxide, for all thicknesses, applies both in creation during irradiation and in annihilation during annealing. An explanation is proposed based on the common defect origin of hole traps and potential surface states.

Organic and inorganic molecules as probes of mineral surfaces (Invited)

NASA Astrophysics Data System (ADS)

Sverjensky, D. A.

2010-12-01

Although the multi-site nature of mineral surfaces is to be expected based on the underlying crystal structure, definitive evidence of the need to use more than one site in modelling proton surface charge or adsorption of a single adsorbate at the mineral-water interface is lacking. Instead, a single-site approach affords a practical way of averaging over all possible crystal planes and sites in a powdered mineral sample. Extensive analysis of published proton surface charge and adsorption of metals on oxide mineral surfaces can be undertaken with a single site density for each mineral based on tritium exchange or estimation from averages of the site densities of likely exposed surfaces. Even in systems with competing metals (e.g. Cu and Pb on hematite), the same site density as used for proton surface charge can be employed depending on the reaction stoichiometry. All of this indicates that protons and metals can bind to a great variety of sites with the same overall site density. However, simple oxyanions such as carbonate, sulfate, selenate, arsenate and arsenite require a much lower site density for a given mineral. For example, on goethite these oxyanions utilize a site density that correlates with the BET surface area of the goethite. In this way, the oxyanions can be thought of as selectively probing the available sites on the mineral. The correlation probably arises because goethites with different BET surface areas have different proportions of singly and multiply-bonded oxygens, and only the singly-bonded oxygens are useful for inner-sphere surface complexation by the ligand exchange mechanism. Small organic molecules behave in a remarkably similar way. For example, adsorption of oxalate on goethite, and aspartate, glutamate, dihydroxyphenylalanine, lysine and arginine on rutile are all consistent with a much smaller site density than those required for metals such as calcium or neodymium. Overall, these results suggest that both inorganic oxyanions and organic molecules containing carboxylate functional groups serve as much more sensitive probes of the surface structures of minerals than do protons or metals.

On contribution of known atomic partial charges of protein backbone in electrostatic potential density maps.

PubMed

Wang, Jimin

2017-06-01

Partial charges of atoms in a molecule and electrostatic potential (ESP) density for that molecule are known to bear a strong correlation. In order to generate a set of point-field force field parameters for molecular dynamics, Kollman and coworkers have extracted atomic partial charges for each of all 20 amino acids using restrained partial charge-fitting procedures from theoretical ESP density obtained from condensed-state quantum mechanics. The magnitude of atomic partial charges for neutral peptide backbone they have obtained is similar to that of partial atomic charges for ionized carboxylate side chain atoms. In this study, the effect of these known atomic partial charges on ESP is examined using computer simulations and compared with the experimental ESP density recently obtained for proteins using electron microscopy. It is found that the observed ESP density maps are most consistent with the simulations that include atomic partial charges of protein backbone. Therefore, atomic partial charges are integral part of atomic properties in protein molecules and should be included in model refinement. © 2017 The Protein Society.

Development of a classical force field for the oxidized Si surface: application to hydrophilic wafer bonding.

PubMed

Cole, Daniel J; Payne, Mike C; Csányi, Gábor; Spearing, S Mark; Colombi Ciacchi, Lucio

2007-11-28

We have developed a classical two- and three-body interaction potential to simulate the hydroxylated, natively oxidized Si surface in contact with water solutions, based on the combination and extension of the Stillinger-Weber potential and of a potential originally developed to simulate SiO(2) polymorphs. The potential parameters are chosen to reproduce the structure, charge distribution, tensile surface stress, and interactions with single water molecules of a natively oxidized Si surface model previously obtained by means of accurate density functional theory simulations. We have applied the potential to the case of hydrophilic silicon wafer bonding at room temperature, revealing maximum room temperature work of adhesion values for natively oxidized and amorphous silica surfaces of 97 and 90 mJm(2), respectively, at a water adsorption coverage of approximately 1 ML. The difference arises from the stronger interaction of the natively oxidized surface with liquid water, resulting in a higher heat of immersion (203 vs 166 mJm(2)), and may be explained in terms of the more pronounced water structuring close to the surface in alternating layers of larger and smaller densities with respect to the liquid bulk. The computed force-displacement bonding curves may be a useful input for cohesive zone models where both the topographic details of the surfaces and the dependence of the attractive force on the initial surface separation and wetting can be taken into account.

Controlling the charge state of supported nanoparticles in catalysis: lessons from model systems.

