Ferroelectric control of metal-insulator transition

NASA Astrophysics Data System (ADS)

He, Xu; Jin, Kui-juan; Ge, Chen; Ma, Zhong-shui; Yang, Guo-zhen

2016-03-01

We propose a method of controlling the metal-insulator transition of one perovskite material at its interface with another ferroelectric material based on first principle calculations. The operating principle is that the rotation of oxygen octahedra tuned by the ferroelectric polarization can modulate the superexchange interaction in this perovskite. We designed a tri-color superlattice of (BiFeO3)N/LaNiO3/LaTiO3, in which the BiFeO3 layers are ferroelectric, the LaNiO3 layer is the layer of which the electronic structure is to be tuned, and LaTiO3 layer is inserted to enhance the inversion asymmetry. By reversing the ferroelectric polarization in this structure, there is a metal-insulator transition of the LaNiO3 layer because of the changes of crystal field splitting of the Ni eg orbitals and the bandwidth of the Ni in-plane eg orbital. It is highly expected that a metal-transition can be realized by designing the structures at the interfaces for more materials.

Method of boronizing transition metal surfaces

DOEpatents

Koyama, Koichiro; Shimotake, Hiroshi.

1983-08-16

A method is presented for preparing a boride layer on a transition metal substrate for use in corrosive environments or as a harden surface in machine applications. This method is particularly useful in treating current collectors for use within a high temperature and corrosive electrochemical cell environment. A melt of a alkali metal boride tetrafluoride salt including such as KF to lower its melting point is prepared including a dissolved boron containing material, for instance NiB, MnB[sub 2], or CrB[sub 2]. A transition metal to be coated is immersed in the melt at a temperature of no more than 700 C and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface. 4 figs.

Method of boronizing transition metal surfaces

DOEpatents

Koyama, Koichiro; Shimotake, Hiroshi

1983-01-01

A method is presented for preparing a boride layer on a transition metal substrate for use in corrosive environments or as a harden surface in machine applications. This method is particularly useful in treating current collectors for use within a high temperature and corrosive electrochemical cell environment. A melt of a alkali metal boride tetrafluoride salt including such as KF to lower its melting point is prepared including a dissolved boron containing material, for instance NiB, MnB.sub.2, or CrB.sub.2. A transition metal to be coated is immersed in the melt at a temperature of no more than 700.degree. C. and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface.

Anomalous Insulator-Metal Transition in Boron Nitride-Graphene Hybrid Atomic Layers

DTIC Science & Technology

2012-08-13

REPORT Anomalous insulator-metal transition in boron nitride-graphene hybrid atomic layers 14 . ABSTRACT 16. SECURITY CLASSIFICATION OF: The study of...from the DFT calculation. The calculated transmission through a N terminated zigzag edged h-BN nanodomain embedded in graphene is shown in Fig. 14 , with...Energy ε − ε F (eV) 0 0.5 1 1.5 2 Tr an sm is si on FIG. 14 . (Color online) Transmission through a N terminated zigzag edged h-BN nanodomain embedded in

Superfluidity of dipolar excitons in a transition metal dichalcogenide double layer

NASA Astrophysics Data System (ADS)

Berman, Oleg L.; Kezerashvili, Roman Ya.

2017-09-01

We study formation and superfluidity of dipolar excitons in double layer heterostructures formed by two transition metal dichalcogenide (TMDC) atomically thin layers. Considering screening effects for an electron-hole interaction via the harmonic oscillator approximation for the Keldysh potential, the analytical expressions for the exciton energy spectrum and the mean field critical temperature Tc for the superfluidity are obtained. It is shown that binding energies of A excitons are larger than for B excitons. The mean field critical temperature for a two-component dilute exciton system in a TMDC double layer is analyzed and shown that the latter is an increasing function of the factor Q , determined by the effective masses of A and B excitons and their reduced mass. Comparison of the calculations for Tc performed by employing the Coulomb and Keldysh interactions demonstrates the importance of screening effects in TMDC.

Superconducting Metallic Glass Transition-Edge-Sensors

NASA Technical Reports Server (NTRS)

Hays, Charles C. (Inventor)

2013-01-01

A superconducting metallic glass transition-edge sensor (MGTES) and a method for fabricating the MGTES are provided. A single-layer superconducting amorphous metal alloy is deposited on a substrate. The single-layer superconducting amorphous metal alloy is an absorber for the MGTES and is electrically connected to a circuit configured for readout and biasing to sense electromagnetic radiation.

Differential genotoxicity of diphenyl diselenide (PhSe)2 and diphenyl ditelluride (PhTe)2

PubMed Central

Meinerz, Daiane Francine; Allebrandt, Josiane; Mariano, Douglas O.C.; Waczuk, Emily P.; Soares, Felix Antunes

2014-01-01

Organoselenium compounds have been pointed out as therapeutic agents. In contrast, the potential therapeutic aspects of tellurides have not yet been demonstrated. The present study evaluated the comparative toxicological effects of diphenyl diselenide (PhSe)2 and diphenyl ditelluride (PhTe)2 in mice after in vivo administration. Genotoxicity (as determined by comet assay) and mutagenicicity were used as end-points of toxicity. Subcutaneous administration of high doses of (PhSe)2 or (PhTe)2 (500 µmol/kg) caused distinct genotoxicity in mice. (PhSe)2 significantly decreased the DNA damage index after 48 and 96 h of its injection (p < 0.05). In contrast, (PhTe) caused a significant increase in DNA damage (p < 0.05) after 48 and 96 h of intoxication. (PhSe)2 did not cause mutagenicity but (PhTe)2 increased the micronuclei frequency, indicating its mutagenic potential. The present study demonstrated that acute in vivo exposure to ditelluride caused genotoxicity in mice, which may be associated with pro-oxidant effects of diphenyl ditelluride. In addition, the use of this compound and possibly other related tellurides must be carefully controlled. PMID:24711962

Metal–insulator transition in a transition metal dichalcogenide: Dependence on metal contacts

NASA Astrophysics Data System (ADS)

Shimazu, Y.; Arai, K.; Iwabuchi, T.

2018-03-01

Transition metal dichalcogenides are promising layered materials for realizing novel nanoelectronic and nano-optoelectronic devices. Molybdenum disulfide (MoS2), a typical transition metal dichalcogenide, has been extensively investigated due to the presence of a sizable band gap, which enables the use of MoS2 as a channel material in field-effect transistors (FET). The gate-voltage-tunable metal–insulator transition and superconductivity using MoS2 have been demonstrated in previous studies. These interesting phenomena can be considered as quantum phase transitions in two-dimensional systems. In this study, we observed that the transport properties of thin MoS2 flakes in FET geometry significantly depend on metal contacts. On comparing Ti/Au with Al contacts, it was found that the threshold voltages for FET switching and metal–insulator transition were considerably lower for the device with Al contacts. This result indicated the significant influence of the Al contacts on the properties of MoS2 devices.

Layered transition metal carboxylates: synthesis, structural aspects and observation of multi-step magnetic transition through phase diagram.

PubMed

Sen, Rupam; Mal, Dasarath; Lopes, Armandina M L; Brandão, Paula; Araújo, João P; Lin, Zhi

2013-10-01

Two new layered transition metal carboxylate frameworks, [Co3(L)2(H2O)6]·2H2O () and [Ni3(L)2(H2O)6]·2H2O () (L = tartronate anion or hydroxymalonic acid), have been synthesized and characterized by X-ray single crystal analysis. Both compounds have similar 2D structures. In both compounds there are two types of metal centers where one center is doubly bridged by the alkoxy oxygen atoms through μ2-O bridging to form a 1D infinite chain parallel to the crystallographic b-axis with the corners shared between the metal polyhedra. Magnetic susceptibility measurements revealed the existence of antiferromagnetic short range correlations between Co(Ni) intra-chain metal centers (with exchange constants JCo = -22.6 and JNi = -35.4 K). At low temperatures, long range order is observed in both compounds at Néel temperatures of 11 (for ) and 16 (for ) K, revealing that other exchange interactions, rather than the intra-chain ones, play a role in these systems. Whereas compound has an antiferromagnetic ground state, compound exhibits a ferromagnetic component, probably due to spin canting. Isothermal magnetization data unveiled a rich phase diagram with three metamagnetic phase transitions below 8 K in compound .

Break the electron- hole balance and pressure induced superconductivity in Tungsten Ditelluride

NASA Astrophysics Data System (ADS)

Song, Fengqi; Pan, Xing-Chen

Tungsten ditelluride has garnered immense interest due to the recent discovery of titanic unsaturated magnetoresistance up to 60 Tesla and its possible topological metal nature. The titanic unsaturated magnetoresistance is attributed to the perfect compensation between the opposite carriers in this material. Motivated by the small and sensitive Fermi surface of 5d electronic orbitals, we break the electron-hole balance by the application of high pressure. Superconductivity sharply appears at the pressure of 2.5 GPa, quickly reaching a maximum critical temperature of 7 K at around 16.8 GPa, and followed by a monotonic decrease in Tc with increasing pressure exhibiting the typical dome-shaped superconducting phase. What's more, linear magnetoresistance dominates the transport behavior under high pressure instead of semi-classical parabolic magnetoresistance, like in other topological metals. Refence: Nature Commun. 6, 7805 (2015), arXiv 1505, 07968. The authors would like to thank the National Key Projects for Basic Research in China, the National Natural Science Foundation of China , the NSF of Jiangsu Province, the PAPD project, and the Fundamental Research Funds for the Central Universities.

Band-edges and band-gap in few-layered transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Bhunia, Hrishikesh; Pal, Amlan J.

2018-05-01

We have considered liquid-exfoliated transition metal dichalcogenides (WS2, WSe2, MoS2, and MoSe2) and studied their band-edges and band-gap through scanning tunneling spectroscopy (STS) and density of states. A monolayer, bilayer (2L), and trilayer (3L) of each of the layered materials were characterized to derive the energies. Upon an increase in the number of layers, both the band-edges were found to shift towards the Fermi energy. The results from the exfoliated nanosheets have been compared with reported STS studies of MoS2 and WSe2 formed through chemical vapor deposition or molecular beam epitaxy methods; an uncontrolled lattice strain existed in such 2L and 3L nanoflakes due to mismatch in stacking-patterns between the monolayers affecting their energies. In the present work, the layers formed through the liquid-exfoliation process retained their interlayer coupling or stacking-sequence prevalent to the bulk and hence allowed determination of band-energies in these strain-free two-dimensional materials.

Half-Metallic Ferromagnetism and Stability of Transition Metal Pnictides and Chalcogenides

NASA Astrophysics Data System (ADS)

Liu, Bang-Gui

It is highly desirable to explore robust half-metallic ferromagnetic materials compatible with important semiconductors for spintronic applications. A state-of-the-art full potential augmented plane wave method within the densityfunctional theory is reliable enough for this purpose. In this chapter we review theoretical research on half-metallic ferromagnetism and structural stability of transition metal pnictides and chalcogenides. We show that some zincblende transition metal pnictides are half-metallic and the half-metallic gap can be fairly wide, which is consistent with experiment. Systematic calculations reveal that zincblende phases of CrTe, CrSe, and VTe are excellent half-metallic ferromagnets. These three materials have wide half-metallic gaps, are low in total energy with respect to the corresponding ground-state phases, and, importantly, are structurally stable. Halfmetallic ferromagnetism is also found in wurtzite transition metal pnictides and chalcogenides and in transition-metal doped semiconductors as well as deformed structures. Some of these half-metallic materials could be grown epitaxially in the form of ultrathin .lms or layers suitable for real spintronic applications.

Single-layer transition metal sulfide catalysts

DOEpatents

Thoma, Steven G [Albuquerque, NM

2011-05-31

Transition Metal Sulfides (TMS), such as molybdenum disulfide (MoS.sub.2), are the petroleum industry's "workhorse" catalysts for upgrading heavy petroleum feedstocks and removing sulfur, nitrogen and other pollutants from fuels. We have developed an improved synthesis technique to produce SLTMS catalysts, such as molybdenum disulfide, with potentially greater activity and specificity than those currently available. Applications for this technology include heavy feed upgrading, in-situ catalysis, bio-fuel conversion and coal liquefaction.

Layered transition metal thiophosphates /MPX3/ as photoelectrodes in photoelectrochemical cells

NASA Technical Reports Server (NTRS)

Byvik, C. E.; Smith, B. T.; Reichman, B.

1982-01-01

Layered crystals of the transition metal thiophosphates were synthesized and characterized for use as photoelectrodes in photoelectrochemical cells. Crystals incorporating tin and manganese show n-type response while those with iron and nickel show p-type response. These materials have a measured indirect bandgap of about 2.1 eV. They show ability to photoelectrolyze water in acid solutions with onset potentials which change in a Nernstian way as the PH of the solution changes. The onset potential is near zero volts versus a saturated calomel electrode at pH 2. At n-type crystals, oxygen could be evolved upon irradiation at underpotentials of 850 mV and at p-type crystals, hydrogen could be evolved at underpotentials of 400 mV, indicating a net gain in energy conversion. All crystals were unstable in basic solution. Liquid junction photovoltaic cells in iodide-triiodide acid solution using these layered materials were also constructed and found to have low efficiences.

Even–odd layer-dependent magnetotransport of high-mobility Q-valley electrons in transition metal disulfides

PubMed Central

Wu, Zefei; Xu, Shuigang; Lu, Huanhuan; Khamoshi, Armin; Liu, Gui-Bin; Han, Tianyi; Wu, Yingying; Lin, Jiangxiazi; Long, Gen; He, Yuheng; Cai, Yuan; Yao, Yugui; Zhang, Fan; Wang, Ning

2016-01-01

In few-layer transition metal dichalcogenides (TMDCs), the conduction bands along the ΓK directions shift downward energetically in the presence of interlayer interactions, forming six Q valleys related by threefold rotational symmetry and time reversal symmetry. In even layers, the extra inversion symmetry requires all states to be Kramers degenerate; whereas in odd layers, the intrinsic inversion asymmetry dictates the Q valleys to be spin-valley coupled. Here we report the transport characterization of prominent Shubnikov-de Hass (SdH) oscillations and the observation of the onset of quantum Hall plateaus for the Q-valley electrons in few-layer TMDCs. Universally in the SdH oscillations, we observe a valley Zeeman effect in all odd-layer TMDC devices and a spin Zeeman effect in all even-layer TMDC devices, which provide a crucial information for understanding the unique properties of multi-valley band structures of few-layer TMDCs. PMID:27651106

Tunable phase transition in single-layer TiSe2 via electric field

NASA Astrophysics Data System (ADS)

Liu, Lei; Zhuang, Houlong L.

2018-06-01

Phase transition represents an intriguing physical phenomenon that exists in a number of single-layer transition-metal dichalcogenides. This phenomenon often occurs below a critical temperature and breaks the long-range crystalline order leading to a reconstructed superstructure called the charge-density wave (CDW) structure, which can therefore be recovered by external stimuli such as temperature. Alternatively, we show here that another external stimulation, electric field can also result in the phase transition between the regular and CDW structures of a single-layer transition-metal dichalcogenide. We used single-layer TiSe2 as an example to elucidate the mechanism of the CDW followed by calculations of the electronic structure using a hybrid density functional. We found that applying electric field can tune the phase transition between the 1T and CDW phases of single-layer TiSe2. Our work opens up a route of tuning the phase transition of single-layer materials via electric field.

In vivo treatment with diphenyl ditelluride induces neurodegeneration in striatum of young rats: Implications of MAPK and Akt pathways

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

Heimfarth, Luana; Loureiro, Samanta Oliveira; Dutra, Márcio Ferreira

2012-10-15

In the present report 15 day-old Wistar rats were injected with 0.3 μmol of diphenyl ditelluride (PhTe){sub 2}/kg body weight and parameters of neurodegeneration were analyzed in slices from striatum 6 days afterwards. We found hyperphosphorylation of intermediate filament (IF) proteins from astrocyte (glial fibrillary acidic protein—GFAP and vimentin) and from neuron (low-, medium- and high molecular weight neurofilament subunits: NF-L, NF-M and NF-H, respectively) and increased MAPK (Erk, JNK and p38MAPK) as well as PKA activities. The treatment induced reactive astrogliosis in the striatum, evidenced by increased GFAP and vimentin immunocontent as well as their mRNA overexpression. Also, (PhTe){submore » 2} significantly increased the propidium iodide (PI) positive cells in NeuN positive population without altering PI incorporation into GFAP positive cells, indicating that in vivo exposure to (PhTe){sub 2} provoked neuronal damage. Immunohistochemistry showed a dramatic increase of GFAP staining characteristic of reactive astrogliosis. Moreover, increased caspase 3 in (PhTe){sub 2} treated striatal slices suggested apoptotic cell death. (PhTe){sub 2} exposure decreased Akt immunoreactivity, however phospho-GSK-3-β (Ser9) was unaltered, suggesting that this kinase is not directly implicated in the neurotoxicity of this compound. Therefore, the present results shed light into the mechanisms of (PhTe){sub 2}-induced neurodegeneration in rat striatum, evidencing a critical role for the MAPK and Akt signaling pathways and disruption of cytoskeletal homeostasis, which could be related with apoptotic neuronal death and astrogliosis. -- Highlights: ► Diphenyl ditelluride causes apoptotic neuronal death in the striatum of young rats. ► Diphenyl ditelluride causes reactive astrogliosis in the striatum of rats. ► Diphenyl ditelluride disrupts the homeostasis of the cytoskeleton of the striatum. ► The actions of diphenyl ditelluride are mediated by MAPK and

Ultrathin and Atomically Flat Transition-Metal Oxide: Promising Building Blocks for Metal-Insulator Electronics.

PubMed

Cui, Qingsong; Sakhdari, Maryam; Chamlagain, Bhim; Chuang, Hsun-Jen; Liu, Yi; Cheng, Mark Ming-Cheng; Zhou, Zhixian; Chen, Pai-Yen

2016-12-21

We present a new and viable template-assisted thermal synthesis method for preparing amorphous ultrathin transition-metal oxides (TMOs) such as TiO 2 and Ta 2 O 5 , which are converted from crystalline two-dimensional (2D) transition-metal dichalcogenides (TMDs) down to a few atomic layers. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning transmission electron microscopy (STEM) were used to characterize the chemical composition and bonding, surface morphology, and atomic structure of these ultrathin amorphous materials to validate the effectiveness of our synthesis approach. Furthermore, we have fabricated metal-insulator-metal (MIM) diodes using the TiO 2 and Ta 2 O 5 as ultrathin insulating layers with low potential barrier heights. Our MIM diodes show a clear transition from direct tunneling to Fowler-Nordheim tunneling, which was not observed in previously reported MIM diodes with TiO 2 or Ta 2 O 5 as the insulating layer. We attribute the improved performance of our MIM diodes to the excellent flatness and low pinhole/defect densities in our TMO insulting layers converted from 2D TMDs, which enable the low-threshold and controllable electron tunneling transport. We envision that it is possible to use the ultrathin TMOs converted from 2D TMDs as the insulating layer of a wide variety of metal-insulator and field-effect electronic devices for various applications ranging from microwave mixing, parametric conversion, infrared photodetection, emissive energy harvesting, to ultrafast electronic switching.

Synthesis-microstructure-performance relationship of layered transition metal oxides as cathode for rechargeable sodium batteries prepared by high-temperature calcination.

PubMed

Xie, Man; Luo, Rui; Lu, Jun; Chen, Renjie; Wu, Feng; Wang, Xiaoming; Zhan, Chun; Wu, Huiming; Albishri, Hassan M; Al-Bogami, Abdullah S; El-Hady, Deia Abd; Amine, Khalil

2014-10-08

Research on sodium batteries has made a comeback because of concern regarding the limited resources and cost of lithium for Li-ion batteries. From the standpoint of electrochemistry and economics, Mn- or Fe-based layered transition metal oxides should be the most suitable cathode candidates for affordable sodium batteries. Herein, this paper reports a novel cathode material, layered Na1+x(Fey/2Niy/2Mn1-y)1-xO2 (x = 0.1-0.5), synthesized through a facile coprecipitation process combined with subsequent calcination. For such cathode material calcined at 800 °C for 20 h, the Na/Na1+x(Fey/2Niy/2Mn1-y)1-xO2 (x = 0.4) electrode exhibited a good capacity of 99.1 mAh g(-1) (cycled at 1.5-4.0 V) and capacity retention over 87% after 50 cycles. Optimization of this material would make layered transition metal oxides a strong candidate for the Na-ion battery cathode.

Technologies for deposition of transition metal oxide thin films: application as functional layers in “Smart windows” and photocatalytic systems

NASA Astrophysics Data System (ADS)

Gesheva, K.; Ivanova, T.; Bodurov, G.; Szilágyi, I. M.; Justh, N.; Kéri, O.; Boyadjiev, S.; Nagy, D.; Aleksandrova, M.

2016-02-01

“Smart windows” are envisaged for future low-energy, high-efficient architectural buildings, as well as for the car industry. By switching from coloured to fully bleached state, these windows regulate the energy of solar flux entering the interior. Functional layers in these devices are the transition metals oxides. The materials (transitional metal oxides) used in smart windows can be also applied as photoelectrodes in water splitting photocells for hydrogen production or as photocatalytic materials for self-cleaning surfaces, waste water treatment and pollution removal. Solar energy utilization is recently in the main scope of numerous world research laboratories and energy organizations, working on protection against conventional fuel exhaustion. The paper presents results from research on transition metal oxide thin films, fabricated by different methods - atomic layer deposition, atmospheric pressure chemical vapour deposition, physical vapour deposition, and wet chemical methods, suitable for flowthrough production process. The lower price of the chemical deposition processes is especially important when the method is related to large-scale glazing applications. Conclusions are derived about which processes are recently considered as most prospective, related to electrochromic materials and devices manufacturing.

First-principles design of nanostructured hybrid photovoltaics based on layered transition metal phosphates

DOE PAGES

Lentz, Levi C.; Kolpak, Alexie M.

2017-04-28

The performance of bulk organic and hybrid organic-inorganic heterojunction photovoltaics is often limited by high carrier recombination arising from strongly bound excitons and low carrier mobility. Structuring materials to minimize the length scales required for exciton separation and carrier collection is therefore a promising approach for improving efficiency. In this work, first-principles computations are employed to design and characterize a new class of photovoltaic materials composed of layered transition metal phosphates (TMPs) covalently bound to organic absorber molecules to form nanostructured superlattices. Using a combination of transition metal substitution and organic functionalization, the electronic structure of these materials is systematicallymore » tuned to design a new hybrid photovoltaic material predicted to exhibit very low recombination due to the presence of a local electric field and spatially isolated, high mobility, two-dimensional electron and hole conducting channels. Furthermore, this material is predicted to have a large open-circuit voltage of 1.7 V. Here, this work suggests that hybrid TMPs constitute an interesting class of materials for further investigation in the search for achieving high efficiency, high power, and low cost photo Zirconium phosphate was chosen, in part, due to previous experiment voltaics.« less

First-principles design of nanostructured hybrid photovoltaics based on layered transition metal phosphates

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

Lentz, Levi C.; Kolpak, Alexie M.

The performance of bulk organic and hybrid organic-inorganic heterojunction photovoltaics is often limited by high carrier recombination arising from strongly bound excitons and low carrier mobility. Structuring materials to minimize the length scales required for exciton separation and carrier collection is therefore a promising approach for improving efficiency. In this work, first-principles computations are employed to design and characterize a new class of photovoltaic materials composed of layered transition metal phosphates (TMPs) covalently bound to organic absorber molecules to form nanostructured superlattices. Using a combination of transition metal substitution and organic functionalization, the electronic structure of these materials is systematicallymore » tuned to design a new hybrid photovoltaic material predicted to exhibit very low recombination due to the presence of a local electric field and spatially isolated, high mobility, two-dimensional electron and hole conducting channels. Furthermore, this material is predicted to have a large open-circuit voltage of 1.7 V. Here, this work suggests that hybrid TMPs constitute an interesting class of materials for further investigation in the search for achieving high efficiency, high power, and low cost photo Zirconium phosphate was chosen, in part, due to previous experiment voltaics.« less

Tuning Ising superconductivity with layer and spin-orbit coupling in two-dimensional transition-metal dichalcogenides.

PubMed

de la Barrera, Sergio C; Sinko, Michael R; Gopalan, Devashish P; Sivadas, Nikhil; Seyler, Kyle L; Watanabe, Kenji; Taniguchi, Takashi; Tsen, Adam W; Xu, Xiaodong; Xiao, Di; Hunt, Benjamin M

2018-04-12

Systems simultaneously exhibiting superconductivity and spin-orbit coupling are predicted to provide a route toward topological superconductivity and unconventional electron pairing, driving significant contemporary interest in these materials. Monolayer transition-metal dichalcogenide (TMD) superconductors in particular lack inversion symmetry, yielding an antisymmetric form of spin-orbit coupling that admits both spin-singlet and spin-triplet components of the superconducting wavefunction. Here, we present an experimental and theoretical study of two intrinsic TMD superconductors with large spin-orbit coupling in the atomic layer limit, metallic 2H-TaS 2 and 2H-NbSe 2 . We investigate the superconducting properties as the material is reduced to monolayer thickness and show that high-field measurements point to the largest upper critical field thus reported for an intrinsic TMD superconductor. In few-layer samples, we find the enhancement of the upper critical field is sustained by the dominance of spin-orbit coupling over weak interlayer coupling, providing additional candidate systems for supporting unconventional superconducting states in two dimensions.

Intercalation of Transition Metals into Stacked Benzene Rings: A Model Study of the Intercalation of Transition Metals into Bilayered Graphene.

PubMed

Youn, Il Seung; Kim, Dong Young; Singh, N Jiten; Park, Sung Woo; Youn, Jihee; Kim, Kwang S

2012-01-10

Structures of neutral metal-dibenzene complexes, M(C6H6)2 (M = Sc-Zn), are investigated by using Møller-Plesset second order perturbation theory (MP2). The benzene molecules change their conformation and shape upon complexation with the transition metals. We find two types of structures: (i) stacked forms for early transition metal complexes and (ii) distorted forms for late transition metal ones. The benzene molecules and the metal atom are bound together by δ bonds which originate from the interaction of π-MOs and d orbitals. The binding energy shows a maximum for Cr(C6H6)2, which obeys the 18-electron rule. It is noticeable that Mn(C6H6)2, a 19-electron complex, manages to have a stacked structure with an excess electron delocalized. For other late transition metal complexes having more than 19 electrons, the benzene molecules are bent or stray away from each other to reduce the electron density around a metal atom. For the early transition metals, the M(C6H6) complexes are found to be more weakly bound than M(C6H6)2. This is because the M(C6H6) complexes do not have enough electrons to satisfy the 18-electron rule, and so the M(C6H6)2 complexes generally tend to have tighter binding with a shorter benzene-metal length than the M(C6H6) complexes, which is quite unusual. The present results could provide a possible explanation of why on the Ni surface graphene tends to grow in a few layers, while on the Cu surface the weak interaction between the copper surface and graphene allows for the formation of a single layer of graphene, in agreement with chemical vapor deposition experiments.

UV light induced insulator-metal transition in ultra-thin ZnO/TiOx stacked layer grown by atomic layer deposition

NASA Astrophysics Data System (ADS)

Saha, D.; Misra, P.; Joshi, M. P.; Kukreja, L. M.

2016-08-01

In the present study, atomic layer deposition has been used to grow a series of Ti incorporated ZnO thin films by vertically stacking different numbers (n = 1-7) of ZnO/TiOx layers on (0001) sapphire substrates. The effects of defect states mediated chemisorption of O2 and/OH groups on the electrical properties of these films have been investigated by illuminating the samples under UV light inside a high vacuum optical cryostat. The ultra-thin film having one stacked layer (n = 1) did not show any change in its electrical resistance upon UV light exposure. On the contrary, marginal drop in the electrical resistivity was measured for the samples with n ≥ 3. Most surprisingly, the sample with n = 2 (thickness ˜ 12 nm) showed an insulator to metal transition upon UV light exposure. The temperature dependent electrical resistivity measurement on the as grown film (n = 2) showed insulating behaviour, i.e., diverging resistivity on extrapolation to T→ 0 K. However, upon UV light exposure, it transformed to a metallic state, i.e., finite resistivity at T → 0 K. Such an insulator-metal transition plausibly arises due to the de-trapping of conduction electrons from the surface defect sites which resulted in an upward shift of the Fermi level above the mobility edge. The low-temperature electron transport properties on the insulating film (n = 2) were investigated by a combined study of zero field electrical resistivity ρ(T) and magnetoresistance (MR) measurements. The observed negative MR was found to be in good agreement with the magnetic field induced suppression of quantum interference between forward-going paths of tunnelling electrons. Both ρ(T) and MR measurements provided strong evidence for the Efros-Shklovskii type variable range hopping conduction in the low-temperature (≤40 K) regime. Such studies on electron transport in ultra-thin n-type doped ZnO films are crucial to achieve optimum functionality with long term reliability of ZnO based transparent

Understanding topological phase transition in monolayer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Choe, Duk-Hyun; Sung, Ha-Jun; Chang, K. J.

2016-03-01

Despite considerable interest in layered transition metal dichalcogenides (TMDs), such as M X2 with M =(Mo ,W ) and X =(S ,Se ,Te ) , the physical origin of their topological nature is still poorly understood. In the conventional view of topological phase transition (TPT), the nontrivial topology of electron bands in TMDs is caused by the band inversion between metal d - and chalcogen p -orbital bands where the former is pulled down below the latter. Here, we show that, in TMDs, the TPT is entirely different from the conventional speculation. In particular, M S2 and M S e2 exhibits the opposite behavior of TPT such that the chalcogen p -orbital band moves down below the metal d -orbital band. More interestingly, in M T e2 , the band inversion occurs between the metal d -orbital bands. Our findings cast doubts on the common view of TPT and provide clear guidelines for understanding the topological nature in new topological materials to be discovered.

Resonant-Raman Intensities of N-layer Transition Metal Dichalcogenides from First Principles

NASA Astrophysics Data System (ADS)

Miranda, Henrique; Froehlicher, Guillaume; Lorchat, Ettienne; Fernique, François; Molina-Sánchez, Alejandro; Berciaud, Stéphane; Wirtz, Ludger

Transition metal dichalcogenides (TMDs) have interesting optical and electronic properties that make them good candidates for nano-engineering applications. Raman spectroscopy provides information about the vibrational modes and optical spectrum at the same time: when the laser energy is close to an electronic transition, the intensity is increased due to resonance. We investigate these effects combining different ab initio methods: we obtain ground-state and vibrational properties from density functional theory and the optical absorption spectrum using GW corrections and the Bethe-Salpeter equation to account for the excitonic effects which are known to play an important role in TMDs. Using a quasi-static finite differences approach, we calculate the dielectric susceptibility for different light polarizations and different phonon modes in order to determine the Raman tensor of TMDs, in particular of multi-layer and bulk MoTe2. We explain recent experimental results for the splitting of high-frequency modes and deviations from the non-resonant Raman model. We also give a brief outlook on possible improvements of the methodology.

Unified Description of the Optical Phonon Modes inN-Layer MoTe2

NASA Astrophysics Data System (ADS)

Froehlicher, Guillaume; Lorchat, Etienne; Fernique, François; Joshi, Chaitanya; Molina-Sánchez, Alejandro; Wirtz, Ludger; Berciaud, Stéphane

2015-10-01

$N$-layer transition metal dichalcogenides provide a unique platform to investigate the evolution of the physical properties between the bulk (three dimensional) and monolayer (quasi two-dimensional) limits. Here, using high-resolution micro-Raman spectroscopy, we report a unified experimental description of the $\\Gamma$-point optical phonons in $N$-layer $2H$-molybdenum ditelluride (MoTe$_2$). We observe a series of $N$-dependent low-frequency interlayer shear and breathing modes (below $40~\\rm cm^{-1}$, denoted LSM and LBM) and well-defined Davydov splittings of the mid-frequency modes (in the range $100-200~\\rm cm^{-1}$, denoted iX and oX), which solely involve displacements of the chalcogen atoms. In contrast, the high-frequency modes (in the range $200-300~\\rm cm^{-1}$, denoted iMX and oMX), arising from displacements of both the metal and chalcogen atoms, exhibit considerably reduced splittings. The manifold of phonon modes associated with the in-plane and out-of-plane displacements are quantitatively described by a force constant model, including interactions up to the second nearest neighbor and surface effects as fitting parameters. The splittings for the iX and oX modes observed in $N$-layer crystals are directly correlated to the corresponding bulk Davydov splittings between the $E_{2u}/E_{1g}$ and $B_{1u}/A_{1g}$ modes, respectively, and provide a measurement of the frequencies of the bulk silent $E_{2u}$ and $B_{1u}$ optical phonon modes. Our analysis could readily be generalized to other layered crystals.

Electric field-triggered metal-insulator transition resistive switching of bilayered multiphasic VOx

NASA Astrophysics Data System (ADS)

Won, Seokjae; Lee, Sang Yeon; Hwang, Jungyeon; Park, Jucheol; Seo, Hyungtak

2018-01-01

Electric field-triggered Mott transition of VO2 for next-generation memory devices with sharp and fast resistance-switching response is considered to be ideal but the formation of single-phase VO2 by common deposition techniques is very challenging. Here, VOx films with a VO2-dominant phase for a Mott transition-based metal-insulator transition (MIT) switching device were successfully fabricated by the combined process of RF magnetron sputtering of V metal and subsequent O2 annealing to form. By performing various material characterizations, including scanning transmission electron microscopy-electron energy loss spectroscopy, the film is determined to have a bilayer structure consisting of a VO2-rich bottom layer acting as the Mott transition switching layer and a V2O5/V2O3 mixed top layer acting as a control layer that suppresses any stray leakage current and improves cyclic performance. This bilayer structure enables excellent electric field-triggered Mott transition-based resistive switching of Pt-VOx-Pt metal-insulator-metal devices with a set/reset current ratio reaching 200, set/reset voltage of less than 2.5 V, and very stable DC cyclic switching upto 120 cycles with a great set/reset current and voltage distribution less than 5% of standard deviation at room temperature, which are specifications applicable for neuromorphic or memory device applications. [Figure not available: see fulltext.

The mesospheric metal layer topside: Examples of simultaneous metal observations

NASA Astrophysics Data System (ADS)

Höffner, J.; Friedman, J. S.

2005-09-01

We show examples of common volume observations of three metals by lidar focusing on the altitude of the topside of the meteoric metal layer as described by Höffner and Friedman (H&F) [The mesospheric metal layer topside: a possible connection to meteoroids, Atmos. Chem. Phys. 4 (2004) 801 808]. In contrast to H&F, we will focus on time scales of a few hours and less whereas the previous study examined the seasonally averaged climatological state on time scales of several days or weeks, and we examine the entire topside, whereas H&F focused on data at 113 km. The examples, taken under different observation conditions in 1997 and 1998 at Kühlungsborn, Germany (54°N, 15°E), show that the metal layers can often be observed at altitudes as high as 130 km if the signal is integrated over a period of several hours. Under such conditions it is possible to derive reasonably good metal abundance ratios from nocturnally averaged data, which, in turn, allow the discussion of metal abundance ratios to broaden from a single altitude as discussed in H&F to an altitude range extending as high as 130 km. The examples herein show, for the first time, that it is possible to track the transition in the metal abundance ratios from the main layer to an altitude region that has not been studied in the past by lidar. On shorter time scales, small structures are detectable and observable, sometimes above 120 km, resulting in, on average, a broad but weak topside layer above 105 km. In particular, the example of 26 27 October 1997, obtained during enhanced meteor activity, is an indication that this broad layer may result from meteor ablation occurring in this altitude range during the observation. Ratios of metal densities for Ca, Fe, K, and Na are remarkably consistent above about 110 km and in close agreement with the results of H&F. They are less consistent with ratios measured in individual meteor trails and appear to have little relation to the ratios measured in CI meteorites

Photoinduced charge transfer from vacuum-deposited molecules to single-layer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Osada, Kazuki; Tanaka, Masatoshi; Ohno, Shinya; Suzuki, Takanori

2016-06-01

Variations of photoluminescence (PL) and Raman spectra of single-layer MoS2, MoSe2, WS2, and WSe2 due to the vacuum deposition of C60 or copper phthalocyanine (CuPc) molecules have been investigated. PL spectra are decomposed into two competitive components, an exciton and a charged exciton (trion), depending on carrier density. The variation of PL spectra is interpreted in terms of charge transfer across the interfaces between transition metal dichalcogenides (TMDs) and dopant molecules. We find that deposited C60 molecules inject photoexcited electrons into MoS2, MoSe2, and WS2 or holes into WSe2. CuPc molecules also inject electrons into MoS2, MoSe2, and WS2, while holes are depleted from WSe2 to CuPc. We then propose a band alignment between TMDs and dopant molecules. Peak shifts of Raman spectra and doped carrier density estimated using a three-level model also support the band alignment. We thus demonstrate photoinduced charge transfer from dopant molecules to single-layer TMDs.

Electronic band structure of 4d and 5d transition metal trichalcogenides

NASA Astrophysics Data System (ADS)

Sugita, Yusuke; Miyake, Takashi; Motome, Yukitoshi

2018-05-01

Transition metal trichalcogenides (TMTs), a family of van der Waals materials, have gained increasing interests from the discovery of magnetism in few-layer forms. Although TMTs with 3d transition metal elements have been studied extensively, much less is explored for the 4d and 5d cases, where the interesting interplay between electron correlations and the relativistic spin-orbit coupling is expected. Using ab initio calculations, we here investigate the electronic property of TMTs with 4d and 5d transition metal elements. We show that the band structures exhibit multiple node-like features near the Fermi level. These are the remnant of multiple Dirac cones that were recently discovered in the monolayer cases. Our results indicate that the peculiar two-dimensional multiple Dirac cones are concealed even in the layered bulk systems.

