Dhananjay Kumar, North Carolina Agricultural and Technical State University
Ningzhong Bao, Nanjing Tech University
Sergio D'Addato, Università di Modena e Reggio Emilia
Arunava Gupta, University of Alabama
NT2.1: Photocatalysis and Water Splittiing
Tuesday PM, March 29, 2016
PCC North, 100 Level, Room 132 AB
2:30 PM - NT2.1.01
Nano-Topographical, Electrical and Mechanical Studies of the Terrace and Edge Sites on WSe2
Zhuangqun Huang 1,Jesus Velazquez 1,Jimmy John 1,Adam Pieterick 1,Xinghao Zhou 1,Manuel Soriaga 1,Hans Lewerenz 1,Thomas Mueller 2,Bruce Brunschwig 1,Nathan Lewis 1
2 Bruker Nano Surfaces Goleta United States,1 Joint Center for Artificial Photosynthesis California Institute of Technology Pasadena United States,1 Joint Center for Artificial Photosynthesis California Institute of Technology Pasadena United States2 Bruker Nano Surfaces Goleta United StatesShow Abstract
Innovative routes for the fabrication of semiconductors that are both stable and able to efficiently convert solar energy to molecular Hydrogen under the conditions required for the safe and operation of a solar-fuel generator will be imperative to the development of the next generation of such devices. Layered Transition-Metal Dichalcogenides (TMDCs) are suitable candidates for efficient and stable photoelectrosynthetic hydrogen generation in acidic and alkaline media, with inherent stability in harsh electrochemical environments. Furthermore, TMDCs are capable of dual functionality in such devices, having demonstrated both efficient photoconversion and electrocatalysis. Tungsten diselenide (WSe2) is an attractive TMDC material for this purpose, owning to its high light absorption coeffiecnt, 1.2 eV band gap and anisotropic properties. We investigate fundamental insights into the factors that determine the photoelectrical properties of WSe2. The present work focuses on nano- topographical, electrical and mechanical studies of the WSe2 in the absence and presence of catalysts, including the density of edge sites, surface potential profile, local current mapping and the nano lithography. These studies were performed mostly based on the PeakForce-based tapping AFM mode. Our studies show that the surface work functions and stiffness of the edge sites are different from the basal plan. The edge sites are also more conductive while showing inhomogeneous conductivity. Hence, WSe2 displays distinct chemical and physical differences when terrace and edge sites are compared. Therefore, performance optimization of the WSe2 photoelectrode requires the control of both density and electrical/chemical properties of the edge sites.
Acknowledgement: This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award Number DE-SC0004993. Research was in part carried out at the Molecular Materials Research Center of the Beckman Institute of the California Institute of Technology.
 Velazquez et. al. “A Scanning Probe Investigation of the Role of Surface Motifs in the Behavior of p-WSe2 Photocathodes”, Energy & Environmental Science, 2015, (Accepted)
2:45 PM - *NT2.1.02
Metal Oxide Nanosheets for Light-Induced Water Splitting
Kazuhiko Maeda 1
1 Tokyo Institute of Technology Tokyo Japan,Show Abstract
Semiconductor oxide nanosheets derived from layered metal oxides have attracted attention in various fields due to their unique structural properties. The anisotropic feature of nanosheets, which have a thickness of ~1 nm and lateral dimensions ranging from several hundred nanometers to a few micrometer, seems to be advantageous for heterogeneous photocatalysts, as the diffusion length of photogenerated electrons and holes to the surface is shortened, resulting in higher activity.
For application in photocatalysis, the composition of a metal oxide determines the band structure of the material, which has a strong impact on photocatalytic activity, as the reactivity of electrons and holes for surface redox reactions is determined by the band-edge potentials. Therefore, precise control of energy band structure is essential to designing a highly efficient photocatalyst. To date, however, such band-structure-controlled nanosheets have not been devised, and how the band gap structure affect photocatalytic activity remains little explored. We prepared perovskite nanosheets of HCa2–xSrxNb3–yTayO10, and found that the conduction band-edge potentials were successfully controlled by cationic substitution. These nanosheets functioned as highly efficient heterogeneous photocatalysts for H2 evolution from an aqueous methanol solution under band-gap irradiation. The activity was found to depend on the composition. The highest activity was obtained with HCa2Nb2TaO10 nanosheets, giving an apparent quantum yield (AQY) of ~80% at 300 nm. This is the highest value among nanosheet-based photocatalysts reported so far.
