• 17β estradiol regulation of connexin 43-based gap junction and mechanosensitivity through classical estrogen receptor pathway in osteocyte-like MLO-Y4 cells.

      Ren, Jian; Wang, Xuhui; Wang, Guangchao; Wu, Junhua (Elsevier, 2013-04)
      Connexin 43 (Cx43) plays an essential role in osteocyte mechanotransduction. Although estrogen involves in the adaptive responses of bone cells to mechanical loadings, its effects on osteocytic Cx43-based gap junction intercellular communication (GJIC) remain obscure. We found that 17β estradiol (E2) up-regulated Cx43, and enhanced GJIC in osteocyte-like MLO-Y4 cells in fluorescence recovery after photobleaching (FRAP) assay. Combination of E2 pre-treatment and oscillating fluid flow (OFF) further enhanced Cx43 expression and mitogen-activated protein kinase (MAPK) phosphorylation, comparing to E2 or OFF treatment alone. Both blocking of classical estrogen receptors (ERα/β) by fulvestrant and ERα knockdown by small interfering RNA inhibited E2-mediated Cx43 increase, while a GPR30-specific agonist G-1 failed to promote Cx43 expression. Our results suggest that the presence of E2 enhanced Cx43-based GJIC mainly via ERα/β pathway, and sensitized osteocytes to mechanical loading. © 2012 Elsevier Inc. All rights reserved.
    • 17β-estradiol rapidly activates calcium release from intracellular stores via the GPR30 pathway and MAPK phosphorylation in osteocyte-like MLO-Y4 cells

      Ren, Jian; Wu, Junhua (Springer Nature, 2012-03-06)
      Estrogen regulates critical cellular functions, and its deficiency initiates bone turnover and the development of bone mass loss in menopausal females. Recent studies have demonstrated that 17β-estradiol (E 2) induces rapid non-genomic responses that activate downstream signaling molecules, thus providing a new perspective to understand the relationship between estrogen and bone metabolism. In this study, we investigated rapid estrogen responses, including calcium release and MAPK phosphorylation, in osteocyte-like MLO-Y4 cells. E 2 elevated [Ca 2+] i and increased Ca 2+ oscillation frequency in a dose-dependent manner. Immunolabeling confirmed the expression of three estrogen receptors (ERα, ERβ, and G protein-coupled receptor 30 [GPR30]) in MLO-Y4 cells and localized GPR30 predominantly to the plasma membrane. E 2 mobilized calcium from intracellular stores, and the use of selective agonist(s) for each ER showed that this was mediated mainly through the GPR30 pathway. MAPK phosphorylation increased in a biphasic manner, with peaks occurring after 7 and 60 min. GPR30 and classical ERs showed different temporal effects on MAPK phosphorylation and contributed to MAPK phosphorylation sequentially. ICI182,780 inhibited E 2 activation of MAPK at 7 min, while the GPR30 agonist G-1 and antagonist G-15 failed to affect MAPK phosphorylation levels. G-1-mediated MAPK phosphorylation at 60 min was prevented by prior depletion of calcium stores. Our data suggest that E 2 induces the non-genomic responses Ca 2+ release and MAPK phosphorylation to regulate osteocyte function and indicate that multiple receptors mediate rapid E 2 responses. © 2012 Springer Science+Business Media, LLC.
    • 2D Sn-doped ZnO ultrathin nanosheet networks for enhanced acetone gas sensing application

      Al-Hadeethi, Yas; Umar, Ahmad; Al-Heniti, Saleh. H.; Kumar, Rajesh; Kim, S.H.; Zhang, Xixiang; Raffah, Bahaaudin M. (Elsevier BV, 2016-11-10)
      In this paper, we report the synthesis, characterizations and gas sensing application of 2D Sn-doped ZnO ultrathin nanosheet networks synthesized by a simple and facile hydrothermal process. The synthesized nanosheets were characterized using several techniques in terms of their morphological, structural, optical and compositional properties. The detailed characterizations confirmed that the nanosheets are pure, grown in high-density, possessing well-crystalline wurtzite hexagonal phase and exhibiting good optical properties. Further, the synthesized nanosheets were used as functional material to develop nanosensor device by coating it on the alumina substrate with suitable electrodes. The fabricated sensor device was tested towards acetone gas which exhibited a maximum sensitivity of 5.556 (Ra/Rg) for 200 ppm of acetone at 320 °C.
    • 3D Membrane Imaging and Porosity Visualization