PubMed

Pacchioni, Gianfranco; Freund, Hans-Joachim

2018-04-26

Model systems are very important to identify the working principles of real catalysts, and to develop concepts that can be used in the design of new catalytic materials. In this review we report examples of the use of model systems to better understand and control the occurrence of charge transfer at the interface between supported metal nanoparticles and oxide surfaces. In the first part of this article we concentrate on the nature of the support, and on the basic difference in metal/oxide bonding going from a wide-gap non-reducible oxide material to reducible oxide semiconductors. The roles of oxide nanostructuring, bulk and surface defectiveness, and doping with hetero-atoms are also addressed, as they are all aspects that severely affect the metal/oxide interaction. Particular attention is given to the experimental measures of the occurrence of charge transfer at the metal/oxide interface. In this respect, systems based on oxide ultrathin films are particularly important as they allow the use of scanning probe spectroscopies which, often in combination with other measurements and with first principles theoretical simulations, allow full characterization of small supported nanoparticles and their charge state. In a few selected cases, a precise count of the electrons transferred between the oxide and the supported nanoparticle has been possible. Charge transfer can occur through thin, two-dimensional oxide layers also thanks to their structural flexibility. The flow of charge through the oxide film and the formation of charged adsorbates are accompanied in fact by a substantial polaronic relaxation of the film surface which can be rationalized based on electrostatic arguments. In the final part of this review the relationships between model systems and real catalysts are addressed by discussing some examples of how lessons learned from model systems have helped in rationalizing the behavior of real catalysts under working conditions.

Electrical characterization of amorphous Al2O3 dielectric films on n-type 4H-SiC

NASA Astrophysics Data System (ADS)

Khosa, R. Y.; Thorsteinsson, E. B.; Winters, M.; Rorsman, N.; Karhu, R.; Hassan, J.; Sveinbjörnsson, E. Ö.

2018-02-01

We report on the electrical properties of Al2O3 films grown on 4H-SiC by successive thermal oxidation of thin Al layers at low temperatures (200°C - 300°C). MOS capacitors made using these films contain lower density of interface traps, are more immune to electron injection and exhibit higher breakdown field (5MV/cm) than Al2O3 films grown by atomic layer deposition (ALD) or rapid thermal processing (RTP). Furthermore, the interface state density is significantly lower than in MOS capacitors with nitrided thermal silicon dioxide, grown in N2O, serving as the gate dielectric. Deposition of an additional SiO2 film on the top of the Al2O3 layer increases the breakdown voltage of the MOS capacitors while maintaining low density of interface traps. We examine the origin of negative charges frequently encountered in Al2O3 films grown on SiC and find that these charges consist of trapped electrons which can be released from the Al2O3 layer by depletion bias stress and ultraviolet light exposure. This electron trapping needs to be reduced if Al2O3 is to be used as a gate dielectric in SiC MOS technology.

Charge density on thin straight wire, revisited

NASA Astrophysics Data System (ADS)

Jackson, J. D.

2000-09-01

The question of the equilibrium linear charge density on a charged straight conducting "wire" of finite length as its cross-sectional dimension becomes vanishingly small relative to the length is revisited in our didactic presentation. We first consider the wire as the limit of a prolate spheroidal conductor with semi-minor axis a and semi-major axis c when a/c<<1. We then treat an azimuthally symmetric straight conductor of length 2c and variable radius r(z) whose scale is defined by a parameter a. A procedure is developed to find the linear charge density λ(z) as an expansion in powers of 1/Λ, where Λ≡ln(4c2/a2), beginning with a uniform line charge density λ0. We show, for this rather general wire, that in the limit Λ>>1 the linear charge density becomes essentially uniform, but that the tiny nonuniformity (of order 1/Λ) is sufficient to produce a tangential electric field (of order Λ0) that cancels the zeroth-order field that naively seems to belie equilibrium. We specialize to a right circular cylinder and obtain the linear charge density explicitly, correct to order 1/Λ2 inclusive, and also the capacitance of a long isolated charged cylinder, a result anticipated in the published literature 37 years ago. The results for the cylinder are compared with published numerical computations. The second-order correction to the charge density is calculated numerically for a sampling of other shapes to show that the details of the distribution for finite 1/Λ vary with the shape, even though density becomes constant in the limit Λ→∞. We give a second method of finding the charge distribution on the cylinder, one that approximates the charge density by a finite polynomial in z2 and requires the solution of a coupled set of linear algebraic equations. Perhaps the most striking general observation is that the approach to uniformity as a/c→0 is extremely slow.