It is also known that certain nanoparticulate metals or metal oxides on a semiconductor photocatalyst work as cocatalysts to promote water reduction and/or oxidation. In heterogeneous photocatalysis, the effect of cocatalyst size on the water-splitting performance had not been examined at sizes smaller than 1 nm due to the lack of an effective preparation method and a suitable photocatalyst. We have very recently demonstrated that metal nanoclusters (such as Pt) of <1 nm in size could be deposited on the interlayer nanospace of KCa2Nb3O10 using the electrostatic attraction between a cationic metal complex and a negatively charged Ca2Nb3O10– sheet, without the aid of any additional reagent. The material obtained exhibited 8 times greater photocatalytic activity for overall water splitting under band-gap irradiation than the previously reported analog using a RuO2 promoter. This study highlighted the superior functionality of < 1 nm Pt nanoclusters for photocatalytic overall water splitting
3:30 PM - NT2.1.04
Hierarchically Nanostructured Core-Shell MoO2-MoS2 Nanofibers and Their Application toward Hydrogen Evolution
Yosep Han 1,Navaneet Ramabadran 2,Youngin Lee 3,Kyu Hwan Lee 4,Seil Kim 5,Yong-Ho Choa 5,Youngwoo Rheem 2,Nosang Myung 2
1 Chemical and Environmental Engineering University of California-Riverside Riverside United States,2 Materials Science and Engineering Program University of California-Riverside Riverside United States3 Department of Materials Science and Engineering Seoul Korea (the Republic of)4 Korea Institute of Materials Science Changwon Korea (the Republic of)5 Department of Fusion Chemical Engineering Hanyang University Gyeonggi-do Korea (the Republic of)1 Chemical and Environmental Engineering University of California-Riverside Riverside United States,2 Materials Science and Engineering Program University of California-Riverside Riverside United StatesShow Abstract
Currently, hydrocarbon reformation accounts for 96% of commercially available hydrogen, usually with high concentrations of carbon-rich molecules. This poses a problem for achieving carbon neutrality in the plethora of hydrogen-dependent processes. Transition metal chalcogenides (TMCs) (e.g., MoS2, WS2, and WSe2) have been investigated as earth abundant catalyst for hydrogen gas evolution to replace precious Pt-based catalyst.
In this work, hierarchically core-shell MoO2-MoS2 nanofibers with controlled morphology and composition were fabricated by combining various fabrication techniques including electrospinning, rapid thermal annealing, and CVD sulfurization to enhance HER properties. Design of Experiment (DOE) and dimensionless analysis will be utilized during electrospinning to optimize nanofiber diameter and morphology utilizing physical properties of both precursor solutions and electrospinning parameters. Several complementary techniques, including FE-SEM, HR-TEM, XRD, nitrogen physisorption isotherm and XPS were used to systemically evaluate the material and physical properties of the nanofibers. Lastly, the HER experiments were conducted under different pH (0, 1, 3 and 5) conditions to determine surface overpotential and Tafel slope.
3:45 PM - NT2.1.05
Tailoring of Sputtered Nano-Crystalline ZnO films by γ- Irradiation
Amanullah Fatehmulla 1,Ahmed Alfaifi 1,Abdullah Albassam 1,Mohamed Aslam 1,Mohammed Shahabuddin 1,Hameed Naseem 2
1 Physics and Astronomy King Saud University Riyadh Saudi Arabia,2 Electrical Engineering University of Arkansas Fayetteville United StatesShow Abstract
Nanocrystalline zinc oxide thin films deposited on glass substrates by sputtering technique were subjected to γ- irradiation with an equivalent intensity of 1.404 kG/hour for extended periods of time (40 to 160 min). The irradiated samples were characterized to understand the changes in structural, morphological, optical and electrical properties. XRD patterns showed that the intensity of orientation peak (002) enhanced with the increase of gamma irradiation doses and the grain size increased marginally. The micro strain (ε) and dislocation density (δ) values decreased. The bond length (L) as well as the texture coefficient TC (hkl) values exhibited an increasing trend signifying plenty of grains in a given (hkl) direction. AFM studies displayed spherical nature of the crystallites and showed an increase in their size with the increase of irradiation doses. As the gamma irradiation dose increased, the transmittance decreased in the visible range. In addition, the transmittance curve showed creeping behavior towards the red wavelength indicating the decrease in energy gap. These results corroborated well with the XRD as well as AFM studies. We noticed that resistance decreased substantially when measured just after irradiation. Aging effect was distinct which showed gradual increasing trend. The results have been explained keeping in view of employing the tailored films with gamma irradiation for possible optoelectronic applications.
4:30 PM - NT2.1.06
Cyclic Azasilanes: A Versatile Class of Precursors for ALD SiO2 and Molecular Layer Deposition
Nick Strandwitz 1,Ling Ju 1
1 Lehigh Univ Bethlehem United States,Show Abstract
SiO2 is the most widely used dielectric material in the semiconductor industry and the continuous miniaturization of features requires ultrathin SiO2 films which are difficult to produce by traditional fabrication techniques such as chemical vapor deposition or thermal oxidation. Atomic layer deposition (ALD) is capable of accurately controlling the thickness of thin films at the atomic scale. However, ALD SiO2 growth usually requires catalysts, high temperatures, and/or a large precursor flux. Recently, aminosilanes were demonstrated to be promising precursors for low temperature SiO2 growth which was free of catalysts or corrosive by-products. The amino ligand catalyzes the reaction, so is described as a “self-catalysed” reaction. We have examined a new group of volatile aminosilanes, cyclic azasilanes, to grow thin SiO2 through ring-opening reaction under a wide range of temperatures. The unstable Si-N bonding makes this class of molecules chemically reactive with hydroxyl surfaces to form a monolayer. Subsequent oxidation with O3 afford silanol groups, which are amenable to further reaction with cyclic azasilanes. The growth rates obtained are 0.6-1.2 Å/cycle for various silanes under different ALD conditions, due to side chain structure variation of silane precursors. This offers a novel group of chemicals for the preparation of ALD SiO2 and also the interfacial functionality, enables detailed study of the adsorption of silanes and surface oxidation mechanism, and may be helpful for the design of ALD precursors for SiO2 and hybrid molecular layer deposited films.