The Acoustoelectric and Electric Characterization of Single Layer Transition Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Preciado, Edwin Sabas

The acoustoelectric effect in single-layer molybdenum disulfide (MoS2) and tungsten diselenide (WSe2) is studied in a hybrid setup. Such effects, which rely on the transfer of momentum from surface acoustic waves (SAWs), are generated on the surface of lithium niobate (LiNbO3) to the carriers in MoS2 and WSe2, resulting in an attenuation and velocity shift of the wave and giving rise to an acoustoelectric current. This dissertation examines the feasibility of integrating high-quality, single-layer MoS2 and WSe2 onto LiNbO3 to ultimately fabricate and characterize a hybrid chip that combines the functionality of a field-effect transistor (FET) and SAW device. MoS2 and WSe2 were synthesized by chemical vapor deposition (CVD) directly onto a chemically-reduced LiNbO3 substrate. LiNbO3 is a ferroelectric material that offers a unique blend of piezoelectric and birefringent properties, yet it lacks both optical activity and semiconductor transport. The prototypical device exhibits electrical characteristics that are competitive with MoS2 and WSe2 devices on silicon. These results demonstrate both a sound-driven battery and an acoustic photodetector, and ultimately open directions to non-invasive investigation of electrical properties of single-layer films. The experiments reveal close agreement between transport measurements utilizing conventional contacts and SAW spectroscopy. This approach will set forth the possibility of contact-free transport characterization of two-dimensional (2D) transition metal dichalcogenides (TMD) films, avoiding such concerns as the role of charge transfer at contacts as an artifact of such measurements.

Optically adjustable valley Hall current in single-layer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Sengupta, Parijat; Pavlidis, Dimitris; Shi, Junxia

2018-02-01

The illumination of a single-layer transition metal dichalcogenide with an elliptically polarized light beam is shown to give rise to a differential rate of inter-band carrier excitation between the valence and conduction states around the valley edges, K and K' . This rate with a linear dependence on the beam ellipticity and inverse of the optical gap manifests as an asymmetric Fermi distribution between the valleys or a non-equilibrium population which under an external field and a Berry curvature induced anomalous velocity, results in an externally tunable finite valley Hall current. Surface imperfections that influence the excitation rates are included through the self-consistent Born approximation. Further, we describe applications centered around circular dichroism, quantum computing, and spin torque via optically excited spin currents within the framework of the suggested formalism. A closing summary points to the possibility of extending the calculations to composite charged particles like trions. The role of the substrate in renormalizing the fundamental band gap and moderating the valley Hall current is also discussed.

Optical and Excitonic Properties of Atomically Thin Transition-Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Berkelbach, Timothy C.; Reichman, David R.

2018-03-01

Starting with the isolation of a single sheet of graphene, the study of layered materials has been one of the most active areas of condensed matter physics, chemistry, and materials science. Single-layer transition-metal dichalcogenides are direct-gap semiconducting analogs of graphene that exhibit novel electronic and optical properties. These features provide exciting opportunities for the discovery of both new fundamental physical phenomena as well as innovative device platforms. Here, we review the progress associated with the creation and use of a simple microscopic framework for describing the optical and excitonic behavior of few-layer transition-metal dichalcogenides, which is based on symmetry, band structure, and the effective interactions between charge carriers in these materials. This approach provides an often quantitative account of experiments that probe the physics associated with strong electron–hole interactions in these quasi two-dimensional systems and has been successfully employed by many groups to both describe and predict emergent excitonic behavior in these layered semiconducting systems.

Metal-insulator transitions

NASA Astrophysics Data System (ADS)

Imada, Masatoshi; Fujimori, Atsushi; Tokura, Yoshinori

1998-10-01

Metal-insulator transitions are accompanied by huge resistivity changes, even over tens of orders of magnitude, and are widely observed in condensed-matter systems. This article presents the observations and current understanding of the metal-insulator transition with a pedagogical introduction to the subject. Especially important are the transitions driven by correlation effects associated with the electron-electron interaction. The insulating phase caused by the correlation effects is categorized as the Mott Insulator. Near the transition point the metallic state shows fluctuations and orderings in the spin, charge, and orbital degrees of freedom. The properties of these metals are frequently quite different from those of ordinary metals, as measured by transport, optical, and magnetic probes. The review first describes theoretical approaches to the unusual metallic states and to the metal-insulator transition. The Fermi-liquid theory treats the correlations that can be adiabatically connected with the noninteracting picture. Strong-coupling models that do not require Fermi-liquid behavior have also been developed. Much work has also been done on the scaling theory of the transition. A central issue for this review is the evaluation of these approaches in simple theoretical systems such as the Hubbard model and t-J models. Another key issue is strong competition among various orderings as in the interplay of spin and orbital fluctuations. Experimentally, the unusual properties of the metallic state near the insulating transition have been most extensively studied in d-electron systems. In particular, there is revived interest in transition-metal oxides, motivated by the epoch-making findings of high-temperature superconductivity in cuprates and colossal magnetoresistance in manganites. The article reviews the rich phenomena of anomalous metallicity, taking as examples Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Ru compounds. The diverse phenomena include strong spin and

First-order metal-insulator transitions in vanadates from first principles

NASA Astrophysics Data System (ADS)

Kumar, Anil; Rabe, Karin

2013-03-01

Materials that exhibit first-order metal-insulator transitions, with the accompanying abrupt change in the conductivity, have potential applications as switches in future electronic devices. Identification of materials and exploration of the atomic-scale mechanisms for switching between the two electronic states is a focus of current research. In this work, we search for first-order metal-insulator transitions in transition metal compounds, with a particular focus on d1 and d2 systems, by using first principles calculations to screen for an alternative low-energy state having not only a electronic character opposite to that of the ground state, but a distinct structure and/or magnetic ordering which would permit switching by an applied field or stress. We will present the results of our investigation of the perovskite compounds SrVO3, LaVO3, CaVO3, YVO3, LaTiO3 and related layered phase, including superlattices and Ruddlesden-Popper phases. While the pure compounds do not satisfy the search criteria, the layered phases show promising results.

Low resistance barrier layer for isolating, adhering, and passivating copper metal in semiconductor fabrication

DOEpatents

Weihs, Timothy P.; Barbee, Jr., Troy W.

2002-01-01

Cubic or metastable cubic refractory metal carbides act as barrier layers to isolate, adhere, and passivate copper in semiconductor fabrication. One or more barrier layers of the metal carbide are deposited in conjunction with copper metallizations to form a multilayer characterized by a cubic crystal structure with a strong (100) texture. Suitable barrier layer materials include refractory transition metal carbides such as vanadium carbide (VC), niobium carbide (NbC), tantalum carbide (TaC), chromium carbide (Cr.sub.3 C.sub.2), tungsten carbide (WC), and molybdenum carbide (MoC).

Transition metal dichalcogenides and beyond: synthesis, properties, and applications of single- and few-layer nanosheets.

PubMed

Lv, Ruitao; Robinson, Joshua A; Schaak, Raymond E; Sun, Du; Sun, Yifan; Mallouk, Thomas E; Terrones, Mauricio

2015-01-20

CONSPECTUS: In the wake of the discovery of the remarkable electronic and physical properties of graphene, a vibrant research area on two-dimensional (2D) layered materials has emerged during the past decade. Transition metal dichalcogenides (TMDs) represent an alternative group of 2D layered materials that differ from the semimetallic character of graphene. They exhibit diverse properties that depend on their composition and can be semiconductors (e.g., MoS2, WS2), semimetals (e.g., WTe2, TiSe2), true metals (e.g., NbS2, VSe2), and superconductors (e.g., NbSe2, TaS2). The properties of TMDs can also be tailored according to the crystalline structure and the number and stacking sequence of layers in their crystals and thin films. For example, 2H-MoS2 is semiconducting, whereas 1T-MoS2 is metallic. Bulk 2H-MoS2 possesses an indirect band gap, but when 2H-MoS2 is exfoliated into monolayers, it exhibits direct electronic and optical band gaps, which leads to enhanced photoluminescence. Therefore, it is important to learn to control the growth of 2D TMD structures in order to exploit their properties in energy conversion and storage, catalysis, sensing, memory devices, and other applications. In this Account, we first introduce the history and structural basics of TMDs. We then briefly introduce the Raman fingerprints of TMDs of different layer numbers. Then, we summarize our progress on the controlled synthesis of 2D layered materials using wet chemical approaches, chemical exfoliation, and chemical vapor deposition (CVD). It is now possible to control the number of layers when synthesizing these materials, and novel van der Waals heterostructures (e.g., MoS2/graphene, WSe2/graphene, hBN/graphene) have recently been successfully assembled. Finally, the unique optical, electrical, photovoltaic, and catalytic properties of few-layered TMDs are summarized and discussed. In particular, their enhanced photoluminescence (PL), photosensing, photovoltaic conversion, and

Bonding and electronics of the MoTe2/Ge interface under strain

NASA Astrophysics Data System (ADS)

Szary, Maciej J.; Michalewicz, Marek T.; Radny, Marian W.

2017-05-01

Understanding the interface formation of a conventional semiconductor with a monolayer of transition-metal dichalcogenides provides a necessary platform for the anticipated applications of dichalcogenides in electronics and optoelectronics. We report here, based on the density functional theory, that under in-plane tensile strain, a 2H semiconducting phase of the molybdenum ditelluride (MoTe2) monolayer undergoes a semiconductor-to-metal transition and in this form bonds covalently to bilayers of Ge stacked in the [111] crystal direction. This gives rise to the stable bonding configuration of the MoTe2/Ge interface with the ±K valley metallic, electronic interface states exclusively of a Mo 4 d character. The atomically sharp Mo layer represents therefore an electrically active (conductive) subsurface δ -like two-dimensional profile that can exhibit a valley-Hall effect. Such system can develop into a key element of advanced semiconductor technology or a novel device concept.

Transition-metal-ion-mediated polymerization of dopamine: mussel-inspired approach for the facile synthesis of robust transition-metal nanoparticle-graphene hybrids.

PubMed

Yang, Liping; Kong, Junhua; Zhou, Dan; Ang, Jia Ming; Phua, Si Lei; Yee, Wu Aik; Liu, Hai; Huang, Yizhong; Lu, Xuehong

2014-06-16

Inspired by the high transition-metal-ion content in mussel glues, and the cross-linking and mechanical reinforcement effects of some transition-metal ions in mussel threads, high concentrations of nickel(II), cobalt(II), and manganese(II) ions have been purposely introduced into the reaction system for dopamine polymerization. Kinetics studies were conducted for the Ni(2+)-dopamine system to investigate the polymerization mechanism. The results show that the Ni(2+) ions could accelerate the assembly of dopamine oligomers in the polymerization process. Spectroscopic and electron microscopic studies reveal that the Ni(2+) ions are chelated with polydopamine (PDA) units, forming homogeneous Ni(2+)-PDA complexes. This facile one-pot approach is utilized to construct transition-metal-ion-PDA complex thin coatings on graphene oxide, which can be carbonized to produce robust hybrid nanosheets with well-dispersed metallic nickel/metallic cobalt/manganese(II) oxide nanoparticles embedded in PDA-derived thin graphitic carbon layers. The nickel-graphene hybrid prepared by using this approach shows good catalytic properties and recyclability for the reduction of p-nitrophenol. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Control of the metal-insulator transition in vanadium dioxide by modifying orbital occupancy

NASA Astrophysics Data System (ADS)

Aetukuri, Nagaphani B.; Gray, Alexander X.; Drouard, Marc; Cossale, Matteo; Gao, Li; Reid, Alexander H.; Kukreja, Roopali; Ohldag, Hendrik; Jenkins, Catherine A.; Arenholz, Elke; Roche, Kevin P.; Dürr, Hermann A.; Samant, Mahesh G.; Parkin, Stuart S. P.

2013-10-01

External control of the conductivity of correlated oxides is one of the most promising schemes for realizing energy-efficient electronic devices. Vanadium dioxide (VO2), an archetypal correlated oxide compound, undergoes a temperature-driven metal-insulator transition near room temperature with a concomitant change in crystal symmetry. Here, we show that the metal-insulator transition temperature of thin VO2(001) films can be changed continuously from ~285 to ~345K by varying the thickness of the RuO2 buffer layer (resulting in different epitaxial strains). Using strain-, polarization- and temperature-dependent X-ray absorption spectroscopy, in combination with X-ray diffraction and electronic transport measurements, we demonstrate that the transition temperature and the structural distortion across the transition depend on the orbital occupancy in the metallic state. Our findings open up the possibility of controlling the conductivity in atomically thin VO2 layers by manipulating the orbital occupancy by, for example, heterostructural engineering.

Newtype single-layer magnetic semiconductor in transition-metal dichalcogenides VX2 (X = S, Se and Te)

NASA Astrophysics Data System (ADS)

Fuh, Huei-Ru; Chang, Ching-Ray; Wang, Yin-Kuo; Evans, Richard F. L.; Chantrell, Roy W.; Jeng, Horng-Tay

2016-09-01

We present a newtype 2-dimensional (2D) magnetic semiconductor based on transition-metal dichalcogenides VX2 (X = S, Se and Te) via first-principles calculations. The obtained indirect band gaps of monolayer VS2, VSe2, and VTe2 given from the generalized gradient approximation (GGA) are respectively 0.05, 0.22, and 0.20 eV, all with integer magnetic moments of 1.0 μB. The GGA plus on-site Coulomb interaction U (GGA + U) enhances the exchange splittings and raises the energy gap up to 0.38~0.65 eV. By adopting the GW approximation, we obtain converged G0W0 gaps of 1.3, 1.2, and 0.7 eV for VS2, VSe2, and VTe2 monolayers, respectively. They agree very well with our calculated HSE gaps of 1.1, 1.2, and 0.6 eV, respectively. The gap sizes as well as the metal-insulator transitions are tunable by applying the in-plane strain and/or changing the number of stacking layers. The Monte Carlo simulations illustrate very high Curie-temperatures of 292, 472, and 553 K for VS2, VSe2, and VTe2 monolayers, respectively. They are nearly or well beyond the room temperature. Combining the semiconducting energy gap, the 100% spin polarized valence and conduction bands, the room temperature TC, and the in-plane magnetic anisotropy together in a single layer VX2, this newtype 2D magnetic semiconductor shows great potential in future spintronics.

Temperature and electric field induced metal-insulator transition in atomic layer deposited VO2 thin films

NASA Astrophysics Data System (ADS)

Tadjer, Marko J.; Wheeler, Virginia D.; Downey, Brian P.; Robinson, Zachary R.; Meyer, David J.; Eddy, Charles R.; Kub, Fritz J.

2017-10-01

Amorphous vanadium oxide (VO2) films deposited by atomic layer deposition (ALD) were crystallized with an ex situ anneal at 660-670 °C for 1-2 h under a low oxygen pressure (10-4 to 10-5 Torr). Under these conditions the crystalline VO2 phase was maintained, while formation of the V2O5 phase was suppressed. Electrical transition from the insulator to the metallic phase was observed in the 37-60 °C range, with an ROFF/RON ratio of up to about 750 and ΔTC ≅ 7-10 °C. Lateral electric field applied across two-terminal device structures induced a reversible phase change, with a room temperature transition field of about 25 kV/cm in the VO2 sample processed with the 2 h long O2 anneal. Both the width and slope of the field induced MIT I-V hysteresis were dependent upon the VO2 crystalline quality.

Structural phase transition in monolayer MoTe2 driven by electrostatic doping

NASA Astrophysics Data System (ADS)

Wang, Ying; Xiao, Jun; Zhu, Hanyu; Li, Yao; Alsaid, Yousif; Fong, King Yan; Zhou, Yao; Wang, Siqi; Shi, Wu; Wang, Yuan; Zettl, Alex; Reed, Evan J.; Zhang, Xiang

2017-10-01

Monolayers of transition-metal dichalcogenides (TMDs) exhibit numerous crystal phases with distinct structures, symmetries and physical properties. Exploring the physics of transitions between these different structural phases in two dimensions may provide a means of switching material properties, with implications for potential applications. Structural phase transitions in TMDs have so far been induced by thermal or chemical means; purely electrostatic control over crystal phases through electrostatic doping was recently proposed as a theoretical possibility, but has not yet been realized. Here we report the experimental demonstration of an electrostatic-doping-driven phase transition between the hexagonal and monoclinic phases of monolayer molybdenum ditelluride (MoTe2). We find that the phase transition shows a hysteretic loop in Raman spectra, and can be reversed by increasing or decreasing the gate voltage. We also combine second-harmonic generation spectroscopy with polarization-resolved Raman spectroscopy to show that the induced monoclinic phase preserves the crystal orientation of the original hexagonal phase. Moreover, this structural phase transition occurs simultaneously across the whole sample. This electrostatic-doping control of structural phase transition opens up new possibilities for developing phase-change devices based on atomically thin membranes.

Effects of Transition-Metal Mixing on Na Ordering and Kinetics in Layered P 2 Oxides

NASA Astrophysics Data System (ADS)

Zheng, Chen; Radhakrishnan, Balachandran; Chu, Iek-Heng; Wang, Zhenbin; Ong, Shyue Ping

2017-06-01

Layered P 2 oxides are promising cathode materials for rechargeable sodium-ion batteries. In this work, we systematically investigate the effects of transition-metal (TM) mixing on Na ordering and kinetics in the NaxCo1 -yMnyO2 model system using density-functional-theory (DFT) calculations. The DFT-predicted 0-K stability diagrams indicate that Co-Mn mixing reduces the energetic differences between Na orderings, which may account for the reduction of the number of phase transformations observed during the cycling of mixed-TM P 2 layered oxides compared to a single TM. Using ab initio molecular-dynamics simulations and nudged elastic-band calculations, we show that the TM composition at the Na(1) (face-sharing) site has a strong influence on the Na site energies, which in turn impacts the kinetics of Na diffusion towards the end of the charge. By employing a site-percolation model, we establish theoretical upper and lower bounds for TM concentrations based on their effect on Na(1) site energies, providing a framework to rationally tune mixed-TM compositions for optimal Na diffusion.

Tests on Double Layer Metalization

NASA Technical Reports Server (NTRS)

Woo, D. S.

1983-01-01

28 page report describes experiments in fabrication of integrated circuits with double-layer metalization. Double-layer metalization requires much less silicon "real estate" and allows more flexibility in placement of circuit elements than does single-layer metalization.

Metal deposition using seed layers

DOEpatents

Feng, Hsein-Ping; Chen, Gang; Bo, Yu; Ren, Zhifeng; Chen, Shuo; Poudel, Bed

2013-11-12

Methods of forming a conductive metal layers on substrates are disclosed which employ a seed layer to enhance bonding, especially to smooth, low-roughness or hydrophobic substrates. In one aspect of the invention, the seed layer can be formed by applying nanoparticles onto a surface of the substrate; and the metallization is achieved by electroplating an electrically conducting metal onto the seed layer, whereby the nanoparticles serve as nucleation sites for metal deposition. In another approach, the seed layer can be formed by a self-assembling linker material, such as a sulfur-containing silane material.

Mapping of Low-Frequency Raman Modes in CVD-Grown Transition Metal Dichalcogenides: Layer Number, Stacking Orientation and Resonant Effects

PubMed Central

O’Brien, Maria; McEvoy, Niall; Hanlon, Damien; Hallam, Toby; Coleman, Jonathan N.; Duesberg, Georg S.

2016-01-01

Layered inorganic materials, such as the transition metal dichalcogenides (TMDs), have attracted much attention due to their exceptional electronic and optical properties. Reliable synthesis and characterization of these materials must be developed if these properties are to be exploited. Herein, we present low-frequency Raman analysis of MoS2, MoSe2, WSe2 and WS2 grown by chemical vapour deposition (CVD). Raman spectra are acquired over large areas allowing changes in the position and intensity of the shear and layer-breathing modes to be visualized in maps. This allows detailed characterization of mono- and few-layered TMDs which is complementary to well-established (high-frequency) Raman and photoluminescence spectroscopy. This study presents a major stepping stone in fundamental understanding of layered materials as mapping the low-frequency modes allows the quality, symmetry, stacking configuration and layer number of 2D materials to be probed over large areas. In addition, we report on anomalous resonance effects in the low-frequency region of the WS2 Raman spectrum. PMID:26766208

Graphene and graphene-like layered transition metal dichalcogenides in energy conversion and storage.

PubMed

Wang, Hua; Feng, Hongbin; Li, Jinghong

2014-06-12

Being confronted with the energy crisis and environmental problems, the exploration of clean and renewable energy materials as well as their devices are urgently demanded. Two-dimensional (2D) atomically-thick materials, graphene and grpahene-like layered transition metal dichalcogenides (TMDs), have showed vast potential as novel energy materials due to their unique physicochemical properties. In this Review, we outline the typical application of graphene and grpahene-like TMDs in energy conversion and storage fields, and hope to promote the development of 2D TMDs in this field through the analysis and comparisons with the relatively natural graphene. First, a brief introduction of electronic structures and basic properties of graphene and TMDs are presented. Then, we summarize the exciting progress of these materials made in both energy conversion and storage field including solar cells, electrocatalysis, supercapacitors and lithium ions batteries. Finally, the prospects and further developments in these exciting fields of graphene and graphene-like TMDs materials are also suggested. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Edge Delamination of Monolayer Transition Metal Dichalcogenides.

PubMed

Ly, Thuc Hue; Yun, Seok Joon; Thi, Quoc Huy; Zhao, Jiong

2017-07-25

Delamination of thin films from the supportive substrates is a critical issue within the thin film industry. The emergent two-dimensional, atomic layered materials, including transition metal dichalcogenides, are highly flexible; thus buckles and wrinkles can be easily generated and play vital roles in the corresponding physical properties. Here we introduce one kind of patterned buckling behavior caused by the delamination from a substrate initiated at the edges of the chemical vapor deposition synthesized monolayer transition metal dichalcogenides, led by thermal expansion mismatch. The atomic force microscopy and optical characterizations clearly showed the puckered structures associated with the strain, whereas the transmission electron microscopy revealed the special sawtooth-shaped edges, which break the geometrical symmetry for the buckling behavior of hexagonal samples. The condition of the edge delamination is in accordance with the fracture behavior of thin film interfaces. This edge delamination and buckling process is universal for most ultrathin two-dimensional materials, which requires more attention in various future applications.

A comparative study of layered transition metal oxide cathodes for application in sodium-ion battery.

PubMed

Hasa, Ivana; Buchholz, Daniel; Passerini, Stefano; Hassoun, Jusef

2015-03-11

Herein, we report a study on P-type layered sodium transition metal-based oxides with a general formula of NaxMO2 (M = Ni, Fe, Mn). We synthesize the materials via coprecipitation followed by annealing in air and rinsing with water, and we examine the electrodes as cathodes for sodium-ion batteries using a propylene carbonate-based electrolyte. We fully investigate the effect of the Ni-to-Fe ratio, annealing temperature, and sodium content on the electrochemical performances of the electrodes. The impact of these parameters on the structural and electrochemical properties of the materials is revealed by X-ray diffraction, scanning electron microscopy, and cyclic voltammetry, respectively. The suitability of this class of P-type materials for sodium battery application is finally demonstrated by cycling tests revealing an excellent electrochemical performance in terms of delivered capacity (i.e., about 200 mAh g(-1)) and charge-discharge efficiency (approaching 100%).

Predicting a new phase (T'') of two-dimensional transition metal di-chalcogenides and strain-controlled topological phase transition

NASA Astrophysics Data System (ADS)

Ma, Fengxian; Gao, Guoping; Jiao, Yalong; Gu, Yuantong; Bilic, Ante; Zhang, Haijun; Chen, Zhongfang; Du, Aijun

2016-02-01

Single layered transition metal dichalcogenides have attracted tremendous research interest due to their structural phase diversities. By using a global optimization approach, we have discovered a new phase of transition metal dichalcogenides (labelled as T''), which is confirmed to be energetically, dynamically and kinetically stable by our first-principles calculations. The new T'' MoS2 phase exhibits an intrinsic quantum spin Hall (QSH) effect with a nontrivial gap as large as 0.42 eV, suggesting that a two-dimensional (2D) topological insulator can be achieved at room temperature. Most interestingly, there is a topological phase transition simply driven by a small tensile strain of up to 2%. Furthermore, all the known MX2 (M = Mo or W; X = S, Se or Te) monolayers in the new T'' phase unambiguously display similar band topologies and strain controlled topological phase transitions. Our findings greatly enrich the 2D families of transition metal dichalcogenides and offer a feasible way to control the electronic states of 2D topological insulators for the fabrication of high-speed spintronics devices.Single layered transition metal dichalcogenides have attracted tremendous research interest due to their structural phase diversities. By using a global optimization approach, we have discovered a new phase of transition metal dichalcogenides (labelled as T''), which is confirmed to be energetically, dynamically and kinetically stable by our first-principles calculations. The new T'' MoS2 phase exhibits an intrinsic quantum spin Hall (QSH) effect with a nontrivial gap as large as 0.42 eV, suggesting that a two-dimensional (2D) topological insulator can be achieved at room temperature. Most interestingly, there is a topological phase transition simply driven by a small tensile strain of up to 2%. Furthermore, all the known MX2 (M = Mo or W; X = S, Se or Te) monolayers in the new T'' phase unambiguously display similar band topologies and strain controlled topological

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

NASA Astrophysics Data System (ADS)

Knisley, Thomas Joseph

The advancing complexity of advanced microelectronic devices is placing rigorous demands on currently used PVD and CVD deposition techniques. The ALD deposition method is proposed to meet the film thickness and conformality constraints needed by the semiconductor industry in future manufacturing processes. Unfortunately, there is a limited number of chemical precursors available that have high thermal stability, reactivity, and vapor pressure suitable for ALD film growth to occur. These properties collectively contribute to the lack of suitable transition metal precursors available for use in ALD. In this thesis, we report the discovery of a series of novel transition metal diazadienate precursors that promising properties deemed suitable for ALD. The volatility and thermal stability of the new transition metal diazadienyl compounds were studied by preparative sublimation and capillary tube melting point/decomposition experiments. Thermogravimetric analyses (TGA) demonstrate precursor residues of less than 4% at 500 °C. In addition, sublimation data, melting points, and decomposition temperatures for all complexes are presented. The manganese diazadienyl complex has the highest decomposition temperature of the series of complexes produced (325 °C). During preparative sublimations, the product recoveries of all transition metal diazadienyl complexes were greater than 92.0% with nonvolatile residues of less than 7.0%. This is an excellent indication that these complexes may be suitable candidates as metal precursors for ALD. Nickel nitride (NixN) films have been studied as an intermediate material for the formation of both nickel metal and nickel silicide using chemical vapor deposition. Herein, we describe the ALD growth of nickel nitride thin films from bis(1,4-di-tert-butyl-1,3-diazabutadiene) nickel(II) (Ni(tBu2DAD)2) and 1,1-dimethylhydrazine. An ALD window for the deposition of nickel nitride films on 500 nm thermal SiO2 substrates was observed between 225

Pressure-induced structural and electronic transitions, metallization, and enhanced visible-light responsiveness in layered rhenium disulphide

NASA Astrophysics Data System (ADS)

Wang, Pei; Wang, Yonggang; Qu, Jingyu; Zhu, Qiang; Yang, Wenge; Zhu, Jinlong; Wang, Liping; Zhang, Weiwei; He, Duanwei; Zhao, Yusheng

2018-06-01

Triclinic rhenium disulphide (Re S2 ) is a promising candidate for postsilicon electronics because of its unique optic-electronic properties. The electrical and optical properties of Re S2 under high pressure, however, remain unclear. Here we present a joint experimental and theoretical study on the structure, electronic, and vibrational properties, and visible-light responses of Re S2 up to 50 GPa. There is a direct-to-indirect band-gap transition in 1 T -Re S2 under low-pressure regime up to 5 GPa. Upon further compression, 1 T -Re S2 undergoes a structural transition to distorted-1 T' phase at 7.7 GPa, followed by the isostructural metallization at 38.5 GPa. Both in situ Raman spectrum and electronic structure analysis reveal that interlayer sulfur-sulfur interaction is greatly enhanced during compression, leading to the remarkable modifications on the electronic properties observed in our subsequent experimental measurements, such as band-gap closure and enhanced photoresponsiveness. This study demonstrates the critical role of pressure in tuning materials properties and the potential usage of layered Re S2 for pressure-responsive optoelectronic applications.

Molecular precursor routes to transition metal sulfides

NASA Astrophysics Data System (ADS)

Dinnage, Christopher Walker

This thesis is primarily concerned with the synthesis of homoleptic early transition meta thiolates and the subsequent preparation of bulk and thin-film metal disulfides from these compounds. Chapter 1 gives an introduction into the properties, preparation procedures and uses of bulk and thin-film transition metal disulfides as well as giving an overview of early transition metal thiolates synthesied so far in the literature (for titanium, zirconium, tantalum and niobium). Chapter 2 is concerned with the synthesis of a number of ionic and neutral transition metal thiolates. The main synthetic methodologies discussed in this chapter include substitution reactions of transition metal amides and alkyls with thiols, salt metathesis reactions of transition metal chlorides with alkali metal thiolates or with a base / thiol and the use of Grignard reagents. Chapter 3 discusses the preparation of bulk transition metal disulfides using the thiolates prepared in the previous chapter via a thio "sol-gel" route. The preparation of a range of bulk metal and mixed-metal disulfides using transition metal chlorides and hexamethyldisilathiane is also discussed in this chapter. Finally, chapter 4 is concerned with the attempted preparation of thin-films of some transition metal disulfides. Decomposition studies of some of the thiolates prepared in chapter 2 are discussed using thermal gravimetric analysis. Vapour-phase deposition studies are also explored in order to test the potential of the transition metal thiolates as precursors to the disulfides. Experiments using low-pressure chemical vapour deposition and aerosol-assisted chemical vapour deposition are also described.

Schottky solar cell using few-layered transition metal dichalcogenides toward large-scale fabrication of semitransparent and flexible power generator.

PubMed

Akama, Toshiki; Okita, Wakana; Nagai, Reito; Li, Chao; Kaneko, Toshiro; Kato, Toshiaki

2017-09-20

Few-layered transition metal dichalcogenides (TMDs) are known as true two-dimensional materials, with excellent semiconducting properties and strong light-matter interaction. Thus, TMDs are attractive materials for semitransparent and flexible solar cells for use in various applications. Hoewver, despite the recent progress, the development of a scalable method to fabricate semitransparent and flexible solar cells with mono- or few-layered TMDs remains a crucial challenge. Here, we show easy and scalable fabrication of a few-layered TMD solar cell using a Schottky-type configuration to obtain a power conversion efficiency (PCE) of approximately 0.7%, which is the highest value reported with few-layered TMDs. Clear power generation was also observed for a device fabricated on a large SiO 2 and flexible substrate, demonstrating that our method has high potential for scalable production. In addition, systematic investigation revealed that the PCE and external quantum efficiency (EQE) strongly depended on the type of photogenerated excitons (A, B, and C) because of different carrier dynamics. Because high solar cell performance along with excellent scalability can be achieved through the proposed process, our fabrication method will contribute to accelerating the industrial use of TMDs as semitransparent and flexible solar cells.

Microwave-assisted synthesis of transition metal phosphide

DOEpatents

Viswanathan, Tito

2014-12-30

A method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of preparing a transition metal lignosulfonate, mixing the transition metal lignosulfonate with phosphoric acid to form a mixture, and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.

Geometric confinement effects on the metal-insulator transition temperature and stress relaxation in VO2 thin films grown on silicon

NASA Astrophysics Data System (ADS)

Viswanath, Changhyun Ko, B.; Yang, Zheng; Ramanathan, Shriram

2011-03-01

VO2 undergoes a sharp metal-insulator transition at ˜67 °C with several orders of change in conductivity and optical transmittance. Understanding and control of the properties of vanadium oxide layers grown on technologically relevant substrates such as Si (100) single crystals is therefore of great interest. In this work, we show tunability of metal-insulator transition temperature as well as recoverable stress in VO2 thin films grown on Si substrate by introducing nanoscale atomic layer deposited HfO2 interfacial layers with no degradation in the resistance ratio. For a confined VO2 film, the metal-insulator transition temperature is suppressed by ˜16 °C and the recoverable stress is 150 MPa, compared to 400 MPa for a bare film. These observations are further correlated with in situ variable temperature measurement of stress changes occurring during the phase transition. Structural and microstructural studies on the various samples have been carried out by x ray diffraction and cross-sectional transmission electron microscopy. The strategy of tuning the metal-insulator transition characteristics by nanoscale interfacial dielectrics is of broader relevance in design of programmable materials and integration into solid state devices for electronics.

Solution processed transition metal oxide anode buffer layers for efficiency and stability enhancement of polymer solar cells

NASA Astrophysics Data System (ADS)

Ameen, M. Yoosuf; Shamjid, P.; Abhijith, T.; Reddy, V. S.

2018-01-01

Polymer solar cells were fabricated with solution-processed transition metal oxides, MoO3 and V2O5 as anode buffer layers (ABLs). The optimized device with V2O5 ABL exhibited considerably higher power conversion efficiency (PCE) compared to the devices based on MoO3 and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) ABLs. The space charge limited current measurements and impedance spectroscopy results of hole-only devices revealed that V2O5 provided a very low charge transfer resistance and high hole mobility, facilitating efficient hole transfer from the active layer to the ITO anode. More importantly, incorporation of V2O5 as ABL resulted in substantial improvement in device stability compared to MoO3 and PEDOT:PSS based devices. Unencapsulated PEDOT:PSS-based devices stored at a relative humidity of 45% have shown complete failure within 96 h. Whereas, MoO3 and V2O5 based devices stored in similar conditions retained 22% and 80% of their initial PCEs after 96 h. Significantly higher stability of the V2O5-based device is ascribed to the reduction in degradation of the anode/active layer interface, as evident from the electrical measurements.

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).

Transition Metal Compounds Towards Holography

PubMed Central

Dieckmann, Volker; Eicke, Sebastian; Springfeld, Kristin; Imlau, Mirco

2012-01-01

We have successfully proposed the application of transition metal compounds in holographic recording media. Such compounds feature an ultra-fast light-induced linkage isomerization of the transition-metal–ligand bond with switching times in the sub-picosecond regime and lifetimes from microseconds up to hours at room temperature. This article highlights the photofunctionality of two of the most promising transition metal compounds and the photophysical mechanisms that are underlying the hologram recording. We present the latest progress with respect to the key measures of holographic media assembled from transition metal compounds, the molecular embedding in a dielectric matrix and their impressive potential for modern holographic applications. PMID:28817028

Low temperature synthesis of transition metal oxides containing surfactant ions

NASA Astrophysics Data System (ADS)

Janauer, Gerald Gilbert

1998-11-01

Recently there has been much interest in reacting vanadium oxides hydrothermally with cationic surfactants to form novel layered compounds. A series of new transition metal oxides, however, has also been formed at or near room temperature in open containers. Synthesis, characterization, and proposed mechanisms of formation are the focus of this work. Low temperature reactions of vanadium pentoxide and ammonium transition metallates with long chain amine surfactants, such as dodecyltrimethylammonium bromide yielded interesting new products many of which are layered phases. DTAsb4\\ Hsb2Vsb{10}Osb{28}. 8Hsb2O, a layered highly crystalline phase, is the first such phase for which a single crystal X-ray structure has been determined. The unit cell for this material was found to be triclinic with space group P1-, cell parameters a=9.8945(3)A, b=11.5962(1)A, c=21.9238(2)A, alpha=95.153(2)sp°,\\ beta=93.778(1)sp°, and gamma=101.360(1)sp°. Additionally, a novel tungsten, a molybdenum and a dichromate phase will be discussed. Both the tungsten and the dichromate materials were indexed from their powder diffraction patterns yielding monoclinic unit cells. The tungsten material was found to have a=50.56(4)A, b=54.41(4)A, c=13.12(1)A, and beta=99.21sp°. The dichromate compound was determined to have a=26.757(5)A, b=10.458(2)A, c=14.829(3)A and beta=98.01(1)sp°. Interlayer spacings for the lamellar dichromate and molybdenum phases were d001 = 28.7 A, and d001 = 22.9 A. The synthesis, characterization, composition, and structure of these transition metal oxide-surfactant materials will be discussed.

Janus monolayers of transition metal dichalcogenides.

PubMed

Lu, Ang-Yu; Zhu, Hanyu; Xiao, Jun; Chuu, Chih-Piao; Han, Yimo; Chiu, Ming-Hui; Cheng, Chia-Chin; Yang, Chih-Wen; Wei, Kung-Hwa; Yang, Yiming; Wang, Yuan; Sokaras, Dimosthenis; Nordlund, Dennis; Yang, Peidong; Muller, David A; Chou, Mei-Yin; Zhang, Xiang; Li, Lain-Jong

2017-08-01

Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS 2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

Role of interfacial transition layers in VO2/Al2O3 heterostructures

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

Zhou, Honghui; Chisholm, Matthew F; Yang, Tsung-Han

2011-01-01

Epitaxial VO2 films grown by pulsed laser deposition (PLD) on c-cut sapphire substrates ((0001) Al2O3) were studied by aberration-corrected scanning transmission electron microscopy (STEM). A number of film/substrate orientation relationships were found and are discussed in the context of the semiconductor-metal transition (SMT) characteristics. A structurally and electronically modified buffer layer was revealed on the interface and was attributed to the interface free-energy minimization process of accommodating the symmetry mismatch between the substrate and the film. This interfacial transition layer is expected to affect the SMT behavior when the interfacial region is a significant fraction of the VO2 film thickness.