Energetic mapping of oxide traps in MoS2 field-effect transistors

NASA Astrophysics Data System (ADS)

Illarionov, Yury Yu; Knobloch, Theresia; Waltl, Michael; Rzepa, Gerhard; Pospischil, Andreas; Polyushkin, Dmitry K.; Furchi, Marco M.; Mueller, Thomas; Grasser, Tibor

2017-06-01

The performance of MoS2 transistors is strongly affected by charge trapping in oxide traps with very broad distributions of time constants. These defects degrade the mobility and additionally lead to the hysteresis of the gate transfer characteristics, which presents a crucial performance and reliability issue for these new technologies. Here we perform a detailed study of the hysteresis in double-gated MoS2 FETs and show that this issue is nothing else than a combination of threshold voltage shifts resulting from positive and negative bias-temperature instabilities. While these instabilities are well known from silicon devices, they are even more important in 2D devices given the considerably larger defect densities. Most importantly, the magnitudes of these threshold voltage shifts depend strongly on the density and energetic alignment of the active oxide traps. Based on this, we introduce the incremental hysteresis sweep method which allows for an accurate mapping of these defects and extract their energy distributions from simulations. By applying our method to analyze the impact of oxide traps situated in the Al2O3 top gate of several devices, we confirm its versatility. Since all 2D devices investigated so far suffer from a similar hysteresis behavior, the incremental hysteresis sweep method provides a unique and powerful way for the detailed characterization of their defect bands.

Atomic-scale understanding of non-stoichiometry effects on the electrochemical performance of Ni-rich cathode materials

NASA Astrophysics Data System (ADS)

Kong, Fantai; Liang, Chaoping; Longo, Roberto C.; Zheng, Yongping; Cho, Kyeongjae

2018-02-01

As the next-generation high energy capacity cathode materials for Li-ion batteries, Ni-rich oxides face the problem of obtaining near-stoichiometric phases due to excessive Ni occupying Li sites. These extra-Ni-defects drastically affect the electrochemical performance. Despite of its importance, the fundamental correlation between such defects and the key electrochemical properties is still poorly understood. In this work, using density-functional-theory, we report a comprehensive study on the effects of non-stoichiometric phases on properties of Ni-rich layered oxides. For instance, extra-Ni-defects trigger charge disproportionation reaction within the system, alleviating the Jahn-Teller distortion of Ni3+ ions, which constitutes an important reason for their low formation energies. Kinetic studies of these defects reveal their immobile nature, creating a "pillar effect" that increases the structural stability. Ab initio molecular dynamics revealed Li depletion regions surrounding extra-Ni-defects, which are ultimate responsible for the arduous Li diffusion and re-intercalation, resulting in poor rate performance and initial capacity loss. Finally, the method with combination of high valence cation doping and ion-exchange synthesis is regarded as the most promising way to obtain stoichiometric oxides. Overall, this work not only deepens our understanding of non-stoichiometric Ni-rich layered oxides, but also enables further optimizations of high energy density cathode materials.

Enhancing Mo:BiVO 4 Solar Water Splitting with Patterned Au Nanospheres by Plasmon-Induced Energy Transfer [Rational Nanopositioning for BiVO 4 Solar Water Splitting by Plasmon-induced Energy Transfer

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

Kim, Jung Kyu; Shi, Xinjian; Jeong, Myung Jin

Here, plasmonic metal nanostructures have been extensively investigated to improve the performance of metal oxide photoanodes for photoelectrochemical (PEC) solar water splitting cells. Most of these studies have focused on the effects of those metal nanostructures on enhancing light absorption and enabling direct energy transfer via hot electrons. However, several recent studies have shown that plasmonic metal nanostructures can improve the PEC performance of metal oxide photoanodes via another mechanism known as plasmon–induced resonant energy transfer (PIRET). However, this PIRET effect has not yet been tested for the molybdenum–doped bismuth vanadium oxide (Mo:BiVO 4), regarded as one of the bestmore » metal oxide photoanode candidates. Here, this study constructs a hybrid Au nanosphere/Mo:BiVO 4 photoanode interwoven in a hexagonal pattern to investigate the PIRET effect on the PEC performance of Mo:BiVO 4. This study finds that the Au nanosphere array not only increases light absorption of the photoanode as expected, but also improves both its charge transport and charge transfer efficiencies via PIRET, as confirmed by time–correlated single photon counting and transient absorption studies. As a result, incorporating the Au nanosphere array increases the photocurrent density of Mo:BiVO 4 at 1.23 V versus RHE by ≈2.2–fold (2.83 mA cm –2).« less

Enhancing Mo:BiVO 4 Solar Water Splitting with Patterned Au Nanospheres by Plasmon-Induced Energy Transfer [Rational Nanopositioning for BiVO 4 Solar Water Splitting by Plasmon-induced Energy Transfer

DOE PAGES

Kim, Jung Kyu; Shi, Xinjian; Jeong, Myung Jin; ...