4:45 PM - *NT2.1.07
Bifunctional Cobalt Sulfide for Flexible Supercapacitor and Hydrogen Evolution Reaction
E Alqurashi 1,Z Wang 1,Pawan Kahol 1,Petar Dvornic 1,Ram Gupta 1
1 Pittsburg State Univ Pittsburg United States,Show Abstract
With the ever increasing demands on energy and environmental protection, there is an urgent need to develop multifunctional, high performance and durable materials for energy production and energy storage applications. Hydrogen generated from water splitting is an alternative and renewable energy source, and presently, platinum is one of the most effective catalyst for its generation. However, its wide application is limited due to its high cost and it is essential to develop low-cost and earth-abundant materials to replace precious-platinum based catalysts. Recently, chalcogenides have attracted considerable attention for these purposes where molybdenum disulfide shows some promise for hydrogen production but its charge storage capacity is low compared to metal oxides. In this work, we have developed a facile method for the synthesis of nanostructured cobalt sulfides which were then tested for supercapacitors as well as electro-catalyst for hydrogen generation, and their potential application for supercapacitors using cyclic voltammeter and galvanostatic charge discharge method. The maximum specific capacitance of 335 F/g was observed in 3 M NaOH electrolyte. A quasi-solid state supercapacitor device was fabricated by sandwiching two electrodes separated by an ion transporting layer, and the effect of temperature on the charge storage properties of the device was investigated for high temperature applications. The specific capacitance improved when operating temperature was raised from 10 to 70 oC. In addition to this, cobalt sulfides also showed a promising behavior as electro-catalyst for hydrogen generation, and their catalytic activity was observed to be significantly higher than that of molybdenum disulfide. Our results clearly suggest that these cobalt sulfides could be used as bifunctional material for energy generation and storage.
5:15 PM - NT2.1.09
Highly Active Hydrogen Evolution Electrocatalyst Based on Novel Cobalt-Nickel Sulfide Composite Electrode
Davide Ansovini 2,Coryl Jing Jun Lee 1,Chin Sheng Chua 1,Lay Ting Ong 1,Robert Raja 2,Yee-Fun Lim 1
1 Institute of Materials Research and Engineering, A*STAR Singapore Singapore,2 School of Chemistry University of Southampton Southampton United Kingdom,1 Institute of Materials Research and Engineering, A*STAR Singapore Singapore2 School of Chemistry University of Southampton Southampton United KingdomShow Abstract
Solar-driven electrocatalytic water splitting holds great potential as a sustainable way of storing energy via the production of hydrogen (H2) and oxygen (O2), which can be subsequently recombined in a fuel cell with generation of energy on demand. Currently Pt-based electrodes are the most active hydrogen evolution reaction (HER) catalysts with negligible overpotentials and high stability. The main drawback is due by the high cost of the Pt which limits its utilization on industrial scale.1 During the past 10 years numerous efforts have been devoted to the identification of active, stable and low-cost HER electrocatalysts able to efficiently work under harsh (acidic and/or basic) and/or neutral electrolytes. Particularly, first-row transition metal sulfides such as CoS2, NiS2, FeS2, have recently emerged as a promising class of active HER electrocatalysts.2 Among the above-mentioned compounds, CoS2-based electrodes have proved to be extremely interesting HER catalysts because of their metal-like electrical conductivity, chemical stability in acid and base and low cost. In this work, a novel CoS2-Ni3S2-Ni17S18/Ni foam composite material was synthesized through a simple method based on the thermal decomposition of a cobalt-thiourea molecular precursor onto the 3D metallic support. The obtained electrode exhibited outstanding activity toward the hydrogen evolution reaction, requiring small overpotentials of 152 mV and 183 mV at a current density of 10 mA cm-2 in acidic (0.5 M H2SO4) and basic (1 M KOH) media, respectively. Remarkably the activity under alkaline medium is the highest ever reported among the CoS2-based HER catalysts. The determination of the Tafel slopes gave insights into the mechanism involved during the HER, suggesting a Heyrovsky rate-determining step (RDS) in acidic and a Volmer-Heyrovsky RDS in basic electrolyte. The material was characterized through X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), linear sweep voltammetry (LSV), electrochemical impedence spectroscopy (EIS) and chronoamperometry analysis (CA). The origin of its high activity was mainly attributed to the low electrical resistance and the high surface area of the composite electrode as shown by EIS analysis, with efficient and rapid electron injection from the metallic Ni foam to the highly dispersed CoS2 active sites. Indeed, the in-situ thermal generation of CoS2 nanoparticles onto the Ni foam plays a fundamental role in having a low electrical resistance as a result of the strong binding between the two phases. A detailed characterization analysis was also performed on samples subjected to chronoamperometry tests in acidic and basic environments, evidencing the occurrence of some minor structural modifications on the electrode.