Scalable salt-templated synthesis of two-dimensional transition metal oxides

PubMed Central

Xiao, Xu; Song, Huaibing; Lin, Shizhe; Zhou, Ying; Zhan, Xiaojun; Hu, Zhimi; Zhang, Qi; Sun, Jiyu; Yang, Bo; Li, Tianqi; Jiao, Liying; Zhou, Jun; Tang, Jiang; Gogotsi, Yury

2016-01-01

Two-dimensional atomic crystals, such as two-dimensional oxides, have attracted much attention in energy storage because nearly all of the atoms can be exposed to the electrolyte and involved in redox reactions. However, current strategies are largely limited to intrinsically layered compounds. Here we report a general strategy that uses the surfaces of water-soluble salt crystals as growth templates and is applicable to not only layered compounds but also various transition metal oxides, such as hexagonal-MoO3, MoO2, MnO and hexagonal-WO3. The planar growth is hypothesized to occur via a match between the crystal lattices of the salt and the growing oxide. Restacked two-dimensional hexagonal-MoO3 exhibits high pseudocapacitive performances (for example, 300 F cm−3 in an Al2(SO4)3 electrolyte). The synthesis of various two-dimensional transition metal oxides and the demonstration of high capacitance are expected to enable fundamental studies of dimensionality effects on their properties and facilitate their use in energy storage and other applications. PMID:27103200

Method for dry etching of transition metals

DOEpatents

Ashby, Carol I. H.; Baca, Albert G.; Esherick, Peter; Parmeter, John E.; Rieger, Dennis J.; Shul, Randy J.

1998-01-01

A method for dry etching of transition metals. The method for dry etching of a transition metal (or a transition metal alloy such as a silicide) on a substrate comprises providing at least one nitrogen- or phosphorous-containing .pi.-acceptor ligand in proximity to the transition metal, and etching the transition metal to form a volatile transition metal/.pi.-acceptor ligand complex. The dry etching may be performed in a plasma etching system such as a reactive ion etching (RIE) system, a downstream plasma etching system (i.e. a plasma afterglow), a chemically-assisted ion beam etching (CAIBE) system or the like. The dry etching may also be performed by generating the .pi.-acceptor ligands directly from a ligand source gas (e.g. nitrosyl ligands generated from nitric oxide), or from contact with energized particles such as photons, electrons, ions, atoms, or molecules. In some preferred embodiments of the present invention, an intermediary reactant species such as carbonyl or a halide ligand is used for an initial chemical reaction with the transition metal, with the intermediary reactant species being replaced at least in part by the .pi.-acceptor ligand for forming the volatile transition metal/.pi.-acceptor ligand complex.

Control of interlayer physics in 2H transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Wang, Kuang-Chung; Stanev, Teodor K.; Valencia, Daniel; Charles, James; Henning, Alex; Sangwan, Vinod K.; Lahiri, Aritra; Mejia, Daniel; Sarangapani, Prasad; Povolotskyi, Michael; Afzalian, Aryan; Maassen, Jesse; Klimeck, Gerhard; Hersam, Mark C.; Lauhon, Lincoln J.; Stern, Nathaniel P.; Kubis, Tillmann

2017-12-01

It is assessed in detail both experimentally and theoretically how the interlayer coupling of transition metal dichalcogenides controls the electronic properties of the respective devices. Gated transition metal dichalcogenide structures show electrons and holes to either localize in individual monolayers, or delocalize beyond multiple layers—depending on the balance between spin-orbit interaction and interlayer hopping. This balance depends on the layer thickness, momentum space symmetry points, and applied gate fields. The design range of this balance, the effective Fermi levels, and all relevant effective masses is analyzed in great detail. A good quantitative agreement of predictions and measurements of the quantum confined Stark effect in gated MoS2 systems unveils intralayer excitons as the major source for the observed photoluminescence.

Optically induced metal-to-dielectric transition in Epsilon-Near-Zero metamaterials

PubMed Central

Kaipurath, R. M.; Pietrzyk, M.; Caspani, L.; Roger, T.; Clerici, M.; Rizza, C.; Ciattoni, A.; Di Falco, A.; Faccio, D.

2016-01-01

Epsilon-Near-Zero materials exhibit a transition in the real part of the dielectric permittivity from positive to negative value as a function of wavelength. Here we study metal-dielectric layered metamaterials in the homogenised regime (each layer has strongly subwavelength thickness) with zero real part of the permittivity in the near-infrared region. By optically pumping the metamaterial we experimentally show that close to the Epsilon-Near-Zero (ENZ) wavelength the permittivity exhibits a marked transition from metallic (negative permittivity) to dielectric (positive permittivity) as a function of the optical power. Remarkably, this transition is linear as a function of pump power and occurs on time scales of the order of the 100 fs pump pulse that need not be tuned to a specific wavelength. The linearity of the permittivity increase allows us to express the response of the metamaterial in terms of a standard third order optical nonlinearity: this shows a clear inversion of the roles of the real and imaginary parts in crossing the ENZ wavelength, further supporting an optically induced change in the physical behaviour of the metamaterial. PMID:27292270

HIGH-PRESSURE PHYSICS. Direct observation of an abrupt insulator-to-metal transition in dense liquid deuterium.

PubMed

Knudson, M D; Desjarlais, M P; Becker, A; Lemke, R W; Cochrane, K R; Savage, M E; Bliss, D E; Mattsson, T R; Redmer, R

2015-06-26

Eighty years ago, it was proposed that solid hydrogen would become metallic at sufficiently high density. Despite numerous investigations, this transition has not yet been experimentally observed. More recently, there has been much interest in the analog of this predicted metallic transition in the dense liquid, due to its relevance to planetary science. Here, we show direct observation of an abrupt insulator-to-metal transition in dense liquid deuterium. Experimental determination of the location of this transition provides a much-needed benchmark for theory and may constrain the region of hydrogen-helium immiscibility and the boundary-layer pressure in standard models of the internal structure of gas-giant planets. Copyright © 2015, American Association for the Advancement of Science.

Transition Metals and Virulence in Bacteria.

PubMed

Palmer, Lauren D; Skaar, Eric P

2016-11-23

Transition metals are required trace elements for all forms of life. Due to their unique inorganic and redox properties, transition metals serve as cofactors for enzymes and other proteins. In bacterial pathogenesis, the vertebrate host represents a rich source of nutrient metals, and bacteria have evolved diverse metal acquisition strategies. Host metal homeostasis changes dramatically in response to bacterial infections, including production of metal sequestering proteins and the bombardment of bacteria with toxic levels of metals. In response, bacteria have evolved systems to subvert metal sequestration and toxicity. The coevolution of hosts and their bacterial pathogens in the battle for metals has uncovered emerging paradigms in social microbiology, rapid evolution, host specificity, and metal homeostasis across domains. This review focuses on recent advances and open questions in our understanding of the complex role of transition metals at the host-pathogen interface.

A nonperturbing boundary-layer transition detector

NASA Astrophysics Data System (ADS)

Ohare, J. E.

1985-11-01

A laser interferometer technique is being applied to the characterization of boundary-layer conditions on models in supersonic and hypersonic wind tunnels. The boundary-layer transition detector (BLTD), based on lateral interferometry, is applicable for determining the turbulence frequency spectrum of boundary layers in compressible flow. The turbulence, in terms of air density fluctuations, is detected by monitoring interferometric fringe phase shifts (in real time) formed by one beam which passes through the boundary layer and a reference beam which is outside the boundary layer. This technique is nonintrusive to the flow field unlike other commonly used methods such as pitot tube probing and hot-wire anemometry. Data which depict boundary-layer transition from laminar to turbulent flow are presented to provide comparisons of the BLTD with other measurement methods. Spectra from the BLTD reveals the presence of a high-frequency peak during transition which is characteristic of spectra obtained with hot wires. The BLTD is described along with operational requirements and limitations.

Towards Natural Transition in Compressible Boundary Layers

DTIC Science & Technology

2016-06-29

AFRL-AFOSR-CL-TR-2016-0011 Towards natural transition in compressible boundary layers Marcello Faraco de Medeiros FUNDACAO PARA O INCREMENTO DA...to 29-03-2016 Towards natural transition in compressible boundary layers FA9550-11-1-0354 Marcello A. Faraco de Medeiros Germán Andrés Gaviria...unlimited. 109 Final report Towards natural transition in compressible boundary layers Principal Investigator: Marcello Augusto Faraco de Medeiros

A nonperturbing boundary-layer transition detection

NASA Astrophysics Data System (ADS)

Ohare, J. E.

1985-01-01

A laser interferometer technique is being applied to the characterization of boundary-layer conditions on models in supersonic and hypersonic wind tunnels in the von Karman Facility at Arnold Engineering Development Center (AEDC). The Boundary-Layer Transition Detector (BLTD), based on lateral interferometry, is applicable for determining the turbulence frequency spectrum of boundary layers in compressible flow. The turbulence, in terms of air density fluctuations, is detected by monitoring interferometric fringe phase shifts (in real time) formed by one beam which passes through the boundary layer and a reference beam which is outside the boundary layer. This technique is nonintrusive to the flow field unlike other commonly used methods such as pitot tube probing and hot-wire anemometry. Model boundary-layer data are presented at Mach 8 and compared with data recorded using other methods during boundary-layer transition from laminar to turbulent flow. Spectra from the BLTD reveal the presence of a high-frequency peak during transition, which is characteristic of spectra obtained with hot wires. The BLTD is described along with operational requirements and limitations.

A Nonperturbing Boundary-Layer Transition Detector

NASA Astrophysics Data System (ADS)

O'Hare, J. E.

1986-01-01

A laser interferometer technique is being applied to the characterization of boundary-layer conditions on models in supersonic and hypersonic wind tunnels in the von Kaman Facility at Arnold Engineering Development Center (AEDC). The Boundary-Layer Transition Detector (BLTD), based on lateral interferometry, is applicable for determining the turbulence frequency spectrum of boundary layers in compressible flow. The turbulence, in terms of air density fluctuations, is detected by monitoring interferometric fringe phase shifts (in real time) formed by one beam which passes through the boundary layer and a reference beam which is outside the boundary layer. This technique is nonintrusive to the flow field unlike other commonly used methods such as pitot tube probing and hot-wire anemometry. Model boundary-layer data are presented at Mach 8 and compared with data recorded using other methods during boundary-layer transition from laminar to turbulent flow. Spectra from the BLTD reveal the presence of a high-frequency peak during transition, which is characteristic of spectra obtained with hot wires. The BLTD is described along with operational requirements and limitations.

Method for dry etching of transition metals

DOEpatents

Ashby, C.I.H.; Baca, A.G.; Esherick, P.; Parmeter, J.E.; Rieger, D.J.; Shul, R.J.

1998-09-29

A method for dry etching of transition metals is disclosed. The method for dry etching of a transition metal (or a transition metal alloy such as a silicide) on a substrate comprises providing at least one nitrogen- or phosphorus-containing {pi}-acceptor ligand in proximity to the transition metal, and etching the transition metal to form a volatile transition metal/{pi}-acceptor ligand complex. The dry etching may be performed in a plasma etching system such as a reactive ion etching (RIE) system, a downstream plasma etching system (i.e. a plasma afterglow), a chemically-assisted ion beam etching (CAIBE) system or the like. The dry etching may also be performed by generating the {pi}-acceptor ligands directly from a ligand source gas (e.g. nitrosyl ligands generated from nitric oxide), or from contact with energized particles such as photons, electrons, ions, atoms, or molecules. In some preferred embodiments of the present invention, an intermediary reactant species such as carbonyl or a halide ligand is used for an initial chemical reaction with the transition metal, with the intermediary reactant species being replaced at least in part by the {pi}-acceptor ligand for forming the volatile transition metal/{pi}-acceptor ligand complex.

Transition Metals and Virulence in Bacteria

PubMed Central

Palmer, Lauren D.; Skaar, Eric P.

2016-01-01

Transition metals are required trace elements for all forms of life. Due to their unique inorganic and redox properties, transition metals serve as cofactors for enzymes and other proteins. In bacterial pathogenesis, the vertebrate host represents a rich source of nutrient metals, and bacteria have evolved diverse metal acquisition strategies. Host metal homeostasis changes dramatically in response to bacterial infections, including production of metal sequestering proteins and the bombardment of bacteria with toxic levels of metals. Presumably, in response, bacteria have evolved systems to subvert metal sequestration and toxicity. The coevolution of hosts and their bacterial pathogens in the battle for metals has uncovered emerging paradigms in social microbiology, rapid evolution, host specificity, and metal homeostasis across domains. This review focuses on recent advances and open questions in our understanding of the complex role of transition metals at the host-pathogen interface. PMID:27617971

Multilayered thermal insulation formed of zirconia bonded layers of zirconia fibers and metal oxide fibers and method for making same

DOEpatents

Wrenn, Jr., George E.; Holcombe, Jr., Cressie E.

1988-01-01

A multilayered thermal insulating composite is formed of a first layer of zirconia-bonded zirconia fibers for utilization near the hot phase or surface of a furnace or the like. A second layer of zirconia-bonded metal oxide fibers is attached to the zirconia fiber layer by a transition layer formed of intermingled zirconia fibers and metal oxide fibers. The thermal insulation is fabricated by vacuum molding with the layers being sequentially applied from aqueous solutions containing the fibers to a configured mandrel. A portion of the solution containing the fibers forming the first layer is intermixed with the solution containing the fibers of the second layer for forming the layer of mixed fibers. The two layers of fibers joined together by the transition layer are saturated with a solution of zirconium oxynitrate which provides a zirconia matrix for the composite when the fibers are sintered together at their nexi.

Multilayered thermal insulation formed of zirconia bonded layers of zirconia fibers and metal oxide fibers and method for making same

DOEpatents

Wrenn, G.E. Jr.; Holcombe, C.E. Jr.

1988-09-13

A multilayered thermal insulating composite is formed of a first layer of zirconia-bonded zirconia fibers for utilization near the hot phase or surface of a furnace or the like. A second layer of zirconia-bonded metal oxide fibers is attached to the zirconia fiber layer by a transition layer formed of intermingled zirconia fibers and metal oxide fibers. The thermal insulation is fabricated by vacuum molding with the layers being sequentially applied from aqueous solutions containing the fibers to a configured mandrel. A portion of the solution containing the fibers forming the first layer is intermixed with the solution containing the fibers of the second layer for forming the layer of mixed fibers. The two layers of fibers joined together by the transition layer are saturated with a solution of zirconium oxynitrate which provides a zirconia matrix for the composite when the fibers are sintered together at their nexi.

Photoluminescence Architectures for Disease Diagnosis: From Graphene to Thin-Layer Transition Metal Dichalcogenides and Oxides.

PubMed

He, Xiao-Peng; Tian, He

2016-01-13

Ever since the discovery of graphene, increasing efforts have been devoted to the use of this stellar material as well as the development of other graphene-like materials such as thin-layer transition metal dichalcogenides and oxides (TMD/Os) for a variety of applications. Because of their large surface area and unique optical properties, these two-dimensional materials with a size ranging from the micro- to the nanoscale have been employed as the substrate to construct photoluminescence architectures for disease diagnosis as well as theranostics. These architectures are built through the simple self-assembly of labeled biomolecular probes with the substrate material, leading to signal quenching. Upon the specific interaction of the architecture with a target biomarker, the signal can be spontaneously restored in a reversible manner. Meanwhile, by co-loading therapeutic agents and employing the inherent photo-thermal properties of the material substrates, a combined disease imaging and therapy (theranostics) can be achieved. This review highlights the latest advances in the construction and application of graphene and TMD/O based thin-layer material composites for single-target and multiplexed detection of a variety of biomarkers and theranostics. These versatile material architectures, owing to their ease in preparation, low cost and flexibility in functionalization, provide promising tools for both basic biochemical research and clinical applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronics and optoelectronics of two-dimensional transition metal dichalcogenides.

PubMed

Wang, Qing Hua; Kalantar-Zadeh, Kourosh; Kis, Andras; Coleman, Jonathan N; Strano, Michael S

2012-11-01

The remarkable properties of graphene have renewed interest in inorganic, two-dimensional materials with unique electronic and optical attributes. Transition metal dichalcogenides (TMDCs) are layered materials with strong in-plane bonding and weak out-of-plane interactions enabling exfoliation into two-dimensional layers of single unit cell thickness. Although TMDCs have been studied for decades, recent advances in nanoscale materials characterization and device fabrication have opened up new opportunities for two-dimensional layers of thin TMDCs in nanoelectronics and optoelectronics. TMDCs such as MoS(2), MoSe(2), WS(2) and WSe(2) have sizable bandgaps that change from indirect to direct in single layers, allowing applications such as transistors, photodetectors and electroluminescent devices. We review the historical development of TMDCs, methods for preparing atomically thin layers, their electronic and optical properties, and prospects for future advances in electronics and optoelectronics.

Two-dimensional inorganic analogues of graphene: transition metal dichalcogenides.

PubMed

Jana, Manoj K; Rao, C N R

2016-09-13

The discovery of graphene marks a major event in the physics and chemistry of materials. The amazing properties of this two-dimensional (2D) material have prompted research on other 2D layered materials, of which layered transition metal dichalcogenides (TMDCs) are important members. Single-layer and few-layer TMDCs have been synthesized and characterized. They possess a wide range of properties many of which have not been known hitherto. A typical example of such materials is MoS2 In this article, we briefly present various aspects of layered analogues of graphene as exemplified by TMDCs. The discussion includes not only synthesis and characterization, but also various properties and phenomena exhibited by the TMDCs.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'. © 2016 The Author(s).

Two-dimensional inorganic analogues of graphene: transition metal dichalcogenides

PubMed Central

Jana, Manoj K.; Rao, C. N. R.

2016-01-01

The discovery of graphene marks a major event in the physics and chemistry of materials. The amazing properties of this two-dimensional (2D) material have prompted research on other 2D layered materials, of which layered transition metal dichalcogenides (TMDCs) are important members. Single-layer and few-layer TMDCs have been synthesized and characterized. They possess a wide range of properties many of which have not been known hitherto. A typical example of such materials is MoS2. In this article, we briefly present various aspects of layered analogues of graphene as exemplified by TMDCs. The discussion includes not only synthesis and characterization, but also various properties and phenomena exhibited by the TMDCs. This article is part of the themed issue ‘Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene’. PMID:27501969

High-resolution structural studies of ultra-thin magnetic, transition metal overlayers and two-dimensional transition metal oxides using synchrotron radiation

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

Kellar, S.A.

This thesis report the surface-structure determination of three, ultra-thin magnetic transition-metal films, Fe/Au(100), Mn/Ni(100), and Mn/Cu(100) using Angle-Resolved Photoemission Extended Fine Structure (ARPEFS) and photoelectron holography. These structural studies are the first to use non-s initial states in the ARPEFS procedure. This thesis also reports an ARPEFS surface-structure determination of a two-dimensional transition-metal oxide, [(1 x 1)O/W(110)] x 12. The authors have analyzed the ARPFES signal from the Au 4f{sub 7/5} core level of the Au(1 ML)/Fe(15 ML)/Au(100) system. The analysis shows that the Fe grows layer by layer with one monolayer of gold, acting as a surfactant, remaining onmore » top of the growing Fe layers. These surface gold atoms sit in the four-fold hollow site, 1.67 {+-} 0.02 A above the iron surface. The grown Fe layer is very much like the bulk, bcc iron, with an interlayer spacing of 1.43 {+-} 0.03 A. Analysis of the Mn 3p ARPEFS signals from c(2 x 2)Mn/Ni(100) and c(2 x 2)Mn/Cu(100) shows that the Mn forms highly corrugated surface alloys. The corrugation of the Mn/Ni(100) and Mn/Cu(100) systems are 0.24 {+-} 0.02 A and 0.30 {+-} 0.04 A respectively. In both cases the Mn is sticking above the plane of the surface substrate atoms. For the Mn/Ni(100) system the first layer Ni is contracted 4% from the bulk value. The Mn/Cu(100) system shows bulk spacing for the substrate Cu. Photoelectron holography shows that the Mn/Ni interface is very abrupt with very little Mn leaking into the second layer, while the Mn/Cu(100) case has a significant amount of Mn leaking into the second layer. A new, five-element electrostatic electron lens was developed for hemispherical electron-energy analyzers. This lens system can be operated at constant transverse or constants angular magnification, and has been optimized for use with the very small photon-spot sizes. Improvements to the hemispherical electron-energy analyzer are also discussed.« less

In-Flight Boundary-Layer Transition of a Large Flat Plate at Supersonic Speeds

NASA Technical Reports Server (NTRS)

Banks, D. W.; Frederick, M. A.; Tracy, R. R.; Matisheck, J. R.; Vanecek, N. D.

2012-01-01

A flight experiment was conducted to investigate the pressure distribution, local-flow conditions, and boundary-layer transition characteristics on a large flat plate in flight at supersonic speeds up to Mach 2.00. The tests used a NASA testbed aircraft with a bottom centerline mounted test fixture. The primary objective of the test was to characterize the local flow field in preparation for future tests of a high Reynolds number natural laminar flow test article. A second objective was to determine the boundary-layer transition characteristics on the flat plate and the effectiveness of using a simplified surface coating. Boundary-layer transition was captured in both analog and digital formats using an onboard infrared imaging system. Surface pressures were measured on the surface of the flat plate. Flow field measurements near the leading edge of the test fixture revealed the local flow characteristics including downwash, sidewash, and local Mach number. Results also indicated that the simplified surface coating did not provide sufficient insulation from the metallic structure, which likely had a substantial effect on boundary-layer transition compared with that of an adiabatic surface. Cold wall conditions were predominant during the acceleration to maximum Mach number, and warm wall conditions were evident during the subsequent deceleration.

Tungsten ditelluride for a nanosecond Ho,Pr:LiLuF4 laser at 2.95 µm

NASA Astrophysics Data System (ADS)

Yan, Zhengyu; Li, Tao; Zhao, Jia; Zhao, Shengzhi; Yang, Kejian; Li, Guiqiu; Li, Dechun; Zhang, Shuaiyi; Li, Jian

2018-04-01

The linear and nonlinear absorption characteristics of a home-built multilayer tungsten ditelluride (WTe2) saturable absorber at ~3 µm were demonstrated for the first time. A passively Q-switched Ho,Pr:LiLuF4 laser was realized by inserting the WTe2-saturable absorber into a plane-concave laser cavity. A maximum average output power of 128 mW, with a pulse duration of 366 ns at a repetition rate of 92 kHz was obtained under an absorbed pump power of 3.67 W, corresponding to a pulse energy of 1.4 µJ.

Effect of ZnO buffer layer on phase transition properties of vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Zhu, Huiqun; Li, Lekang; Li, Chunbo

2016-03-01

VO2 thin films were prepared on ZnO buffer layers by DC magnetron sputtering at room temperature using vanadium target and post annealing at 400 °C. The ZnO buffer layers with different thickness deposited on glass substrates by magnetron sputtering have a high visible and near infrared optical transmittance. The electrical resistivity and the phase transition properties of the VO2/ZnO composite thin films in terms of temperature were investigated. The results showed that the resistivity variation of VO2 thin film with ZnO buffer layer deposited for 35 min was 16 KΩ-cm. The VO2/ZnO composite thin films exhibit a reversible semiconductor-metal phase transition at 48 °C.

Antiferroelectricity in lanthanum doped zirconia without metallic capping layers and post-deposition/-metallization anneals

NASA Astrophysics Data System (ADS)

Wang, Zheng; Gaskell, Anthony Arthur; Dopita, Milan; Kriegner, Dominik; Tasneem, Nujhat; Mack, Jerry; Mukherjee, Niloy; Karim, Zia; Khan, Asif Islam

2018-05-01

We report the effects of lanthanum doping/alloying on antiferroelectric (AFE) properties of ZrO2. Starting with pure ZrO2, an increase in La doping leads to the narrowing of the AFE double hysteresis loops and an increase in the critical voltage/electric field for AFE → ferroelectric transition. At higher La contents, the polarization-voltage characteristics of doped/alloyed ZrO2 resemble that of a non-linear dielectric without any discernible AFE-type hysteresis. X-ray diffraction based analysis indicates that the increased La content while preserving the non-polar, parent AFE, tetragonal P42/nmc phase leads to a decrease in tetragonality and the (nano-)crystallite size and an increase in the unit cell volume. Furthermore, antiferroelectric behavior is obtained in the as-deposited thin films without requiring any capping metallic layers and post-deposition/-metallization anneals due to which our specific atomic layer deposition system configuration crystallizes and stabilizes the AFE tetragonal phase during growth.

Metallic conduction induced by direct anion site doping in layered SnSe2

PubMed Central

Kim, Sang Il; Hwang, Sungwoo; Kim, Se Yun; Lee, Woo-Jin; Jung, Doh Won; Moon, Kyoung-Seok; Park, Hee Jung; Cho, Young-Jin; Cho, Yong-Hee; Kim, Jung-Hwa; Yun, Dong-Jin; Lee, Kyu Hyoung; Han, In-taek; Lee, Kimoon; Sohn, Yoonchul

2016-01-01

The emergence of metallic conduction in layered dichalcogenide semiconductor materials by chemical doping is one of key issues for two-dimensional (2D) materials engineering. At present, doping methods for layered dichalcogenide materials have been limited to an ion intercalation between layer units or electrostatic carrier doping by electrical bias owing to the absence of appropriate substitutional dopant for increasing the carrier concentration. Here, we report the occurrence of metallic conduction in the layered dichalcogenide of SnSe2 by the direct Se-site doping with Cl as a shallow electron donor. The total carrier concentration up to ~1020 cm−3 is achieved by Cl substitutional doping, resulting in the improved conductivity value of ~170 S·cm−1 from ~1.7 S·cm−1 for non-doped SnSe2. When the carrier concentration exceeds ~1019 cm−3, the conduction mechanism is changed from hopping to degenerate conduction, exhibiting metal-insulator transition behavior. Detailed band structure calculation reveals that the hybridized s-p orbital from Sn 5s and Se 4p states is responsible for the degenerate metallic conduction in electron-doped SnSe2. PMID:26792630

Metallic conduction induced by direct anion site doping in layered SnSe2.

PubMed

Kim, Sang Il; Hwang, Sungwoo; Kim, Se Yun; Lee, Woo-Jin; Jung, Doh Won; Moon, Kyoung-Seok; Park, Hee Jung; Cho, Young-Jin; Cho, Yong-Hee; Kim, Jung-Hwa; Yun, Dong-Jin; Lee, Kyu Hyoung; Han, In-taek; Lee, Kimoon; Sohn, Yoonchul

2016-01-21

The emergence of metallic conduction in layered dichalcogenide semiconductor materials by chemical doping is one of key issues for two-dimensional (2D) materials engineering. At present, doping methods for layered dichalcogenide materials have been limited to an ion intercalation between layer units or electrostatic carrier doping by electrical bias owing to the absence of appropriate substitutional dopant for increasing the carrier concentration. Here, we report the occurrence of metallic conduction in the layered dichalcogenide of SnSe2 by the direct Se-site doping with Cl as a shallow electron donor. The total carrier concentration up to ~10(20) cm(-3) is achieved by Cl substitutional doping, resulting in the improved conductivity value of ~170 S · cm(-1) from ~1.7 S · cm(-1) for non-doped SnSe2. When the carrier concentration exceeds ~10(19) cm(-3), the conduction mechanism is changed from hopping to degenerate conduction, exhibiting metal-insulator transition behavior. Detailed band structure calculation reveals that the hybridized s-p orbital from Sn 5s and Se 4p states is responsible for the degenerate metallic conduction in electron-doped SnSe2.

Visualizing Type-II Weyl Points in Tungsten Ditelluride by Quasiparticle Interference.

PubMed

Lin, Chun-Liang; Arafune, Ryuichi; Liu, Ro-Ya; Yoshimura, Masato; Feng, Baojie; Kawahara, Kazuaki; Ni, Zeyuan; Minamitani, Emi; Watanabe, Satoshi; Shi, Youguo; Kawai, Maki; Chiang, Tai-Chang; Matsuda, Iwao; Takagi, Noriaki

2017-11-28

Weyl semimetals (WSMs) are classified into two types, type I and II, according to the topology of the Weyl point, where the electron and hole pockets touch each other. Tungsten ditelluride (WTe 2 ) has garnered a great deal of attention as a strong candidate to be a type-II WSM. However, the Weyl points for WTe 2 are located above the Fermi level, which has prevented us from identifying the locations and the connection to the Fermi arc surface states by using angle-resolved photoemission spectroscopy. Here, we present experimental proof that WTe 2 is a type-II WSM. We measured energy-dependent quasiparticle interference patterns with a cryogenic scanning tunneling microscope, revealing the position of the Weyl point and its connection with the Fermi arc surface states, in agreement with prior theoretical predictions. Our results provide an answer to this crucial question and stimulate further exploration of the characteristics of WSMs.

Calculation of the superconducting transition temperature of a graphene layer doped with titanium and palladium

NASA Astrophysics Data System (ADS)

Vazquez, Gerardo; Magana, Fernando; Salas-Torres, Osiris

We explore the structural interactions between graphene and transition metals such as palladium (Pd) and titanium (Ti) and the possibility of inducing superconductivity in a graphene sheet in two cases, one by doping its surface with palladium atoms sit on the center of the hexagons of the graphene layer and other by covering the graphene layer with two layers of titanium metal atoms. The results here were obtained from first-principles density functional theory in the local density approximation. The Quantum-Espresso package was used with norm conserving pseudopotentials. All of the structures considered were relaxed to their minimum energy configuration. Phonon frequencies were calculated using the linear-response technique on several phonon wave-vector mesh. The electron-phonon coupling parameter was calculated with several electron momentum k-mesh. The superconducting critical temperature was estimated using the Allen-Dynes formula with μ* = 0.1 - 0.15. We note that palladium and titanium are good candidate materials to show a metal-to-superconductor transition. We thank Dirección General de Asuntos del Personal Académico de la Universidad Nacional Autónoma de México, partial financial support by Grant IN-106514 and we also thank Miztli Super-Computing center the technical assistance.

Modelling the transitional boundary layer

NASA Technical Reports Server (NTRS)

Narasimha, R.

1990-01-01

Recent developments in the modelling of the transition zone in the boundary layer are reviewed (the zone being defined as extending from the station where intermittency begins to depart from zero to that where it is nearly unity). The value of using a new non-dimensional spot formation rate parameter, and the importance of allowing for so-called subtransitions within the transition zone, are both stressed. Models do reasonably well in constant pressure 2-dimensional flows, but in the presence of strong pressure gradients further improvements are needed. The linear combination approach works surprisingly well in most cases, but would not be so successful in situations where a purely laminar boundary layer would separate but a transitional one would not. Intermittency-weighted eddy viscosity methods do not predict peak surface parameters well without the introduction of an overshooting transition function whose connection with the spot theory of transition is obscure. Suggestions are made for further work that now appears necessary for developing improved models of the transition zone.

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.

Large scale simulations of the mechanical properties of layered transition metal ternary compounds for fossil energy power system applications

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

Ching, Wai-Yim

2014-12-31

Advanced materials with applications in extreme conditions such as high temperature, high pressure, and corrosive environments play a critical role in the development of new technologies to significantly improve the performance of different types of power plants. Materials that are currently employed in fossil energy conversion systems are typically the Ni-based alloys and stainless steels that have already reached their ultimate performance limits. Incremental improvements are unlikely to meet the more stringent requirements aimed at increased efficiency and reduce risks while addressing environmental concerns and keeping costs low. Computational studies can lead the way in the search for novel materialsmore » or for significant improvements in existing materials that can meet such requirements. Detailed computational studies with sufficient predictive power can provide an atomistic level understanding of the key characteristics that lead to desirable properties. This project focuses on the comprehensive study of a new class of materials called MAX phases, or Mn+1AXn (M = a transition metal, A = Al or other group III, IV, and V elements, X = C or N). The MAX phases are layered transition metal carbides or nitrides with a rare combination of metallic and ceramic properties. Due to their unique structural arrangements and special types of bonding, these thermodynamically stable alloys possess some of the most outstanding properties. We used a genomic approach in screening a large number of potential MAX phases and established a database for 665 viable MAX compounds on the structure, mechanical and electronic properties and investigated the correlations between them. This database if then used as a tool for materials informatics for further exploration of this class of intermetallic compounds.« less

Trends in hydrogen chemisorption on transition metals

NASA Astrophysics Data System (ADS)

Muscat, J. P.

1981-10-01

A systematic study of H adsorption on the close-packed surfaces of the transition metals in the 3d and 4d series is presented. The effect of the TM d band on the chemisorption bond is investigated, by embedding a cluster of TM muffin tins at the surface of an effective jellium-like medium. It is found that the broad and incomplete H/jellium resonance is narrowed, shifted down and made to contain more electrons as a result of hybridization with the TM d states. These effects are larger in the case of the 4d metals, thus indicating a greater participation in the chemisorption bond of the d electrons for these metals than for the 3d metals. Calculation of one-electron energy differences on going from the H on jellium system to that of H on the TM cluster are presented. Trends for the one-electron energy differences are compared to trends in experimental chemisorption energy. H adsorption in the three-fold hollow site with no secondlayer TM atom below the H site is favoured for the hcp metals, while no discernible preference between the two hollow sites is recorded for the fcc metals, with the exception of Rh where the site with no second-layer TM atom below is preferred.

PREFACE: INERA Workshop: Transition Metal Oxide Thin Films-functional Layers in "Smart windows" and Water Splitting Devices. Parallel session of the 18th International School on Condensed Matter Physics

NASA Astrophysics Data System (ADS)

2014-11-01

The Special issue presents the papers for the INERA Workshop entitled "Transition Metal Oxides as Functional Layers in Smart windows and Water Splitting Devices", which was held in Varna, St. Konstantin and Elena, Bulgaria, from the 4th-6th September 2014. The Workshop is organized within the context of the INERA "Research and Innovation Capacity Strengthening of ISSP-BAS in Multifunctional Nanostructures", FP7 Project REGPOT 316309 program, European project of the Institute of Solid State Physics at the Bulgarian Academy of Sciences. There were 42 participants at the workshop, 16 from Sweden, Germany, Romania and Hungary, 11 invited lecturers, and 28 young participants. There were researchers present from prestigious European laboratories which are leaders in the field of transition metal oxide thin film technologies. The event contributed to training young researchers in innovative thin film technologies, as well as thin films characterization techniques. The topics of the Workshop cover the field of technology and investigation of thin oxide films as functional layers in "Smart windows" and "Water splitting" devices. The topics are related to the application of novel technologies for the preparation of transition metal oxide films and the modification of chromogenic properties towards the improvement of electrochromic and termochromic device parameters for possible industrial deployment. The Workshop addressed the following topics: Metal oxide films-functional layers in energy efficient devices; Photocatalysts and chemical sensing; Novel thin film technologies and applications; Methods of thin films characterizations; From the 37 abstracts sent, 21 manuscripts were written and later refereed. We appreciate the comments from all the referees, and we are grateful for their valuable contributions. Guest Editors: Assoc. Prof. Dr.Tatyana Ivanova Prof. DSc Kostadinka Gesheva Prof. DSc Hassan Chamatti Assoc. Prof. Dr. Georgi Popkirov Workshop Organizing Committee Prof

Phase Transition of Single-Layer Molybdenum Disulfide Nanosheets under Mechanical Loading Based on Molecular Dynamics Simulations.

PubMed

Pang, Haosheng; Li, Minglin; Gao, Chenghui; Huang, Haili; Zhuo, Weirong; Hu, Jianyue; Wan, Yaling; Luo, Jing; Wang, Weidong

2018-03-27

The single-layer molybdenum disulfide (SLMoS2) nanosheets have been experimentally discovered to exist in two different polymorphs, which exhibit different electrical properties, metallic or semiconducting. Herein, molecular dynamics (MD) simulations of nanoindentation and uniaxial compression were conducted to investigate the phase transition of SLMoS2 nanosheets. Typical load-deflection curves, stress-strain curves, and local atomic structures were obtained. The loading force decreases sharply and then increases again at a critical deflection under the nanoindentation, which is inferred to the phase transition. In addition to the layer thickness, some related bond lengths and bond angles were also found to suddenly change as the phase transition occurs. A bell-like hollow, so-called residual deformation, was found to form, mainly due to the lattice distortion around the waist of the bell. The effect of indenter size on the residual hollow was also analyzed. Under the uniaxial compression along the armchair direction, a different phase transition, a uniformly quadrilateral structure, was observed when the strain is greater than 27.7%. The quadrilateral structure was found to be stable and exhibit metallic conductivity in view of the first-principle calculation.

Overcoming nanoscale friction barriers in transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Cammarata, Antonio; Polcar, Tomas

2017-08-01

We study the atomic contributions to the nanoscale friction in layered M X2 (M =Mo , W; X =S , Se, Te) transition metal dichalcogenides by combining ab initio techniques with group-theoretical analysis. Starting from stable atomic configurations, we propose a computational method, named normal-modes transition approximation (NMTA), to individuate possible sliding paths from only the analysis of the phonon modes of the stable geometry. The method provides a way to decompose the atomic displacements realizing the layer sliding in terms of phonon modes of the stable structure, so as to guide the selection and tuning of specific atomic motions promoting M X2 sheets gliding, and to adjust the corresponding energy barrier. The present results show that main contributions to the nanoscale friction are due to few low frequency phonon modes, corresponding to rigid shifts of M X2 layers. We also provide further evidences that a previously reported Ti-doped MoS2 phase is a promising candidate as new material with enhanced tribologic properties. The NMTA approach can be exploited to tune the energetic and the structural features of specific phonon modes, and, thanks to its general formulation, can also be applied to any solid state system, irrespective of the chemical composition and structural topology.

In-Flight Boundary-Layer Transition on a Large Flat Plate at Supersonic Speeds

NASA Technical Reports Server (NTRS)

Banks, Daniel W.; Fredericks, Michael Alan; Tracy, Richard R.; Matisheck, Jason R.; Vanecek, Neal D.