2017-10-04

Here, plasmonic metal nanostructures have been extensively investigated to improve the performance of metal oxide photoanodes for photoelectrochemical (PEC) solar water splitting cells. Most of these studies have focused on the effects of those metal nanostructures on enhancing light absorption and enabling direct energy transfer via hot electrons. However, several recent studies have shown that plasmonic metal nanostructures can improve the PEC performance of metal oxide photoanodes via another mechanism known as plasmon–induced resonant energy transfer (PIRET). However, this PIRET effect has not yet been tested for the molybdenum–doped bismuth vanadium oxide (Mo:BiVO 4), regarded as one of the bestmore » metal oxide photoanode candidates. Here, this study constructs a hybrid Au nanosphere/Mo:BiVO 4 photoanode interwoven in a hexagonal pattern to investigate the PIRET effect on the PEC performance of Mo:BiVO 4. This study finds that the Au nanosphere array not only increases light absorption of the photoanode as expected, but also improves both its charge transport and charge transfer efficiencies via PIRET, as confirmed by time–correlated single photon counting and transient absorption studies. As a result, incorporating the Au nanosphere array increases the photocurrent density of Mo:BiVO 4 at 1.23 V versus RHE by ≈2.2–fold (2.83 mA cm –2).« less

Surface states and annihilation characteristics of positrons trapped at the oxidized Cu(100) surface

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Weiss, A. H.

2013-06-01

In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Oxidation of the Cu(100) surface has been studied by performing an ab-initio investigation of the stability and electronic structure of the Cu(100) missing row reconstructed surface at various on-surface and subsurface oxygen coverages ranging from 0.5 to 1.5 monolayers using density functional theory (DFT). All studied structures have been found to be energetically more favorable as compared to structures formed by purely on-surface oxygen adsorption. The observed decrease in the positron work function when oxygen atoms occupy on-surface and subsurface sites has been attributed to a significant charge redistribution within the first two layers, buckling effects within each layer and an interlayer expansion. The computed positron binding energy, positron surface state wave function, and annihilation probabilities of the surface trapped positrons with relevant core electrons demonstrate their sensitivity to oxygen coverage, atomic structure of the topmost layers of surfaces, and charge transfer effects. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). The results presented provide an explanation for the changes observed in the probability of annihilation of surface trapped positrons with Cu 3p core-level electrons as a function of annealing temperature.

Determination of the surface charge density and temperature dependence of purple membrane by electric force microscopy.

PubMed

Du, Huiwen; Li, Denghua; Wang, Yibing; Wang, Chenxuan; Zhang, Dongdong; Yang, Yan-lian; Wang, Chen

2013-08-29

We report here the measurement of the temperature-dependent surface charge density of purple membrane (PM) by using electrostatic force microscopy (EFM). The surface charge density was measured to be 3.4 × 10(5) e/cm(2) at room temperature and reaches the minimum at around 52 °C. The initial decrease of the surface charge density could be attributed to the reduced dipole alignment because of the thermally induced protein mobility in PM. The increase of charge density at higher temperature could be ascribed to the weakened interaction between proteins and the lipids, which leads to the exposure of the charged amino acids. This work could be a benefit to the direct assessment of the structural stability and electric properties of biological membranes at the nanoscale.

Improving the Thermochemical Energy Storage Performance of the Mn2 O3 /Mn3 O4 Redox Couple by the Incorporation of Iron.