1. Q.Lu et al., Nature Communications, 2015, 6, 6567
2. D. Kong et al., Energy Environ. Sci., 2013, 6, 3553-3558.
5:30 PM - NT2.1.10
Transition Metal Chalcogenide Based Elelctrocatalysts for Water Oxidation/Reduction
Manashi Nath 1,Jahangir Masud 1,Abdurazag Swesi 1
1 Missouri Samp;T Rolla United States,Show Abstract
Transition metal chalcogenides has been a heartthrob of solid state chemists owing to the richness of properties they exhibit as well as their structure-property correlation. In addition to their viable optoelectronic properties, it has been recently observed that some of these transition metal chalcogenide (especially selenides) show high electrocatalytic activities for oxygen evolution/reduction reactions (OER/ORR respectively) and hydrogen evolution reaction (HER). Recently we have formulated some new transition metal chalcogenide based compositions which show an enhanced catalytic activity for OER based on their d-electron occupancy and structural parameters. Among these the Ni-based selenide thin films and nanostructures show much better catalyst activity along with lower onset potential for O2 evolution outperforming the state-of-the-art precious metal based catalysts. It was also observed that doping other transitional metals in the Nickel selenide matrix led to enhancing catalyst efficiency. The catalysts were synthesized mainly through electrodeposition on different substrates like Au-coated glass, Au-coated Si as well as glassy carbon (GC). The nanostructured catalysts were made through chemical vapor deposition (CVD) and solvothermal reaction. In a separate approach nanorod and nanotube arrays of these electrocatalysts were grown through electrodeposition on lithographically patterned nanoelectrodes. Nanostructuring typically led to much better efficiency with low catalyst volume, with the nanorod/nanotube pattern producing the highest activity with lowest electrode coverage with the active material. The catalytic activities for OER, ORR and HER were investigated through detailed electrochemical measurements including linear scale voltammetry, chronoamperometry, Tafel slope analysis as well as determination of Faradaic efficiency through rotating ring disk electrode studies. Interestingly some of these selenides showed bifunctional or trifunctional nature showing efficient catalytic activity for OER-HER and OER-HER-ORR processes, respectively. In this talk we will present a systematic study of the selenide based electrocatalysts including binary (NixSey, CoxSey) as well as ternary chalcogenides, NixMySen (M = Fe, Co, Mn, Al) and investigating their catalytic activities for OER, HER, and ORR reactions. We will also discuss the effect of d-electron counts, electronic structure and morphology on the catalytic efficiency.
5:45 PM - NT2.1.11
Plasmonic Enhanced Optical Disk Reactor for Wastewater Treatment
Mu Ku Chen 1,Wen Ting Hsieh 1,Yu Lim Chen 1,I Da Chiang 1,Hung I Lin 2,Pei Ru Wu 1,Jia-Wern Chen 1,Din Ping Tsai 2
1 Department of Physics National Taiwan University Taipei Taiwan,2 Research Center for Applied Sciences Academia Sinica Taipei Taiwan1 Department of Physics National Taiwan University Taipei Taiwan,2 Research Center for Applied Sciences Academia Sinica Taipei TaiwanShow Abstract
A process of growing large-area plasmonic-nano-particles-decorated ZnO nanorods on the polycarbonate optical disk substrate was developed, while a corresponding photocatalytic rotational reactor was fabricated. Hydrothermal process was adapted to grow ZnO nanorods perpendicular to the optical disk substrate at relatively lower temperature. The optical disk substrate has advantages of durable property in fast rotation and high impact-resistance. The plasmonic nano-particles, in this case, silver nano-particles, were deposed on the ZnO nanorods by direct sputtering. The morphology of ZnO nanorods and plasmonic nano-particles was investigated by Scanning Electron Microscope (SEM).The photocatalytic activity of the sample was evaluated by the degradation of methyl orange (MO) as a model compound in aqueous solution, and the decomposition rate of MO molecules is monitored by the optical spectroscopy measurements. In the optimized condition, less than 10% of the MO remained in the aqueous solution after a 20-minute treatment in the rotational reactor with our sample.
NT2.2: Poster Session I: Oxide Thin-Films
Wednesday AM, March 30, 2016
Sheraton, Third Level, Phoenix Ballroom
9:00 PM - NT2.2.01
Magnetic Multifunctional Nanostructures as High-Efficiency Catalysts for Oxygen Evolution Reaction
Sammu Handi Umanga Iroshini De Silva 1,Wipula Liyanage 1,Manashi Nath 1
1 Department of Chemistry Missouri University of Science amp; Technology Rolla United States,Show Abstract
The search for high-efficiency and environmentally benign water splitting catalysts has been on the rise since this process is a source of renewable, clean energy. However the process is inherently slow, especially for the production of O2 from H2O (water oxidation) due to the high electron count and energy intensive bond formation. Hence the search for novel OER catalyst has led researchers to focus on various families of compounds including oxides and recently selenides. Multifunctional nanostructures containing the semiconductor electrocatalyst grafted onto an optically active component might boost the catalytic activity even further due to efficient charge injection. Magnetically active catalysts will also be lucrative since that might induce better adhesion of the oxygenated species at the catalytically active site. In this presentation we introduce multifunctional, magnetic Au3Pd–CoSe nanostructures as high-efficiency OER electrocatalysts. These multifunctional nanostructures were synthesized in a horizontal tube furnace by a chemical vapor deposition (CVD) reaction with cobalt acetylacetonate and elemental selenium on Au-Pd sputter coated silica substrate at 800°C. These multifunctional nanostructures were further characterized by powder X-ray diffraction, scanning and transmission electron microscopy. The morphology was mostly bifunctional Janus-like nanoparticles, which showed soft ferromagnetic behavior. These bifunctional nanoparticles were coated on the anodes of a water oxidation cell and it was observed that these nanoparticles showed a higher OER activity with lower onset potential for O2 evolution as compared to the conventional oxide-based OER electrocatalysts. In this presentation details about the catalytic activity studied through electrochemical characterization, mechanistic details along with synthesis and other properties will be discussed.