      Sundaramoorthi, Ganesh; Hadwiger, Markus; Ben Romdhane, Mohamed; Behzad, Ali Reza; Madhavan, Poornima; Nunes, Suzana Pereira (American Chemical Society (ACS), 2016-03-03)
      Ultrafiltration asymmetric porous membranes were imaged by two microscopy methods, which allow 3D reconstruction: Focused Ion Beam and Serial Block Face Scanning Electron Microscopy. A new algorithm was proposed to evaluate porosity and average pore size in different layers orthogonal and parallel to the membrane surface. The 3D-reconstruction enabled additionally the visualization of pore interconnectivity in different parts of the membrane. The method was demonstrated for a block copolymer porous membrane and can be extended to other membranes with application in ultrafiltration, supports for forward osmosis, etc, offering a complete view of the transport paths in the membrane.
    • 3D visualization of the internal nanostructure of polyamide thin films in RO membranes

      Pacheco Oreamuno, Federico; Sougrat, Rachid; Reinhard, Martin; Leckie, James O.; Pinnau, Ingo (Elsevier BV, 2015-11-02)
      The front and back surfaces of fully aromatic polyamide thin films isolated from reverse osmosis (RO) membranes were characterized by TEM, SEM and AFM. The front surfaces were relatively rough showing polyamide protuberances of different sizes and shapes; the back surfaces were all consistently smoother with very similar granular textures formed by polyamide nodules of 20–50 nm. Occasional pore openings of approximately the same size as the nodules were observed on the back surfaces. Because traditional microscopic imaging techniques provide limited information about the internal morphology of the thin films, TEM tomography was used to create detailed 3D visualizations that allowed the examination of any section of the thin film volume. These tomograms confirmed the existence of numerous voids within the thin films and revealed structural characteristics that support the water permeance difference between brackish water (BWRO) and seawater (SWRO) RO membranes. Consistent with a higher water permeance, the thin film of the BWRO membrane ESPA3 contained relatively more voids and thinner sections of polyamide than the SWRO membrane SWC3. According to the tomograms, most voids originate near the back surface and many extend all the way to the front surface shaping the polyamide protuberances. Although it is possible for the internal voids to be connected to the outside through the pore openings on the back surface, it was verified that some of these voids comprise nanobubbles that are completely encapsulated by polyamide. TEM tomography is a powerful technique for investigating the internal nanostructure of polyamide thin films. A comprehensive knowledge of the nanostructural distribution of voids and polyamide sections within the thin film may lead to a better understanding of mass transport and rejection mechanisms in RO membranes.
    • Additive-Morphology Interplay and Loss Channels in “All-Small-Molecule” Bulk-heterojunction (BHJ) Solar Cells with the Nonfullerene Acceptor IDTTBM

      Liang, Ru-Ze; Babics, Maxime; Seitkhan, Akmaral; Wang, Kai; Geraghty, Paul Bythell; Lopatin, Sergei; Cruciani, Federico; Firdaus, Yuliar; Caporuscio, Marco; Jones, David J.; Beaujuge, Pierre (Wiley-Blackwell, 2017-12-16)
      Achieving efficient bulk-heterojunction (BHJ) solar cells from blends of solution-processable small-molecule (SM) donors and acceptors is proved particularly challenging due to the complexity in obtaining a favorable donor–acceptor morphology. In this report, the BHJ device performance pattern of a set of analogous, well-defined SM donors—DR3TBDTT (DR3), SMPV1, and BTR—used in conjunction with the SM acceptor IDTTBM is examined. Examinations show that the nonfullerene “All-SM” BHJ solar cells made with DR3 and IDTTBM can achieve power conversion efficiencies (PCEs) of up to ≈4.5% (avg. 4.0%) when the solution-processing additive 1,8-diiodooctane (DIO, 0.8% v/v) is used in the blend solutions. The figures of merit of optimized DR3:IDTTBM solar cells contrast with those of “as-cast” BHJ devices from which only modest PCEs <1% can be achieved. Combining electron energy loss spectrum analyses in scanning transmission electron microscopy mode, carrier transport measurements via “metal-insulator-semiconductor carrier extraction” methods, and systematic recombination examinations by light-dependence and transient photocurrent analyses, it is shown that DIO plays a determining role—establishing a favorable lengthscale for the phase-separated SM donor–acceptor network and, in turn, improving the balance in hole/electron mobilities and the carrier collection efficiencies overall.
    • Advanced characterization of dissolved organic matter released by bloom-forming marine algae