PubMed

Carrillo, Alfonso J; Serrano, David P; Pizarro, Patricia; Coronado, Juan M

2015-06-08

Redox cycles of manganese oxides (Mn2 O3 /Mn3 O4 ) are a promising alternative for thermochemical heat storage systems coupled to concentrated solar power plants as manganese oxides are abundant and inexpensive materials. Although their cyclability for such a purpose has been proved, sintering processes, related to the high-temperature conditions at which charge-discharge cycles are performed, generally cause a cycle-to-cycle decrease in the oxidation rate of Mn3 O4 . To guarantee proper operation, both reactions should present stable reaction rates. In this study, it has been demonstrated that the incorporation of Fe, which is also an abundant material, into the manganese oxides improves the redox performance of this system by increasing the heat storage density, narrowing the redox thermal hysteresis, and, above all, stabilizing and enhancing the oxidation rate over long-term operation, which counteracts the negative effects caused by sintering, although its presence is not avoided. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen-Rich Lithium Oxide Phases Formed at High Pressure for Potential Lithium-Air Battery Electrode.

PubMed

Yang, Wenge; Kim, Duck Young; Yang, Liuxiang; Li, Nana; Tang, Lingyun; Amine, Khalil; Mao, Ho-Kwang

2017-09-01

The lithium-air battery has great potential of achieving specific energy density comparable to that of gasoline. Several lithium oxide phases involved in the charge-discharge process greatly affect the overall performance of lithium-air batteries. One of the key issues is linked to the environmental oxygen-rich conditions during battery cycling. Here, the theoretical prediction and experimental confirmation of new stable oxygen-rich lithium oxides under high pressure conditions are reported. Three new high pressure oxide phases that form at high temperature and pressure are identified: Li 2 O 3 , LiO 2 , and LiO 4 . The LiO 2 and LiO 4 consist of a lithium layer sandwiched by an oxygen ring structure inherited from high pressure ε-O 8 phase, while Li 2 O 3 inherits the local arrangements from ambient LiO 2 and Li 2 O 2 phases. These novel lithium oxides beyond the ambient Li 2 O, Li 2 O 2 , and LiO 2 phases show great potential in improving battery design and performance in large battery applications under extreme conditions.

Molecular orbital evaluation of charge flow dynamics in natural pigments based photosensitizers.

PubMed

Heera, Thekinneydath Rajan; Cindrella, Louis

2010-03-01

The relationship between structure and photo electrochemical property of ten natural pigments from plants, insects and microbes has been analyzed using density functional theory (DFT) at the B3LYP/6-31G(d) level. The essential parameters for their photoelectrochemical behaviour such as ground state geometries, electronic transition energies and oxidation potentials are computed. The attachment tendency of the anchoring groups, expressed as the deprotonation order, is determined by calculating the proton affinities at different sites of the molecules. A thorough analysis of the charge flow dynamics in the molecular orbitals (HOMO and LUMO) of these molecules has been carried out and presented to emphasize the role of these orbitals in effective charge separation, the important feature of photosensitizers for DSSC. This study highlights that the flexible spatial orientation provided by the bridging aliphatic unsaturation favours the oscillator strength and the hydroxyl anchor group attached to the ring of delocalized pi electron cloud acts as the effective anchor.

Singlet Oxygen Formation during the Charging Process of an Aprotic Lithium-Oxygen Battery.

PubMed

Wandt, Johannes; Jakes, Peter; Granwehr, Josef; Gasteiger, Hubert A; Eichel, Rüdiger-A

2016-06-06

Aprotic lithium-oxygen (Li-O2 ) batteries have attracted considerable attention in recent years owing to their outstanding theoretical energy density. A major challenge is their poor reversibility caused by degradation reactions, which mainly occur during battery charge and are still poorly understood. Herein, we show that singlet oxygen ((1) Δg ) is formed upon Li2 O2 oxidation at potentials above 3.5 V. Singlet oxygen was detected through a reaction with a spin trap to form a stable radical that was observed by time- and voltage-resolved in operando EPR spectroscopy in a purpose-built spectroelectrochemical cell. According to our estimate, a lower limit of approximately 0.5 % of the evolved oxygen is singlet oxygen. The occurrence of highly reactive singlet oxygen might be the long-overlooked missing link in the understanding of the electrolyte degradation and carbon corrosion reactions that occur during the charging of Li-O2 cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Materials and techniques for spacecraft static charge control

NASA Technical Reports Server (NTRS)

Amore, L. J.; Eagles, A. E.