9:00 PM - NT2.2.02
Formation of Insulating Oxide Films with Hydrolysis Reaction of Alkoxide Precursors in Supercritical Fluid CO2: Chemistry, Morphology, Characterization and Film Thickness
Joanna Wang 1,Chien Wai 2,Gail Brown 1,Scott Apt 1,Howard Smith 1,Laraba Kendig 1
1 Materials and Manufacturing Directorate Wright-Patterson Air Force Base Wright Patterson AFB United States,2 University of Idaho Moscow United StatesShow Abstract
Insulating silicon dioxide (SiO2) films can be produced by hydrolysis of metal alkoxide precursors using tetraethylorthosilicate (TEOS) in the presence of an acid catalyst in supercritical fluid carbon dioxide (sc-CO2). In this study, silicon dioxide films are formed on different substrates using TEOS as a source of silicon, and acetic acid (HAc) as a catalyst. The chemical equation of the SiO2 film formation can be expressed as Si(OCH2CH3)4 + 2H2O -- SiO2 + 4CH3CH2OH. Water required for the hydrolysis reactions is from in situ generation of esterification and condensation reactions involving HAc and the alcohol produced. Without the catalyst, the hydrolysis of TEOS proceeds very slowly. The amount of the acid catalyst requires careful control to avoid excess acidity that may damage the nanoparticle layers. The acid catalyzed deposition reaction actually starts at room temperature but produces decent films in sc-CO2 at moderately high temperatures (e.g., 50 oC).
Supercritical fluid CO2 is known to have near zero surface tension and provides an ideal medium for fabrication of SiO2 films. Formation of SiO2 films via hydrolysis reaction in sc-CO2 is more rapid compared to the traditional hydrolysis reaction at room temperature. In general, metal alkoxide hydrolysis reactions carried out in a closed sc-CO2 system is not affected by moisture in air compared with traditional open-air hydrolysis systems. Using sc-CO2 as a reaction medium also eliminates undesirable organic solvents utilized in traditional alkoxide hydrolysis reactions
The attenuated total reflectance-Fourier Transform infrared (ATR-FTIR), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and electron diffraction (ED) measurements were conducted to characterize the films. XRD and ED measurements demonstrated the SiO2 films produced were amorphous. EDS, ATR-FTIR and XPS spectra showed elemental composition of the films formed on the substrate surfaces to be SiO2. The effects of pressure, amount of TEOS, reaction time and the amount of catalyst on the film quality and thickness are discussed.
9:00 PM - NT2.2.03
Dielectric Functions and Vibrational Properties of VO2 Thin Films Grown on Various Sapphire Substrates Using Sputtering Deposition
Daeho Jung 1,Hyeonseob So 1,Kun Hee Ko 1,Jun-Woo Park 1,Nguyen Thi Thu Trang 4,Seokhyun Yoon 4,Tae Dong Kang 3,Hosun Lee 1
1 Department of Applied Physics Kyung Hee Univ Yong-In Korea (the Republic of),4 Department of Physics Ewha Womans University Seoul Korea (the Republic of)2 Center for Correlated Electron Systems Institute for Basic Sciences Seoul Korea (the Republic of),3 Department of Physics and Astronomy Seoul National University Seoul Korea (the Republic of)Show Abstract
Vanadium dioxide (VO2) has been studied most intensively due to its near-room-temperature phase transition as well as its high phase stability. It undergoes a first-order metal-insulator transition (MIT) around 68oC from a high-temperature metallic phase to a low-temperature insulating phase, which is accompanied by a structural phase transition from a high-temperature tetragonal (Rutile, R) structure to a low-temperature monoclinic (M1) structure. The crystallographic orientation of a VO2 thin film depends strongly on the orientation of the sapphire substrate. It can have an application for thermochromic smart window and thermal switching devices as well as other electronic and optical applications.
VO2 thin films with the thickness of 120 nm were grown on c-, r-, a-, and m-plane sapphire as well as SiO2/Si substrates under identical conditions by RF reactive sputtering deposition from a VO2 target. The sputtering pressure was set at 6 mTorr with 10 sccm flow of O2 gas. All samples were grown 500oC, and subsequently annealed with 1 sccm of O2 gas flow rate for 20 min.
The structural and morphological properties of all the VO2 thin films were studied using X-ray diffraction (XRD) and scanning electron microscopy. The electrical and optical properties of all the VO2 thin films were studied using four point probe measurement, Raman spectroscopy, and spectroscopic ellipsometry. The grain sizes of VO2 films were different depending on the substrate orientations. The MIT temperature (TMI) varied with substrate orientations. The (011)-oriented VO2 films on the r-plane sapphire showed the lowest TMI of about 48.7oC, while the (020)-VO2 films on the c-plane sapphire displayed the highest TMI of about 64.0oC. The (002)-VO2 films on the m-plane sapphire and the (101)-VO2 films on a-plane sapphire exhibited TMI of about 52.7oC and 48.7oC, respectively. The VO2 films grown on SiO2/Si substrate showed (132) and (204) phases with TMI = 59.8oC. The observed variations of TMI with substrate orientations were due to the change in grain size and/or lattice strain. Raman spectroscopy showed that the MIT transitions were accompanied with M1-to-M2 phase transition rather than the direct M1 to tetragonal transition, for VO2 films on c-plane substrate. Using spectroscopic ellipsometry, the anisotropic dielectric functions of the VO2 thin films grown on the sapphire and SiO2/Si substrates were obtained near TMI, although only isotropic dielectric functions were reported so far in literature. The effect of MIT on the anisotropic dielectric functions of VO2 thin films are discussed in consideration of grain size and strain configuration.