      Rehman, Zahid Ur; Jeong, Sanghyun; Tabatabai, S. Assiyeh Alizadeh; Emwas, Abdul-Hamid M.; Leiknes, TorOve (Informa UK Limited, 2017-06-01)
      Algal organic matter (AOM), produced by marine phytoplankton during bloom periods, may adversely affect the performance of membrane processes in seawater desalination. The polysaccharide fraction of AOM has been related to (bio)fouling in micro-filtration and ultrafiltration, and reverse osmosis membranes. However, so far, the chemical structure of the polysaccharides released by bloom-forming algae is not well understood. In this study, dissolved fraction of AOM produced by three algal species (Chaetoceros affinis, Nitzschia epithemoides and Hymenomonas spp.) was characterized using liquid chromatography–organic carbon detection (LC-OCD) and fluorescence spectroscopy. Chemical structure of polysaccharides isolated from the AOM solutions at stationary phase was analyzed using proton nuclear magnetic resonance (H-NMR). The results showed that production and composition of dissolved AOM varied depending on algal species and their growth stage. AOM was mainly composed of biopolymers (BP; i.e., polysaccharides and proteins [PN]), but some refractory substances were also present.H-NMR spectra confirmed the predominance of carbohydrates in all samples. Furthermore, similar fingerprints were observed for polysaccharides of two diatom species, which differed considerably from that of coccolithophores. Based on the findings of this study,H-NMR could be used as a method for analyzing chemical profiles of algal polysaccharides to enhance the understanding of their impact on membrane fouling.
    • [Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

      Alhilaly, Mohammad J.; Bootharaju, Megalamane Siddaramappa; Joshi, Chakra Prasad; Besong, Tabot M.D.; Emwas, Abdul-Hamid M.; Juarez-Mosqueda, Rosalba; Kaappa, Sami; Malola, Sami; Adil, Karim; Shkurenko, Aleksander; Hakkinen, Hannu; Eddaoudi, Mohamed; Bakr, Osman (American Chemical Society (ACS), 2016-10-13)
      Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag-67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag-67(SPhMe2)(32)(PPh3)(8)](3+). The crystal structure shows an Ag-23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag-13, core was formed through an unprecedented centered cuboctahedron, i.e., Ag-13, unlike the common centered Ag-13 icosahedron geometry. Two types of ligand motifs, eight AgS3P and eight bridging thiols, were found to stabilize the whole cluster. The optical spectrum of this NC displayed highly structured multiple absorption peaks. The electronic structure and optical spectrum of Ag-67 were computed using time-dependent density functional theory (TDDFT) for both the full cluster [Ag-67(SPhMe2)(32)(PPh3)(8)](3+) and a reduced model [Ag-67(SH)(32)(PH3)(8)](3+). The lowest metal-to-metal transitions in the range 500-800 nm could be explained by considering the reduced model that shows almost identical electronic states to 32 free electrons in a jellium box. The successful synthesis of the large box-shaped Ag-67 NC facilitated by the combined use of phosphine and thiol paves the way for synthesizing other metal clusters with unprecedented shapes by judicious choice of thiols and phosphines.
    • Air-Stable Surface-Passivated Perovskite Quantum Dots for Ultra-Robust, Single- and Two-Photon-Induced Amplified Spontaneous Emission