2012-01-01

A flight experiment was conducted to investigate the pressure distribution, local flow conditions, and boundary-layer transition characteristics on a large flat plate in flight at supersonic speeds up to Mach 2.0. The primary objective of the test was to characterize the local flow field in preparation for future tests of a high Reynolds number natural laminar flow test article. The tests used a F-15B testbed aircraft with a bottom centerline mounted test fixture. A second objective was to determine the boundary-layer transition characteristics on the flat plate and the effectiveness of using a simplified surface coating for future laminar flow flight tests employing infrared thermography. Boundary-layer transition was captured using an onboard infrared imaging system. The infrared imagery was captured in both analog and digital formats. Surface pressures were measured with electronically scanned pressure modules connected to 60 surface-mounted pressure orifices. The local flow field was measured with five 5-hole conical probes mounted near the leading edge of the test fixture. Flow field measurements revealed the local flow characteristics including downwash, sidewash, and local Mach number. Results also indicated that the simplified surface coating did not provide sufficient insulation from the metallic structure, which likely had a substantial effect on boundary-layer transition compared with that of an adiabatic surface. Cold wall conditions were predominant during the acceleration to maximum Mach number, and warm wall conditions were evident during the subsequent deceleration. The infrared imaging system was able to capture shock wave impingement on the surface of the flat plate in addition to indicating laminar-to-turbulent boundary-layer transition.

1T' transition metal telluride atomic layers for plasmon-free SERS at femtomolar levels.

PubMed

Tao, Li; Chen, Kun; Chen, Zefeng; Cong, Chunxiao; Qiu, Caiyu; Chen, Jiajie; Wang, Ximiao; Chen, Huanjun; Yu, Ting; Xie, Weiguang; Deng, Shaozhi; Xu, Jianbin

2018-06-21

Plasmon-free surface enhanced Raman scattering (SERS) based on the chemical mechanism (CM) is drawing great attention due to its capability for controllable molecular detection. However, in comparison to the conventional noble-metal-based SERS technique driven by plasmonic electromagnetic mechanism (EM), the low sensitivity in the CM-based SERS is the dominant barrier towards its practical applications. Herein, we demonstrate the 1T' transition metal telluride atomic layers (WTe2 and MoTe2) as ultrasensitive platforms for CM-based SERS. The SERS sensitivities of analyte dyes on 1T'-W(Mo)Te2 reach EM-comparable ones and become even greater when it is integrated with a Bragg reflector. In addition, the dye fluorescence signals are efficiently quenched, making the SERS spectra more distinguishable. As a proof of concept, the SERS signals of analyte Rhodamine 6G (R6G) are detectable even with an ultralow concentration of 40 (400) fM on pristine 1T'-W(Mo)Te2, and the corresponding Raman enhancement factor (EF) reaches 1.8×109 (1.6×108). The limit concentration of detection and the EF of R6G can be further enhanced into 4 (40) fM and 4.4×1010 (6.2×109), respectively, when 1T'-W(Mo)Te2 is integrated on the Bragg reflector. The strong interaction between the analyte and 1T'-W(Mo)Te2 and the abundant density of states near the Fermi level of the semimetal 1T'-W(Mo)Te2 in combination gives rise to the promising SERS effects by promoting the charge transfer resonance in the analyte-telluride complex. Our findings reveal that the 1T'-W(Mo)Te2 as a plasmon-free SERS mediator can deliver an ultrahigh Raman enhancement for analytes, whose EF is even comparable to that by plasmon-driven noble metal SERS materials.

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

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

Lukatskaya, Maria R.; Kota, Sankalp; Lin, Zifeng

In this study, the use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improvedmore » ion accessibility to redox-active sites. A macroporous Ti 3C 2T x MXene film delivered up to 210 F g –1 at scan rates of 10 V s –1, surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ~1,500 F cm –3 reaching the previously unmatched volumetric performance of RuO 2.« less

Ultra-high-rate pseudocapacitive energy storage in two-dimensional transition metal carbides

NASA Astrophysics Data System (ADS)

Lukatskaya, Maria R.; Kota, Sankalp; Lin, Zifeng; Zhao, Meng-Qiang; Shpigel, Netanel; Levi, Mikhael D.; Halim, Joseph; Taberna, Pierre-Louis; Barsoum, Michel W.; Simon, Patrice; Gogotsi, Yury

2017-08-01

The use of fast surface redox storage (pseudocapacitive) mechanisms can enable devices that store much more energy than electrical double-layer capacitors (EDLCs) and, unlike batteries, can do so quite rapidly. Yet, few pseudocapacitive transition metal oxides can provide a high power capability due to their low intrinsic electronic and ionic conductivity. Here we demonstrate that two-dimensional transition metal carbides (MXenes) can operate at rates exceeding those of conventional EDLCs, but still provide higher volumetric and areal capacitance than carbon, electrically conducting polymers or transition metal oxides. We applied two distinct designs for MXene electrode architectures with improved ion accessibility to redox-active sites. A macroporous Ti3C2Tx MXene film delivered up to 210 F g-1 at scan rates of 10 V s-1, surpassing the best carbon supercapacitors known. In contrast, we show that MXene hydrogels are able to deliver volumetric capacitance of ˜1,500 F cm-3 reaching the previously unmatched volumetric performance of RuO2.

Multiple Dirac cones and topological magnetism in honeycomb-monolayer transition metal trichalcogenides

NASA Astrophysics Data System (ADS)

Sugita, Yusuke; Miyake, Takashi; Motome, Yukitoshi

2018-01-01

The discovery of monolayer graphene has initiated two fertile fields in condensed matter physics: Dirac semimetals and atomically thin layered materials. When these trends meet again in transition metal compounds, which possess spin and orbital degrees of freedom and strong electron correlations, more exotic phenomena are expected to emerge in the cross section of topological states of matter and Mott physics. Here, we show by using ab initio calculations that a monolayer form of transition metal trichalcogenides (TMTs), which has a honeycomb network of 4 d and 5 d transition metal cations, may exhibit multiple Dirac cones in the electronic structure of the half-filled eg orbitals. The Dirac cones are gapped by the spin-orbit coupling under the trigonal lattice distortion and, hence, can be tuned by tensile strain. Furthermore, we show that electron correlations and carrier doping turn the multiple Dirac semimetal into a topological ferromagnet with high Chern number. Our findings indicate that the honeycomb-monolayer TMTs provide a good playground for correlated Dirac electrons and topologically nontrivial magnetism.

Resin infusion of layered metal/composite hybrid and resulting metal/composite hybrid laminate

NASA Technical Reports Server (NTRS)

Cano, Roberto J. (Inventor); Grimsley, Brian W. (Inventor); Weiser, Erik S. (Inventor); Jensen, Brian J. (Inventor)

2009-01-01

A method of fabricating a metal/composite hybrid laminate is provided. One or more layered arrangements are stacked on a solid base to form a layered structure. Each layered arrangement is defined by a fibrous material and a perforated metal sheet. A resin in its liquid state is introduced along a portion of the layered structure while a differential pressure is applied across the laminate structure until the resin permeates the fibrous material of each layered arrangement and fills perforations in each perforated metal sheet. The resin is cured thereby yielding a metal/composite hybrid laminate.

Chemical control of orbital polarization in artificially structured transition-metal oxides: La2NiXO6 (X=B,Al,Ga,In) from first principles

NASA Astrophysics Data System (ADS)

Han, M. J.; Marianetti, C. A.; Millis, A. J.

2010-10-01

The application of modern layer-by-layer growth techniques to transition-metal oxide materials raises the possibility of creating new classes of materials with rationally designed correlated electron properties. An important step toward this goal is the demonstration that electronic structure can be controlled by atomic composition. In compounds with partially occupied transition-metal d shells, one important aspect of the electronic structure is the relative occupancy of different d orbitals. Previous work has established that strain and quantum confinement can be used to influence orbital occupancy. In this paper we demonstrate a different modality for orbital control in transition-metal oxide heterostructures, using density-functional band calculations supplemented by a tight-binding analysis to show that the choice of nontransition-metal counterion X in transition-metal oxide heterostructures composed of alternating LaNiO3 and LaXO3 units strongly affects orbital occupancy, changing the magnitude and in some cases the sign of the orbital polarization.

Bypass transition in compressible boundary layers

NASA Technical Reports Server (NTRS)

Vandervegt, J. J.

1992-01-01

Transition to turbulence in aerospace applications usually occurs in a strongly disturbed environment. For instance, the effects of free-stream turbulence, roughness and obstacles in the boundary layer strongly influence transition. Proper understanding of the mechanisms leading to transition is crucial in the design of aircraft wings and gas turbine blades, because lift, drag and heat transfer strongly depend on the state of the boundary layer, laminar or turbulent. Unfortunately, most of the transition research, both theoretical and experimental, has focused on natural transition. Many practical flows, however, defy any theoretical analysis and are extremely difficult to measure. Morkovin introduced in his review paper the concept of bypass transition as those forms of transition which bypass the known mechanisms of linear and non-linear transition theories and are currently not understood by experiments. In an effort to better understand the mechanisms leading to transition in a disturbed environment, experiments are conducted studying simpler cases, viz. the effects of free stream turbulence on transition on a flat plate. It turns out that these experiments are very difficult to conduct, because generation of free stream turbulence with sufficiently high fluctuation levels and reasonable homogeneity is non trivial. For a discussion see Morkovin. Serious problems also appear due to the fact that at high Reynolds numbers the boundary layers are very thin, especially in the nose region of the plate where the transition occurs, which makes the use of very small probes necessary. The effects of free-stream turbulence on transition are the subject of this research and are especially important in a gas turbine environment, where turbulence intensities are measured between 5 and 20 percent, Wang et al. Due to the fact that the Reynolds number for turbine blades is considerably lower than for aircraft wings, generally a larger portion of the blade will be in a laminar

Superconductivity in transition metals.

PubMed

Slocombe, Daniel R; Kuznetsov, Vladimir L; Grochala, Wojciech; Williams, Robert J P; Edwards, Peter P

2015-03-13

A qualitative account of the occurrence and magnitude of superconductivity in the transition metals is presented, with a primary emphasis on elements of the first row. Correlations of the important parameters of the Bardeen-Cooper-Schrieffer theory of superconductivity are highlighted with respect to the number of d-shell electrons per atom of the transition elements. The relation between the systematics of superconductivity in the transition metals and the periodic table high-lights the importance of short-range or chemical bonding on the remarkable natural phenomenon of superconductivity in the chemical elements. A relationship between superconductivity and lattice instability appears naturally as a balance and competition between localized covalent bonding and so-called broken covalency, which favours d-electron delocalization and superconductivity. In this manner, the systematics of superconductivity and various other physical properties of the transition elements are related and unified. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Evolution of electronic structure as a function of layer thickness in group-VIB transition metal dichalcogenides: emergence of localization prototypes.

PubMed

Zhang, Lijun; Zunger, Alex

2015-02-11

Layered group-VIB transition metal dichalcogenides (with the formula of MX2) are known to show a transition from an indirect band gap in the thick n-monolayer stack (MX2)n to a direct band gap at the n = 1 monolayer limit, thus converting the system into an optically active material suitable for a variety of optoelectronic applications. The origin of this transition has been attributed predominantly to quantum confinement effect at reduced n. Our analysis of the evolution of band-edge energies and wave functions as a function of n using ab initio density functional calculations including the long-range dispersion interaction reveals (i) the indirect-to-direct band gap transformation is triggered not only by (kinetic-energy controlled) quantum confinement but also by (potential-energy controlled) band repulsion and localization. On its own, neither of the two effects can explain by itself the energy evolution of the band-edge states relevant to the transformation; (ii) when n decreased, there emerge distinct regimes with characteristic localization prototypes of band-edge states deciding the optical response of the system. They are distinguished by the real-space direct/indirect in combination with momentum-space direct/indirect nature of electron and hole states and give rise to distinct types of charge distribution of the photoexcited carriers that control excitonic behaviors; (iii) the various regimes associated with different localization prototypes are predicted to change with modification of cations and anions in the complete MX2 (M = Cr, Mo, W and X = S, Se, Te) series. These results offer new insight into understanding the excitonic properties (e.g., binding energy, lifetime etc.) of multiple layered MX2 and their heterostructures.

Nucleic acid-functionalized transition metal nanosheets for biosensing applications

PubMed Central

Mo, Liuting; Li, Juan; Liu, Qiaoling; Qiu, Liping; Tan, Weihong

2017-01-01

In clinical diagnostics, as well as food and environmental safety practices, biosensors are powerful tools for monitoring biological or biochemical processes. Two-dimensional (2D) transition metal nanomaterials, including transition metal chalcogenides (TMCs) and transition metal oxides (TMOs), are receiving growing interest for their use in biosensing applications based on such unique properties as high surface area and fluorescence quenching abilities. Meanwhile, nucleic acid probes based on Watson-Crick base-pairing rules are also being widely applied in biosensing based on their excellent recognition capability. In particular, the emergence of functional nucleic acids in the 1980s, especially aptamers, has substantially extended the recognition capability of nucleic acids to various targets, ranging from small organic molecules and metal ions to proteins and cells. Based on π-π stacking interaction between transition metal nanosheets and nucleic acids, biosensing systems can be easily assembled. Therefore, the combination of 2D transition metal nanomaterials and nucleic acids brings intriguing opportunities in bioanalysis and biomedicine. In this review, we summarize recent advances of nucleic acid-functionalized transition metal nanosheets in biosensing applications. The structure and properties of 2D transition metal nanomaterials are first discussed, emphasizing the interaction between transition metal nanosheets and nucleic acids. Then, the applications of nucleic acid-functionalized transition metal nanosheet-based biosensors are discussed in the context of different signal transducing mechanisms, including optical and electrochemical approaches. Finally, we provide our perspectives on the current challenges and opportunities in this promising field. PMID:27020066

Synthesizing new types of ultrathin 2D metal oxide nanosheets via half-successive ion layer adsorption and reaction

NASA Astrophysics Data System (ADS)

Gao, Linjie; Li, Yaguang; Xiao, Mu; Wang, Shufang; Fu, Guangsheng; Wang, Lianzhou

2017-06-01

Two-dimensional (2D) metal oxide nanosheets have demonstrated their great potential in a broad range of applications. The existing synthesis strategies are mainly preparing 2D nanosheets from layered and specific transition metal oxides. How to prepare the other types of metal oxides as ultrathin 2D nanosheets remains unsolved, especially for metal oxides containing alkali, alkaline earth metal, and multiple metal elements. Herein, we developed a half-successive ion layer adsorption and reaction (SILAR) method, which could synthesize those types of metal oxides as ultrathin 2D nanosheets. The synthesized 2D metal oxides nanosheets are within 1 nm level thickness and 500 m2 · g-1 level surface area. This method allows us to develop many new types of ultrathin 2D metal oxides nanosheets that have never been prepared before.

Probing the Band Structure of Ultrathin MoTe2 via Strain

NASA Astrophysics Data System (ADS)

Aslan, Burak; Datye, Isha; Kuo, Hsueh-Hui; Mleczko, Michal; Fisher, Ian; Pop, Eric; Heinz, Tony

Molybdenum ditelluride (MoTe2) is a semiconducting layered group VI transition metal dichalcogenide with an optical band gap of 1.1 and 0.9 eV in the monolayer and bulk, respectively. The bulk crystal possesses an indirect gap whereas the monolayer has a direct one. It is still under debate whether the direct-to-indirect gap crossover occurs at the monolayer or bilayer limit at room temperature, resulting from the fact that the two gaps are very close to one another in ultrathin crystals. We take advantage of this closeness by tuning the two gaps with in-plane tensile strain. In particular, we employ photoluminescence and absorption spectroscopy to probe the near-band-edge optical transitions and study their line-shapes to distinguish the direct and indirect gaps in few-layer MoTe2. We observe that the applied strain redshifts the direct and indirect gaps at different rates and strongly affects the spectral widths of the optical transitions. Our observations help us understand what contributes to the broadening of the A exciton peak in ultrathin MoTe2 and how the direct-to-indirect gap crossover occurs with decreasing thickness.

Electrochemical study of lithiated transition metal oxide composite for single layer fuel cell

NASA Astrophysics Data System (ADS)

Hu, Huiqing; Lin, Qizhao; Muhammad, Afzal; Zhu, Bin

2015-07-01

This study analyzed the effect of various semiconductors of transition metal oxides in modified lithiated NiO on the electrochemical performance of a single layer fuel cell (SLFC). A typical ionic conductor Ce0.8Sm0.2O2-δ (SDC) and three types of semiconductors Li0.3Ni0.6Cu0.07Sr0.03O2-δ (LNCuS), Li0.3Ni0.6Mn0.07Sr0.03O2-δ (LNMnS) and Li0.3Ni0.6Co0.07Sr0.03O2-δ (LNCoS), were the fundamental components of the SLFCs. The components were characterized by using X-ray diffraction (XRD), a scanning electron microscope (SEM), and an energy-dispersive X-ray spectrometer (EDS). The stability of the synthesized materials was evaluated using thermal gravity analysis (TGA). The ohmic resistances at 500 °C were 0.36, 0.48 and 0.58 Ω cm2 for 6SDC-4LNMnS, 6SDC-4LNCoS and 6SDC-4LNCuS, respectively. Among the three SLFCs, the single cell with 6SDC-4LNMnS achieves the highest power density (422 mW cm-2) but the lowest temperature stability, while the single cell with 6SDC-4LNCuS achieved the lowest power density (331 mW cm-2) but the highest temperature stability during the operation temperature.

Mesoporous Transition Metal Oxides for Supercapacitors.

PubMed

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-10-14

Recently, transition metal oxides, such as ruthenium oxide (RuO₂), manganese dioxide (MnO₂), nickel oxides (NiO) and cobalt oxide (Co₃O₄), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO₂, MnO₂, NiO, Co₃O₄ and nickel cobaltite (NiCo₂O₄), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

Establishing Dual Electrogenerated Chemiluminescence and Multicolor Electrochromism in Functional Ionic Transition-Metal Complexes

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

Puodziukynaite, Egle; Oberst, Justin L.; Dyer, Aubrey L.

A combination of electrochromism and electroluminescence in functional materials could lead to single-layer dual electrochromic/electroluminescent (EC/EL) display devices, capable of simultaneous operation in emissive and reflective modes. Whereas such next generation displays could provide optimal visibility in any ambient lighting situation, materials available that exhibit such characteristics in the active layer are limited due to the required intrinsic multifunctionality (i.e., redox activity, electroluminescence, electrochromism, and ion conductivity) and to date can only be achieved via the rational design of ionic transition-metal complexes. Reported herein is the synthesis and characterization of a new family of acrylate-containing ruthenium (tris)bipyridine-based coordination complexes withmore » multifunctional characteristics. Potential use of the presented compounds in EC/EL devices is established, as they are applied as cross-linked electrochromic films and electrochemiluminescent layers in light-emitting electrochemical cell devices. Electrochromic switching of the polymeric networks between yellow, orange, green, brown and transmissive states is demonstrated, and electrochemiluminescent devices based on the complexes synthesized show red-orange to deep red emission with λmax ranging from 680 to 722 nm and luminance up to 135 cd/m². Additionally, a dual EC/EL device prototype is presented where light emission and multicolor electrochromism occur from the same pixel comprised of a single active layer, demonstrating a true combination of these properties in ionic transition-metal complexes.« less

Core-level spectra and binding energies of transition metal nitrides by non-destructive x-ray photoelectron spectroscopy through capping layers

NASA Astrophysics Data System (ADS)

Greczynski, G.; Primetzhofer, D.; Lu, J.; Hultman, L.

2017-02-01

We present the first measurements of x-ray photoelectron spectroscopy (XPS) core level binding energies (BE:s) for the widely-applicable group IVb-VIb polycrystalline transition metal nitrides (TMN's) TiN, VN, CrN, ZrN, NbN, MoN, HfN, TaN, and WN as well as AlN and SiN, which are common components in the TMN-based alloy systems. Nitride thin film samples were grown at 400 °C by reactive dc magnetron sputtering from elemental targets in Ar/N2 atmosphere. For XPS measurements, layers are either (i) Ar+ ion-etched to remove surface oxides resulting from the air exposure during sample transfer from the growth chamber into the XPS system, or (ii) in situ capped with a few nm thick Cr or W overlayers in the deposition system prior to air-exposure and loading into the XPS instrument. Film elemental composition and phase content is thoroughly characterized with time-of-flight elastic recoil detection analysis (ToF-E ERDA), Rutherford backscattering spectrometry (RBS), and x-ray diffraction. High energy resolution core level XPS spectra acquired with monochromatic Al Kα radiation on the ISO-calibrated instrument reveal that even mild etching conditions result in the formation of a nitrogen-deficient surface layer that substantially affects the extracted binding energy values. These spectra-modifying effects of Ar+ ion bombardment increase with increasing the metal atom mass due to an increasing nitrogen-to-metal sputter yield ratio. The superior quality of the XPS spectra obtained in a non-destructive way from capped TMN films is evident from that numerous metal peaks, including Ti 2p, V 2p, Zr 3d, and Hf 4f, exhibit pronounced satellite features, in agreement with previously published spectra from layers grown and analyzed in situ. In addition, the N/metal concentration ratios are found to be 25-90% higher than those obtained from the corresponding ion-etched surfaces, and in most cases agree very well with the RBS and ToF-E ERDA values. The N 1 s BE:s extracted from

Mass fractionation processes of transition metal isotopes

NASA Astrophysics Data System (ADS)

Zhu, X. K.; Guo, Y.; Williams, R. J. P.; O'Nions, R. K.; Matthews, A.; Belshaw, N. S.; Canters, G. W.; de Waal, E. C.; Weser, U.; Burgess, B. K.; Salvato, B.

2002-06-01

Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper and iron isotope fractionation during various inorganic and biological processes. These results demonstrate that: (1) naturally occurring inorganic processes can fractionate Fe isotope to a detectable level even at temperature ˜1000°C, which challenges the previous view that Fe isotope variations in natural system are unique biosignatures; (2) multiple-step equilibrium processes at low temperatures may cause large mass fractionation of transition metal isotopes even when the fractionation per single step is small; (3) oxidation-reduction is an importation controlling factor of isotope fractionation of transition metal elements with multiple valences, which opens a wide range of applications of these new isotope systems, ranging from metal-silicate fractionation in the solar system to uptake pathways of these elements in biological systems; (4) organisms incorporate lighter isotopes of transition metals preferentially, and transition metal isotope fractionation occurs stepwise along their pathways within biological systems during their uptake.

Nucleic acid-functionalized transition metal nanosheets for biosensing applications.

PubMed

Mo, Liuting; Li, Juan; Liu, Qiaoling; Qiu, Liping; Tan, Weihong

2017-03-15

In clinical diagnostics, as well as food and environmental safety practices, biosensors are powerful tools for monitoring biological or biochemical processes. Two-dimensional (2D) transition metal nanomaterials, including transition metal chalcogenides (TMCs) and transition metal oxides (TMOs), are receiving growing interest for their use in biosensing applications based on such unique properties as high surface area and fluorescence quenching abilities. Meanwhile, nucleic acid probes based on Watson-Crick base-pairing rules are also being widely applied in biosensing based on their excellent recognition capability. In particular, the emergence of functional nucleic acids in the 1980s, especially aptamers, has substantially extended the recognition capability of nucleic acids to various targets, ranging from small organic molecules and metal ions to proteins and cells. Based on π-π stacking interaction between transition metal nanosheets and nucleic acids, biosensing systems can be easily assembled. Therefore, the combination of 2D transition metal nanomaterials and nucleic acids brings intriguing opportunities in bioanalysis and biomedicine. In this review, we summarize recent advances of nucleic acid-functionalized transition metal nanosheets in biosensing applications. The structure and properties of 2D transition metal nanomaterials are first discussed, emphasizing the interaction between transition metal nanosheets and nucleic acids. Then, the applications of nucleic acid-functionalized transition metal nanosheet-based biosensors are discussed in the context of different signal transducing mechanisms, including optical and electrochemical approaches. Finally, we provide our perspectives on the current challenges and opportunities in this promising field. Copyright © 2016 Elsevier B.V. All rights reserved.

Theoretical ultra-fast spectroscopy in transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Molina-Sanchez, Alejandro; Sangalli, Davide; Marini, Andrea; Wirtz, Ludger

Semiconducting 2D-materials like the transition metal dichalcogenides (TMDs) MoS2, MoSe2, WS2, WSe2 are promising alternatives to graphene for designing novel opto-electronic devices. The strong spin-orbit interaction along with the breaking of inversion symmetry in single-layer TMDs allow using the valley-index as a new quantum number. The practical use of valley physics depends on the lifetimes of valley-polarized excitons which are affected by scattering at phonons, impurities and by carrier-carrier interactions. The carrier dynamics can be monitored using ultra-fast spectroscopies such as pump-probe experiments. The carrier dynamics is simulated using non-equilibrium Green's function theory in an ab-initio framework. We include carrier relaxation through electron-phonon interaction. We obtain the transient absorption spectra of single-layer TMD and compare our simulations with recent pump-probe experiments

Orbiter Boundary Layer Transition Prediction Tool Enhancements

NASA Technical Reports Server (NTRS)

Berry, Scott A.; King, Rudolph A.; Kegerise, Michael A.; Wood, William A.; McGinley, Catherine B.; Berger, Karen T.; Anderson, Brian P.

2010-01-01

Updates to an analytic tool developed for Shuttle support to predict the onset of boundary layer transition resulting from thermal protection system damage or repair are presented. The boundary layer transition tool is part of a suite of tools that analyze the local aerothermodynamic environment to enable informed disposition of damage for making recommendations to fly as is or to repair. Using mission specific trajectory information and details of each d agmea site or repair, the expected time (and thus Mach number) of transition onset is predicted to help define proper environments for use in subsequent thermal and stress analysis of the thermal protection system and structure. The boundary layer transition criteria utilized within the tool were updated based on new local boundary layer properties obtained from high fidelity computational solutions. Also, new ground-based measurements were obtained to allow for a wider parametric variation with both protuberances and cavities and then the resulting correlations were calibrated against updated flight data. The end result is to provide correlations that allow increased confidence with the resulting transition predictions. Recently, a new approach was adopted to remove conservatism in terms of sustained turbulence along the wing leading edge. Finally, some of the newer flight data are also discussed in terms of how these results reflect back on the updated correlations.

Electrical Conductivity in Transition Metals

ERIC Educational Resources Information Center

Talbot, Christopher; Vickneson, Kishanda

2013-01-01

The aim of this "Science Note" is to describe how to test the electron-sea model to determine whether it accurately predicts relative electrical conductivity for first-row transition metals. In the electron-sea model, a metal crystal is viewed as a three-dimensional array of metal cations immersed in a sea of delocalised valence…

Transition metal oxide as anode interface buffer for impedance spectroscopy

NASA Astrophysics Data System (ADS)

Xu, Hui; Tang, Chao; Wang, Xu-Liang; Zhai, Wen-Juan; Liu, Rui-Lan; Rong, Zhou; Pang, Zong-Qiang; Jiang, Bing; Fan, Qu-Li; Huang, Wei

2015-12-01

Impedance spectroscopy is a strong method in electric measurement, which also shows powerful function in research of carrier dynamics in organic semiconductors when suitable mathematical physical models are used. Apart from this, another requirement is that the contact interface between the electrode and materials should at least be quasi-ohmic contact. So in this report, three different transitional metal oxides, V2O5, MoO3 and WO3 were used as hole injection buffer for interface of ITO/NPB. Through the impedance spectroscopy and PSO algorithm, the carrier mobilities and I-V characteristics of the NPB in different devices were measured. Then the data curves were compared with the single layer device without the interface layer in order to investigate the influence of transitional metal oxides on the carrier mobility. The careful research showed that when the work function (WF) of the buffer material was just between the work function of anode and the HOMO of the organic material, such interface material could work as a good bridge for carrier injection. Under such condition, the carrier mobility measured through impedance spectroscopy should be close to the intrinsic value. Considering that the HOMO (or LUMO) of most organic semiconductors did not match with the work function of the electrode, this report also provides a method for wide application of impedance spectroscopy to the research of carrier dynamics.

The stability boundary of group-III transition metal diboride ScB 2 (0 0 0 1) surfaces

NASA Astrophysics Data System (ADS)

Zhao, Hui; Qin, Na

2012-01-01

Experimental observations and theoretical investigations exhibit that a group-IV(V) transition metal diboride (0 0 0 1) surface is terminated with a 1 × 1 TM(B) layer. As to a group-III transition metal diboride, we have investigated the stability boundary of ScB2 (0 0 0 1) surfaces using first principles total energy plane-wave pseudopotential method based on density functional theory. The Mulliken charge population analysis shows that Sc atoms in the second layer cannot provide B atoms in the first layer with sufficient electrons to form a complete graphene-like boron layer. We also found that the charge transfer between the first and the second layer for the B-terminated surface is more than that for Sc-terminated surface. It elucidates the reason that the outermost interlayer spacing contract more strongly in the B-terminated surface than in the Sc-terminated surface. The surface energies of both terminated ScB2 (0 0 0 1) surfaces as a function of the chemical potential of B are also calculated to check the relative stability of the two surface structures.

Solder for oxide layer-building metals and alloys

DOEpatents

Kronberg, James W.

1992-01-01

A low temperature solder and method for soldering an oxide layer-building metal such as aluminum, titanium, tantalum or stainless steel. The comosition comprises tin and zinc; germanium as a wetting agent; preferably small amounts of copper and antimony; and a grit, such as silicon carbide. The grit abrades any oxide layer formed on the surface of the metal as the germanium penetrates beneath and loosens the oxide layer to provide good metal-to-metal contact. The germanium comprises less than aproximatley 10% by weight of the solder composition so that it provides sufficient wetting action but does not result in a melting temperature above approximately 300.degree. C. The method comprises the steps rubbing the solder against the metal surface so the grit in the solder abrades the surface while heating the surface until the solder begins to melt and the germanium penetrates the oxide layer, then brushing aside any oxide layer loosened by the solder.

Solder for oxide layer-building metals and alloys

DOEpatents

Kronberg, J.W.

1992-09-15

A low temperature solder and method for soldering an oxide layer-building metal such as aluminum, titanium, tantalum or stainless steel is disclosed. The composition comprises tin and zinc; germanium as a wetting agent; preferably small amounts of copper and antimony; and a grit, such as silicon carbide. The grit abrades any oxide layer formed on the surface of the metal as the germanium penetrates beneath and loosens the oxide layer to provide good metal-to-metal contact. The germanium comprises less than approximately 10% by weight of the solder composition so that it provides sufficient wetting action but does not result in a melting temperature above approximately 300 C. The method comprises the steps rubbing the solder against the metal surface so the grit in the solder abrades the surface while heating the surface until the solder begins to melt and the germanium penetrates the oxide layer, then brushing aside any oxide layer loosened by the solder.

Chromatic Mechanical Response in 2-D Layered Transition Metal Dichalcogenide (TMDs) based Nanocomposites

PubMed Central

Rahneshin, Vahid; Khosravi, Farhad; Ziolkowska, Dominika A.; Jasinski, Jacek B.; Panchapakesan, Balaji

2016-01-01

The ability to convert photons of different wavelengths directly into mechanical motion is of significant interest in many energy conversion and reconfigurable technologies. Here, using few layer 2H-MoS2 nanosheets, layer by layer process of nanocomposite fabrication, and strain engineering, we demonstrate a reversible and chromatic mechanical response in MoS2-nanocomposites between 405 nm to 808 nm with large stress release. The chromatic mechanical response originates from the d orbitals and is related to the strength of the direct exciton resonance A and B of the few layer 2H-MoS2 affecting optical absorption and subsequent mechanical response of the nanocomposite. Applying uniaxial tensile strains to the semiconducting few-layer 2H-MoS2 crystals in the nanocomposite resulted in spatially varying energy levels inside the nanocomposite that enhanced the broadband optical absorption up to 2.3 eV and subsequent mechanical response. The unique photomechanical response in 2H-MoS2 based nanocomposites is a result of the rich d electron physics not available to nanocomposites based on sp bonded graphene and carbon nanotubes, as well as nanocomposite based on metallic nanoparticles. The reversible strain dependent optical absorption suggest applications in broad range of energy conversion technologies that is not achievable using conventional thin film semiconductors. PMID:27713550

Mesoporous Transition Metal Oxides for Supercapacitors

PubMed Central

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-01-01

Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors. PMID:28347088

Spatially resolved surface valence gradient and structural transformation of lithium transition metal oxides in lithium-ion batteries.

PubMed

Liu, Hanshuo; Bugnet, Matthieu; Tessaro, Matteo Z; Harris, Kristopher J; Dunham, Mark J R; Jiang, Meng; Goward, Gillian R; Botton, Gianluigi A

2016-10-26

Layered lithium transition metal oxides are one of the most important types of cathode materials in lithium-ion batteries (LIBs) that possess high capacity and relatively low cost. Nevertheless, these layered cathode materials suffer structural changes during electrochemical cycling that could adversely affect the battery performance. Clear explanations of the cathode degradation process and its initiation, however, are still under debate and not yet fully understood. We herein systematically investigate the chemical evolution and structural transformation of the LiNi x Mn y Co 1-x-y O 2 (NMC) cathode material in order to understand the battery performance deterioration driven by the cathode degradation upon cycling. Using high-resolution electron energy loss spectroscopy (HR-EELS) we clarify the role of transition metals in the charge compensation mechanism, particularly the controversial Ni 2+ (active) and Co 3+ (stable) ions, at different states-of-charge (SOC) under 4.6 V operation voltage. The cathode evolution is studied in detail from the first-charge to long-term cycling using complementary diagnostic tools. With the bulk sensitive 7 Li nuclear magnetic resonance (NMR) measurements, we show that the local ordering of transition metal and Li layers (R3[combining macron]m structure) is well retained in the bulk material upon cycling. In complement to the bulk measurements, we locally probe the valence state distribution of cations and the surface structure of NMC particles using EELS and scanning transmission electron microscopy (STEM). The results reveal that the surface evolution of NMC is initiated in the first-charging step with a surface reduction layer formed at the particle surface. The NMC surface undergoes phase transformation from the layered structure to a poor electronic and ionic conducting transition-metal oxide rock-salt phase (R3[combining macron]m → Fm3[combining macron]m), accompanied by irreversible lithium and oxygen loss. In addition to

Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks

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

Ogut, Serdar

The primary goals of our research program is to develop and apply state-of-the-art first-principles methods to predict electronic and optical properties of three systems of significant scientific and technological interest: transition metal clusters, organic dyes, and metal-organic frameworks. These systems offer great opportunities to manipulate light for a wide ranging list of energy-related scientific problems and applications. During this grant period, we focused our investigations on the development, implementation, and benchmarking of many-body Green’s function methods (GW approximation and the Bethe-Salpeter equation) to examine excited-state properties of transition metal/transition-metal-oxide clusters and organic molecules that comprise the building blocks of dyesmore » and metal-organic frameworks.« less

A liquid-liquid transition can exist in monatomic transition metals with a positive melting slope

PubMed Central

Lee, Byeongchan; Lee, Geun Woo

2016-01-01

Liquid-liquid transitions under high pressure are found in many elemental materials, but the transitions are known to be associated with either sp-valent materials or f-valent rare-earth elements, in which the maximum or a negative slope in the melting line is readily suggestive of the transition. Here we find a liquid-liquid transition with a positive melting slope in transition metal Ti from structural, electronic, and thermodynamic studies using ab-initio molecular dynamics calculations, showing diffusion anomaly, but no density anomaly. The origin of the transition in liquid Ti is a pressure-induced increase of local structures containing very short bonds with directionality in electronic configurations. This behavior appears to be characteristic of the early transition metals. In contrast, the late transition metal liquid Ni does not show the L-L transition with pressure. This result suggests that the possibility of the L-L transition decreases from early to late transition metals as electronic structures of late transition metals barely have a Jahn-Teller effect and bond directionality. Our results generalize that a phase transition in disordered materials is found with any valence band regardless of the sign of the melting slope, but related to the symmetry of electronic structures of constituent elements. PMID:27762334

Ceramic TBS/porous metal compliant layer

NASA Technical Reports Server (NTRS)

Tolokan, Robert P.; Jarrabet, G. P.

1992-01-01

Technetics Corporation manufactures metal fiber materials and components used in aerospace applications. Our technology base is fiber metal porous sheet material made from sinter bonded metal fibers. Fiber metals have percent densities (metal content by volume) from 10 to 65 percent. Various topics are covered and include the following: fiber metal materials, compliant layer thermal bayer coatings (TBC's), pad properties, ceramic/pad TBC design, thermal shock rig, fabrication, and applications.

Boundary-Layer Transition on a Slender Cone in Hypervelocity Flow with Real Gas Effects

NASA Astrophysics Data System (ADS)

Jewell, Joseph Stephen

method to control transition location with boundary layer gas injection is investigated. An appropriate porous-metal injector section for the cone is designed and fabricated, and the efficacy of injected CO2 for delaying transition is gauged at various mass flow rates, and compared with both no injection and chemically inert argon injection cases. While CO2 injection seems to delay transition, and argon injection seems to promote it, the experimental results are inconclusive and matching computations do not predict a reduction in N factor from any CO2 injection condition computed.

Boundary Layer Transition on X-43A

NASA Technical Reports Server (NTRS)

Berry, Scott; Daryabeigi, Kamran; Wurster, Kathryn; Bittner, Robert

2008-01-01

The successful Mach 7 and 10 flights of the first fully integrated scramjet propulsion systems by the Hyper-X (X-43A) program have provided the means with which to verify the original design methodologies and assumptions. As part of Hyper-X s propulsion-airframe integration, the forebody was designed to include a spanwise array of vortex generators to promote boundary layer transition ahead of the engine. Turbulence at the inlet is thought to provide the most reliable engine design and allows direct scaling of flight results to groundbased data. Pre-flight estimations of boundary layer transition, for both Mach 7 and 10 flight conditions, suggested that forebody boundary layer trips were required to ensure fully turbulent conditions upstream of the inlet. This paper presents the results of an analysis of the thermocouple measurements used to infer the dynamics of the transition process during the trajectories for both flights, on both the lower surface (to assess trip performance) and the upper surface (to assess natural transition). The approach used in the analysis of the thermocouple data is outlined, along with a discussion of the calculated local flow properties that correspond to the transition events as identified in the flight data. The present analysis has confirmed that the boundary layer trips performed as expected for both flights, providing turbulent flow ahead of the inlet during critical portions of the trajectory, while the upper surface was laminar as predicted by the pre-flight analysis.