 K. Okimura et al., J. Appl. Phys. 115, 153501 (2014).
 M. Nazari et al., Phys. Rev. B 87, 035142 (2013).
9:00 PM - NT2.2.04
Electronic Structure Engineering of Catalytic Activity in Epitaxial SrRuO3 Thin Films
Seokjae Oh 1,Sang A Lee 2,Jae-Yeol Hwang 3,Minseok Choi 4,Chulmin Youn 5,Ji-Woong Kim 6,Sungmin Woo 1,Jong-Seong Bae 7,Sungkyun Park 6,Suyoun Lee 8,Seo Hyoung Chang 9,Taekjib Choi 5,Sung Wng Kim 10,Woo Seok Choi 1
1 Department of Physics Sungkyunkwan Univ Suwon Korea (the Republic of),1 Department of Physics Sungkyunkwan Univ Suwon Korea (the Republic of),2 Institute of Basic Science Sungkyunkwan Univ Suwon Korea (the Republic of)3 Center for Integrated Nanostructure Physics Institute for Basic Science (IBS) Sungkyunkwan Univ Suwon Korea (the Republic of)4 Materials Modeling and Characterization Department Korea Institute of Materials Science Changwon Korea (the Republic of)5 Department of Nanotechnology and Advanced Materials Engineering Sejong Univ Seoul Korea (the Republic of)6 Department of Physics Pusan National Univ Busan Korea (the Republic of)7 Busan Center Korea Basic Science Institute Busan Korea (the Republic of)8 Electronic Materials Research Center Korea Institute of Science and Technology Seoul Korea (the Republic of)9 Department of Physics Pukyung National University Busan Korea (the Republic of)3 Center for Integrated Nanostructure Physics Institute for Basic Science (IBS) Sungkyunkwan Univ Suwon Korea (the Republic of),10 Department of Energy Sciences Sungkyunkwan Univ Suwon Korea (the Republic of)Show Abstract
Recently, complex oxides are attracting a lot of attention as catalyst due to their intrinsically high electrochemical activity. Especially, perovskite oxides show promising activity in oxygen evolution reaction (OER), which is an essential step in many energy conversion and storage mechanisms. In this presentation, we study the crystal and electronic structures of perovskite SrRuO3 (SRO) and their close correlation with the OER activity. Originally, stoichiometric epitaxial SRO thin films have orthorhombic structure. However, when elemental defects such as RuO vacancies are introduced, an orthorhombic to tetragonal structural phase transition occurs. The structural phase transition as well as the elemental vacancies accompanies a drastic change in the electronic structure. In particular, the charge transfer transition (from O 2p to Ru 3d t2g) decreases and the d-d transition (from Ru 3d t2g to eg) enhances for the tetragonal SrRuO3 thin films. Concomitant with the structural and electronic phase transitions, we observe an increase of OER activity by almost 30% within a single materials system. We will discuss the strong correlation between the electronic structure and chemical activity in epitaxial SRO thin films, in terms of suggesting a descriptor for electrocatalytic activity.
9:00 PM - NT2.2.05
A Detailed Investigation on the Electrical Characterizations of the ZrO2 MOS Capacitors
Senol Kaya 2,Ercan Yilmaz 2,Ramazan Lok 2,Aliekber Aktag 2,Huseyin Karacali 2
1 Aban Izzet Baysal Univ Bolu Turkey,2 Center for Nuclear Radition Dedetors Research and Applications Abant Izzet Baysal University BOLU Turkey,2 Center for Nuclear Radition Dedetors Research and Applications Abant Izzet Baysal University BOLU TurkeyShow Abstract
Owing to the continuous improvement of integrated circuit (IC), performance for microelectronic industry, many gate oxide materials e.g., HfO2, Al2O3, TiO2, ZnO, and etc.., have been fabricated and electrically characterized. Zirconium oxide (ZrO2) is also one of the promising gate oxide materials for MOS-based technology with high dielectric constant value (24), good thermodynamic stability in contact with Si, a suitably large band gap, and low lattice mismatch with Si (100). Besides these attractive characteristics of ZrO2, the performance of MOS-based devices depends on the interface state density (Nit), and barrier height (ΦB). Therefore we investigated detailed electrical characteristics of the ZrO2 MOS capacitors for different frequencies. The ZrO2 thin films were deposited by reactive sputtering methods and then annealed 700 0C under nitrogen enviroment. The electrical characteristics of the ZrO2 MOS capacitors were studied by capacitance-voltage and conductance voltage characteristics for 50 kHz, 500 kHz and 1 MHz frequencies. The obtained results shows that capacitance increase with decreasing the appied voltage frequencies due to contribution of frequency dependent charge capacitance to measured capacitance. In addition, the conductance peaks increase with increasing the appied voltage frequencies. Moreover the calculated Nit and ΦB parameters are increase, with increasing frequencies. This variation on the calculated devices characteristics may be attributing to the reordering and restructuring of the time dependent defects and trap sides under applied voltage frequencies. Moreover, the calculated Nit paremeters are order of 1010 which is very close the conventional SiO2/ Si interface.