      Pan, Jun; Sarmah, Smritakshi P.; Banavoth, Murali; Dursun, Ibrahim; Peng, Wei; Parida, Manas R.; Liu, Jiakai; Sinatra, Lutfan; AlYami, Noktan; Zhao, Chao; Alarousu, Erkki; Ng, Tien Khee; Ooi, Boon S.; Bakr, Osman; Mohammed, Omar F. (American Chemical Society (ACS), 2015-12-01)
      We demonstrate ultra-air- and photostable CsPbBr3 quantum dots (QDs) by using an inorganic–organic hybrid ion pair as the capping ligand. This passivation approach to perovskite QDs yields high photoluminescence quantum yield with unprecedented operational stability in ambient conditions (60 ± 5% lab humidity) and high pump fluences, thus overcoming one of the greatest challenges impeding the development of perovskite-based applications. Due to the robustness of passivated perovskite QDs, we were able to induce ultrastable amplified spontaneous emission (ASE) in solution processed QD films not only through one photon but also through two-photon absorption processes. The latter has not been observed before in the family of perovskite materials. More importantly, passivated perovskite QD films showed remarkable photostability under continuous pulsed laser excitation in ambient conditions for at least 34 h (corresponds to 1.2 × 108 laser shots), substantially exceeding the stability of other colloidal QD systems in which ASE has been observed.
    • AlGaN-based deep-ultraviolet light-emitting diodes grown on high-quality AlN template using MOVPE

      Yan, Jianchang; Wang, Junxi; Zhang, Yun; Cong, Peipei; Sun, Lili; Tian, Yingdong; Zhao, Chao; Li, Jinmin (Elsevier BV, 2015-03)
      In this article, we report the growth of high-quality AlN film using metal-organic vapor phase epitaxy. Three layers of middle-temperature (MT) AlN were introduced during the high-temperature (HT) AlN growth. During the MT-AlN layer growth, aluminum and nitrogen sources were closed for 6 seconds after every 5-nm MT-AlN, while H2 carrier gas was always on. The threading dislocation density in an AlN epi-layer on a sapphire substrate was reduced by almost half. AlGaN-based deep-ultraviolet light-emitting diodes were further fabricated based on the AlN/sapphire template. At 20 mA driving current, the emitted peak wavelength is 284.5 nm and the light output power exceeds 3 mW.
    • All-polymer bistable resistive memory device based on nanoscale phase-separated PCBM-ferroelectric blends

      Khan, Yasser; Bhansali, Unnat Sampatraj; Cha, Dong Kyu; Alshareef, Husam N. (Wiley-Blackwell, 2012-11-21)
      All polymer nonvolatile bistable memory devices are fabricated from blends of ferroelectric poly(vinylidenefluoride-trifluoroethylene (P(VDF-TrFE)) and n-type semiconducting [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). The nanoscale phase separated films consist of PCBM domains that extend from bottom to top electrode, surrounded by a ferroelectric P(VDF-TrFE) matrix. Highly conducting poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) polymer electrodes are used to engineer band offsets at the interfaces. The devices display resistive switching behavior due to modulation of this injection barrier. With careful optimization of the solvent and processing conditions, it is possible to spin cast very smooth blend films (Rrms ≈ 7.94 nm) and with good reproducibility. The devices exhibit high Ion/I off ratios (≈3 × 103), low read voltages (≈5 V), excellent dielectric response at high frequencies (Ïμr ≈ 8.3 at 1 MHz), and excellent retention characteristics up to 10 000 s. Copyright © 2013 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.
    • Alternative Thieno[3,2-b][1]benzothiophene Isoindigo Polymers for Solar Cell Applications

      Neophytou, Marios; Bryant, Daniel; Lopatin, Sergei; Chen, Hu; Hallani, Rawad K.; Cater, Lewis; McCulloch, Iain; Yue, Wan (Wiley-Blackwell, 2018-03-05)
      This work reports the synthesis, characterization, photophysical, and photovoltaic properties of five new thieno[3,2-b][1]benzothiophene isoindigo (TBTI)-containing low bandgap donor-acceptor conjugated polymers with a series of comonomers and different side chains. When TBTI is combined with different electron-rich moieties, even small structural variations can have significant impact on thin film morphology of the polymer:phenyl C70 butyric acid methyl ester (PCBM) blends. More importantly, high-resolution electron energy loss spectroscopy is used to investigate the phase-separated bulk heterojunction domains, which can be accurately and precisely resolved, enabling an enhanced correlation between polymer chemical structure, photovoltaic device performance, and morphology.
    • Amorphous NiFe-OH/NiFeP Electrocatalyst Fabricated at Low Temperature for Water Oxidation Applications