Spectroscopic studies of transition-metal ions in molten alkali-metal carboxylates

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

Maroni, V.A.; Maciejewski, M.L.

This paper presents the results of electronic absorption and /sup 13/C-NMR measurements on molten alkali metal formates and acetates and on solutions of selected 3d transition metal ions therein. These studies provide a unique opportunity to explore (1) the highly ordered nature of alkali carboxylates, (2) the ligand field properties of acetate and formate ions, and (3) the coordination chemistry of the 3d transition metals in molten carboxylates. 1 figure, 2 tables.

Environmentally relevant metal and transition metal ions enhance Fc epsilon RI-mediated mast cell activation.

PubMed Central

Walczak-Drzewiecka, Aurelia; Wyczólkowska, Janina; Dastych, Jaroslaw

2003-01-01

Upon contact with allergen, sensitized mast cells release highly active proinflammatory mediators. Allergen-mediated mast cell activation is an important mechanism in the pathogenesis of atopic asthma. Asthmatic patients are especially susceptible to air pollution. Epidemiologic studies found a positive correlation between severity of symptoms among asthmatic patients and the level of particulate matter (PM) in the air. Among the constituents of PM are metals and transition metals, which could mediate some of its adverse effects on human health. We sought to determine the effect of metal and transition metal ions on allergen-mediated mast cell activation. We observed that several metal and transition metal ions activated mast cells and enhanced allergen-mediated mast cell activation. Thus, Al(3+), Cd(2+), and Sr(2+) induced release of granule-associated N-acetyl-ss-d-hexosaminidase, and Al(3+) and Ni(2+) enhanced antigen-mediated release. Metal and transition metal ions also induced significant secretion of interleukin (IL)-4 and increased antigen-mediated IL-4 secretion in mast cells. These effects of metal and transition metal ions on mast cells were observed at concentrations that do not result in direct cytotoxicity and might be relevant for environmental exposure. Thus, metals and transition metals could increase the level of allergen-mediated mast cell activation, which might be one of the mechanisms mediating exacerbation of allergen-driven asthma symptoms by air pollution. PMID:12727598

Achieving high capacity and rate capability in layered lithium transition metal oxide cathodes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Ahn, Juhyeon; Susanto, Dieky; Noh, Jae-Kyo; Ali, Ghulam; Cho, Byung Won; Chung, Kyung Yoon; Kim, Jong Hak; Oh, Si Hyoung

2017-08-01

In this study, we target to find a new composition for a layered mixed metal oxide, which has a high structural stability and a good electrochemical performance. Our strategy is to alter the transition metal composition focusing on the relative amounts of redox active Ni and Co to the inactive Mn, based on highly-stabilized LiNi1/3Co1/3Mn1/3O2. X-ray absorption near-edge structure and X-ray diffraction analyses show that the degree of cation disorder decreases on increasing the ratio of Ni and Co to Mn, by the presence of Ni3+, suggesting that slightly higher Ni and Co contents lead to improved structural stability. Electrochemical studies demonstrate that LiNi0.4Co0.4Mn0.2O2 cathodes exhibit considerable improvements in both the reversible capacity and the rate capabilities at a voltage range of 2.5-4.6 V. In situ XRD measurements reveal that LiNi0.4Co0.4Mn0.2O2 maintains a single-phase and undergoes lesser structural variations compared to controlled compositions during a delithiation process up to 4.6 V, while achieving a high reversible capacity over 200 mAh g-1. As a result, LiNi0.4Co0.4Mn0.2O2 experiences fewer structural degradations during electrochemical cycling, which explains the excellent long-term cycling performance.

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy.

PubMed

Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

2016-02-24

Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

PubMed Central

Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

2016-01-01

Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge. PMID:26908198

Rapid Mapping of Lithiation Dynamics in Transition Metal Oxide Particles with Operando X-ray Absorption Spectroscopy

NASA Astrophysics Data System (ADS)

Nowack, Lea; Grolimund, Daniel; Samson, Vallerie; Marone, Federica; Wood, Vanessa

2016-02-01

Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.

Transition metal nitride coated with atomic layers of Pt as a low-cost, highly stable electrocatalyst for the oxygen reduction reaction

DOE PAGES

Tian, Xinlong; Adzic, Radoslav R.; Luo, Junming; ...

2016-02-10

Here, the main challenges to the commercial viability of polymer electrolyte membrane fuel cells are (i) the high cost associated with using large amounts of Pt in fuel cell cathodes to compensate for the sluggish kinetics of the oxygen reduction reaction, (ii) catalyst degradation, and (iii) carbon-support corrosion. To address these obstacles, our group has focused on robust, carbon-free transition metal nitride materials with low Pt content that exhibit tunable physical and catalytic properties. Here, we report on the high performance of a novel catalyst with low Pt content, prepared by placing several layers of Pt atoms on nanoparticles ofmore » titanium nickel binary nitride. For the ORR, the catalyst exhibited a more than 400% and 200% increase in mass activity and specific activity, respectively, compared with the commercial Pt/C catalyst. It also showed excellent stability/durability, experiencing only a slight performance loss after 10,000 potential cycles, while TEM results showed its structure had remained intact. The catalyst’s outstanding performance may have resulted from the ultrahigh dispersion of Pt (several atomic layers coated on the nitride nanoparticles), and the excellent stability/durability may have been due to the good stability of nitride and synergetic effects between ultrathin Pt layer and the robust TiNiN support.« less

Electric Field-Dependent Photoluminescence in Multilayer Transition Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Stanev, T. K.; Henning, A.; Sangwan, V. K.; Speiser, N.; Stern, N. P.; Lauhon, L. J.; Hersam, M. C.; Wang, K.; Valencia, D.; Charles, J.; Kubis, T. C.

Owing to interlayer coupling, transition metal dichalcogenides (TMDCs) such as MoS2 exhibit strong layer dependence of optical and electronic phenomena such as the band gap and trion and neutral exciton population dynamics. Here, we systematically measure the effect of layer number on the optical response of multilayer MoS2 in an external electric field, observing field and layer number dependent emission energy and photoluminescence intensity. These effects are studied in few (2-6) and bulk (11 +) layered structures at low temperatures. In MoS2\\ the observed layer dependence arises from several mechanisms, including interlayer charge transfer, band structure, Stark Effect, Fermi level changes, screening, and surface effects, so it can be challenging to isolate how these mechanisms impact the observables. Because it behaves like a stack of weakly interacting monolayers rather than multilayer or bulk, ReS2 provides a comparison to traditional TMDCs to help isolate the underlying physical mechanisms dictating the response of multilayers. This work is supported by the National Science Foundation MRSEC program (DMR-1121262), and the 2-DARE Grant (EFRI-1433510). N.P.S. is an Alfred P. Sloan Research Fellow.

Synthesis of millimeter-scale transition metal dichalcogenides single crystals

DOE PAGES

Gong, Yongji; Ye, Gonglan; Lei, Sidong; ...

2016-02-10

The emergence of semiconducting transition metal dichalcogenide (TMD) atomic layers has opened up unprecedented opportunities in atomically thin electronics. Yet the scalable growth of TMD layers with large grain sizes and uniformity has remained very challenging. Here is reported a simple, scalable chemical vapor deposition approach for the growth of MoSe2 layers is reported, in which the nucleation density can be reduced from 105 to 25 nuclei cm -2, leading to millimeter-scale MoSe 2 single crystals as well as continuous macrocrystalline films with millimeter size grains. The selective growth of monolayers and multilayered MoSe2 films with well-defined stacking orientation canmore » also be controlled via tuning the growth temperature. In addition, periodic defects, such as nanoscale triangular holes, can be engineered into these layers by controlling the growth conditions. The low density of grain boundaries in the films results in high average mobilities, around ≈42 cm 2 V -1 s -1, for back-gated MoSe 2 transistors. This generic synthesis approach is also demonstrated for other TMD layers such as millimeter-scale WSe 2 single crystals.« less

First-principles simulations of Graphene/Transition-metal-Dichalcogenides/Graphene Field-Effect Transistor

NASA Astrophysics Data System (ADS)

Li, Xiangguo; Wang, Yun-Peng; Zhang, X.-G.; Cheng, Hai-Ping

A prototype field-effect transistor (FET) with fascinating properties can be made by assembling graphene and two-dimensional insulating crystals into three-dimensional stacks with atomic layer precision. Transition metal dichalcogenides (TMDCs) such as WS2, MoS2 are good candidates for the atomically thin barrier between two layers of graphene in the vertical FET due to their sizable bandgaps. We investigate the electronic properties of the Graphene/TMDCs/Graphene sandwich structure using first-principles method. We find that the effective tunnel barrier height of the TMDC layers in contact with the graphene electrodes has a layer dependence and can be modulated by a gate voltage. Consequently a very high ON/OFF ratio can be achieved with appropriate number of TMDC layers and a suitable range of the gate voltage. The spin-orbit coupling in TMDC layers is also layer dependent but unaffected by the gate voltage. These properties can be important in future nanoelectronic device designs. DOE/BES-DE-FG02-02ER45995; NERSC.

Transition metal partially supported graphene: Magnetism and oscillatory electrostatic potentials

DOE PAGES

Liu, Xiaojie; Wang, Cai-Zhuang

2017-08-07

Using first-principles calculations here, we show that Mn and Cr layers under graphene exhibit almost zero magnetic moment due to anti-ferromagnetic order, while ferromagnetic coupling in Fe, Co, and Ni leads to large magnetic moment. The transition metal partially supported graphene, with a mixture of supported and pristine areas, exhibits an oscillatory electrostatic potential, thus alternating the electric field across the supported and pristine areas. Such an effect can be utilized to control mass transport and nanostructure self-organization on graphene at the atomic level.

Transition metal partially supported graphene: Magnetism and oscillatory electrostatic potentials

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

Liu, Xiaojie; Wang, Cai-Zhuang

Using first-principles calculations here, we show that Mn and Cr layers under graphene exhibit almost zero magnetic moment due to anti-ferromagnetic order, while ferromagnetic coupling in Fe, Co, and Ni leads to large magnetic moment. The transition metal partially supported graphene, with a mixture of supported and pristine areas, exhibits an oscillatory electrostatic potential, thus alternating the electric field across the supported and pristine areas. Such an effect can be utilized to control mass transport and nanostructure self-organization on graphene at the atomic level.

Band engineering in transition metal dichalcogenides: Stacked versus lateral heterostructures

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

Guo, Yuzheng; Robertson, John

2016-06-06

We calculate a large difference in the band alignments for transition metal dichalcogenide (TMD) heterojunctions when arranged in the stacked layer or lateral (in-plane) geometries, using direct supercell calculations. The stacked case follows the unpinned limit of the electron affinity rule, whereas the lateral geometry follows the strongly pinned limit of alignment of charge neutrality levels. TMDs therefore provide one of the few clear tests of band alignment models, whereas three-dimensional semiconductors give less stringent tests because of accidental chemical trends in their properties.

Selective-area growth and controlled substrate coupling of transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Bersch, Brian M.; Eichfeld, Sarah M.; Lin, Yu-Chuan; Zhang, Kehao; Bhimanapati, Ganesh R.; Piasecki, Aleksander F.; Labella, Michael, III; Robinson, Joshua A.

2017-06-01

Developing a means for true bottom-up, selective-area growth of two-dimensional (2D) materials on device-ready substrates will enable synthesis in regions only where they are needed. Here, we demonstrate seed-free, site-specific nucleation of transition metal dichalcogenides (TMDs) with precise control over lateral growth by utilizing an ultra-thin polymeric surface functionalization capable of precluding nucleation and growth. This polymer functional layer (PFL) is derived from conventional photoresists and lithographic processing, and is compatible with multiple growth techniques, precursors (metal organics, solid-source) and TMDs. Additionally, we demonstrate that the substrate can play a major role in TMD transport properties. With proper TMD/substrate decoupling, top-gated field-effect transistors (FETs) fabricated with selectively-grown monolayer MoS2 channels are competitive with current reported MoS2 FETs. The work presented here demonstrates that substrate surface engineering is key to realizing precisely located and geometrically-defined 2D layers via unseeded chemical vapor deposition techniques.

Site specific physics in RT5 (R = rare earths and T = transition metals) materials

NASA Astrophysics Data System (ADS)

Paudyal, Durga

Most of RT5 compounds form in hexagonal CaCu5-type structure with three non-equivalent sites: R (1a), T (2c), and T (3g). R atoms sit in the middle of the T (2c) hexagonal layers. Advanced density functional theory calculations including on-site electron correlation and spin orbit coupling show crystal field split localized R 4f states, which are responsible for the large part of the magnetic anisotropy exhibited by these systems. In addition, the hexagonal T (2c) layers help enhancing the magnetic anisotropy. Partially quenched R 4f orbital moment is the origin of magnetic anisotropy which also helps enhancing magnetic moment. The interchange of T sites by other transition metals and the partial substitution of R atoms by transition metals could optimize needed magnetic moment and magnetic anisotropy by forming a complex geometry structure favoring permanent magnetic properties. This research is supported by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing office.

Computer graphic visualization of orbiter lower surface boundary-layer transition

NASA Technical Reports Server (NTRS)

Throckmorton, D. A.; Hartung, L. C.

1984-01-01

Computer graphic techniques are applied to the processing of Shuttle Orbiter flight data in order to create a visual presentation of the extent and movement of the boundary-layer transition front over the orbiter lower surface during entry. Flight-measured surface temperature-time histories define the onset and completion of the boundary-layer transition process at any measurement location. The locus of points which define the spatial position of the boundary-layer transition front on the orbiter planform is plotted at each discrete time for which flight data are available. Displaying these images sequentially in real-time results in an animated simulation of the in-flight boundary-layer transition process.

Transition Metal Switchable Mirror

ScienceCinema

None

2017-12-09

The switchable-mirrors technology was developed by Tom Richardson and Jonathan Slack of Berkeley Lab's Environmental Energy Technologies Division. By using transition metals rather than the rare earth metals used in the first metal-hydride switchable mirrors, Richardson and Slack were able to lower the cost and simplify the manufacturing process. Energy performance is improved as well, because the new windows can reflect or transmit both visible and infrared light. Besides windows for offices and homes, possible applications include automobile sunroofs, signs and displays, aircraft windows, and spacecraft.

Transition Metal Switchable Mirror

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

None

2009-08-21

The switchable-mirrors technology was developed by Tom Richardson and Jonathan Slack of Berkeley Lab's Environmental Energy Technologies Division. By using transition metals rather than the rare earth metals used in the first metal-hydride switchable mirrors, Richardson and Slack were able to lower the cost and simplify the manufacturing process. Energy performance is improved as well, because the new windows can reflect or transmit both visible and infrared light. Besides windows for offices and homes, possible applications include automobile sunroofs, signs and displays, aircraft windows, and spacecraft.

Ternary metal-rich sulfide with a layered structure

DOEpatents

Franzen, Hugo F.; Yao, Xiaoqiang

1993-08-17

A ternary Nb-Ta-S compound is provided having the atomic formula, Nb.sub.1.72 Ta.sub.3.28 S.sub.2, and exhibiting a layered structure in the sequence S-M3-M2-M1-M2-M3-S wherein S represents sulfur layers and M1, M2, and M3 represent Nb/Ta mixed metal layers. This sequence generates seven sheets stacked along the [001] direction of an approximate body centered cubic crystal structure with relatively weak sulfur-to-sulfur van der Waals type interactions between adjacent sulfur sheets and metal-to-metal bonding within and between adjacent mixed metal sheets.

Compositional dependence of elastic moduli for transition-metal oxide spinels

NASA Astrophysics Data System (ADS)

Reichmann, H. J.; Jacobsen, S. D.; Boffa Ballaran, T.

2012-12-01

Spinel phases (AB2O4) are common non-silicate oxides in the Earth's crust and upper mantle. A characteristic of this mineral group is the ability to host a wide range of transition metals. Here we summarize the influence of transition metals (Fe, Zn, and Mn) on the pressure dependence of elastic moduli of related spinels (magnetite, gahnite, and franklinite) using GHz-ultrasonic interferometry. Measurements were carried out up to 10 GPa in diamond-anvil cells using hydrostatic pressure media. Transition metals with unfilled 3d orbitals strongly influence the elastic properties of spinels. Franklinite (Zn,Mn)Fe2O4 and magnetite Fe3O4 with transition metals on both A and B cation sites exhibit pressure-induced mode softening of C44, whereas C44 of gahnite(ZnAl2O4) and spinel (MgAl2O4) exhibit positive pressure derivatives of the shear moduli. Spinels with two transition elements tend to undergo phase changes at a lower pressure than those with none or only one transition metal. Along the Mn-Zn solid solution, the variation of moduli with composition is non-linear, and a mid-range franklinite composition studied here shows a minimum in C44 compared with either end-member: MnFe2O 4 or ZnFe2O4. In general, the linear variation of sound velocity with density (Birch's Law) is followed by spinels, however spinels containing only one or no transition metals follow a distinct slope from those containing transition metals on both A and B sites. The Cauchy relation, 0.5(C12 - C44) = P is fulfilled by spinels with only one or no transition metals, suggesting that that Coulomb interactions dominate. Spinels with two transition metals fail to meet the Cauchy relation, indicating strong directional dependence and covalent character of bonding. The bonding character of transition metals is crucial to understanding the elastic behavior of natural and synthetic spinel solid solutions containing transition metals.

The metal-insulator transition in Fe(1.01-x)Cu(x)Se.

PubMed

Williams, A J; McQueen, T M; Ksenofontov, V; Felser, C; Cava, R J

2009-07-29

Iron selenide, Fe(1.01)Se, the layered parent compound of the recently discovered superconducting arsenide family, has previously been shown to be non-magnetic and superconducting with a critical temperature of 8 K. Here we show that copper can be substituted at the iron site in Fe(1.01)Se up to a solubility limit of 20-30%, after which a first-order transition to the three-dimensional CuFeSe(2) structure type is observed. As little as 1.5% copper is sufficient to suppress the superconductivity, and 4% drives the system through a metal-insulator transition. A local magnetic moment is introduced, which maximizes near 12% doping, where a spin-glass transition near 15 K is observed.

(S)TEM analysis of functional transition metal oxides

NASA Astrophysics Data System (ADS)

Chi, Miaofang

Perovskite vanadates (AVO3) form an ideal family to study the structure-property relationships in transition metal oxides because their physical properties can easily be tailored by varying the A-site cations. (S)TEM is an ideal tool for this type of study due to its capacity for simultaneous imaging and chemical analysis. Determination of the oxidation state of vanadium in complex oxides have been carried out by electron energy loss spectroscopy. SrVO3/LaAlO3 is then studied both experimentally and theoretically as a prototype system. Extra electrons have been detected on the interface layer, and further proven to originate mainly from a change in the local bonding configuration of V at the La-O terminated substrate surface. Cr-containing stainless steel deposited with a LaCrO3 thin-film layer is a promising interconnect material of Solid Oxide Fuel Cells (SOFC). Our investigation on its microstructural evolution reveals that the LaCrO 3 thin film plays a role in inhibiting the growth of an oxide layer on the metal surface and thus protects the surface of the stainless steel. Ca-doped LaCoO3 is a promising SOFC cathode material. The domain structures and the oxidation state of Co in Ca-doped LaCoO3, which are directly related to its mechanical properties and electronic conductivity, are investigated by in-situ TEM and EELS. The formation of microcracks is observed during thermal cycles. Ca-doping in LaCoO3 is shown to not only improve the electronic conductivity of the material, but is also likely to strengthen the grain boundaries. The realization of its application in SOFCs depends on depressing the ferroelastisity to reduce strain formation during thermal cycles. The application of the (S)TEM techniques used for studying the perovskite systems are further extended to other compounds containing transition metal elements. The refractory minerals from Comet 81 P/Wild-2 are studied to investigate the formation of the early solar system. A relatively high Ti3+/Ti 4

Boundary Layer Transition Results From STS-114

NASA Technical Reports Server (NTRS)

Berry, Scott A.; Horvath, Thomas J.; Cassady, Amy M.; Kirk, Benjamin S.; Wang, K. C.; Hyatt, Andrew J.

2006-01-01

The tool for predicting the onset of boundary layer transition from damage to and/or repair of the thermal protection system developed in support of Shuttle Return to Flight is compared to the STS-114 flight results. The Boundary Layer Transition (BLT) Tool is part of a suite of tools that analyze the aerothermodynamic environment of the local thermal protection system to allow informed disposition of damage for making recommendations to fly as is or to repair. Using mission specific trajectory information and details of each damage site or repair, the expected time of transition onset is predicted to help determine the proper aerothermodynamic environment to use in the subsequent thermal and stress analysis of the local structure. The boundary layer transition criteria utilized for the tool was developed from ground-based measurements to account for the effect of both protuberances and cavities and has been calibrated against flight data. Computed local boundary layer edge conditions provided the means to correlate the experimental results and then to extrapolate to flight. During STS-114, the BLT Tool was utilized and was part of the decision making process to perform an extravehicular activity to remove the large gap fillers. The role of the BLT Tool during this mission, along with the supporting information that was acquired for the on-orbit analysis, is reviewed. Once the large gap fillers were removed, all remaining damage sites were cleared for reentry as is. Post-flight analysis of the transition onset time revealed excellent agreement with BLT Tool predictions.

First-row transition metal hydrogenation and hydrosilylation catalysts

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

Trovitch, Ryan J.; Mukhopadhyay, Tufan K.; Pal, Raja

Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

Countering the Segregation of Transition-Metal Ions in LiMn1/3 Co1/3 Ni1/3 O2 Cathode for Ultralong Life and High-Energy Li-Ion Batteries.

PubMed

Luo, Dong; Fang, Shaohua; Tamiya, Yu; Yang, Li; Hirano, Shin-Ichi

2016-08-01

High-voltage layered lithium transition-metal oxides are very promising cathodes for high-energy Li-ion batteries. However, these materials often suffer from a fast degradation of cycling stability due to structural evolutions. It seriously impedes the large-scale application of layered lithium transition-metal oxides. In this work, an ultralong life LiMn1/3 Co1/3 Ni1/3 O2 microspherical cathode is prepared by constructing an Mn-rich surface. Its capacity retention ratio at 700 mA g(-1) is as large as 92.9% after 600 cycles. The energy dispersive X-ray maps of electrodes after numerous cycles demonstrate that the ultralong life of the as-prepared cathode is attributed to the mitigation of TM-ions segregation. Additionally, it is discovered that layered lithium transition-metal oxide cathodes with an Mn-rich surface can mitigate the segregation of TM ions and the corrosion of active materials. This study provides a new strategy to counter the segregation of TM ions in layered lithium transition-metal oxides and will help to the design and development of high-energy cathodes with ultralong life. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Subnanometer to nanometer transition metal CO oxidation catalysts

DOEpatents

Vajda, Stefan; Fortunelli, Alessandro; Yasumatsu, Hisato

2017-12-26

The present invention provides a catalyst defined in part by a conductive substrate; a film overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises between 8 and 11 atoms. Further provided is a catalyst defined in part by a conductive substrate; a layer overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises at least two metals.

Nonlinear Transient Growth and Boundary Layer Transition

NASA Technical Reports Server (NTRS)

Paredes, Pedro; Choudhari, Meelan M.; Li, Fei

2016-01-01

Parabolized stability equations (PSE) are used in a variational approach to study the optimal, non-modal disturbance growth in a Mach 3 at plate boundary layer and a Mach 6 circular cone boundary layer. As noted in previous works, the optimal initial disturbances correspond to steady counter-rotating streamwise vortices, which subsequently lead to the formation of streamwise-elongated structures, i.e., streaks, via a lift-up effect. The nonlinear evolution of the linearly optimal stationary perturbations is computed using the nonlinear plane-marching PSE for stationary perturbations. A fully implicit marching technique is used to facilitate the computation of nonlinear streaks with large amplitudes. To assess the effect of the finite-amplitude streaks on transition, the linear form of plane- marching PSE is used to investigate the instability of the boundary layer flow modified by spanwise periodic streaks. The onset of bypass transition is estimated by using an N- factor criterion based on the amplification of the streak instabilities. Results show that, for both flow configurations of interest, streaks of sufficiently large amplitude can lead to significantly earlier onset of transition than that in an unperturbed boundary layer without any streaks.

Effect of layered manufacturing techniques, alloy powders, and layer thickness on metal-ceramic bond strength.

PubMed

Ekren, Orhun; Ozkomur, Ahmet; Ucar, Yurdanur

2018-03-01

Direct metal laser sintering (DMLS) and direct metal laser melting (DMLM) have become popular for fabricating the metal frameworks of metal-ceramic restorations. How the type of layered manufacturing device, layer thickness, and alloy powder may affect the bond strength of ceramic to metal substructure is unclear. The purpose of this in vitro study was to evaluate the bond strength of dental porcelain to metal frameworks fabricated using different layered manufacturing techniques (DMLS and DMLM), Co-Cr alloy powders, and layer thicknesses and to evaluate whether a correlation exists between the bond strength and the number of ceramic remnants on the metal surface. A total of 75 bar-shaped metal specimens (n=15) were fabricated using either DMLS or DMLM. The powder alloys used were Keramit NP-S and EOS-Cobalt-Chrome SP-2 with layer thicknesses of 20 μm and 30 μm. After ceramic application, the metal-ceramic bond strength was evaluated with a 3-point-bend test. Three-way ANOVA followed by the Tukey honest significance difference test were used for statistical analysis (α=.05). De-bonding surface microstructure was observed with scanning electron microscopy. Energy dispersive spectroscopy analysis was conducted to evaluate the correlation between ceramic remnants on the metal surface and bond strength values. The mean bond strength value of DMLS was significantly higher than that of DMLM. While no statistically significant difference was found between layer thicknesses, alloy powders closely affected bond strength. Statistical comparisons revealed that the highest bond strength could be achieved with DMLS-Cobalt-Chrome SP2-20μm, and the lowest bond strength was observed in DMLS-Keramit NP-S-20μm (P≤.05). No correlation was found between porcelain remnants on the metal surface and bond strength values. The layered manufacturing device and the alloy powders evaluated in the current study closely affected the bond strength of dental porcelain to a metal framework

In-plane x-ray diffraction for characterization of monolayer and few-layer transition metal dichalcogenide films

NASA Astrophysics Data System (ADS)

Chubarov, Mikhail; Choudhury, Tanushree H.; Zhang, Xiaotian; Redwing, Joan M.

2018-02-01

There is significant interest in the growth of single crystal monolayer and few-layer films of transition metal dichalcogenides (TMD) and other 2D materials for scientific exploration and potential applications in optics, electronics, sensing, catalysis and others. The characterization of these materials is crucial in determining the properties and hence the applications. The ultra-thin nature of 2D layers presents a challenge to the use of x-ray diffraction (XRD) analysis with conventional Bragg-Brentano geometry in analyzing the crystallinity and epitaxial orientation of 2D films. To circumvent this problem, we demonstrate the use of in-plane XRD employing lab scale equipment which uses a standard Cu x-ray tube for the analysis of the crystallinity of TMD monolayer and few-layer films. The applicability of this technique is demonstrated in several examples for WSe2 and WS2 films grown by chemical vapor deposition on single crystal substrates. In-plane XRD was used to determine the epitaxial relation of WSe2 grown on c-plane sapphire and on SiC with an epitaxial graphene interlayer. The evolution of the crystal structure orientation of WS2 films on sapphire as a function of growth temperature was also examined. Finally, the epitaxial relation of a WS2/WSe2 vertical heterostructure deposited on sapphire substrate was determined. We observed that WSe2 grows epitaxially on both substrates employed in this work under all conditions studied while WS2 exhibits various preferred orientations on sapphire substrate which are temperature dependent. In contrast to the sapphire substrate, WS2 deposited on WSe2 exhibits only one preferred orientation which may provide a route to better control the orientation and crystal quality of WS2. In the case of epitaxial graphene on SiC, no graphene-related peaks were observed in in-plane XRD while its presence was confirmed using Raman spectroscopy. This demonstrates the limitation of the in-plane XRD technique for characterizing low

Using Dopants to Tune Oxygen Vacancy Formation in Transition Metal Oxide Resistive Memory.

PubMed

Jiang, Hao; Stewart, Derek A

2017-05-17

Introducing dopants is an important way to tailor and improve electronic properties of transition metal oxides used as high-k dielectric thin films and resistance switching layers in leading memory technologies, such as dynamic and resistive random access memory (ReRAM). Ta 2 O 5 has recently received increasing interest because Ta 2 O 5 -based ReRAM demonstrates high switching speed, long endurance, and low operating voltage. However, advances in optimizing device characteristics with dopants have been hindered by limited and contradictory experiments in this field. We report on a systematic study on how various metal dopants affect oxygen vacancy formation in crystalline and amorphous Ta 2 O 5 from first principles. We find that isoelectronic dopants and weak n-type dopants have little impact on neutral vacancy formation energy and that p-type dopants can lower the formation energy significantly by introducing holes into the system. In contrast, n-type dopants have a deleterious effect and actually increase the formation energy for charged oxygen vacancies. Given the similar doping trend reported for other binary transition metal oxides, this doping trend should be universally valid for typical binary transition metal oxides. Based on this guideline, we propose that p-type dopants (Al, Hf, Zr, and Ti) can lower the forming/set voltage and improve retention properties of Ta 2 O 5 ReRAM.

Evaluation of transition metal oxide as carrier-selective contacts for silicon heterojunction solar cells

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

Ding, L.; Boccard, Matthieu; Holman, Zachary

2015-04-06

"Reducing light absorption in the non-active solar cell layers, while enabling the extraction of the photogenerated minority carriers at quasi-Fermi levels are two key factors to improve current generation and voltage, and therefore efficiency of silicon heterojunction solar devices. To address these two critical aspects, transition metal oxide materials have been proposed as alternative to the n- and p-type amorphous silicon used as electron and hole selective contacts, respectively. Indeed, transition metal oxides such as molybdenum oxide, titanium oxide, nickel oxide or tungsten oxide combine a wide band gap typically over 3 eV with a band structure and theoretical bandmore » alignment with silicon that results in high transparency to the solar spectrum and in selectivity for the transport of only one carrier type. Improving carrier extraction or injection using transition metal oxide has been a topic of investigation in the field of organic solar cells and organic LEDs; from these pioneering works a lot of knowledge has been gained on materials properties, ways to control these during synthesis and deposition, and their impact on device performance. Recently, the transfer of some of this knowledge to silicon solar cells and the successful application of some metal oxide to contact heterojunction devices have gained much attention. In this contribution, we investigate the suitability of various transition metal oxide films (molybdenum oxide, titanium oxide, and tungsten oxide) deposited either by thermal evaporation or sputtering as transparent hole or electron selective transport layer for silicon solar cells. In addition to systematically characterize their optical and structural properties, we use photoemission spectroscopy to relate compound stoichiometry to band structure and characterize band alignment to silicon. The direct silicon/metal oxide interface is further analyzed by quasi-steady state photoconductance decay method to assess the quality of

Transition Metal Switchable Mirror

ScienceCinema

None

2017-12-29

The switchable-mirrors technology was developed by Tom Richardson and Jonathan Slack of Berkeley Lab's Environmental Energy Technologies Division. By using transition metals rather than the rare earth metals used in the first metal-hydride switchable mirrors, Richardson and Slack were able to lower the cost and simplify the manufacturing process. Energy performance is improved as well, because the new windows can reflect or transmit both visible and infrared light. Besides windows for offices and homes, possible applications include automobile sunroofs, signs and displays, aircraft windows, and spacecraft. More information at: http://windows.lbl.gov/materials/chromogenics/default.htm

Transition Metal Switchable Mirror

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

None

2009-08-21

The switchable-mirrors technology was developed by Tom Richardson and Jonathan Slack of Berkeley Lab's Environmental Energy Technologies Division. By using transition metals rather than the rare earth metals used in the first metal-hydride switchable mirrors, Richardson and Slack were able to lower the cost and simplify the manufacturing process. Energy performance is improved as well, because the new windows can reflect or transmit both visible and infrared light. Besides windows for offices and homes, possible applications include automobile sunroofs, signs and displays, aircraft windows, and spacecraft. More information at: http://windows.lbl.gov/materials/chromogenics/default.htm

Laser modification of macroscopic properties of metal surface layer

NASA Astrophysics Data System (ADS)

Kostrubiec, Franciszek

1995-03-01

Surface laser treatment of metals comprises a number of diversified technological operations out of which the following can be considered the most common: oxidation and rendering surfaces amorphous, surface hardening of steel, modification of selected physical properties of metal surface layers. In the paper basic results of laser treatment of a group of metals used as base materials for electric contacts have been presented. The aim of the study was to test the usability of laser treatment from the viewpoint of requirements imposed on materials for electric contacts. The results presented in the paper refer to two different surface treatment technologies: (1) modification of infusible metal surface layer: tungsten and molybdenum through laser fusing of their surface layer and its crystallization, and (2) modification of surface layer properties of other metals through laser doping of their surface layer with foreign elements. In the paper a number of results of experimental investigations obtained by the team under the author's supervision are presented.

Establishing Dual Electrogenerated Chemiluminescence and Multi-Color Electrochromism in Functional Ionic Transition Metal Complexes

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

Puodziukynaite, Egle; Oberst, Justin L.; Dyer, Aubrey L.

A combination of electrochromism and electroluminescence in functional materials could lead to single-layer dual electrochromic/electroluminescent (EC/EL) display devices, capable of simultaneous operation in emissive and reflective modes. Whereas such next generation displays could provide optimal visibility in any ambient lighting situation, materials available that exhibit such characteristics in the active layer are limited due to the required intrinsic multifunctionality (i.e., redox activity, electroluminescence, electrochromism, and ion conductivity) and to date can only be achieved via the rational design of ionic transition-metal complexes. Reported herein is the synthesis and characterization of a new family of acrylate-containing ruthenium (tris)bipyridine-based coordination complexes withmore » multifunctional characteristics. Potential use of the presented compounds in EC/EL devices is established, as they are applied as cross-linked electrochromic films and electrochemiluminescent layers in light-emitting electrochemical cell devices. Electrochromic switching of the polymeric networks between yellow, orange, green, brown and transmissive states is demonstrated, and electrochemiluminescent devices based on the complexes synthesized show red-orange to deep red emission with λ{sub max} ranging from 680 to 722 nm and luminance up to 135 cd/m{sup 2}. Additionally, a dual EC/EL device prototype is presented where light emission and multicolor electrochromism occur from the same pixel comprised of a single active layer, demonstrating a true combination of these properties in ionic transition-metal complexes.« less

Tuning interfacial exchange interactions via electronic reconstruction in transition-metal oxide heterostructures

DOE PAGES

Li, Binzhi; Chopdekar, Rajesh V.; N'Diaye, Alpha T.; ...

2016-10-10

The impact of interfacial electronic reconstruction on the magnetic characteristics of La0.7Sr0.3CoO3 (LSCO)/La0.7Sr0.3MnO3 (LSMO) superlattices was investigated as a function of layer thickness using a combination of soft x-ray magnetic spectroscopy and bulk magnetometry. We found that the magnetic properties of the LSCO layers are impacted by two competing electronic interactions occurring at the LSCO/substrate and LSMO/LSCO interfaces. For thin LSCO layers (< 5 nm), the heterostructures exist in a highly coupled state where the chemically distinct layers behave as a single magnetic compound with magnetically active Co2+ ions. As the LSCO thickness increases, a high coercivity LSCO layer developsmore » which biases a low coercivity layer, which is composed not only of the LSMO layer, but also an interfacial LSCO layer. These results suggest a new route to tune the magnetic properties of transition metal oxide heterostructures through careful control of the interface structure.« less

Critical Transitions in Thin Layer Turbulence

NASA Astrophysics Data System (ADS)

Benavides, Santiago; Alexakis, Alexandros

2017-11-01

We investigate a model of thin layer turbulence that follows the evolution of the two-dimensional motions u2 D (x , y) along the horizontal directions (x , y) coupled to a single Fourier mode along the vertical direction (z) of the form uq (x , y , z) = [vx (x , y) sin (qz) ,vy (x , y) sin (qz) ,vz (x , y) cos (qz) ] , reducing thus the system to two coupled, two-dimensional equations. Its reduced dimensionality allows a thorough investigation of the transition from a forward to an inverse cascade of energy as the thickness of the layer H = π / q is varied.Starting from a thick layer and reducing its thickness it is shown that two critical heights are met (i) one for which the forward unidirectional cascade (similar to three-dimensional turbulence) transitions to a bidirectional cascade transferring energy to both small and large scales and (ii) one for which the bidirectional cascade transitions to a unidirectional inverse cascade when the layer becomes very thin (similar to two-dimensional turbulence). The two critical heights are shown to have different properties close to criticality that we are able to analyze with numerical simulations for a wide range of Reynolds numbers and aspect ratios. This work was Granted access to the HPC resources of MesoPSL financed by the Region Ile de France and the project Equip@Meso (reference ANR-10-EQPX-29-01).

A Transition to Metallic Hydrogen: Evidence of the Plasma Phase Transition

NASA Astrophysics Data System (ADS)

Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

The insulator-metal transition in hydrogen is one of the most outstanding problems in condensed matter physics. The high-pressure metallic phase is now predicted to be liquid atomic from T =0 K to very high temperatures. We have conducted measurements of optical properties of hot dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K in a diamond anvil cell using pulsed laser heating of the sample. We present evidence in two forms: a plateau in the heating curves (average laser power vs temperature) characteristic of a first-order phase transition with latent heat, and changes in transmittance and reflectance characteristic of a metal for temperatures above the plateau temperature. For thick films the reflectance saturates at ~0.5. The phase line of this transition has a negative slope in agreement with theories of the so-called plasma phase transition. The NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H supported this research.

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.