This work is supported by the Ministry of Development of Turkey under Contract Number: 2012K120360
9:00 PM - NT2.2.07
Electrochemically Controlled p-Type Cuprous Oxide Films with Antimony Incorporation and Their Photovoltaic Performances
Seung Ki Baek 1,Hyung Koun Cho 1
1 Sungkyunkwan Univ Suwon Korea (the Republic of),Show Abstract
Cuprous oxide (Cu2O) is a natively p-type semiconductor known as an earth abundant and ecofriendly compound material with favorable optical properties for photoelectronic devices such as solar cells and photoelectrochemical cells. Suitable bandgap and high absorption coefficient of the p-type Cu2O make it a good candidate as a photocathode for hydrogen evolution in water splitting systems. Nevertheless, although the Shockley–Queisser limit for Cu2O is around 20 % and the theoretical photocurrent is −14.7 mA/cm2 under an AM 1.5 spectrum, the highest energy conversion efficiency of Cu2O is still below 5%. One reason for the low efficiency is the high density of intrinsic defects in the Cu2O films, which create trap states and reduce minority carrier diffusion. Thus, to produce more conductive p-type Cu2O, two approaches are available: i) doping acceptors in the Cu2O for high hole density, or ii) depositing the Cu2O with high crystalline quality for high hole mobility. Here, a novel dopant, antimony (Sb) is firstly used in the electrodeposition process for Cu2O films of high conductivity and high quality. The addition of a small amount of Sb in the Cu2O (Cu2O:Sb) exhibited significantly improved crystalline quality and vertically well-aligned grain boundaries, resulting in enhanced electrical conductivity and optical properties. After the addition of Sb, the electrical resistivity of Cu2O film was decreased from 2.4 × 105 to 1.4 × 104 Ωcm, and the Hall mobility was significantly increased from 2.1 to 28.5 cm2/Vs. Although, Cu2O:Sb exhibits a high optical transmittance exceeding 70 % in visible region due to vertical-aligned structure with high crystallinity, photocurrent generation of the Cu2O/Cu2O:Sb stacked structure was improved to -2 mA/cm2 (0V vs. RHE, pH 5) without photocatalyst due to high crystalline Cu2O deposited on thin Cu2O:Sb layer.
9:00 PM - NT2.2.08
Microstructural Tuning and Its Influence on the Piezoelectric Properties of Sodium Bismuth Titanate Thin Films, A Lead Free Piezoelectric Grown by Pulsed Laser Deposition
Kumaraswamy Miriyala 1,Ranjith Ramadurai 1
1 Department of Materials Science and Metallurgical Engineering Indian Institute of Technology Hyderabad Hyderabad India,Show Abstract
Among the lead free piezoelectric compounds Sodium Bismuth Titanate (Na0.5Bi0.5TiO3: NBT) show promising features that could replace the existing lead based piezoelectric materials in various applications. In this work, we report the effect of substrate temperature (400, 575, 600, 625, 650 0C), oxygen partial pressures (50, 100, 150and 200mTorr) on the crystallographic orientations and microstructural evolution of NBT thin films grown on (111) Pt/TiO2/SiO2/Si substrate by pulsed laser deposition (PLD) technique. From the X-ray diffraction studies, the phase pure films possess three different types of crystallographic orientations: (i) a preferred orientation along <220> only (ii) films possessing a high intense (220) reflection with other intensities present in smaller percentage (iii) films stabilized into polycrystalline nature. Field Emission Scanning Electron Microscopy (FE-SEM) studies reveal that the microstructure tunability was successfully achieved with varying the temperature and oxygen partial pressures. The films grown at 600, 575 0C temperatures possess spherical grain morphology with the grain size varying from few tens of nano meters to 100 nm on average, with increasing the oxygen pressures. However the films grown at 625, 650 0C temperatures possessed a faceted columnar grain growth at 50mTorr pressure. The transformation of morphology from, fine grains to columnar grains could be achieved by varying the oxygen partial pressures. We have also observed a dense fine grain structure to complete columnar growth of the film with increasing the temperature. Further the piezoresponse force microscopy (PFM) studies reveals that the highly oriented sample possess a strong in-plane piezoresponse whereas polycrystalline film possess an equal amount of left and right domain orientations. A strong influence of surface roughness and morphology was observed in the formation of domain walls. The inter-relation between the surface features, grain orientation and domain wall formation will be detailed in this work. Piezoelectric coefficient measurements were also performed and the piezocoefficient (d33) value was approximately 15-18 pm/V for various samples that were studied.
9:00 PM - NT2.2.10
The p-Type Conductivity of BaNaSnO3 Thin Film System
Hyukwoo Kwon 2,Sangwon Shin 2,Kookrin Char 2
1 Institute of Applied Physics Gwan-ak Gu Korea (the Republic of),2 Physics amp; Astronomy Seoul National University Seoul Korea (the Republic of),Show Abstract
Ba1-xNaxSnO3 thin film system is epitaxially grown by the pulsed laser deposition method. Structural study shows that all of films have the single phase and grown along the c-axis of the substrate. Images of the transmission electron microscopy reveal that Na impurity atoms substitute Ba sites as the proper way. Transport measurement data at the room temperature exhibits that the resistivity of the system decreases upon the Na doping. The activation energy of Na impurity level is obtained from the temperature dependent resistivity data. Its carrier type is confirmed by the change of the resistivity under the changing of the environmental gas at the high temperature.
Based on fundamental properties, the p – n junction of Ba1-xNaxSnO3/Ba1-xLaxSnO3 are fabricated. Electrical contacts on both material show ohmic behaviors respectively. I – V characteristics of this junction at the room temperature show the typical behavior of the p – n junction made by a usual semiconductor p – n junction. The C – V measurement reveals that the p-type region of this junction is entirely depleted as a narrow diode due to a relatively large activation energy of the Na impurity. High temperature I – V characteristics show that its behavior becomes ideal because of the rapid increasing of the hole carriers and shrinking of the depletion width. High temperature C – V characteristics will be measured to confirm that the depletion width is reduced depending on the temperature. From the experimental data, the change of Vbi and the ideality of this junction will be acquired.