1977-01-01

An overview of the design, development, fabrication, and testing of transparent conductive coatings and conductive lattices deposited or formed on high resistivity spacecraft dielectric materials to obtain control static charge buildup on spacecraft external surfaces is presented. Fabrication techniques for the deposition of indium/tin oxide coatings and copper grid networks on Kapton and FEP Teflon films and special frit coatings for OSR and solar cell cover glasses are discussed. The techniques include sputtering, photoetching, silkscreening, and mechanical processes. A facility designed and built to simulate the electron plasma at geosynchronous altitudes is described along with test procedures. The results of material characterizations as well as electron irradiation aging effects in this facility for spacecraft polymers treated to control static charge are presented. The data presents results for electron beam energies up to 30 kV and electron current densities of 30 nA/cm squared. Parameters measured include secondary emission, surface leakage, and through the sample currents as a function of primary beam energy and voltage.

A low-overpotential potassium-oxygen battery based on potassium superoxide.

PubMed

Ren, Xiaodi; Wu, Yiying

2013-02-27

Li-O(2) battery is regarded as one of the most promising energy storage systems for future applications. However, its energy efficiency is greatly undermined by the large overpotentials of the discharge (formation of Li(2)O(2)) and charge (oxidation of Li(2)O(2)) reactions. The parasitic reactions of electrolyte and carbon electrode induced by the high charging potential cause the decay of capacity and limit the battery life. Here, a K-O(2) battery is report that uses K(+) ions to capture O(2)(-) to form the thermodynamically stable KO(2) product. This allows for the battery to operate through the one-electron redox process of O(2)/O(2)(-). Our studies confirm the formation and removal of KO(2) in the battery cycle test. Furthermore, without the use of catalysts, the battery shows a low discharge/charge potential gap of less than 50 mV at a modest current density, which is the lowest one that has ever been reported in metal-oxygen batteries.

Effect of low thermal budget annealing on surface passivation of silicon by ALD based aluminum oxide films.

PubMed

Vandana; Batra, Neha; Gope, Jhuma; Singh, Rajbir; Panigrahi, Jagannath; Tyagi, Sanjay; Pathi, P; Srivastava, S K; Rauthan, C M S; Singh, P K

2014-10-21

Thermal ALD deposited Al2O3 films on silicon show a marked difference in surface passivation quality as a function of annealing time (using a rapid thermal process). An effective and quality passivation is realized in short anneal duration (∼100 s) in nitrogen ambient which is reflected in the low surface recombination velocity (SRV <10 cm s(-1)). The deduced values are close to the best reported SRV obtained by the high thermal budget process (with annealing time between 10-30 min), conventionally used for improved surface passivation. Both as-deposited and low thermal budget annealed films show the presence of positive fixed charges and this is never been reported in the literature before. The role of field and chemical passivation is investigated in terms of fixed charge and interface defect densities. Further, the importance of the annealing step sequence in the MIS structure fabrication protocol is also investigated from the view point of its effect on the nature of fixed charges.

Space and surface charge behavior analysis of charge-eliminated polymer films

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

Oda, Tetsuji; Takashima, Kazunori; Ichiyama, Shinichiro

1995-12-31

Charge behavior of corona-charged or charge eliminated polymer films being dipped in the city water were studied. They were polytetrafluoroethylene (PTFE teflon{trademark}), polypropylene (PP), low density or high density polyethylene (LDPE or HDPE) thin films which are as grown (native) or plasma-processed. The plasma processing at low pressure was tested as antistatic processing. Charge elimination was done by being dipped in alcohol or city water. TSDC analysis and surface charge profile measurement were done for both charged and charge eliminated polymer films. Surface charge density of plasma processed polymer films just after corona charging is roughly the same as thatmore » of an original film. There is little difference between surface charge density profile of a native film and that of a plasma processed film. A large hetero current peak of TSDC was observed at room temperature for a processed film. It was found that the hetero peak disappears after charge elimination process. A pressure pulse wave method by using a pulse-driven piezoelectric PVDF polymer film as a piezoelectric actuator was newly developed to observe real space charge distribution. A little difference of internal space charge distribution between the plasma processed film and the native one after corona charging is found.« less

Electric double layer at metal oxide surfaces:static properties of the cassiterite-water interface.

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

Vlcek, L.; Zhang, Z.; Machesky, M .L.