Bypass transition and spot nucleation in boundary layers

NASA Astrophysics Data System (ADS)

Kreilos, Tobias; Khapko, Taras; Schlatter, Philipp; Duguet, Yohann; Henningson, Dan S.; Eckhardt, Bruno

2016-08-01

The spatiotemporal aspects of the transition to turbulence are considered in the case of a boundary-layer flow developing above a flat plate exposed to free-stream turbulence. Combining results on the receptivity to free-stream turbulence with the nonlinear concept of a transition threshold, a physically motivated model suggests a spatial distribution of spot nucleation events. To describe the evolution of turbulent spots a probabilistic cellular automaton is introduced, with all parameters directly obtained from numerical simulations of the boundary layer. The nucleation rates are then combined with the cellular automaton model, yielding excellent quantitative agreement with the statistical characteristics for different free-stream turbulence levels. We thus show how the recent theoretical progress on transitional wall-bounded flows can be extended to the much wider class of spatially developing boundary-layer flows.

Polarization and resistive switching behavior of ferroelectric tunnel junctions with transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Li, Tao; Lipatov, Alexey; Sharma, Pankaj; Lee, Hyungwoo; Eom, Chang-Beom; Sinitskii, Alexander; Gruverman, Alexei; Alexei Gruverman Team; Alexander Sinitskii Team; Chang-Beom Eom Team

Transition metal dichalcogenides (TMDs) are emerging 2-dimensional (2D) materials of the MX2 type, where M is a transition metal atom (Mo, W, Ti, Sn, Zr, etc.) and X is a chalcogen atom (S, Se, or Te.). Comparing to graphene, TMDs have a sizable band gap and can be metal, half-metal, semiconductor or superconductor. Their band structures can be tuned by external bias voltage, mechanical force, or light illumination. Their rich physical properties make TMDs potential candidates for a variety of applications in nanoelectronics and optoelectronics. Ferroelectric tunnel junctions (FTJs) are actively studied as a next-generation of non-volatile memory elements. An FTJ comprises a ferroelectric tunnel barrier sandwiched between two electrodes. In this work, we investigate the resistive switching behavior of MoS2/BaTiO3-based FTJs. The ON/OFF ratio can be modulated via electric or mechanical control of the switched polarization fraction opening a possibility of tunable electroresistance effect. Effect of optical illumination on the polarization reversal dynamics has been observed and analyzed based on the polarization-induced modulation of the MoS2 layered electronic properties.

Comparison of Methods for Determining Boundary Layer Edge Conditions for Transition Correlations

NASA Technical Reports Server (NTRS)

Liechty, Derek S.; Berry, Scott A.; Hollis, Brian R.; Horvath, Thomas J.

2003-01-01

Data previously obtained for the X-33 in the NASA Langley Research Center 20-Inch Mach 6 Air Tunnel have been reanalyzed to compare methods for determining boundary layer edge conditions for use in transition correlations. The experimental results were previously obtained utilizing the phosphor thermography technique to monitor the status of the boundary layer downstream of discrete roughness elements via global heat transfer images of the X-33 windward surface. A boundary layer transition correlation was previously developed for this data set using boundary layer edge conditions calculated using an inviscid/integral boundary layer approach. An algorithm was written in the present study to extract boundary layer edge quantities from higher fidelity viscous computational fluid dynamic solutions to develop transition correlations that account for viscous effects on vehicles of arbitrary complexity. The boundary layer transition correlation developed for the X-33 from the viscous solutions are compared to the previous boundary layer transition correlations. It is shown that the boundary layer edge conditions calculated using an inviscid/integral boundary layer approach are significantly different than those extracted from viscous computational fluid dynamic solutions. The present results demonstrate the differences obtained in correlating transition data using different computational methods.

Modeling of the heat transfer in bypass transitional boundary-layer flows

NASA Technical Reports Server (NTRS)

Simon, Frederick F.; Stephens, Craig A.

1991-01-01

A low Reynolds number k-epsilon turbulence model and conditioned momentum, energy and turbulence equations were used to predict bypass transition heat transfer on a flat plate in a high-disturbance environment with zero pressure gradient. The use of conditioned equations was demonstrated to be an improvement over the use of the global-time-averaged equations for the calculation of velocity profiles and turbulence intensity profiles in the transition region of a boundary layer. The approach of conditioned equations is extended to include heat transfer and a modeling of transition events is used to predict transition onset and the extent of transition on a flat plate. The events, which describe the boundary layer at the leading edge, result in boundary-layer regions consisting of: (1) the laminar, (2) pseudolaminar, (3) transitional, and (4) turbulent boundary layers. The modeled transition events were incorporated into the TEXSTAN 2-D boundary-layer code which is used to numerically predict the heat transfer. The numerical predictions in general compared well with the experimental data and revealed areas where additional experimental information is needed.

Boundary layer turbulence in transitional and developed states

NASA Astrophysics Data System (ADS)

Park, George Ilhwan; Wallace, James M.; Wu, Xiaohua; Moin, Parviz

2012-03-01

Using the recent direct numerical simulations by Wu and Moin ["Transitional and turbulent boundary layer with heat transfer," Phys. Fluids 22, 85 (2010)] of a flat-plate boundary layer with a passively heated wall, statistical properties of the turbulence in transition at Reθ ≈ 300, from individual turbulent spots, and at Reθ ≈ 500, where the spots merge (distributions of the mean velocity, Reynolds stresses, kinetic energy production, and dissipation rates, enstrophy and its components) have been compared to these statistical properties for the developed boundary layer turbulence at Reθ = 1840. When the distributions in the transitional regions are conditionally averaged so as to exclude locations and times when the flow is not turbulent, they closely resemble the distributions in the developed turbulent state at the higher Reynolds number, especially in the buffer layer. Skin friction coefficients, determined in this conditional manner at the two Reynolds numbers in the transitional flow are, of course, much larger than when their values are obtained by including both turbulent and non-turbulent information there, and the conditional averaged values are consistent with the 1/7th power law approximation. An octant analysis based on the combinations of signs of the velocity and temperature fluctuations, u, v, and θ shows that the momentum and heat fluxes are predominantly of the mean gradient type in both the transitional and developed regions. The fluxes appear to be closely associated with vortices that transport momentum and heat toward and away from the wall in both regions of the flow. The results suggest that there may be little fundamental difference between the nonlinear processes involved in the formation of turbulent spots that appear in transition and those that sustain the turbulence when it is developed. They also support the view that the transport processes and the vortical structures that drive them in developed and transitional boundary

Transition metals in superheat melts

NASA Technical Reports Server (NTRS)

Jakes, Petr; Wolfbauer, Michael-Patrick

1993-01-01

A series of experiments with silicate melts doped with transition element oxides was carried out at atmospheric pressures of inert gas at temperatures exceeding liquidus. As predicted from the shape of fO2 buffer curves in T-fO2 diagrams the reducing conditions for a particular oxide-metal pair can be achieved through the T increase if the released oxygen is continuously removed. Experimental studies suggest that transition metals such as Cr or V behave as siderophile elements at temperatures exceeding liquidus temperatures if the system is not buffered by the presence of other oxide of more siderophile element. For example the presence of FeO prevents the reduction of Cr2O3. The sequence of decreasing siderophility of transition elements at superheat conditions (Mo, Ni, Fe, Cr) matches the decreasing degree of depletion of siderophile elements in mantle rocks as compared to chondrites.

Polysulfide intercalated layered double hydroxides for metal capture applications

DOEpatents

Kanatzidis, Mercouri G.; Ma, Shulan

2017-04-04

Polysulfide intercalated layered double hydroxides and methods for their use in vapor and liquid-phase metal capture applications are provided. The layered double hydroxides comprise a plurality of positively charged host layers of mixed metal hydroxides separated by interlayer spaces. Polysulfide anions are intercalated in the interlayer spaces.

Measurements in a Transitional Boundary Layer Under Low-Pressure Turbine Airfoil Conditions

NASA Technical Reports Server (NTRS)

Simon, Terrence W.; Qiu, Songgang; Yuan, Kebiao; Ashpis, David (Technical Monitor); Simon, Fred (Technical Monitor)

2000-01-01

This report presents the results of an experimental study of transition from laminar to turbulent flow in boundary layers or in shear layers over separation zones on a convex-curved surface which simulates the suction surface of a low-pressure turbine airfoil. Flows with various free-stream turbulence intensity (FSTI) values (0.5%, 2.5% and 10%), and various Reynolds numbers (50,000, 100,000 200,000 and 300,000) are investigated. Reynold numbers in the present study are based on suction surface length and passage exit mean velocity. Flow separation followed by transition within the separated flow region is observed for the lower-Re cases at each of the FSTI levels. At the highest Reynolds numbers and at elevated FSn, transition of the attached boundary layer begins before separation, and the separation zone is small. Transition proceeds in the shear layer over the separation bubble. For both the transitional boundary layer and the transitional shear layer, mean velocity, turbulence intensity and intermittency (the fraction of the time the flow is turbulent) distributions are presented. The present data are compared to published distribution models for bypass transition, intermittency distribution through transition, transition start position, and transition length. A model developed for transition of separated flows is shown to adequately predict the location of the beginning of transition, for these cases, and a model developed for transitional boundary layer flows seems to adequately predict the path of intermittency through transition when the transition start and end are known. These results are useful for the design of low-pressure turbine stages which are known to operate under conditions replicated by these tests.

Review of Orbiter Flight Boundary Layer Transition Data

NASA Technical Reports Server (NTRS)

Mcginley, Catherine B.; Berry, Scott A.; Kinder, Gerald R.; Barnell, maria; Wang, Kuo C.; Kirk, Benjamin S.

2006-01-01

In support of the Shuttle Return to Flight program, a tool was developed to predict when boundary layer transition would occur on the lower surface of the orbiter during reentry due to the presence of protuberances and cavities in the thermal protection system. This predictive tool was developed based on extensive wind tunnel tests conducted after the loss of the Space Shuttle Columbia. Recognizing that wind tunnels cannot simulate the exact conditions an orbiter encounters as it re-enters the atmosphere, a preliminary attempt was made to use the documented flight related damage and the orbiter transition times, as deduced from flight instrumentation, to calibrate the predictive tool. After flight STS-114, the Boundary Layer Transition Team decided that a more in-depth analysis of the historical flight data was needed to better determine the root causes of the occasional early transition times of some of the past shuttle flights. In this paper we discuss our methodology for the analysis, the various sources of shuttle damage information, the analysis of the flight thermocouple data, and how the results compare to the Boundary Layer Transition prediction tool designed for Return to Flight.

Phase stability of transition metals and alloys

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

Hixson, R.S.; Schiferl, D.; Wills, J.M.

1997-06-01

This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This project was focused on resolving unexplained differences in calculated and measured phase transition pressures in transition metals. Part of the approach was to do new, higher accuracy calculations of transmission pressures for group 4B and group 6B metals. Theory indicates that the transition pressures for these baseline metals should change if alloyed with a d-electron donor metal, and calculations done using the Local Density Approximation (LDA) and the Virtual Crystal Approximation (VCA) indicate that this is true. Alloymore » systems were calculated for Ti, Zr and Hf based alloys with various solute concentrations. The second part of the program was to do new Diamond Anvil Cell (DAC) measurements to experimentally verify calculational results. Alloys were prepared for these systems with grain size suitable for Diamond Anvil Cell experiments. Experiments were done on pure Ti as well as Ti-V and Ti-Ta alloys. Measuring unambiguous transition pressures for these systems proved difficult, but a new technique developed yielded good results.« less

One-pot synthesis of CdS nanocrystals hybridized with single-layer transition-metal dichalcogenide nanosheets for efficient photocatalytic hydrogen evolution.

PubMed

Chen, Junze; Wu, Xue-Jun; Yin, Lisha; Li, Bing; Hong, Xun; Fan, Zhanxi; Chen, Bo; Xue, Can; Zhang, Hua

2015-01-19

Exploration of low-cost and earth-abundant photocatalysts for highly efficient solar photocatalytic water splitting is of great importance. Although transition-metal dichalcogenides (TMDs) showed outstanding performance as co-catalysts for the hydrogen evolution reaction (HER), designing TMD-hybridized photocatalysts with abundant active sites for the HER still remains challenge. Here, a facile one-pot wet-chemical method is developed to prepare MS2-CdS (M=W or Mo) nanohybrids. Surprisedly, in the obtained nanohybrids, single-layer MS2 nanosheets with lateral size of 4-10 nm selectively grow on the Cd-rich (0001) surface of wurtzite CdS nanocrystals. These MS2-CdS nanohybrids possess a large number of edge sites in the MS2 layers, which are active sites for the HER. The photocatalytic performances of WS2-CdS and MoS2-CdS nanohybrids towards the HER under visible light irradiation (>420 nm) are about 16 and 12 times that of pure CdS, respectively. Importantly, the MS2-CdS nanohybrids showed enhanced stability after a long-time test (16 h), and 70% of catalytic activity still remained. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electroforming and Switching in Oxides of Transition Metals: The Role of Metal Insulator Transition in the Switching Mechanism

NASA Astrophysics Data System (ADS)

Chudnovskii, F. A.; Odynets, L. L.; Pergament, A. L.; Stefanovich, G. B.

1996-02-01

Electroforming and switching effects in sandwich structures based on anodic films of transition metal oxides (V, Nb, Ti, Fe, Ta, W, Zr, Hf, Mo) have been studied. After being electroformed, some materials exhibited current-controlled negative resistance with S-shapedV-Icharacteristics. For V, Fe, Ti, and Nb oxides, the temperature dependences of the threshold voltage have been measured. As the temperature increased,Vthdecreased to zero at a critical temperatureT0, which depended on the film material. Comparison of theT0values with the temperatures of metal-insulator phase transition for some compounds (Tt= 120 K for Fe3O4, 340 K for VO2, ∼500 K for Ti2O3, and 1070 K for NbO2) showed that switching was related to the transition in the applied electric field. Channels consisting of the above-mentioned lower oxides were formed in the initial anodic films during the electroforming. The possibility of formation of these oxides with a metal-insulator transition was confirmed by thermodynamic calculations.

Semiconducting transition metal oxides.

PubMed

Lany, Stephan

2015-07-22

Open shell transition metal oxides are usually described as Mott or charge transfer insulators, which are often viewed as being disparate from semiconductors. Based on the premise that the presence of a correlated gap and semiconductivity are not mutually exclusive, this work reviews electronic structure calculations on the binary 3d oxides, so to distill trends and design principles for semiconducting transition metal oxides. This class of materials possesses the potential for discovery, design, and development of novel functional semiconducting compounds, e.g. for energy applications. In order to place the 3d orbitals and the sp bands into an integrated picture, band structure calculations should treat both contributions on the same footing and, at the same time, account fully for electron correlation in the 3d shell. Fundamentally, this is a rather daunting task for electronic structure calculations, but quasi-particle energy calculations in GW approximation offer a viable approach for band structure predictions in these materials. Compared to conventional semiconductors, the inherent multivalent nature of transition metal cations is more likely to cause undesirable localization of electron or hole carriers. Therefore, a quantitative prediction of the carrier self-trapping energy is essential for the assessing the semiconducting properties and to determine whether the transport mechanism is a band-like large-polaron conduction or a small-polaron hopping conduction. An overview is given for the binary 3d oxides on how the hybridization between the 3d crystal field symmetries with the O-p orbitals of the ligands affects the effective masses and the likelihood of electron and hole self-trapping, identifying those situations where small masses and band-like conduction are more likely to be expected. The review concludes with an illustration of the implications of the increased electronic complexity of transition metal cations on the defect physics and doping, using

Wavelength-switchable passively mode-locked fiber laser with mechanically exfoliated molybdenum ditelluride on side-polished fiber

NASA Astrophysics Data System (ADS)

Wang, Guomei

2017-11-01

We experimentally investigated the nonlinear saturable absorption characteristics of molybdenum ditelluride (MoTe2) and demonstrated a wavelength-switchable mode-locked erbium-doped fiber laser (EDFL) by using MoTe2 thin film on side-polished fiber (SPF) as saturable absorber. Here, the MoTe2 thin film was efficiently fabricated via mechanical exfoliation method and transferred onto the SPF with the assistance of polydimethylsiloxane (PDMS). MoTe2-covered SPF (MSPF) exhibits the nonlinear saturable absorption for pulses with different polarization states. Optical solitons with spectral bandwidth of 1.06 (1.31) nm centered at ∼1559 (∼1528) nm and pulse duration of 2.46 (2.04) ps can be obtained from the EDFL by adjusting the polarization controller (PC) properly. The time-bandwidth product (TBP) of the pulses was calculated as 0.322 (0.344).

Mott-metal transition in layered perovskite iridate thin films via field-effect doping

NASA Astrophysics Data System (ADS)

Cheema, Suraj; Turcaud, Jeremy; Nelson, Chris; Salahuddin, Sayeef; Ramesh, Ramamoorthy

We report on electrostatic gating of spin-orbit coupled Mott insulator Sr2IrO4 (Sr214) via ferroelectric field effect doping. Field effect doping has been used to modulate electronic phenomena in emerging 2D systems and strongly correlated oxides, but 5 d systems with large spin-orbit coupling have yet to be explored. Upon switching the polarization field of ferroelectric Pb(Zr20Ti80)O3 (PZT) to the down-poled (electron-accumulation) state, temperature-dependent resistivity measurements indicate extremely metallic behavior in the ultrathin Sr214 channel. This work successfully closes the Mott gap in Sr214 in a ''clean'' doping environment free of chemical disorder, thereby strengthening the link to the isostrucutral high-Tc cuprates, as Sr214 has been predicted to host d-wave superconductivity upon electron doping the parent antiferromagnetic insulating phase. Furthermore, the metallic behavior in Sr214 persists for thickness beyond the expected screening length, suggestive of a collective carrier delocalization mechanism. Electrostatically doped carriers prove to be a useful method for tuning the competition between spin-orbit and Coulomb interactions in order to trigger novel phase transitions, such as the Mott-metal crossover. This work was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy, under Contract No. DE-AC02-05CH11231.

Noble-transition metal nanoparticle breathing in a reactive gas atmosphere.

PubMed

Petkov, Valeri; Shan, Shiyao; Chupas, Peter; Yin, Jun; Yang, Lefu; Luo, Jin; Zhong, Chuan-Jian

2013-08-21

In situ high-energy X-ray diffraction coupled to atomic pair distribution function analysis is used to obtain fundamental insight into the effect of the reactive gas environment on the atomic-scale structure of metallic particles less than 10 nm in size. To substantiate our recent discovery we investigate a wide range of noble-transition metal nanoparticles and confirm that they expand and contract radially when treated in oxidizing (O2) and reducing (H2) atmospheres, respectively. The results are confirmed by supplementary XAFS experiments. Using computer simulations guided by the experimental diffraction data we quantify the effect in terms of both relative lattice strain and absolute atomic displacements. In particular, we show that the effect leads to a small percent of extra surface strain corresponding to several tenths of Ångström displacements of the atoms at the outmost layer of the particles. The effect then gradually decays to zero within 4 atomic layers inside the particles. We also show that, reminiscent of a breathing type structural transformation, the effect is reproducible and reversible. We argue that because of its significance and widespread occurrence the effect should be taken into account in nanoparticle research.

Electronic Structure and Band Gap of Fullerenes on Tungsten Surfaces: Transition from a Semiconductor to a Metal Triggered by Annealing.

PubMed

Monazami, Ehsan; McClimon, John B; Rondinelli, James; Reinke, Petra

2016-12-21

The understanding and control of molecule-metal interfaces is critical to the performance of molecular electronics and photovoltaics devices. We present a study of the interface between C 60 and W, which is a carbide-forming transition metal. The complex solid-state reaction at the interface can be exploited to adjust the electronic properties of the molecule layer. Scanning tunneling microscopy/spectroscopy measurements demonstrate the progression of this reaction from wide band gap (>2.5 eV) to metallic molecular surface during annealing from 300 to 800 K. Differential conduction maps with 10 4 scanning tunneling spectra are used to quantify the transition in the density of states and the reduction of the band gap during annealing with nanometer spatial resolution. The electronic transition is spatially homogeneous, and the surface band gap can therefore be adjusted by a targeted annealing step. The modified molecules, which we call nanospheres, are quite resistant to ripening and coalescence, unlike any other metallic nanoparticle of the same size. Densely packed C 60 and isolated C 60 molecules show the same transition in electronic structure, which confirms that the transformation is controlled by the reaction at the C 60 -W interface. Density functional theory calculations are used to develop possible reaction pathways in agreement with experimentally observed electronic structure modulation. Control of the band gap by the choice of annealing temperature is a unique route to tailoring molecular-layer electronic properties.

Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts

DOE PAGES

Hunt, Sean T.; Milina, Maria; Alba-Rubio, Ana C.; ...

2016-05-20

Here, we demonstrated the self-assembly of transition metal carbide nanoparticles coated with atomically thin noble metal monolayers by carburizing mixtures of noble metal salts and transition metal oxides encapsulated in removable silica templates. This approach allows for control of the final core-shell architecture, including particle size, monolayer coverage, and heterometallic composition. Carbon-supported Ti 0.1W 0.9C nanoparticles coated with Pt or bimetallic PtRu monolayers exhibited enhanced resistance to sintering and CO poisoning, achieving an order of magnitude increase in specific activity over commercial catalysts for methanol electrooxidation after 10,000 cycles. These core-shell materials provide a new direction to reduce the loading,more » enhance the activity, and increase the stability of noble metal catalysts.« less

Transition-Metal Decorated Aluminum Nanocrystals.

PubMed

Swearer, Dayne F; Leary, Rowan K; Newell, Ryan; Yazdi, Sadegh; Robatjazi, Hossein; Zhang, Yue; Renard, David; Nordlander, Peter; Midgley, Paul A; Halas, Naomi J; Ringe, Emilie

2017-10-24

Recently, aluminum has been established as an earth-abundant alternative to gold and silver for plasmonic applications. Particularly, aluminum nanocrystals have shown to be promising plasmonic photocatalysts, especially when coupled with catalytic metals or oxides into "antenna-reactor" heterostructures. Here, a simple polyol synthesis is presented as a flexible route to produce aluminum nanocrystals decorated with eight varieties of size-tunable transition-metal nanoparticle islands, many of which have precedence as heterogeneous catalysts. High-resolution and three-dimensional structural analysis using scanning transmission electron microscopy and electron tomography shows that abundant nanoparticle island decoration in the catalytically relevant few-nanometer size range can be achieved, with many islands spaced closely to their neighbors. When coupled with the Al nanocrystal plasmonic antenna, these small decorating islands will experience increased light absorption and strong hot-spot generation. This combination makes transition-metal decorated aluminum nanocrystals a promising material platform to develop plasmonic photocatalysis, surface-enhanced spectroscopies, and quantum plasmonics.

Pressure induced structural phase transition in IB transition metal nitrides compounds

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

Soni, Shubhangi; Kaurav, Netram, E-mail: netramkaurav@yahoo.co.uk; Jain, A.

2015-06-24

Transition metal mononitrides are known as refractory compounds, and they have, relatively, high hardness, brittleness, melting point, and superconducting transition temperature, and they also have interesting optical, electronic, catalytic, and magnetic properties. Evolution of structural properties would be an important step towards realizing the potential technological scenario of this material of class. In the present study, an effective interionic interaction potential (EIOP) is developed to investigate the pressure induced phase transitions in IB transition metal nitrides TMN [TM = Cu, Ag, and Au] compounds. The long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbormore » ions within the Hafemeister and Flygare approach with modified ionic charge are properly incorporated in the EIOP. The vdW coefficients are computed following the Slater-Kirkwood variational method, as both the ions are polarizable. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the reported data.« less

Electron scattering characteristics of polycrystalline metal transition films by in-situ electrical resistance measurements

NASA Astrophysics Data System (ADS)

Trindade, I. G.; Leitão, D.; Fermento, R.; Pogorelev, Y.; Sousa, J. B.

2009-08-01

In-situ electrical resistance measurements were performed to obtain the scattering characteristics of very thin polycrystalline metal transition magnetic alloys grown by ion beam deposition (IBD) on specific underlayers. The experimental curves show size effects at small film thicknesses and important differences between Co 85Fe 15 and Ni 81Fe 19 thin layers grown on identical underlayers of Ta70 Å/Ru13 Å. The largest difference was observed in Ni 81Fe 19 films grown on underlayers of amorphous Ta70 Å. The experimental curves of electrical resistivity/conductivity variation with layer thickness were well fit within the Mayadas and Shatzkes (M-S) model, assuming specific formulations for grain growth with layer thickness.

Bioassembled layered silicate-metal nanoparticle hybrids.

PubMed

Drummy, Lawrence F; Jones, Sharon E; Pandey, Ras B; Farmer, B L; Vaia, Richard A; Naik, Rajesh R

2010-05-01

Here we report on the bioenabled assembly of layered nanohybrids using peptides identified with regard to their affinity to the nanoparticle surface. A dodecamer peptide termed M1, determined from a phage peptide display library, was found to bind to the surface of a layered aluminosilicate (montmorillonite, MMT). Fusion of a metal binding domain to the M1 peptide or the M1 peptide by itself was able to direct the growth of metal nanoparticles, such as gold and cobalt-platinum, respectively, on the MMT. This method of producing hybrid nanoclay materials will have utility in catalytic, optical, biomedical, and composite materials applications.

Diagnostics of boundary layer transition by shear stress sensitive liquid crystals

NASA Astrophysics Data System (ADS)

Shapoval, E. S.

2016-10-01

Previous research indicates that the problem of boundary layer transition visualization on metal models in wind tunnels (WT) which is a fundamental question in experimental aerodynamics is not solved yet. In TsAGI together with Khristianovich Institute of Theoretical and Applied Mechanics (ITAM) a method of shear stress sensitive liquid crystals (LC) which allows flow visualization was proposed. This method allows testing several flow conditions in one wind tunnel run and does not need covering the investigated model with any special heat-insulating coating which spoils the model geometry. This coating is easily applied on the model surface by spray or even by brush. Its' thickness is about 40 micrometers and it does not spoil the surface quality. At first the coating obtains some definite color. Under shear stress the LC coating changes color and this change is proportional to shear stress. The whole process can be visually observed and during the tests it is recorded by camera. The findings of the research showed that it is possible to visualize boundary layer transition, flow separation, shock waves and the flow image on the whole. It is possible to predict that the proposed method of shear stress sensitive liquid crystals is a promise for future research.

Mechanics of Boundary Layer Transition. Part 5: Boundary Layer Stability theory in incompressible and compressible flow

NASA Technical Reports Server (NTRS)

Mack, L. M.

1967-01-01

The fundamentals of stability theory, its chief results, and the physical mechanisms at work are presented. The stability theory of the laminar boundary determines whether a small disturbance introduced into the boundary layer will amplify or damp. If the disturbance damps, the boundary layer remains laminar. If the disturbance amplifies, and by a sufficient amount, then transition to turbulence eventually takes place. The stability theory establishes those states of the boundary layer which are most likely to lead to transition, identifys those frequencies which are the most dangerous, and indicates how the external parameters can best be changed to avoid transition.

Saturn's magnetosheath transition layer

NASA Astrophysics Data System (ADS)

Masters, A.; Hasegawa, H.; Phan, T. D.; Badman, S. V.; Fujimoto, M.; Coates, A. J.; Dougherty, M. K.

2012-09-01

The interaction between the solar wind and a magnetised planet produces a cavity around the planet known as a magnetosphere. Although this cavity effectively shields near-planet space from the solar wind, the occurrence of magnetic reconnection at the manetopause boundary of the magnetosphere allows solar wind energy to enter the system. In the case of Earth's magnetosphere a region of reduced plasma pressure and enhanced magnetic pressure can form in the solar wind immediately adjacent to the magnetopause (which also can form around other planetary magnetospheres). This layer is often referred to as the Magnetosheath Transition Layer (MTL), and Earth's MTL responds strongly to magnetopause reconnection. The nature of magnetopause reconnection at Saturn is unclear. We study Saturn's MTL using data taken by the Cassini spacecraft. We examine the reponse of the layer to local magnetised plasma conditions, compare this response to that of Earth's MTL, and assess whether our results are in agreement with current, limited understanding of magnetopause reconnection at Saturn.

Progress in MOSFET double-layer metalization

NASA Technical Reports Server (NTRS)

Gassaway, J. D.; Trotter, J. D.; Wade, T. E.

1980-01-01

Report describes one-year research effort in VLSL fabrication. Four activities are described: theoretical study of two-dimensional diffusion in SOS (silicon-on-sapphire); setup of sputtering system, furnaces, and photolithography equipment; experiments on double layer metal; and investigation of two-dimensional modeling of MOSFET's (metal-oxide-semiconductor field-effect transistors).

Trends in Ionization Energy of Transition-Metal Elements

ERIC Educational Resources Information Center

Matsumoto, Paul S.

2005-01-01

A rationale for the difference in the periodic trends in the ionization energy of the transition-metal elements versus the main-group elements is presented. The difference is that in the transition-metal elements, the electrons enter an inner-shell electron orbital, while in the main-group elements, the electrons enter an outer-shell electron…

Electrochromic device containing metal oxide nanoparticles and ultraviolet blocking material

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

Garcia, Guillermo; Koo, Bonil; Gregoratto, Ivano

An electrochromic device includes a nanostructured transition metal oxide bronze layer that includes one or more transition metal oxide and one or more dopant. The electrochromic device also includes nanoparticles containing one or more transparent conducting oxide (TCO), a solid state electrolyte, a counter electrode, and at least one protective layer to prevent degradation of the one or more nanostructured transition metal oxide bronze. The nanostructured transition metal oxide bronze selectively modulates transmittance of near-infrared (NIR) and visible radiation as a function of an applied voltage to the device.

Harnessing the metal-insulator transition for tunable metamaterials

NASA Astrophysics Data System (ADS)

Charipar, Nicholas A.; Charipar, Kristin M.; Kim, Heungsoo; Bingham, Nicholas S.; Suess, Ryan J.; Mathews, Scott A.; Auyeung, Raymond C. Y.; Piqué, Alberto

2017-08-01

The control of light-matter interaction through the use of subwavelength structures known as metamaterials has facilitated the ability to control electromagnetic radiation in ways not previously achievable. A plethora of passive metamaterials as well as examples of active or tunable metamaterials have been realized in recent years. However, the development of tunable metamaterials is still met with challenges due to lack of materials choices. To this end, materials that exhibit a metal-insulator transition are being explored as the active element for future metamaterials because of their characteristic abrupt change in electrical conductivity across their phase transition. The fast switching times (▵t < 100 fs) and a change in resistivity of four orders or more make vanadium dioxide (VO2) an ideal candidate for active metamaterials. It is known that the properties associated with thin film metal-insulator transition materials are strongly dependent on the growth conditions. For this work, we have studied how growth conditions (such as gas partial pressure) influence the metalinsulator transition in VO2 thin films made by pulsed laser deposition. In addition, strain engineering during the growth process has been investigated as a method to tune the metal-insulator transition temperature. Examples of both the optical and electrical transient dynamics facilitating the metal-insulator transition will be presented together with specific examples of thin film metamaterial devices.

Monolayer and/or few-layer graphene on metal or metal-coated substrates

DOEpatents

Sutter, Peter Werner; Sutter, Eli Anguelova

2015-04-14

Disclosed is monolayer and/or few-layer graphene on metal or metal-coated substrates. Embodiments include graphene mirrors. In an example, a mirror includes a substrate that has a surface exhibiting a curvature operable to focus an incident beam onto a focal plane. A graphene layer conformally adheres to the substrate, and is operable to protect the substrate surface from degradation due to the incident beam and an ambient environment.

Influence of metal bonding layer on strain transfer performance of FBG

NASA Astrophysics Data System (ADS)

Liu, Hao; Chen, Weimin; Zhang, Peng; Liu, Li; Shu, Yuejie; Wu, Jun

2013-01-01

Metal bonding layer seriously affects the strain transfer performance of Fiber Bragg Grating (FBG). Based on the mode of FBG strain transfer, the influence of the length, the thickness, Poisson's ratio, elasticity modulus of metal bonding layer on the strain transfer coefficient of FBG is analyzed by numerical simulation. FBG is packaged to steel wire using metal bonding technology of FBG. The tensile tests of different bonding lengths and elasticity modulus are carried out. The result shows the strain transfer coefficient of FBGs are 0.9848,0.962 and their average strain sensitivities are 1.076 pm/μɛ,1.099 pm/μɛ when the metal bonding layer is zinc, whose lengths are 15mm, 20mm, respectively. The strain transfer coefficient of FBG packaged by metal bonding layer raises 8.9 percent compared to epoxy glue package. The preliminary experimental results show that the strain transfer coefficient increases with the length of metal bonding layer, decreases with the thickness of metal bonding layer and the influence of Poisson's ratio can be ignored. The experiment result is general agreement with the analysis and provides guidance for metal package of FBG.

Oxide film on metal substrate reduced to form metal-oxide-metal layer structure

NASA Technical Reports Server (NTRS)

Youngdahl, C. A.

1967-01-01

Electrically conductive layer of zirconium on a zirconium-oxide film residing on a zirconium substrate is formed by reducing the oxide in a sodium-calcium solution. The reduced metal remains on the oxide surface as an adherent layer and seems to form a barrier that inhibits further reaction.

Maximum-valence radii of transition metals

PubMed Central

Pauling, Linus

1975-01-01

In many of their compounds the transition metals have covalence 9, forming nine bonds with use of nine hybrid spd bond orbitals. A set of maximum-valence single-bond radii is formulated for use in these compounds. These radii are in reasonably good agreement with observed bond lengths. Quadruple bonds between two transition metal atoms are about 50 pm (iron-group atoms) or 55 pm (palladium and platinum-group atoms) shorter than single bonds. This amount of shortening corresponds to four bent single bonds with the best set of bond angles, 79.24° and 128.8°. PMID:16578730

Impurities in Antiferromagnetic Transition-Metal Oxides - Symmetry and Optical Transitions

NASA Astrophysics Data System (ADS)

Petersen, John Emil, III

The study of antiferromagnetic transition-metal oxides is an extremely active area in the physical sciences, where condensed matter physics, inorganic chemistry, and materials science blend together. The sheer number of potential commercial applications is staggering, but much of the fundamental science remains unexplained. This is not due to a lack of effort, however, as theorists have been struggling to understand these materials for decades - particularly the character of the band edges and first optical transitions. The difficulty lies in the strong correlation or Coloumb attraction between the electrons in the anisotropic d orbitals, which conventional band theory cannot describe adequately. The correlation problem is approached here by the well-accepted method of adding a Hubbard potential energy term to the ground state Hamiltonian, calculated within Density Functional Theory. The frequency-dependent complex dielectric function is calculated within the Independent Particle Approximation, and optical transitions are evaluated in multiple different ways. Peaks in the imaginary part of the dielectric function are compared energetically to orbitally decomposed density of states calculations. Optical transitions are typically analyzed in terms of atomic orbitals, which, strictly speaking, gives misleading results. Here, however, from the calculated data, two alternative interpretations are analyzed for each material studied. The first employs rigorous group theoretical analysis to determine allowed electric-dipole transitions, taking into account both orbital hybridization and crystal symmetry. The second interpretation is that of metal cation site hopping. In this interpretation, carriers hop from the x2 - y2 d orbital of one metal cation lattice site to the next metal cation site which is antiferromagnetically aligned. At times, thoughout this work, one interpretation is favorable to the other. Which interpretation is most valid depends on the material

Tunable Bragg filters with a phase transition material defect layer

DOE PAGES

Wang, Xi; Gong, Zilun; Dong, Kaichen; ...

2016-01-01

We propose an all-solid-state tunable Bragg filter with a phase transition material as the defect layer. Bragg filters based on a vanadium dioxide defect layer sandwiched between silicon dioxide/titanium dioxide Bragg gratings are experimentally demonstrated. Temperature dependent reflection spectroscopy shows the dynamic tunability and hysteresis properties of the Bragg filter. Temperature dependent Raman spectroscopy reveals the connection between the tunability and the phase transition of the vanadium dioxide defect layer. This work paves a new avenue in tunable Bragg filter designs and promises more applications by combining phase transition materials and optical cavities.

Tunable Bragg filters with a phase transition material defect layer

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

Wang, Xi; Gong, Zilun; Dong, Kaichen

We propose an all-solid-state tunable Bragg filter with a phase transition material as the defect layer. Bragg filters based on a vanadium dioxide defect layer sandwiched between silicon dioxide/titanium dioxide Bragg gratings are experimentally demonstrated. Temperature dependent reflection spectroscopy shows the dynamic tunability and hysteresis properties of the Bragg filter. Temperature dependent Raman spectroscopy reveals the connection between the tunability and the phase transition of the vanadium dioxide defect layer. This work paves a new avenue in tunable Bragg filter designs and promises more applications by combining phase transition materials and optical cavities.

Transition Metal-Oxide Free Perovskite Solar Cells Enabled by a New Organic Charge Transport Layer.

PubMed

Chang, Sehoon; Han, Ggoch Ddeul; Weis, Jonathan G; Park, Hyoungwon; Hentz, Olivia; Zhao, Zhibo; Swager, Timothy M; Gradečak, Silvija

2016-04-06

Various electron and hole transport layers have been used to develop high-efficiency perovskite solar cells. To achieve low-temperature solution processing of perovskite solar cells, organic n-type materials are employed to replace the metal oxide electron transport layer (ETL). Although PCBM (phenyl-C61-butyric acid methyl ester) has been widely used for this application, its morphological instability in films (i.e., aggregation) is detrimental. Herein, we demonstrate the synthesis of a new fullerene derivative (isobenzofulvene-C60-epoxide, IBF-Ep) that serves as an electron transporting material for methylammonium mixed lead halide-based perovskite (CH3NH3PbI(3-x)Cl(x)) solar cells, both in the normal and inverted device configurations. We demonstrate that IBF-Ep has superior morphological stability compared to the conventional acceptor, PCBM. IBF-Ep provides higher photovoltaic device performance as compared to PCBM (6.9% vs 2.5% in the normal and 9.0% vs 5.3% in the inverted device configuration). Moreover, IBF-Ep devices show superior tolerance to high humidity (90%) in air. By reaching power conversion efficiencies up to 9.0% for the inverted devices with IBF-Ep as the ETL, we demonstrate the potential of this new material as an alternative to metal oxides for perovskite solar cells processed in air.