9:00 PM - NT2.2.11
Enhanced Magnetization and Electrical Insulation in La and Gd Co-Doped BiFeO3
Mehmet Bozgeyik 2,Dhiren Pradhan 1,Shalini Kumari 1,Rajesh Katiyar 1,Ram Katiyar 1
1 Department of Physics and Institute for Functional Nanomaterials Univ of Puerto Rico San Juan United States,2 Department of Physics, Faculty of Science and Literature Kahramanmaras Sutcu Imam University Kahramanmaras Turkey,1 Department of Physics and Institute for Functional Nanomaterials Univ of Puerto Rico San Juan United StatesShow Abstract
Multiferroic materials have received extensive studies in recent decades because of wide spread potential applications in nonvolatile memories and information storages. A few single-phase mutiferroic materials exist in nature due to the mutual exclusiveness of electrical and magnetic ordering. The well known lead free single phase and room temperature multiferroic is BiFeO3 (BFO). Most of the researches on BFO are executed to improve its insulation character and weak magnetization which do not allow for practical device applications. For strengthening these weak properties, the common approach is doping BFO for Bi-site, Fe-site or both of them. Recently, we have synthesized La and Gd co-substituted single phase Bi1-xLaxFe1-yGdyO3 (BLFGO) ceramic materials by conventional solid state reaction method and investigated significant enhancement of magnetization and lower dielectric loss compared to BFO. XRD diffraction studies showed the formation of single phase rhombohedrally distorted BLFGO with negligible secondary phase. Shifting of the main (104) peaks of BLFGO to higher angle compared to that of BFO is an evidence of substitutions and slightly distortion in lattice. Temperature dependent Raman spectroscopy studies have been carried out in order to investigate the phonon dynamics after substitutions in lattice sites. We observed all active modes of parent compound, which are another evidence of rhombohedral structure of BLFGO. SEM surface microstructure studies are further proofs of the single phase formation of BLFGO with homogeneous dense round shape grains with various grain sizes ranging from 10 to 1 µm and decreasing grain size, and slightly changing shapes with more increasing Gd ratio. Magnetization measurements indicate the significant increase of magnetization (Mr ~0.08 emu/g) and coercive field of BLFGO compared to BFO. Based on the wide range of temperature and frequency dependent dielectric and impedance spectroscopy it was investigated that dielectric loss values of BLFGO ceramic pellets are significantly lower than that of BFO. Moreover, two significant dielectric anomalies were observed in BLFGO samples around 300 K and 600 K. The anomaly observed ~600 K (around TN) possess strong magnetodielectric coupling. In order to confirm the existence of magnetoelectric (ME) coupling further, frequency dependent impedance measurements have been carried out at different static magnetic field (0 ≤ H ≤2T). The significant changes were observed and indicating the presence of strong ME coupling. The detailed studies on the nature of ME coupling and exact mechanisms behind it are currently underway and will be presented in the meeting.
9:00 PM - NT2.2.12
Fabrication of Heterostructure Consisting of Cubic-LSMO on Hexagonal-ZnO for Electro-Magnetic Devices
Tamio Endo 1
1 Gifu Univ Gifu Japan,Show Abstract
Manganite La(Sr)MnO3 (LSMO) and La(Ba)MnO3 (LBMO) have peculiar properties, that is, paramagnetic p-type semiconductor at high temperatures while ferromagnetic metal at low temperatures. On the other hand, we can fabricate fine crystalline thin film of ZnO which is n-type semiconductor. Though, it is very difficult to convert it into p-type. We are trying to fabricate p-n junctions using p-LSMO (LBMO) and n-ZnO which might show large modulations of p-n characteristics by light illumination as well as by temperature variation. Magnetic field application can also modulate p-n characteristics because of spin alignment due to unique carrier transport based on the electron spin scattering process called as double exchange coupling model. In this study, we examined crystalline orientations of cubic-LSMO on hexagonal ZnO system. We actually obtained the modulations by light and temperature.
First, underlayer of ZnO thin film was deposited on sapphire(SP)-substrate, then overlayers of LSMO thin films were deposited on (0001)ZnO/SP by Ion Beam Sputtering at various substrate temperatures (Ts) at a fixed oxygen partial pressure (Po=1.0 mTorr). LSMO orientations were studied by out-of-plane and in-plane XRD. We tried to explain the Ts-dependences of out-of-plane phase rations and in-plane orientations of LSMO by lattice matching in terms of lattice contraction (or expansion). In this calculation processes, we considered least-common-multiple matching, thermal lattice expansions and lattice polarities. We obtained lattice distortion area corresponding to interface strain energy, and interface coulomb energy. The electrical p-n junction behaviors were obtained by four probe method on the samples of LBMO/ZnO deposited on various substrates.
Results and Discussion
The overlayers of cubic crystalline LSMO showed three orientation growths of (001), (110) and (111) on hexagonal (0001)ZnO/SP-substrate. Two-dimensional 2θχ-φ mapping for the out-of-plane LSMO(111)-grain and (110)-grain on the (0001)ZnO surface shows spots from the (110) (or (1-10)) plane of LSMO(111)-grain which is deviated from the spots from ZnO(10-10) by 30°. Then LSMO(111)-grain grows with single in-plane domain which has LSMO(1-10) parallel to ZnO(11-20). The out-of-plane and in-plane orientations can be interpreted by calculated interface strain energy and Coulombic energy, and also by grain boundary energy. Primitive temperature dependent I-V characteristics of p-n junctions were obtained on the LBMO/ZnO system. The LBMO/ZnO/MgO-substrate shows a curious electrical switching behavior. The I-V and switching are modulated by temperature and light illumination. The magnetization is large at high temperatures and quite large at low temperatures.
9:00 PM - NT2.2.13