2007-03-24

The structure of water at the (110) surface of cassiterite ({alpha}-SnO{sub 2}) at ambient conditions was studied by means of molecular dynamics simulations and X-ray crystal truncation rod experiments and interpreted with the help of the revised MUSIC model of surface protonation. The interactions of the metal oxide in the simulations were described by a recently developed classical force field based on the SPC/E model of water. Two extreme cases of completely hydroxylated and nonhydroxylated surfaces were considered along with a mixed surface with 50% dissociation. To study the dependence of the surface properties on pH, neutral and negatively chargedmore » variants of the surfaces were constructed. Axial and lateral density distributions of water for different types of surfaces were compared to each other and to experimental axial density distributions found by X-ray experiments. Although significant differences were found between the structures of the studied interfaces, the axial distances between Sn and O atoms are very similar and therefore could not be clearly distinguished by the diffraction technique. The explanation of structures observed in the density distributions was provided by a detailed analysis of hydrogen bonding in the interfacial region. It revealed qualitatively different hydrating patterns formed at neutral hydroxylated and nonhydroxylated surfaces and suggested a preference for the dissociative adsorption of water. At negatively charged surfaces, however, the situation can be reversed by the electric field stabilizing a hydrogen bond network similar to that found at the neutral nonhydroxylated surface. Comparison with previously studied rutile ({alpha}-TiO{sub 2}) surfaces provided insight into the differences between the hydration of these two metal oxides, and an important role was ascribed to their different lattice parameters. A link to macroscopic properties was provided by the revised MUSIC surface protonation model. Explicit use of the Sn-O bond lengths based on ab initio calculations and H-bond configurations as inputs led to the prediction of a pH of zero net-proton induced surface charge (pH{sub pzc}) that agrees very well with those determined experimentally (about 4.4 at 298 K).« less

Electric double layer at metal oxide surfaces: Static properties of the cassiterite - Water Interface

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

Vlcek, Lukas; Zhang, Zhan; Machesky, Michael L.

2007-01-01

The structure of water at the (110) surface of cassiterite ({alpha}-SnO{sub 2}) at ambient conditions was studied by means of molecular dynamics simulations and X-ray crystal truncation rod experiments and interpreted with the help of the revised MUSIC model of surface protonation. The interactions of the metal oxide in the simulations were described by a recently developed classical force field based on the SPC/E model of water. Two extreme cases of completely hydroxylated and nonhydroxylated surfaces were considered along with a mixed surface with 50% dissociation. To study the dependence of the surface properties on pH, neutral and negatively chargedmore » variants of the surfaces were constructed. Axial and lateral density distributions of water for different types of surfaces were compared to each other and to experimental axial density distributions found by X-ray experiments. Although significant differences were found between the structures of the studied interfaces, the axial distances between Sn and O atoms are very similar and therefore could not be clearly distinguished by the diffraction technique. The explanation of structures observed in the density distributions was provided by a detailed analysis of hydrogen bonding in the interfacial region. It revealed qualitatively different hydrating patterns formed at neutral hydroxylated and nonhydroxylated surfaces and suggested a preference for the dissociative adsorption of water. At negatively charged surfaces, however, the situation can be reversed by the electric field stabilizing a hydrogen bond network similar to that found at the neutral nonhydroxylated surface. Comparison with previously studied rutile ({alpha}-TiO{sub 2}) surfaces provided insight into the differences between the hydration of these two metal oxides, and an important role was ascribed to their different lattice parameters. A link to macroscopic properties was provided by the revised MUSIC surface protonation model. Explicit use of the Sn-O bond lengths based on ab initio calculations and H-bond configurations as inputs led to the prediction of a pH of zero net-proton induced surface charge (pH{sub pzc}) that agrees very well with those determined experimentally (about 4.4 at 298 K).« less

Effect of distribution, interface property and density of hydrogel-embedded vertically aligned carbon nanotube arrays on the properties of a flexible solid state supercapacitor.

PubMed

Zhu, Qi; Yuan, Xietao; Zhu, Yihao; Ni, Jiangfeng; Zhang, Xiaohua; Yang, Zhaohui

2018-05-11

In this paper we fabricate a robust flexible solid-state supercapacitor (FSC) device by embedding a conductive poly(vinyl alcohol) hydrogel into aligned carbon nanotube (CNT) arrays. We carefully investigate the effect of distribution, interface properties and densification of CNTs in the gel matrix on the electrochemical properties of an FSC. The total electrochemical capacitance of the device is measured to be 227 mF cm -3 with a maximum energy density of 0.02 mWh cm -3 , which is dramatically enhanced compared with a similar device composed of non-parallel CNTs. Additionally, controllable in situ electrochemical oxidation greatly improved the compatibility between the hydrophobic CNTs and the hydrophilic hydrogel, which decreased the resistance of the device and introduced extra pseudocapacitance. After such oxidation treatment the energy storage ability further doubled to 430 mF cm -3 with a maximum energy density of 0.04 mWh cm -3 . The FSCs based on densified CNT arrays exhibited a much higher volumetric capacitance of 1140 mF cm -3 and a larger energy density of 0.1 mWh cm -3 , with a large power density of 14 mW cm -3 . All devices show excellent stability of capacitance after at least 10 000 charge-discharge cycles with a loss of less than 2%. These easy-to-assemble hybrid arrays thus potentially provide a new method for manufacturing wearable devices and implantable medical devices.