Origin of Transitions between Metallic and Insulating States in Simple Metals

DOE PAGES

Naumov, Ivan I.; Hemley, Russell J.

2015-04-17

Unifying principles that underlie recently discovered transitions between metallic and insulating states in elemental solids under pressure are developed. Using group theory arguments and first principles calculations, we show that the electronic properties of the phases involved in these transitions are controlled by symmetry principles not previously recognized. The valence bands in these systems are described by simple and composite band representations constructed from localized Wannier functions centered on points unoccupied by atoms, and which are not necessarily all symmetrical. The character of the Wannier functions is closely related to the degree of s-p(-d) hybridization and reflects multi-center chemical bondingmore » in these insulating states. The conditions under which an insulating state is allowed for structures having an integer number of atoms per primitive unit cell as well as re-entrant (i.e., metal-insulator-metal) transition sequences are detailed, resulting in predictions of novel behavior such as phases having three-dimensional Dirac-like points. The general principles developed are tested and applied to the alkali and alkaline earth metals, including elements where high-pressure insulating phases have been identified or reported (e.g., Li, Na, and Ca).« less

Novel elastic, lattice dynamics and thermodynamic properties of metallic single-layer transition metal phosphides: 2H-M 2P (Mo2P, W2P, Nb2P and Ta2P)

NASA Astrophysics Data System (ADS)

Yin, Jiuren; Wu, Bozhao; Wang, Yanggang; Li, Zhimi; Yao, Yuanpeng; Jiang, Yong; Ding, Yanhuai; Xu, Fu; Zhang, Ping

2018-04-01

Recently, there has been a surge of interest in the research of two-dimensional (2D) phosphides due to their unique physical properties and wide applications. Transition metal phosphides 2H-M 2Ps (Mo2P, W2P, Nb2P and Ta2P) show considerable catalytic activity and energy storage potential. However, the electronic structure and mechanical properties of 2D 2H-M 2Ps are still unrevealed. Here, first-principles calculations are employed to investigate the lattice dynamics, elasticity and thermodynamic properties of 2H-M 2Ps. Results show that M 2Ps with lower stiffness exhibit remarkable lateral deformation under unidirectional loads. Due to the largest average Grüneisen parameter, single-layer Nb2P has the strongest anharmonic vibrations, resulting in the highest thermal expansion coefficient. The lattice thermal conductivities of Ta2P, W2P and Nb2P contradict classical theory, which would predict a smaller thermal conductivity due to the much heavier atom mass. Moreover, the calculations also demonstrate that the thermal conductivity of Ta2P is the highest as well as the lowest thermal expansion, owing to its weak anharmonic phonon scattering and the lowest average Grüneisen parameter. The insight provided by this study may be useful for future experimental and theoretical studies concerning 2D transition metal phosphide materials.

Thickness-dependent metal-to-insulator transition in epitaxial VO2 films

NASA Astrophysics Data System (ADS)

Zhi, Bowen; Gao, Guanyin; Tan, Xuelian; Chen, Pingfan; Wang, Lingfei; Jin, Shaowei; Wu, Wenbin

2014-12-01

The metal-to-insulator transition (MIT) of VO2 films with a thickness of 3-100 nm on TiO2(001) substrates has been investigated. When varying the film thickness from 10 to 100 nm, the MIT temperature was first kept at 290 K in the range of 10-14 nm, and then increased with thickness increasing due to the strain relaxation. The origin of the suppressed transition in VO2 films thinner than 6 nm was also investigated. When prolonging the in situ annealing time, the sharpness, amplitude and width of the transition for 4 nm thick films were all increased, suggesting improved crystallinity rather than Ti diffusion from the substrates. In addition, the MIT was suppressed when the VO2 films were covered by a TiO2 layer, indicating that the interface effect via the confinement of the dimerization of the V atoms should be the main reason.

Molecular beam epitaxy of quasi-freestanding transition metal disulphide monolayers on van der Waals substrates: a growth study

NASA Astrophysics Data System (ADS)

Hall, Joshua; Pielić, Borna; Murray, Clifford; Jolie, Wouter; Wekking, Tobias; Busse, Carsten; Kralj, Marko; Michely, Thomas

2018-04-01

Based on an ultra-high vacuum compatible two-step molecular beam epitaxy synthesis with elemental sulphur, we grow clean, well-oriented, and almost defect-free monolayer islands and layers of the transition metal disulphides MoS2, TaS2 and WS2. Using scanning tunneling microscopy and low energy electron diffraction we investigate systematically how to optimise the growth process, and provide insight into the growth and annealing mechanisms. A large band gap of 2.55 eV and the ability to move flakes with the scanning tunneling microscope tip both document the weak interaction of MoS2 with its substrate consisting of graphene grown on Ir(1 1 1). As the method works for the synthesis of a variety of transition metal disulphides on different substrates, we speculate that it could be of great use for providing hitherto unattainable high quality monolayers of transition metal disulphides for fundamental spectroscopic investigations.

Polaronic Transport in Phosphate Glasses Containing Transition Metal Ions

NASA Astrophysics Data System (ADS)

Henderson, Mark

The goal of this dissertation is to characterize the basic transport properties of phosphate glasses containing various amounts of TIs and to identify and explain any electronic phase transitions which may occur. The P2 O5-V2O5-WO3 (PVW) glass system will be analyzed to find the effect of TI concentration on conduction. In addition, the effect of the relative concentrations of network forming ions (SiO2 and P2O5) on transport will be studied in the P2O5-SiO2-Fe2O 3 (PSF) system. Also presented is a numerical study on a tight-binding model adapted for the purposes of modelling Gaussian traps, mimicking TI's, which are arranged in an extended network. The results of this project will contribute to the development of fundamental theories on the electronic transport in glasses containing mixtures of transition oxides as well as those containing multiple network formers without discernible phase separation. The present study on the PVW follows up on previous investigation into the effect on mixed transition ions in oxide glasses. Past research has focused on glasses containing transition metal ions from the 3d row. The inclusion of tungsten, a 5d transition metal, adds a layer of complexity through the mismatch of the energies of the orbitals contributing to localized states. The data have indicated that a transition reminiscent of a metal-insulator transition (MIT) occurs in this system as the concentration of tungsten increases. As opposed to some other MIT-like transitions found in phosphate glass systems, there seems to be no polaron to bipolaron conversion. Instead, the individual localization parameter for tungsten noticeably decreases dramatically at the transition point as well as the adiabaticity. Another distinctive feature of this project is the study of the PSF system, which contains two true network formers, phosphorous pentoxide (P2O 5) and silicon dioxide (SiO2). It is not usually possible to do a reliable investigation of the conduction properties of

Self-sustained Flow-acoustic Interactions in Airfoil Transitional Boundary Layers

DTIC Science & Technology

2015-07-09

AFRL-AFOSR-VA-TR-2015-0235 Self-sustained flow-acoustic interactions in airfoil transitional boundary layers Vladimir Golubev EMBRY-RIDDLE...From - To)      01-04-2012 to 31-03-2015 4.  TITLE AND SUBTITLE Self-sustained flow-acoustic interactions in airfoil transitional boundary layers 5a...complementary experimental and numerical studies of flow-acoustic resonant interactions in transitional airfoils and their impact on airfoil surface

Redox potential trend with transition metal elements in lithium-ion battery cathode materials

NASA Astrophysics Data System (ADS)

Chen, Zhenlian; Li, Jun

2013-03-01

First-principles calculations are performed to investigate the relationship between the intrinsic voltage and element-lattice for the popular transition metal oxides and polyoxyanionic compounds as cathode materials for lithium-ion batteries. A V-shape redox potential in olivine phosphates LiMPO4 and orthogonal silicates Li2MSiO4 (M =Mn, Fe, Co, Ni), and an N-shape one in layered oxides LiMO2 (M =Mn, Fe, Co, Ni, Cu) relative to transition metal M elements are found to be inversely characteristic of electronic energy contribution, which costs energy in the lithiation process and is defined as electron affinity. The maxima of electron affinity, locating at different elements for different types of crystal lattices are determined by delectronic configurations that cross the turning point of a full occupancy of electronic bands, which is determined by the cooperative effect of crystal field splitting and intraionic exchange interactions. The Ningbo Key Innovation Team, National Natural Science Foundation of China, Postdoctoral Foundation of China

Boundary-Layer Receptivity and Integrated Transition Prediction

NASA Technical Reports Server (NTRS)

Chang, Chau-Lyan; Choudhari, Meelan

2005-01-01

The adjoint parabold stability equations (PSE) formulation is used to calculate the boundary layer receptivity to localized surface roughness and suction for compressible boundary layers. Receptivity efficiency functions predicted by the adjoint PSE approach agree well with results based on other nonparallel methods including linearized Navier-Stokes equations for both Tollmien-Schlichting waves and crossflow instability in swept wing boundary layers. The receptivity efficiency function can be regarded as the Green's function to the disturbance amplitude evolution in a nonparallel (growing) boundary layer. Given the Fourier transformed geometry factor distribution along the chordwise direction, the linear disturbance amplitude evolution for a finite size, distributed nonuniformity can be computed by evaluating the integral effects of both disturbance generation and linear amplification. The synergistic approach via the linear adjoint PSE for receptivity and nonlinear PSE for disturbance evolution downstream of the leading edge forms the basis for an integrated transition prediction tool. Eventually, such physics-based, high fidelity prediction methods could simulate the transition process from the disturbance generation through the nonlinear breakdown in a holistic manner.

Flight Experiment Verification of Shuttle Boundary Layer Transition Prediction Tool

NASA Technical Reports Server (NTRS)

Berry, Scott A.; Berger, Karen T.; Horvath, Thomas J.; Wood, William A.

2016-01-01

Boundary layer transition at hypersonic conditions is critical to the design of future high-speed aircraft and spacecraft. Accurate methods to predict transition would directly impact the aerothermodynamic environments used to size a hypersonic vehicle's thermal protection system. A transition prediction tool, based on wind tunnel derived discrete roughness correlations, was developed and implemented for the Space Shuttle return-to-flight program. This tool was also used to design a boundary layer transition flight experiment in order to assess correlation uncertainties, particularly with regard to high Mach-number transition and tunnel-to-flight scaling. A review is provided of the results obtained from the flight experiment in order to evaluate the transition prediction tool implemented for the Shuttle program.

Sound radiation due to boundary layer transition

NASA Technical Reports Server (NTRS)

Wang, Meng

1993-01-01

This report describes progress made to date towards calculations of noise produced by the laminar-turbulence transition process in a low Mach number boundary layer formed on a rigid wall. The primary objectives of the study are to elucidate the physical mechanisms by which acoustic waves are generated, to clarify the roles of the fluctuating Reynolds stress and the viscous stress in the presence of a solid surface, and to determine the relative efficiency as a noise source of the various transition stages. In particular, we will examine the acoustic characteristics and directivity associated with three-dimensional instability waves, the detached high-shear layer, and turbulent spots following a laminar breakdown. Additionally, attention will be paid to the unsteady surface pressures during the transition, which provide a source of flow noise as well as a forcing function for wall vibration in both aeronautical and marine applications.

Nanodisperse transition metal electrodes (NTME) for electrochemical cells

DOEpatents

Striebel, Kathryn A.; Wen, Shi-Jie

2000-01-01

Disclosed are transition metal electrodes for electrochemical cells using gel-state and solid-state polymers. The electrodes are suitable for use in primary and secondary cells. The electrodes (either negative electrode or positive electrode) are characterized by uniform dispersion of the transition metal at the nanoscale in the polymer. The transition metal moiety is structurally amorphous, so no capacity fade should occur due to lattice expansion/contraction mechanisms. The small grain size, amorphous structure and homogeneous distribution provide improved charge/discharge cycling performance, and a higher initial discharge rate capability. The cells can be cycled at high current densities, limited only by the electrolyte conductivity. A method of making the electrodes (positive and negative), and their usage in electrochemical cells are disclosed.

Microstructures and properties of ceramic particle-reinforced metal matrix composite layers produced by laser cladding

NASA Astrophysics Data System (ADS)

Zhang, Qingmao; He, Jingjiang; Liu, Wenjin; Zhong, Minlin

2005-01-01

Different weight ratio of titanium, zirconium, WC and Fe-based alloy powders were mixed, and cladded onto a medium carbon steel substrate using a 3kW continuous wave CO2 laser, aiming at producing Ceramic particles- reinforced metal matrix composites (MMCs) layers. The microstructures of the layers are typical hypoeutectic, and the major phases are Ni3Si2, TiSi2, Fe3C, FeNi, MC, Fe7Mo3, Fe3B, γ(residual austenite) and M(martensite). The microstructure morphologies of MMCs layers are dendrites/cells. The MC-type reinforcements are in situ synthesis Carbides which main compositions consist of transition elements Zr, Ti, W. The MC-type particles distributed within dendrite and interdendritic regions with different volume fractions for single and overlapping clad layers. The MMCs layers are dense and free of cracks with a good metallurgical bonding between the layer and substrate. The addition ratio of WC in the mixtures has the remarkable effect on the microhardness of clad layers.

Novel penta-graphene nanotubes: strain-induced structural and semiconductor–metal transitions

DOE PAGES

Wang, Zhanyu; Cao, Xinran; Qiao, Chong; ...

2017-11-17

Research into novel one-dimensional (1D) materials and associated structural transitions is of significant scientific interest. It is widely accepted that a 1D system with a short-range interaction cannot have 1D phase transition at finite temperature. In this paper, we propose a series of new stable carbon nanotubes by rolling up penta-graphene sheets, which exhibit fascinating well-defined 1D phase transitions triggered by axial strain. Our first-principles calculations show that such penta-graphene nanotubes (PGNTs) are dynamically stable by phonon calculations, but transform from a tri-layer structure to a highly defective single-walled nanotube at low temperature in molecular dynamics simulations. We show thatmore » moderate compressive strains can drive structural transitions of (4,4), (5,5), and (6,6) PGNTs, during which the distances of neighboring carbon dimers in the inner shell have a sudden drop, corresponding to dimer–dimer nonbonding to bonding transitions. After such transition, the tubes become much more thermally stable and undergo semiconductor–metal transitions under increasing strain. The band gaps of PGNTs are not sensitive to chirality whereas they can be tuned effectively from visible to short-wavelength infrared by appropriate strain, making them appealing materials for flexible nano-optoelectronics. In conclusion, these findings provide useful insight into unusual phase transitions in low-dimensional systems.« less

Novel penta-graphene nanotubes: strain-induced structural and semiconductor–metal transitions

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

Wang, Zhanyu; Cao, Xinran; Qiao, Chong

Research into novel one-dimensional (1D) materials and associated structural transitions is of significant scientific interest. It is widely accepted that a 1D system with a short-range interaction cannot have 1D phase transition at finite temperature. In this paper, we propose a series of new stable carbon nanotubes by rolling up penta-graphene sheets, which exhibit fascinating well-defined 1D phase transitions triggered by axial strain. Our first-principles calculations show that such penta-graphene nanotubes (PGNTs) are dynamically stable by phonon calculations, but transform from a tri-layer structure to a highly defective single-walled nanotube at low temperature in molecular dynamics simulations. We show thatmore » moderate compressive strains can drive structural transitions of (4,4), (5,5), and (6,6) PGNTs, during which the distances of neighboring carbon dimers in the inner shell have a sudden drop, corresponding to dimer–dimer nonbonding to bonding transitions. After such transition, the tubes become much more thermally stable and undergo semiconductor–metal transitions under increasing strain. The band gaps of PGNTs are not sensitive to chirality whereas they can be tuned effectively from visible to short-wavelength infrared by appropriate strain, making them appealing materials for flexible nano-optoelectronics. In conclusion, these findings provide useful insight into unusual phase transitions in low-dimensional systems.« less

Metal Organic Framework-Templated Chemiresistor: Sensing Type Transition from P-to-N Using Hollow Metal Oxide Polyhedron via Galvanic Replacement.

PubMed

Jang, Ji-Soo; Koo, Won-Tae; Choi, Seon-Jin; Kim, Il-Doo

2017-08-30

Facile synthesis of porous nanobuilding blocks with high surface area and uniform catalyst functionalization has always been regarded as an essential requirement for the development of highly sensitive and selective chemical sensors. Metal-organic frameworks (MOFs) are considered as one of the most ideal templates due to their ability to encapsulate ultrasmall catalytic nanoparticles (NPs) in microporous MOF structures in addition to easy removal of the sacrificial MOF scaffold by calcination. Here, we introduce a MOFs derived n-type SnO 2 (n-SnO 2 ) sensing layer with hollow polyhedron structures, obtained from p-n transition of MOF-templated p-type Co 3 O 4 (p-Co 3 O 4 ) hollow cubes during galvanic replacement reaction (GRR). In addition, the Pd NPs encapsulated in MOF and residual Co 3 O 4 clusters partially remained after GRR led to uniform functionalization of efficient cocatalysts (PdO NPs and p-Co 3 O 4 islands) on the porous and hollow polyhedron SnO 2 structures. Due to high gas accessibility through the meso- and macrosized pores in MOF-templated oxides and effective modulation of electron depletion layer assisted by the creation of numerous p-n junctions, the GRR-treated SnO 2 structures exhibited 21.9-fold higher acetone response (R air /R gas = 22.8 @ 5 ppm acetone, 90%RH) compared to MOF-templated p-Co 3 O 4 hollow structures. To the best of our knowledge, the selectivity and response amplitudes reported here for the detection of acetone are superior to those MOF derived metal oxide sensing layers reported so far. Our results demonstrate that highly active MOF-derived sensing layers can be achieved via p-n semiconducting phase transition, driven by a simple and versatile GRR process combined with MOF templating route.

Linear stability theory and three-dimensional boundary layer transition

NASA Technical Reports Server (NTRS)

Spall, Robert E.; Malik, Mujeeb R.

1992-01-01

The viewgraphs and discussion of linear stability theory and three dimensional boundary layer transition are provided. The ability to predict, using analytical tools, the location of boundary layer transition over aircraft-type configurations is of great importance to designers interested in laminar flow control (LFC). The e(sup N) method has proven to be fairly effective in predicting, in a consistent manner, the location of the onset of transition for simple geometries in low disturbance environments. This method provides a correlation between the most amplified single normal mode and the experimental location of the onset of transition. Studies indicate that values of N between 8 and 10 correlate well with the onset of transition. For most previous calculations, the mean flows were restricted to two-dimensional or axisymmetric cases, or have employed simple three-dimensional mean flows (e.g., rotating disk, infinite swept wing, or tapered swept wing with straight isobars). Unfortunately, for flows over general wing configurations, and for nearly all flows over fuselage-type bodies at incidence, the analysis of fully three-dimensional flow fields is required. Results obtained for the linear stability of fully three-dimensional boundary layers formed over both wing and fuselage-type geometries, and for both high and low speed flows are discussed. When possible, transition estimates form the e(sup N) method are compared to experimentally determined locations. The stability calculations are made using a modified version of the linear stability code COSAL. Mean flows were computed using both Navier Stokes and boundary-layer codes.

ZnO buffer layer for metal films on silicon substrates

DOEpatents

Ihlefeld, Jon

2014-09-16

Dramatic improvements in metallization integrity and electroceramic thin film performance can be achieved by the use of the ZnO buffer layer to minimize interfacial energy between metallization and adhesion layers. In particular, the invention provides a substrate metallization method utilizing a ZnO adhesion layer that has a high work of adhesion, which in turn enables processing under thermal budgets typically reserved for more exotic ceramic, single-crystal, or metal foil substrates. Embodiments of the present invention can be used in a broad range of applications beyond ferroelectric capacitors, including microelectromechanical systems, micro-printed heaters and sensors, and electrochemical energy storage, where integrity of metallized silicon to high temperatures is necessary.

Solution-Processed Metal Oxides as Efficient Carrier Transport Layers for Organic Photovoltaics.

PubMed

Choy, Wallace C H; Zhang, Di

2016-01-27

Carrier (electron and hole) transport layers (CTLs) are essential components for boosting the performance of various organic optoelectronic devices such as organic solar cells and organic light-emitting diodes. Considering the drawbacks of conventional CTLs (easily oxidized/unstable, demanding/costly fabrication, etc.), transition metal oxides with good carrier transport/extraction and superior stability have drawn extensive research interest as CTLs for next-generation devices. In recent years, many research efforts have been made toward the development of solution-based metal oxide CTLs with the focus on low- or even room-temperature processes, which can potentially be compatible with the deposition processes of organic materials and can significantly contribute to the low-cost and scale-up of organic devices. Here, the recent progress of different types of solution-processed metal oxide CTLs are systematically reviewed in the context of organic photovoltaics, from synthesis approaches to device performance. Different approaches for further enhancing the performance of solution-based metal oxide CTLs are also discussed, which may push the future development of this exciting field. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid-state chelation of metal ions by ethylenediaminetetraacetate intercalated in a layered double hydroxide.

PubMed

Tarasov, Konstantin A; O'Hare, Dermot; Isupov, Vitaly P

2003-03-24

The solid-state chelation of transition metal ions (Co(2+), Ni(2+), and Cu(2+)) from aqueous solutions into the lithium aluminum layered double hydroxide ([LiAl(2)(OH)(6)]Cl x 0.5H(2)O or LDH) which has been pre-intercalated with EDTA (ethylenediaminetetraacetate) ligand has been investigated. The intercalated metal cations form [M(edta)](2)(-) complexes between the LDH layers as indicated by elemental analysis, powder X-ray diffraction, and IR and UV-vis spectroscopies. If metal chloride or nitrate salts are used in the reaction with the LDH then co-intercalation of either the Cl(-) or NO(3)(-) anions is observed. In the case of metal acetate salts the cations intercalate without the accompanying anion. This can be explained by the different intercalation selectivity of the anions in relation to the LDH. In the latter case the introduction of the positive charge into LDH structure was compensated for by the release from the solid of the equivalent quantity of lithium and hydrogen cations. Time-resolved in-situ X-ray diffraction measurements have revealed that the chelation/intercalation reactions proceed very quickly. The rate of the reaction found for nickel acetate depends on concentration as approximately k[Ni(Ac)(2)](3).

Self assembled multi-layer nanocomposite of graphene and metal oxide materials

DOEpatents

Liu, Jun; Aksay, Ilhan A; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

2013-10-22

Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

Self assembled multi-layer nanocomposite of graphene and metal oxide materials

DOEpatents

Liu, Jun; Aksay, Ilhan A; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

2015-04-28

Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

Self assembled multi-layer nanocomposite of graphene and metal oxide materials

DOEpatents

Liu, Jun; Choi, Daiwon; Kou, Rong; Nie, Zimin; Wang, Donghai; Yang, Zhenguo

2014-09-16

Nanocomposite materials having at least two layers, each layer consisting of one metal oxide bonded to at least one graphene layer were developed. The nanocomposite materials will typically have many alternating layers of metal oxides and graphene layers, bonded in a sandwich type construction and will be incorporated into an electrochemical or energy storage device.

Photocurrent generation in a metallic transition-metal dichalcogenide

NASA Astrophysics Data System (ADS)

Mehmood, Naveed; Rasouli, Hamid Reza; ćakıroǧlu, Onur; Kasırga, T. Serkan

2018-05-01

Photocurrent generation is unexpected in metallic 2D layered materials unless a photothermal mechanism is prevalent. Yet, typical high thermal conductivity and low absorption of the visible spectrum prevent photothermal current generation in metals. Here, we report photoresponse from two-terminal devices of mechanically exfoliated metallic 3R-Nb S2 thin crystals using scanning photocurrent microscopy (SPCM) both at zero and finite bias. SPCM measurements reveal that the photocurrent predominantly emerges from metal/Nb S2 junctions of the two-terminal device at zero bias. At finite biases, along with the photocurrent generated at metal/Nb S2 junctions, now a negative photoresponse from all over the Nb S2 crystal is evident. Among our results, we realized that the observed photocurrent can be explained by the local heating caused by the laser excitation. These findings show that Nb S2 is among a few metallic materials in which photocurrent generation is possible.

Structure-Reactivity Relationships in Multi-Component Transition Metal Oxide Catalysts FINAL Report

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

Altman, Eric I.

2015-10-06

The focus of the project was on developing an atomic-level understanding of how transition metal oxide catalysts function. Over the course of several renewals the specific emphases shifted from understanding how local structure and oxidation state affect how molecules adsorb and react on the surfaces of binary oxide crystals to more complex systems where interactions between different transition metal oxide cations in an oxide catalyst can affect reactivity, and finally to the impact of cluster size on oxide stability and reactivity. Hallmarks of the work were the use of epitaxial growth methods to create surfaces relevant to catalysis yet tractablemore » for fundamental surface science approaches, and the use of scanning tunneling microscopy to follow structural changes induced by reactions and to pinpoint adsorption sites. Key early findings included the identification of oxidation and reduction mechanisms on a tungsten oxide catalyst surface that determine the sites available for reaction, identification of C-O bond cleavage as the rate limiting step in alcohol dehydration reactions on the tungsten oxide surface, and demonstration that reduction does not change the favored reaction pathway but rather eases C-O bond cleavage and thus reduces the reaction barrier. Subsequently, a new reconstruction on the anatase phase of TiO 2 relevant to catalysis was discovered and shown to create sites with distinct reactivity compared to other TiO 2 surfaces. Building on this work on anatase, the mechanism by which TiO 2 enhances the reactivity of vanadium oxide layers was characterized and it was found that the TiO 2 substrate can force thin vanadia layers to adopt structures they would not ordinarily form in the bulk which in turn creates differences in reactivity between supported layers and bulk samples. From there, the work progressed to studying well-defined ternary oxides where synergistic effects between the two cations can induce catalytic properties not seen for

Cross-linking proteins with bimetallic tetracarboxylate compounds of transition metals

DOEpatents

Kostic, Nenad M.; Chen, Jian

1991-03-05

Stable cross-linked complexes of transition-metal tetracarboxylates and proteins are formed. The preferred transition-metal is rhodium. The protein may be collagen or an enzyme such as a proteolytic enzyme.

Switchable wavelength-selective and diffuse metamaterial absorber/emitter with a phase transition spacer layer

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

Wang, Hao; Yang, Yue; Wang, Liping, E-mail: liping.wang@asu.edu

2014-08-18

We numerically demonstrate a switchable metamaterial absorber/emitter by thermally turning on or off the excitation of magnetic resonance upon the phase transition of vanadium dioxide (VO{sub 2}). Perfect absorption peak exists around the wavelength of 5 μm when the excitation of magnetic resonance is supported with the insulating VO{sub 2} spacer layer. The wavelength-selective absorption is switched off when the magnetic resonance is disabled with metallic VO{sub 2} that shorts the top and bottom metallic structures. The resonance wavelength can be tuned with different geometry, and the switchable metamaterial exhibits diffuse behaviors at oblique angles. The results would facilitate the designmore » of switchable metamaterials for active control in energy and sensing applications.« less

Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3d transition metals) alloy catalyst from first-principles.

PubMed

Kim, Chang-Eun; Lim, Dong-Hee; Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo; Hong, Seong-Ahn; Soon, Aloysius; Ham, Hyung Chul

2015-01-21

The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt3M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt3M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt3M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

Intrinsic phonon bands in high quality monolayer T' molybdenum ditelluride

NASA Astrophysics Data System (ADS)

Chen, Shao-Yu; Naylor, Carl; Goldstein, Thomas; Johnson, Charlie; Yan, Jun

Distorted octahedral (T') transition metal dichalcogenide (TMDC) is a type of layered semimetal that has attracted significant recent attention because of its fascination physical, chemical and nontrivial topological properties. Unlike its hexagonal counterpart, monolayer (1L) T'-TMDC is challenging to work with due to rapid sample degradation in air. In this talk, I will discuss well-protected 1L-T' - MoTe2 that exhibits sharp and robust intrinsic Raman bands, with intensities about one order of magnitude stronger than those from bulk T'-MoTe2. The high quality samples enable us to reveal for the first time the set of all nine even-parity zone-center optical phonons. Crystal angle and light polarization resolved measurements further indicate that all the intrinsic Raman modes belong to either z-mode (vibrating along the zigzag Mo atomic chain) or m-modes (vibrating in the mirror plane). Moreover, with the knowledge of vibrational symmetry, we can effectively distinguish the intrinsic modes from Te-metalloid-like modes with energy around 122 and 141 cm-1 which are associated to the sample degradation. Our studies offer a powerful non-destructive method for assessing sample quality, providing the fingerprint as well as key insights in understanding the fundamental properties of 1L T'-TMDCs.

Cross-linking proteins with bimetallic tetracarboxylate compounds of transition metals

DOEpatents

Kostic, N.M.; Chen, J.

1991-03-05

Stable cross-linked complexes of transition-metal tetracarboxylates and proteins are formed. The preferred transition-metal is rhodium. The protein may be collagen or an enzyme such as a proteolytic enzyme. No Drawings

Metal-Insulator Transition in W-doped VO2 Nanowires

NASA Astrophysics Data System (ADS)

Long, Gen; Parry, James; Whittaker, Luisa; Banerjee, Sarbajit; Zeng, Hao

2010-03-01

We report a systematic study of the metal-insulator transition in W-doped VO2 nanowires. Magnetic susceptibility were measured for a bulk amount of VO2 nanowire powder. The susceptibility shows a sharp drop with decreasing temperature corresponding to the metal-insulator transition. The transition shows large temperature hysteresis for cooling and heating. With increasing doping concentration, the transition temperatures decreases systematically from 320 K to 275K. Charge transport measurements on the same nanowires showed similar behavior. XRD and TEM measurements were taken to further determine the structure of the materials in study.

A stable lithium-rich surface structure for lithium-rich layered cathode materials

PubMed Central

Kim, Sangryun; Cho, Woosuk; Zhang, Xiaobin; Oshima, Yoshifumi; Choi, Jang Wook

2016-01-01

Lithium ion batteries are encountering ever-growing demand for further increases in energy density. Li-rich layered oxides are considered a feasible solution to meet this demand because their specific capacities often surpass 200 mAh g−1 due to the additional lithium occupation in the transition metal layers. However, this lithium arrangement, in turn, triggers cation mixing with the transition metals, causing phase transitions during cycling and loss of reversible capacity. Here we report a Li-rich layered surface bearing a consistent framework with the host, in which nickel is regularly arranged between the transition metal layers. This surface structure mitigates unwanted phase transitions, improving the cycling stability. This surface modification enables a reversible capacity of 218.3 mAh g−1 at 1C (250 mA g−1) with improved cycle retention (94.1% after 100 cycles). The present surface design can be applied to various battery electrodes that suffer from structural degradations propagating from the surface. PMID:27886178

The migration mechanism of transition metal ions in LiNi 0.5 Mn 1.5O 4

DOE PAGES

Xu, Gui-Liang; Qin, Yan; Ren, Yang; ...

2015-05-12

The migration of transition metal ions in the oxygen framework was recently proposed to be responsible for the continuous loss of average working potential of high energy density layered–layered composite cathodes for lithium-ion batteries. The potential migration pathway in a model material, LiNi 0.5 Mn 1.5O 4 spinel, was investigated using in situ high-energy X-ray diffraction and in situ neutron diffraction during the solid state synthesis process. It was found that the migration of transition metal ions among octahedral sites is possible by using tetrahedral vacancies as intermediate sites. It was also suggested that the number of electrons in 3dmore » orbitals has a significant impact on their mobility in the hosting oxygen framework.« less

Large enhancement of second harmonic generation from transition-metal dichalcogenide monolayer on grating near bound states in the continuum.

PubMed

Wang, Tiecheng; Zhang, Shihao

2018-01-08

Second harmonic generation from the two-layer structure where a transition-metal dichalcogenide monolayer is put on a one-dimensional grating has been studied. This grating supports bound states in the continuum which have no leakage lying within the continuum of radiation modes, we can enhance the second harmonic generation from the transition-metal dichalcogenide monolayer by more than four orders of magnitude based on the critical field enhancement near the bound states in the continuum. In order to complete this calculation, the scattering matrix theory has been extended to include the nonlinear effect and the scattering matrix of a two-dimensional material including nonlinear terms; furthermore, two methods to observe the bound states in the continuum are considered, where one is tuning the thickness of the grating and the other is changing the incident angle of the electromagnetic wave. We have also discussed various modulation of the second harmonic generation enhancement by adjusting the azimuthal angle of the transition-metal dichalcogenide monolayer.

Boundary-Layer Bypass Transition Over Large-Scale Bodies

DTIC Science & Technology

2016-12-16

shape of the streamwise velocity profile compared to the flat- plate boundary layer. The research showed that the streamwise wavenumber plays a key role...many works on the suppression of the transitional boundary layer. Most of the results in the literature are for the flat- plate boundary layer but the...behaviour of the velocity and pressure changes with the curvature. This work aims to extend the results of the flat- plate boundary layer to a Rankine

Luminescent molecular rods - transition-metal alkynyl complexes.

PubMed

Yam, Vivian Wing-Wah; Wong, Keith Man-Chung

2005-01-01

A number of transition-metal complexes have been reported to exhibit rich luminescence, usually originating from phosphorescence. Such luminescence properties of the triplet excited state with a large Stoke's shift, long lifetime, high luminescence quantum yield as well as lower excitation energy, are envisaged to serve as an ideal candidate in the area of potential applications for chemosensors, dye-sensitized solar cells, flat panel displays, optics, new materials and biological sciences. Organic alkynes (poly-ynes), with extended or conjugatedπ-systems and rigid structure with linear geometry, have become a significant research area due to their novel electronic and physical properties and their potential applications in nanotechnology. Owing to the presence of unsaturated sp-hybridized carbon atoms, the alkynyl unit can serve as a versatile building block in the construction of alkynyl transition-metal complexes, not only throughσ-bonding but also viaπ-bonding interactions. By incorporation of linear alkynyl groups into luminescent transition-metal complexes, the alkynyl moiety with goodσ-donor,π-donor andπ-acceptor abilities is envisaged to tune or perturb the emission behaviors, including emission energy (color), intensity and lifetime by its role as an auxiliary ligand as well as to govern the emission origin from its direct involvement. This review summarizes recent efforts on the synthesis of luminescent rod-like alkynyl complexes with different classes of transition metals and details the effects of the introduction of alkynyl groups on the luminescence properties of the complexes.

Plasmonic enhancement of second-harmonic generation of dielectric layer embedded in metal-dielectric-metal structure

NASA Astrophysics Data System (ADS)

Kang, Byungjun; Imakita, Kenji; Fujii, Minoru; Hayashi, Shinji

2018-03-01

The enhancement of second-harmonic generation from a dielectric layer embedded in a metal-dielectric-metal structure upon excitation of surface plasmon polaritons is demonstrated experimentally. The metal-dielectric-metal structure consisting of a Gex(SiO2)1-x layer sandwiched by two Ag layers was prepared, and the surface plasmon polaritons were excited in an attenuated total reflection geometry. The measured attenuated total reflection spectra exhibited two reflection dips corresponding to the excitation of two different surface plasmon polariton modes. Strong second-harmonic signals were observed under the excitation of these surface plasmon polariton modes. The results demonstrate that the second-harmonic intensity of the Gex(SiO2)1-x layer is highly enhanced relative to that of the single layer deposited on a substrate. Under the excitation of one of the two surface plasmon polariton modes, the estimated enhancement factor falls in a range between 39.9 and 171, while under the excitation of the other surface plasmon polariton mode, it falls in a range between 3.96 and 84.6.

Chemical solution seed layer for rabits tapes

DOEpatents

Goyal, Amit; Paranthaman, Mariappan; Wee, Sung-Hun

2014-06-10

A method for making a superconducting article includes the steps of providing a biaxially textured substrate. A seed layer is then deposited. The seed layer includes a double perovskite of the formula A.sub.2B'B''O.sub.6, where A is rare earth or alkaline earth metal and B' and B'' are different rare earth or transition metal cations. A superconductor layer is grown epitaxially such that the superconductor layer is supported by the seed layer.

Transition-Metal Substitution Doping in Synthetic Atomically Thin Semiconductors

DOE PAGES

Gao, Jian; Kim, Young Duck; Liang, Liangbo; ...

2016-09-20

Semiconductor impurity doping has enabled an entire generation of technology. The emergence of alternative semiconductor material systems, such as transition metal dichalcogenides (TMDCs), requires the development of scalable doping strategies. We report an unprecedented one-pot synthesis for transition-metal substitution in large-area, synthetic monolayer TMDCs. Electron microscopy, optical and electronic transport characterization and ab initio calculations indicate that our doping strategy preserves the attractive qualities of TMDC monolayers, including semiconducting transport and strong direct-gap luminescence. These results are expected to encourage exploration of transition-metal substitution in two-dimensional systems, potentially enabling next-generation optoelectronic technology in the atomically-thin regime.

Preparation and magnetic properties of phthalocyanine-based carbon materials containing transition metals

NASA Astrophysics Data System (ADS)

Honda, Z.; Sato, S.; Hagiwara, M.; Kida, T.; Sakai, M.; Fukuda, T.; Kamata, N.

2016-07-01

A simple method for the preparation of bulk quantities of magnetic carbon materials, which contain uniformly dispersed transition metals (M = Fe, Co, Ni, and Cu) as the magnetic components, is presented. By using highly chlorinated metal phthalocyanine as the building block and potassium as the coupling reagent, phthalocyanine-based carbon materials (PBCMs) containing transition metals were obtained. Our experiments demonstrate the structure of these PBCMs consists of transition metals embedded in graphitic carbon that includes a square planar MN4 magnetic core and the Fe and Co-PBCM possess spontaneous magnetization at room temperature. In addition, carbon-coated transition metal particles were obtained by the Wurtz-type reaction with excess amount of potassium coupling agent. The large transition metal surface area and magnetization of these M-PBCMs are useful for spintronic and catalytic applications.