      Liang, Hanfeng; Gandi, Appala; Xia, Chuan; Hedhili, Mohamed N.; Anjum, Dalaver H.; Schwingenschlögl, Udo; Alshareef, Husam N. (American Chemical Society (ACS), 2017-04-11)
      Water splitting driven by electricity or sunlight is one of the most promising ways to address the global terawatt energy needs of future societies; however, its large-scale application is limited by the sluggish kinetics of the oxygen evolution reaction (OER). NiFe-based compounds, mainly oxides and hydroxides, are well-known OER catalysts and have been intensively studied; however, the utilization of the synergistic effect between two different NiFe-based materials to further boost the OER performance has not been achieved to date. Here, we report the rapid conversion of NiFe double hydroxide into metallic NiFeP using PH3 plasma treatment and further construction of amorphous NiFe hydroxide/NiFeP/Ni foam as efficient and stable oxygen-evolving anodes. The strong electronic interactions between NiFe hydroxide and NiFeP significantly lower the adsorption energy of H2O on the hybrid and thus lead to enhanced OER performance. As a result, the hybrid catalyst can deliver a geometrical current density of 300 mA cm–2 at an extremely low overpotential (258 mV, after ohmic-drop correction), along with a small Tafel slope of 39 mV decade–1 and outstanding long-term durability in alkaline media.
    • Amplification of Surface-Enhanced Raman Scattering Due to Substrate-Mediated Localized Surface Plasmons in Gold Nanodimers

      Yue, Weisheng; Wang, Zhihong; Whittaker, John; Lopez-royo, Francisco; Yang, Yang; Zayats, Anatoly (Royal Society of Chemistry (RSC), 2017-03-28)
      Surface-enhanced Raman scattering (SERS) is ubiquitous in chemical and biochemical sensing, imaging and identification. Maximizing SERS enhancement is a continuous effort focused on the design of appropriate SERS substrates. Here we show that significant improvement in a SERS signal can be achieved with substrates combining localized surface plasmon resonances and a nonresonant plasmonic substrate. By introducing a continuous gold (Au) film underneath Au nanodimers antenna arrays, an over 10-fold increase in SERS enhancement is demonstrated. Triangular, rectangle and disc dimers were studied, with bowtie antenna providing highest SERS enhancement. Simulations of electromagnetic field distributions of the Au nanodimers on the Au film support the observed enhancement dependences. The hybridization of localized plasmonic modes with the image modes in a metal film provides a straightforward way to improve SERS enhancement in designer SERS substrate.
    • Analysis of interlaminar fracture toughness and damage mechanisms in composite laminates reinforced with sprayed multi-walled carbon nanotubes

      Almuhammadi, Khaled; Alfano, Marco; Yang, Yang; Lubineau, Gilles (Elsevier BV, 2014-01)
      The present work is focused on the nanoreinforcement of prepreg based carbon fiber composite laminates to improve delamination resistance. Functionalized multi-walled carbon nanotubes (MWCNTs) were dispersed over the interface between prepreg layers through solvent spraying and the resulting mode I interlaminar fracture toughness was determined. For comparison, baseline samples with neat prepregs were also prepared. Results indicate that the introduction of functionalized MWCNTs can favorably affect the interlaminar fracture toughness, and the associated mechanisms of failure have been investigated. The manufacturing procedures and the interfacial reinforcing mechanism were explored by analyzing (i) the wettability between CNTs-solvent solution and prepreg surface, (ii) CNTs dispersion and (iii) the fractured surfaces through high resolution scanning electron microscopy and Raman mapping. © 2013 Elsevier Ltd.
    • Anisotropic Self-Assembly of Organic–Inorganic Hybrid Microtoroids

      Al-Rehili, Safa’a; Fhayli, Karim; Hammami, Mohamed Amen; Moosa, Basem; Patil, Sachin; Zhang, Daliang; Alharbi, Ohoud; Hedhili, Mohamed N.; Möhwald, Helmuth; Khashab, Niveen M. (American Chemical Society (ACS), 2016-10-24)
      Toroidal structures based on self-assembly of predesigned building blocks are well-established in the literature, but spontaneous self-organization to prepare such structures has not been reported to date. Here, organic–inorganic hybrid microtoroids synthesized by simultaneous coordination-driven assembly of amphiphilic molecules and hydrophilic polymers are reported. Mixing amphiphilic molecules with iron(III) chloride and hydrophilic polymers in water leads, within minutes, to the formation of starlike nanostructures. A spontaneous self-organization of these nanostructures is then triggered to form stable hybrid microtoroids. Interestingly, the toroids exhibit anisotropic hierarchical growth, giving rise to a layered toroidal framework. These microstructures are mechanically robust and can act as templates to host metallic nanoparticles such as gold and silver. Understanding the nature of spontaneous assembly driven by coordination multiple non-covalent interactions can help explain the well-ordered complexity of many biological organisms in addition to expanding the available tools to mimic such structures at a molecular level.
    • Anomalous Hall effect and magnetoresistance behavior in Co/Pd1−xAgx multilayers