All Solid State Rechargeable Lithium Batteries using Block Copolymers

NASA Astrophysics Data System (ADS)

Hallinan, Daniel; Balsara, Nitash

2011-03-01

The growing need for alternative energy and increased demand for mobile technology require higher density energy storage. Existing battery technologies, such as lithium ion, are limited by theoretical energy density as well as safety issues. Other battery chemistries are promising options for dramatically increasing energy density. Safety can be improved by replacing the flammable, reactive liquids used in existing lithium-ion battery electrolytes with polymer electrolytes. Block copolymers are uniquely suited for this task because ionic conductivity and mechanical strength, both important properties in battery formulation, can be independently controlled. In this study, lithium batteries were assembled using lithium metal as negative electrode, polystyrene-b-poly(ethylene oxide) copolymer with lithium salt as electrolyte, and a positive electrode. The positive electrode consisted of polymer electrolyte for ion conduction, carbon for electron conduction, and an active material. Batteries were charged and discharged over many cycles. The battery cycling results were compared to a conventional battery chemistry.

Development of high energy density electrical double layer capacitors

NASA Astrophysics Data System (ADS)

Devarajan, Thamarai selvi

Electrochemical Double Layer capacitors (EDLCs) have shown themselves as a viable energy storage alternative. EDLCs have high power density, faster charge/discharge, wide operating temperature and long cycle life compared to batteries since it stores charge by physical separation. Despites all their advantages, their low energy density stand as a bottleneck for capacitors. This research aims to increase the energy density of EDLC without compromising the power density. Energy is proportional to the square of cell voltage. Cell voltage is mainly dependent on electrolyte breakdown. Electrolytes also provide ions for charge separation and conduction. Therefore various electrolytes (Solutes and Solvents) which can give high concentration, solubility and decomposition potential were characterized in the first part of the research. In that study, a novel ionic liquid OPBF4 had higher capacitance and comparable voltage window compared to commercial TEABF4 in Acetonitrile. However, the increased polarity of the fixed ring O-atom and the ion-ion interaction in OPBF4 was responsible for lowering its conductivity. Oxygenated ionic compounds with alkyl groups had lower stability due to beta elimination between two electron withdrawing atoms. Volume based thermodynamics and quantum chemical calculations were used to calculate ion size, HOMO/LUMO energies, and free energy changes and establish relationship with capacitance, redox potential and melting points respectively. In addition free energy of fusion was used to predict the melting point. Ion size had correlation with capacitance due to compact double layer formation. Free energy changes did not explain the differences in melting point and predicted dielectric constant was inconsistent with the polarity. This is presumably due to using Van der Waals volume instead of crystal structure volume and insufficient incorporation of polarization term. The HOMO/LUMO energies gave direct relation between oxidation and reduction potential at 1mA/cm 2. A brief study on non-polar co-solvents for EDLC was studied. Among the solvents studied, fluorinated solvents had low melting point and viscosity due to incorporation of asymmetry. However, because of low dielectric constant, TEABF4 is insoluble and had to be mixed with other solvents. The mixed fluorinated solvents had slightly higher voltage window due to decreased donicity of lone pairs of electrons. The second approach to increasing energy density is to increase capacitance. Capacitance is mainly dependent on surface area and porosity of electrodes. Nanostructured materials which can offer multiple charge storage are currently of interest. Hence, novel NiSi nanotubes were studied as electrodes for supercapacitor applications. Silicon material has high capacity and these inert electrodes can enable higher capacitance by controlling the porosity and functional groups in specific electrolytes. The Silicon wafers were made porous by anodization using hydrofluoric acid. In order to improve the conductivity, the porous silicon was doped, then plated with Ni using electroless plating method and annealed to form nickel mono silicide. Gold was deposited on the back side of the electrode to enhance conductivity. Our porous NiSi electrodes gave capacitance of about 1185muF /cm2 in 0.5 M H 2SO4. Further investigation of oxide formation and modification of functional groups will help achieve higher capacitance.