      Guo, Z. B.; Mi, W. B.; Manchon, Aurelien; Li, J. Q.; Zhang, Bei; Gonzalez Barba, Priscila; Zhang, Xixiang (AIP Publishing, 2013-02-13)
      In this paper, we report anomalous Hall effect (AHE) correlated with the magnetoresistance behavior in [Co/Pd1-xAg x]n multilayers. For the multilayers with n = 6, the increase in Ag content from x = 0 to 0.52 induces the change in AHE sign from negative surface scattering-dominated AHE to positive interface scattering-dominated AHE, which is accompanied with the transition from anisotropy magnetoresistance (AMR) dominated transport to giant magnetoresistance (GMR) dominated transport. For n = 80, scaling analysis with Rs ∝ρ xx γ yields γ ∼ 3.44 for x = 0.52 which presents GMR-type transport, in contrast to γ ∼ 5.7 for x = 0 which presents AMR-type transport. © 2013 American Institute of Physics.
    • Anomalous Hall effect in Fe/Gd bilayers

      Xu, W. J.; Zhang, Bei; Liu, Z. X.; Wang, Z.; Li, W.; Wu, Z. B.; Yu, R. H.; Zhang, Xixiang (IOP Publishing, 2010-04-01)
      Non-monotonic dependence of anomalous Hall resistivity on temperature and magnetization, including a sign change, was observed in Fe/Gd bilayers. To understand the intriguing observations, we fabricated the Fe/Gd bilayers and single layers of Fe and Gd simultaneously. The temperature and field dependences of longitudinal resistivity, Hall resistivity and magnetization in these films have also been carefully measured. The analysis of these data reveals that these intriguing features are due to the opposite signs of Hall resistivity/or spin polarization and different Curie temperatures of Fe and Gd single-layer films. Copyright (C) EPLA, 2010
    • Anomalous Hall effect in polycrystalline Ni films

      Guo, Zaibing; Mi, Wenbo; Zhang, Qiang; Zhang, Bei; Aboljadayel, Razan; Zhang, Xixiang (Elsevier BV, 2012-02)
      We systematically studied the anomalous Hall effect in a series of polycrystalline Ni films with thickness ranging from 4 to 200 nm. It is found that both the longitudinal and anomalous Hall resistivity increased greatly as film thickness decreased. This enhancement should be related to the surface scattering. In the ultrathin films (46 nm thick), weak localization corrections to anomalous Hall conductivity were studied. The granular model, taking into account the dominated intergranular tunneling, has been employed to explain this phenomenon, which can explain the weak dependence of anomalous Hall resistivity on longitudinal resistivity as well. © 2011 Elsevier Ltd. All rights reserved.
    • Anomalous positive flatband voltage shifts in metal gate stacks containing rare-earth oxide capping layers

      Caraveo-Frescas, J. A.; Hedhili, Mohamed N.; Wang, H.; Schwingenschlögl, Udo; Alshareef, Husam N. (AIP Publishing, 2012-03-09)
      It is shown that the well-known negative flatband voltage (VFB) shift, induced by rare-earth oxide capping in metal gate stacks, can be completely reversed in the absence of the silicon overlayer. Using TaN metal gates and Gd2O3-doped dielectric, we measure a ∼350 mV negative shift with the Si overlayer present and a ∼110 mV positive shift with the Si overlayer removed. This effect is correlated to a positive change in the average electrostatic potential at the TaN/dielectric interface which originates from an interfacial dipole. The dipole is created by the replacement of interfacial oxygen atoms in the HfO2 lattice with nitrogen atoms from TaN.