Dynamic Optical Tuning of Interlayer Interactions in the Transition Metal Dichalcogenides

DOE PAGES

Mannebach, Ehren M.; Nyby, Clara; Ernst, Friederike; ...

2017-11-09

Modulation of weak interlayer interactions between quasi-two-dimensional atomic planes in the transition metal dichalcogenides (TMDCs) provides avenues for tuning their functional properties. Here we show that above-gap optical excitation in the TMDCs leads to an unexpected large-amplitude, ultrafast compressive force between the two-dimensional layers, as probed by in situ measurements of the atomic layer spacing at femtosecond time resolution. We show that this compressive response arises from a dynamic modulation of the interlayer van der Waals interaction and that this represents the dominant light-induced stress at low excitation densities. A simple analytic model predicts the magnitude and carrier density dependencemore » of the measured strains. Furthermore, this work establishes a new method for dynamic, nonequilibrium tuning of correlation-driven dispersive interactions and of the optomechanical functionality of TMDC quasi-two-dimensional materials.« less

Reflective article having a sacrificial cathodic layer

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

Kabagambe, Benjamin; Buchanan, Michael J.; Scott, Matthew S.

The present invention relates to reflective articles, such as solar mirrors, that include a sacrificial cathodic layer. The reflective article, more particularly includes a substrate, such as glass, having a multi-layered coating thereon that includes a lead-free sacrificial cathodic layer. The sacrificial cathodic layer includes at least one transition metal, such as a particulate transition metal, which can be in the form of flakes (e.g., zinc flakes). The sacrificial cathodic layer can include an inorganic matrix formed from one or more organo-titanates. Alternatively, the sacrificial cathodic layer can include an organic polymer matrix (e.g., a crosslinked organic polymer matrix formedmore » from an organic polymer and an aminoplast crosslinking agent). The reflective article also includes an outer organic polymer coating, that can be electrodeposited over the sacrificial cathodic layer.« less

Stable isotopes of transition and post-transition metals as tracers in environmental studies

USGS Publications Warehouse

Bullen, Thomas D.; Baskaran, Mark

2011-01-01

The transition and post-transition metals, which include the elements in Groups 3–12 of the Periodic Table, have a broad range of geological and biological roles as well as industrial applications and thus are widespread in the environment. Interdisciplinary research over the past decade has resulted in a broad understanding of the isotope systematics of this important group of elements and revealed largely unexpected variability in isotope composition for natural materials. Significant kinetic and equilibrium isotope fractionation has been observed for redox sensitive metals such as iron, chromium, copper, molybdenum and mercury, and for metals that are not redox sensitive in nature such as cadmium and zinc. In the environmental sciences, the isotopes are increasingly being used to understand important issues such as tracing of metal contaminant sources and fates, unraveling metal redox cycles, deciphering metal nutrient pathways and cycles, and developing isotope biosignatures that can indicate the role of biological activity in ancient and modern planetary systems.

Neutron Scattering Studies on Correlated Transition-Metal Oxides

NASA Astrophysics Data System (ADS)

Zhu, Mengze

We have explored the collective phenomena of correlated electrons in two different transition-metal oxides, Ruddlesden-Popper type ruthenates (Sr,Ca) n+1RunO3n+1 and inverse-trirutile chromates Cr2MO6 (M = Te, Mo and W), using neutron scattering in combination with various material characterization methods. (Sr,Ca)n+1RunO 3n+1 are 4d transition-metal oxides exhibiting competing magnetic and electronic tendencies. The delicate balance among the competing states can be readily tuned by perturbations, such as chemical doping and magnetic field, which gives rise to emergent phenomena. We have investigated the effects of 3d transition-metal doping on the magnetic and electronic properties of layered ruthenates. For instance, the single-layer (n = 1) Sr2RuO4 is an unconventional superconductor possessing an incommensurate spin density wave instability with a wave vector qic= (0.3 0.3 L) driven by Fermi surface nesting. Upon Fe substitution, we have unveiled an unexpected commensurate spin density wave order with a propagation vector qc= (0.25 0.25 0) in Sr2Ru1-xFexO 4 (x = 0.03 and 0.05), despite the magnetic fluctuations persisting at qic. The latter feature is corroborated by the first principles calculations, which show that Fe doping barely changes the nesting vector of the Fermi surface. These results suggest that in addition to the known incommensurate magnetic instability, Sr2RuO4 is also in proximity to a commensurate magnetic tendency that can be stabilized via Fe doping. We have also studied the effects of a magnetic field. For example, the bilayer (n = 2) Ca3(Ru1-xTi x)2O7 (x = 0.03) is a G-type antiferromagnetic Mott insulator. We have revealed that a modest magnetic field can lead to colossal magnetoresistance arising from an anomalous collapse of the Mott insulating state. Such an insulator-to-metal transition is accompanied by magnetic and structural transitions. These findings call for deeper theoretical studies to reexamine the magnetic field tuning of

Cascade morphology transition in bcc metals

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

Setyawan, Wahyu; Selby, A.; Juslin, Niklas

2015-06-10

Energetic atom collisions in solids induce shockwaves with complex morphologies. In this paper, we establish the existence of a morphological transition in such cascades. The order parameter of the morphology is defined as the exponent,more » $b$, in the defect production curve as a function of cascade energy ($$N_F$$$ \\sim$$$E_{MD}^b$$). Response of different bcc metals can be compared in a consistent energy domain when the energy is normalized by the transition energy, $$\\mu$$, between the high- and the low-energy regime. Using Cr, Fe, Mo and W data, an empirical formula of $$\\mu$$ as a function of displacement threshold energy, $$E_d$$, is presented for bcc metals.« less

Cascade morphology transition in bcc metals

DOE PAGES

Setyawan, Wahyu; Selby, Aaron P.; Juslin, Niklas; ...

2015-05-18

Energetic atom collisions in solids induce shockwaves with complex morphologies. In this paper, we establish the existence of a morphological transition in such cascades. The order parameter of the morphology is defined as the exponent, b, in the defect production curve as a function of cascade energy (N-F similar to E-MD(b)). Response of different bcc metals can be compared in a consistent energy domain when the energy is normalized by the transition energy, mu, between the high-and the low-energy regime. Using Cr, Fe, Mo and W data, an empirical formula of mu as a function of displacement threshold energy, E-d,more » is presented for bcc metals.« less

Trion formation dynamics in monolayer transition metal dichalcogenides

DOE PAGES

Singh, Akashay; Moody, Galan; Schaibley, John R.; ...

2016-01-05

Here, we report charged exciton (trion) formation dynamics in doped monolayer transition metal dichalcogenides, specifically molybdenum diselenide (MoSe 2), using resonant two-color pump-probe spectroscopy. When resonantly pumping the exciton transition, trions are generated on a picosecond time scale through exciton-electron interaction. As the pump energy is tuned from the high energy to low energy side of the inhomogeneously broadened exciton resonance, the trion formation time increases by ~50%. This feature can be explained by the existence of both localized and delocalized excitons in a disordered potential and suggests the existence of an exciton mobility edge in transition metal dichalcogenides.

Novel photoinduced phase transitions in transition metal oxides and diluted magnetic semiconductors.

PubMed

Mizokawa, Takashi

2012-10-23

Some transition metal oxides have frustrated electronic states under multiphase competition due to strongly correlated d electrons with spin, charge, and orbital degrees of freedom and exhibit drastic responses to external stimuli such as optical excitation. Here, we present photoemission studies on Pr0.55(Ca1 - ySry)0.45MnO3 (y = 0.25), SrTiO3, and Ti1 - xCoxO2 (x = 0.05, 0.10) under laser illumination and discuss electronic structural changes induced by optical excitation in these strongly correlated oxides. We discuss the novel photoinduced phase transitions in these transition metal oxides and diluted magnetic semiconductors on the basis of polaronic pictures such as orbital, ferromagnetic, and ferroelectric polarons.

Advanced boundary layer transition measurement methods for flight applications

NASA Technical Reports Server (NTRS)

Holmes, B. J.; Croom, C. C.; Gail, P. D.; Manuel, G. S.; Carraway, D. L.

1986-01-01

In modern laminar flow flight research, it is important to understand the specific cause(s) of laminar to turbulent boundary-layer transition. Such information is crucial to the exploration of the limits of practical application of laminar flow for drag reduction on aircraft. The transition modes of interest in current flight investigations include the viscous Tollmien-Schlichting instability, the inflectional instability at laminar separation, and the crossflow inflectional instability, as well as others. This paper presents the results to date of research on advanced devices and methods used for the study of laminar boundary-layer transition phenomena in the flight environment. Recent advancements in the development of arrayed hot-film devices and of a new flow visualization method are discussed. Arrayed hot-film devices have been designed to detect the presence of laminar separation, and of crossflow vorticity. The advanced flow visualization method utilizes color changes in liquid-crystal coatings to detect boundary-layer transition at high altitude flight conditions. Flight and wind tunnel data are presented to illustrate the design and operation of these advanced methods. These new research tools provide information on disturbance growth and transition mode which is essential to furthering our understanding of practical design limits for applications of laminar flow technology.

Preparation of nanoporous metal foam from high nitrogen transition metal complexes

DOEpatents

Tappan, Bryce C.; Huynh, My Hang V.; Hiskey, Michael A.; Son, Steven F.; Oschwald, David M.; Chavez, David E.; Naud, Darren L.

2006-11-28

Nanoporous metal foams are prepared by ignition of high nitrogen transition metal complexes. The ammonium salts of iron(III) tris[bi(tetrazolato)-amine], cobalt(III) tris(bi(tetrazolato)amine), and high nitrogen compounds of copper and silver were prepared as loose powders, pressed into pellets and wafers, and ignited under an inert atmosphere to form nanoporous metal foam monoliths having very high surface area and very low density.

Transitional-turbulent spots and turbulent-turbulent spots in boundary layers

NASA Astrophysics Data System (ADS)

Wu, Xiaohua; Moin, Parviz; Wallace, James M.; Skarda, Jinhie; Lozano-Durán, Adrián; Hickey, Jean-Pierre

2017-07-01

Two observations drawn from a thoroughly validated direct numerical simulation of the canonical spatially developing, zero-pressure gradient, smooth, flat-plate boundary layer are presented here. The first is that, for bypass transition in the narrow sense defined herein, we found that the transitional-turbulent spot inception mechanism is analogous to the secondary instability of boundary-layer natural transition, namely a spanwise vortex filament becomes a ΛΛ vortex and then, a hairpin packet. Long streak meandering does occur but usually when a streak is infected by a nearby existing transitional-turbulent spot. Streak waviness and breakdown are, therefore, not the mechanisms for the inception of transitional-turbulent spots found here. Rather, they only facilitate the growth and spreading of existing transitional-turbulent spots. The second observation is the discovery, in the inner layer of the developed turbulent boundary layer, of what we call turbulent-turbulent spots. These turbulent-turbulent spots are dense concentrations of small-scale vortices with high swirling strength originating from hairpin packets. Although structurally quite similar to the transitional-turbulent spots, these turbulent-turbulent spots are generated locally in the fully turbulent environment, and they are persistent with a systematic variation of detection threshold level. They exert indentation, segmentation, and termination on the viscous sublayer streaks, and they coincide with local concentrations of high levels of Reynolds shear stress, enstrophy, and temperature fluctuations. The sublayer streaks seem to be passive and are often simply the rims of the indentation pockets arising from the turbulent-turbulent spots.

Instability waves and transition in adverse-pressure-gradient boundary layers

NASA Astrophysics Data System (ADS)

Bose, Rikhi; Zaki, Tamer A.; Durbin, Paul A.

2018-05-01

Transition to turbulence in incompressible adverse-pressure-gradient (APG) boundary layers is investigated by direct numerical simulations. Purely two-dimensional instability waves develop on the inflectional base velocity profile. When the boundary layer is perturbed by isotropic turbulence from the free stream, streamwise elongated streaks form and may interact with the instability waves. Subsequent mechanisms that trigger transition depend on the intensity of the free-stream disturbances. All evidence from the present simulations suggest that the growth rate of instability waves is sufficiently high to couple with the streaks. Under very low levels of free-stream turbulence (˜0.1 % ), transition onset is highly sensitive to the inlet disturbance spectrum and is accelerated if the spectrum contains frequency-wave-number combinations that are commensurate with the instability waves. Transition onset and completion in this regime is characterized by formation and breakdown of Λ vortices, but they are more sporadic than in natural transition. Beneath free-stream turbulence with higher intensity (1-2 % ), bypass transition mechanisms are dominant, but instability waves are still the most dominant disturbances in wall-normal and spanwise perturbation spectra. Most of the breakdowns were by disturbances with critical layers close to the wall, corresponding to inner modes. On the other hand, the propensity of an outer mode to occur increases with the free-stream turbulence level. Higher intensity free-stream disturbances induce strong streaks that favorably distort the boundary layer and suppress the growth of instability waves. But the upward displacement of high amplitude streaks brings them to the outer edge of the boundary layer and exposes them to ambient turbulence. Consequently, high-amplitude streaks exhibit an outer-mode secondary instability.

Metal-phthalocyanine ordered layers on Au(110): Metal-dependent adsorption energy

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

Massimi, Lorenzo, E-mail: lorenzo.massimi@uniroma1.it; Angelucci, Marco; Gargiani, Pierluigi

2014-06-28

Iron-phthalocyanine and cobalt-phthalocyanine chains, assembled along the Au(110)-(1×2) reconstructed channels, present a strong interaction with the Au metallic states, via the central metal ion. X-ray photoemission spectroscopy from the metal-2p core-levels and valence band high-resolution ultraviolet photoelectron spectroscopy bring to light signatures of the interaction of the metal-phthalocyanine single-layer with gold. The charge transfer from Au to the molecule causes the emerging of a metal-2p core level component at lower binding energy with respect to that measured in the molecular thin films, while the core-levels associated to the organic macrocycle (C and N 1s) are less influenced by the adsorption,more » and the macrocycles stabilize the interaction, inducing a strong interface dipole. Temperature Programmed Desorption experiments and photoemission as a function of temperature allow to estimate the adsorption energy for the thin-films, mainly due to the molecule-molecule van der Waals interaction, while the FePc and CoPc single-layers remain adsorbed on the Au surface up to at least 820 K.« less

MoTe2, A novel anode material for sodium ion battery

NASA Astrophysics Data System (ADS)

Panda, Manas Ranjan; Anish Raj, K.; Bao, Qiaoliang; Mitra, Sagar

2018-04-01

2D layered transition metal dichalcogenides are considered as a potential anode for sodium-ion batteries due to their high specific capacity, structural stability and its well-developed two-dimensional layers. 2D layered structure Molybdenum ditelluride (MoTe2) provides a superior Na-ion storage properties in sodium ion battery due to its comparative more interlayer spacing (0.699 nm). In the current study MoTe2 polycrystalline powder sample has been prepared by solid state reaction process, the structural and morphological studies have been carried out by XRD, FE-SEM and EDS etc. XRD study revealsthe well crystalline structure of the material having hexagonal structure. FE-SEM and EDS studies depict the uniformflakes like structure of the material. When it is tested as sodium-ion battery anode by applying a potential window 0.1-2.5 V, the material demonstrates a high capacity and high power performances. The as prepared MoTe2 shows an initial discharge capacity of 376 mA h g-1 and a corresponding discharge capacity of 303 mA h g-1 after the 50th cycle at a current density of 500 mA g-1.

Minnowbrook II 1997 Workshop on Boundary Layer Transition in Turbomachines

NASA Technical Reports Server (NTRS)

LaGraff John E. (Editor); Ashpis, David E. (Editor)

1998-01-01

The volume contains materials presented at the Minnowbrook II - 1997 Workshop on Boundary Layer Transition in Turbomachines, held at Syracuse University Minnowbrook Conference Center, New York, on September 7-10, 1997. The workshop followed the informal format at the 1993 Minnowbrook I workshop, focusing on improving the understanding of late stage (final breakdown) boundary layer transition, with the engineering application of improving design codes for turbomachinery in mind. Among the physical mechanisms discussed were hydrodynamic instabilities, laminar to turbulent transition, bypass transition, turbulent spots, wake interaction with boundary layers, calmed regions, and separation, all in the context of flow in turbomachinery, particularly in compressors and high and low pressure turbines. Results from experiments, DNS, computation, modeling and theoretical analysis were presented. Abstracts and copies of viewgraphs, a specifically commissioned summation paper prepared after the workshop, and a transcript of the extensive working group reports and discussions are included in this volume. They provide recommendations for future research and clearly highlight the need for continued vigorous research in the technologically important area of transition in turbomachines.

Activation of methane by transition metal-substituted aluminophosphate molecular sieves

DOEpatents

Iton, Lennox E.; Maroni, Victor A.

1991-01-01

Aluminophosphate molecular sieves substituted with cobalt, manganese or iron and having the AlPO.sub.4 -34 or AlPO.sub.4 -5, or related AlPO.sub.4 structure activate methane starting at approximately 350.degree. C. Between 400.degree. and 500.degree. C. and at methane pressures .ltoreq.1 atmosphere the rate of methane conversion increases steadily with typical conversion efficiencies at 500.degree. C. approaching 50% and selectivity to the production of C.sub.2+ hydrocarbons approaching 100%. The activation mechanism is based on reduction of the transition metal(III) form of the molecular sieve to the transition metal(II) form with accompanying oxidative dehydrogenation of the methane. Reoxidation of the - transition metal(II) form to the transition metal(III) form can be done either chemically (e.g., using O.sub.2) or electrochemically.

Quantum spin liquids and the metal-insulator transition in doped semiconductors.

PubMed

Potter, Andrew C; Barkeshli, Maissam; McGreevy, John; Senthil, T

2012-08-17

We describe a new possible route to the metal-insulator transition in doped semiconductors such as Si:P or Si:B. We explore the possibility that the loss of metallic transport occurs through Mott localization of electrons into a quantum spin liquid state with diffusive charge neutral "spinon" excitations. Such a quantum spin liquid state can appear as an intermediate phase between the metal and the Anderson-Mott insulator. An immediate testable consequence is the presence of metallic thermal conductivity at low temperature in the electrical insulator near the metal-insulator transition. Further, we show that though the transition is second order, the zero temperature residual electrical conductivity will jump as the transition is approached from the metallic side. However, the electrical conductivity will have a nonmonotonic temperature dependence that may complicate the extrapolation to zero temperature. Signatures in other experiments and some comparisons with existing data are made.

Synthesis and characterization of transition metal oxide/sulfide nanostructures for electrochemical applications

NASA Astrophysics Data System (ADS)

Yilmaz, Gamze

This thesis is essentially oriented to develop low-cost nanostructured transition metal (nickel and vanadium) oxides and sulfides with high energy density, power density and electrochemical stability via strategies of structural design, hybridization, functionalization and surface engineering. Metal oxide and metal oxide/sulfide hybrid nanostructures in several designs, including hierarchical porous nanostructures, hollow polyhedrons, nanocubes, nanoframes, octopod nanoframes, and nanocages, were synthesized to study the contribution of structural design, compositional engineering, functionalization and surface engineering to the electrochemical properties of the materials. Modulated compositional and structural features disclosed the opportunities of large accessible active sites, facile ion transport, robustness and enhanced electrical conductivity. The best electrochemical performance with merits of highest energy density (38.9 Wh kg-1), power density (7.4 kW kg-1) and electrochemical stability (90.9% after 10000 cycles) was obtained for nickel cobalt layered double hydroxide/cobalt sulfide (NiCo-LDH/Co9S8) hybrid hollow polyhedron structure.

Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes)

DOE PAGES

Anasori, Babak; Xie, Yu; Beidaghi, Majid; ...

2015-07-24

The higher the chemical diversity and structural complexity of two-dimensional (2D) materials, the higher the likelihood they possess unique and useful properties. In this paper, density functional theory (DFT) is used to predict the existence of two new families of 2D ordered, carbides (MXenes), M' 2M"C 2 and M' 2M" 2C 3, where M' and M" are two different early transition metals. In these solids, M' layers sandwich M" carbide layers. By synthesizing Mo 2TiC 2T x, Mo 2Ti 2C 3T x, and Cr 2TiC 2T x (where T is a surface termination), we validated the DFT predictions. Since themore » Mo and Cr atoms are on the outside, they control the 2D flakes’ chemical and electrochemical properties. The latter was proven by showing quite different electrochemical behavior of Mo 2TiC 2T x and Ti 3C 2T x. Finally, this work further expands the family of 2D materials, offering additional choices of structures, chemistries, and ultimately useful properties.« less

Electrodeposition of biaxially textured layers on a substrate

DOEpatents

Bhattacharya, Raghu N; Phok, Sovannary; Spagnol, Priscila; Chaudhuri, Tapas

2013-11-19

Methods of producing one or more biaxially textured layer on a substrate, and articles produced by the methods, are disclosed. An exemplary method may comprise electrodepositing on the substrate a precursor material selected from the group consisting of rare earths, transition metals, actinide, lanthanides, and oxides thereof. An exemplary article (150) may comprise a biaxially textured base material (130), and at least one biaxially textured layer (110) selected from the group consisting of rare earths, transition metals, actinides, lanthanides, and oxides thereof. The at least one biaxially textured layer (110) is formed by electrodeposition on the biaxially textured base material (130).

Minnowbrook I: 1993 Workshop on End-Stage Boundary Layer Transition

NASA Technical Reports Server (NTRS)

LaGraff, John E. (Editor)

2007-01-01

This volume contains materials presented at the Minnowbrook I-1993 Workshop on End-Stage Boundary Layer Transition, held at the Syracuse University Minnowbrook Conference Center, New York, from August 15 to 18, 1993. This volume was previously published as a Syracuse University report edited by John E. LaGraff. The workshop organizers were John E. LaGraff (Syracuse University), Terry V. Jones (Oxford University), and J. Paul Gostelow (University of Technology, Sydney). The workshop focused on physical understanding of the late stages of transition from laminar to turbulent flows, with the specific goal of contributing to improving engineering design of turbomachinery and wing airfoils. The workshop participants included academic researchers from the United States and abroad, and representatives from the gas-turbine industry and U.S. government laboratories. To improve interaction and discussions among the participants, no formal papers were required. The physical mechanisms discussed were related to natural and bypass transition, wake-induced transition, effects of freestream turbulence, turbulent spots, hairpin vortices, nonlinear instabilities and breakdown, instability wave interactions, intermittency, turbulence, numerical simulation and modeling of transition, heat transfer in boundary-layer transition, transition in separated flows, laminarization, transition in turbomachinery compressors and turbines, hypersonic boundary-layer transition, and other related topics. This volume contains abstracts and copies of the viewgraphs presented, organized according to the workshop sessions. The workshop summary and the plenary discussion transcript clearly outline future research needs.

Thermodynamic Hydricity of Transition Metal Hydrides

DOE PAGES

Wiedner, Eric S.; Chambers, Matthew B.; Pitman, Catherine L.; ...

2016-08-02

Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bondbreaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H -). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H 2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H 2more » in the presence of a base, and the potential-pK a method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Finally, methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO 2, and the production and oxidation of hydrogen.« less

Effect of Protuberance Shape and Orientation on Space Shuttle Orbiter Boundary-Layer Transition

NASA Technical Reports Server (NTRS)

King, RUdolph A.; Berry, Scott A.; Kegerise, Michael A.

2008-01-01

This document describes an experimental study conducted to examine the effects of protuberances on hypersonic boundary-layer transition. The experiment was conducted in the Langley 20-Inch Mach 6 Tunnel on a series of 0.9%-scale Shuttle Orbiter models. The data were acquired to complement the existing ground-based boundary-layer transition database that was used to develop Version 1.0 of the boundary-layer transition RTF (return-to-flight) tool. The existing ground-based data were all acquired on 0.75%-scale Orbiter models using diamond-shaped ( pizza-box ) trips. The larger model scale facilitated in manufacturing higher fidelity protuberances. The end use of this experimental database will be to develop a technical basis (in the form of a boundary-layer transition correlation) to assess representative protrusion shapes, e.g., gap fillers and protrusions resulting from possible tile repair concepts. The primary objective of this study is to investigate the effects of protuberance-trip location and geometry on Shuttle Orbiter boundary-layer transition. Secondary goals are to assess the effects of gap-filler orientation and other protrusion shapes on boundary-layer transition. Global heat-transfer images using phosphor thermography of the Orbiter windward surface and the corresponding streamwise and spanwise heating distributions were used to infer the state of the boundary layer, i.e., laminar, transitional, or turbulent.

Nanostructured transition metal oxides useful for water oxidation catalysis

DOEpatents

Frei, Heinz M; Jiao, Feng

2013-12-24

The present invention provides for a composition comprising a nanostructured transition metal oxide capable of oxidizing two H.sub.2O molecules to obtain four protons. In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix.

Infrared Imaging of Boundary Layer Transition Flight Experiments

NASA Technical Reports Server (NTRS)

Berry, Scott A.; Horvath, Thomas J., Jr.; Schwartz, Richard; Ross, Martin; Anderson, Brian; Campbell, Charles H.

2008-01-01

The Hypersonic Thermodynamic Infrared Measurement (HYTHIRM) project is presently focused on near term support to the Shuttle program through the development of an infrared imaging capability of sufficient spatial and temporal resolution to augment existing on-board Orbiter instrumentation. Significant progress has been made with the identification and inventory of relevant existing optical imaging assets and the development, maturation, and validation of simulation and modeling tools for assessment and mission planning purposes, which were intended to lead to the best strategies and assets for successful acquisition of quantitative global surface temperature data on the Shuttle during entry. However, there are longer-term goals of providing global infrared imaging support to other flight projects as well. A status of HYTHIRM from the perspective of how two NASA-sponsored boundary layer transition flight experiments could benefit by infrared measurements is provided. Those two flight projects are the Hypersonic Boundary layer Transition (HyBoLT) flight experiment and the Shuttle Boundary Layer Transition Flight Experiment (BLT FE), which are both intended for reducing uncertainties associated with the extrapolation of wind tunnel derived transition correlations for flight application. Thus, the criticality of obtaining high quality flight data along with the impact it would provide to the Shuttle program damage assessment process are discussed. Two recent wind tunnel efforts that were intended as risk mitigation in terms of quantifying the transition process and resulting turbulent wedge locations are briefly reviewed. Progress is being made towards finalizing an imaging strategy in support of the Shuttle BLT FE, however there are no plans currently to image HyBoLT.

Layer-by-Layer Assembled Films of Perylene Diimide- and Squaraine-Containing Metal-Organic Frameworks- like Materials: Solar Energy Capture and Directional Energy Transfer

DOE PAGES

Park, Hea Jung; So, Monica C.; Gosztola, David J.

2016-09-28

We demonstrate that thin films of metal organic framework (MOF)-like materials, containing two perylenedlimides (PDICl4, PDIOPh2) and a squaraine dye (S1); can be fabricated by, layer-by-layer assembly (LbL). Interestingly, these LbL films absorb across the visible light region (400-750 nm) and facilitate directional energy transfer. Due to the high spectral overlap and oriented transition dipole moments of the donor (PDICl4 and PDIOPh2) and acceptor (S1) components, directional long-range energy transfer from the bluest to reddest absorber was successfully demonstrated in the multicomponent MOF-like films. These findings have significant implications for the development of solar energy conversion devices based on MOFs.

Forward-facing steps induced transition in a subsonic boundary layer

NASA Astrophysics Data System (ADS)

Zh, Hui; Fu, Song

2017-10-01

A forward-facing step (FFS) immersed in a subsonic boundary layer is studied through a high-order flux reconstruction (FR) method to highlight the flow transition induced by the step. The step height is a third of the local boundary-layer thickness. The Reynolds number based on the step height is 720. Inlet disturbances are introduced giving rise to streamwise vortices upstream of the step. It is observed that these small-scale streamwise structures interact with the step and hairpin vortices are quickly developed after the step leading to flow transition in the boundary layer.

Polymer thin film as coating layer to prevent corrosion of metal/metal oxide film

NASA Astrophysics Data System (ADS)

Sarkar, Suman; Kundu, Sarathi

2018-04-01

Thin film of polymer is used as coating layer and the corrosion of metal/metal oxide layer is studied with the variation of the thickness of the coating layer. The thin layer of polystyrene is fabricated using spin coating method on copper oxide (CuO) film which is deposited on glass substrate using DC magnetron sputtering technique. Thickness of the polystyrene and the CuO layers are determined using X-ray reflectivity (XRR) technique. CuO thin films coated with the polystyrene layer are exposed to acetic acid (2.5 v/v% aqueous CH3COOH solution) environments and are subsequently analyzed using UV-Vis spectroscopy and atomic force microscopy (AFM). Surface morphology of the film before and after interaction with the acidic environment is determined using AFM. Results obtained from the XRR and UV-Vis spectroscopy confirm that the thin film of polystyrene acts as an anticorrosion coating layer and the strength of the coating depends upon the polymer layer thickness at a constant acid concentration.

Influence of head size on the development of metallic wear and on the characteristics of carbon layers in metal-on-metal hip joints

PubMed Central

Sprecher, Christoph M; Wimmer, Markus A; Milz, Stefan; Taeger, Georg

2009-01-01

Background and purpose Particles originating from the articulating surfaces of hip endoprostheses often induce an inflammatory response, which can be related to implant failure. We therefore analyzed the metal content in capsular tissue from 44 McKee-Farrar metal-on-metal hip prostheses (with 3 different head sizes) and we also analyzed the morphological structure of layers located on articulating surfaces. Methods Atomic absorption spectrometry (AAS) was used to analyze the metal content in capsular tissue. Visually detectable carbon layers located on the articulating surfaces were evaluated using scanning electron microscopy (SEM), energy-dispersive Xray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS). Results Metallic debris was detected in all capsular tissue samples but no statistically significant differences in metal content were found in relation to implant head size. The morphological characteristics of the different layer zones allowed an exact analysis of contact and non-contact areas. Furthermore, surface layers appear to have a protective function because they can prevent sharp-edged particles from damaging the prostheses surface. Interpretation The implant head size does not appear to influence the amount of metallic debris. The layers obviously act like a lubricating agent because the protection function does not occur in regions without layers where the metal surface often shows numerous scratches. As layers are not generated immediately after the implantation of hip prostheses, these findings may at least partially explain the high amount of wear early after implantation. PMID:19421914

Flight-measured laminar boundary-layer transition phenomena including stability theory analysis

NASA Technical Reports Server (NTRS)

Obara, C. J.; Holmes, B. J.

1985-01-01

Flight experiments were conducted on a single-engine turboprop aircraft fitted with a 92-in-chord, 3-ft-span natural laminar flow glove at glove section lift coefficients from 0.15 to 1.10. The boundary-layer transition measurement methods used included sublimating chemicals and surface hot-film sensors. Transition occurred downstream of the minimum pressure point. Hot-film sensors provided a well-defined indication of laminar, laminar-separation, transitional, and turbulent boundary layers. Theoretical calculations of the boundary-layer parameters provided close agreement between the predicted laminar-separation point and the measured transition location. Tollmien-Schlichting (T-S) wave growth n-factors between 15 and 17 were calculated at the predicted point of laminar separation. These results suggest that for many practical airplane cruise conditions, laminar separation (as opposed to T-S instability) is the major cause of transition in predominantly two-dimensional flows.

On the Effects of Surface Roughness on Boundary Layer Transition

NASA Technical Reports Server (NTRS)

Choudhari, Meelan M.; Li, Fei; Chang, Chau-Lyan; Edwards, Jack

2009-01-01

Surface roughness can influence laminar-turbulent transition in many different ways. This paper outlines selected analyses performed at the NASA Langley Research Center, ranging in speed from subsonic to hypersonic Mach numbers and highlighting the beneficial as well as adverse roles of the surface roughness in technological applications. The first theme pertains to boundary-layer tripping on the forebody of a hypersonic airbreathing configuration via a spanwise periodic array of trip elements, with the goal of understanding the physical mechanisms underlying roughness-induced transition in a high-speed boundary layer. The effect of an isolated, finite amplitude roughness element on a supersonic boundary layer is considered next. The other set of flow configurations examined herein corresponds to roughness based laminar flow control in subsonic and supersonic swept wing boundary layers. A common theme to all of the above configurations is the need to apply higher fidelity, physics based techniques to develop reliable predictions of roughness effects on laminar-turbulent transition.

Bypass transition in boundary layers including curvature and favorable pressure gradient effects

NASA Technical Reports Server (NTRS)

Volino, R. J.; Simon, T. W.

1991-01-01

Recent studies of 2-D boundary layers undergoing bypass transition were reviewed. Bypass transition is characterized by the sudden appearance of turbulent spots in boundary layer without first the regular, observable growth of disturbances predicted by linear stability theory. There are no standard criteria or parameters for defining bypass transition, but it is known to be the mode of transition when the flow is disturbed by perturbations of sufficient amplitude.

Accurate identification of layer number for few-layer WS2 and WSe2 via spectroscopic study.

PubMed

Li, Yuanzheng; Li, Xinshu; Yu, Tong; Yang, Guochun; Chen, Heyu; Zhang, Cen; Feng, Qiushi; Ma, Jiangang; Liu, Weizhen; Xu, Haiyang; Liu, Yichun; Liu, Xinfeng

2018-03-23

Transition metal dichalcogenides (TMDs) with a typical layered structure are highly sensitive to their layer number in optical and electronic properties. Seeking a simple and effective method for layer number identification is very important to low-dimensional TMD samples. Herein, a rapid and accurate layer number identification of few-layer WS 2 and WSe 2 is proposed via locking their photoluminescence (PL) peak-positions. As the layer number of WS 2 /WSe 2 increases, it is found that indirect transition emission is more thickness-sensitive than direct transition emission, and the PL peak-position differences between the indirect and direct transitions can be regarded as fingerprints to identify their layer number. Theoretical calculation confirms that the notable thickness-sensitivity of indirect transition derives from the variations of electron density of states of W atom d-orbitals and chalcogen atom p-orbitals. Besides, the PL peak-position differences between the indirect and direct transitions are almost independent of different insulating substrates. This work not only proposes a new method for layer number identification via PL studies, but also provides a valuable insight into the thickness-dependent optical and electronic properties of W-based TMDs.

Raman microscopy of lithium-manganese-rich transition metal oxide cathodes

DOE PAGES

Ruther, Rose E.; Callender, Andrew F.; Zhou, Hui; ...

2014-11-15

Lithium-rich and manganese-rich (LMR) layered transition metal (TM) oxide composites with general formula xLi 2MnO 3·(1-x)LiMO 2 (M = Ni, Co, Mn) are promising cathode candidates for high energy density lithium ion batteries. Lithium-manganese-rich TM oxides crystallize as a nanocomposite layered phase whose structure further evolves with electrochemical cycling. Raman spectroscopy is a powerful tool to monitor the crystal chemistry and correlate phase changes with electrochemical behavior. While several groups have reported Raman spectra of lithium rich TM oxides, the data show considerable variability in terms of both the vibrational features observed and their interpretation. In this paper, Raman microscopymore » is used to investigate lithium-rich and manganese-rich TM cathodes as a function of voltage and electrochemical cycling at various temperatures. No growth of a spinel phase is observed within the cycling conditions. However, analysis of the Raman spectra does indicate the structure of LMR-NMC deviates significantly from an ideal layered phase. Finally, the results also highlight the importance of using low laser power and large sample sizes to obtain consistent data sets.« less

On the stability of the electronic system in transition metal dichalcogenides.

PubMed

Faraggi, M N; Zubizarreta, X; Arnau, A; Silkin, V M

2016-05-11

Based on first-principles calculations, we prove that the origin of charge-density wave formation in metallic layered transition metal dichalcogenides (TMDC) is not due to an electronic effect, like the Fermi surface (FS) nesting, as it had been proposed. In particular, we consider NbSe2, NbS2, TaSe2, and TaS2 as representative examples of 2H-TMDC polytypes. Our main result consists that explicit inclusion of the matrix elements in first-principles calculations of the electron susceptibility [Formula: see text] removes, due to strong momentum dependence of the matrix elements, almost all the information about the FS topologies in the resulting [Formula: see text]. This finding strongly supports an interpretation in which the momentum dependence of the electron-phonon interaction is the only reason why the phenomenon of charge-density waves appears in this class of materials.

Interaction of metal layers with polycrystalline Si

NASA Technical Reports Server (NTRS)

Nakamura, K.; Olowolafe, J. O.; Lau, S. S.; Nicolet, M.-A.; Mayer, J. W.; Shima, R.

1976-01-01

Solid-phase reactions of metal films deposited on 0.5-micron-thick polycrystalline layers of Si grown by chemical vapor deposition at 640 C were investigated by MeV He-4 backscattering spectrometry, glancing angle X-ray diffraction, and SEM observations. For the metals Al, Ag, and Au, which form simple eutectics, heat treatment at temperatures below the eutectic results in erosion of the poly-Si layer and growth of Si crystallites in the metal film. Crystallite formation is observed at temperatures exceeding 550 C for Ag, at those exceeding 400 C for Al, and at those exceeding 200 C for Au films. For Pd, Ni, and Cr, heat treatment results in silicide formation. The same initial silicides (Pd2Si, Ni2Si, and CrSi2), are formed at similar temperatures on single-crystal substrates.

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.

Heat transfer and fluid mechanics measurements in transitional boundary layer flows

NASA Technical Reports Server (NTRS)

Wang, T.; Simon, T. W.; Buddhavarapu, J.

1985-01-01

Experimental results are presented to document hydrodynamic and thermal development of flat-plate boundary layers undergoing natural transition. Local heat transfer coefficients, skin friction coefficients and profiles of velocity, temperature and Reynolds normal and shear stresses are presented. A case with no transition and transitional cases with 0.68% and 2.0% free-stream disturbance intensities were investigated. The locations of transition are consistent with earlier data. A late-laminar state with significant levels of turbulence is documented. In late-transitional and early-turbulent flows, turbulent Prandtl number and conduction layer thickness values exceed, and the Reynolds analogy factor is less than, values previously measured in fully turbulent flows.

Theory of quantum metal to superconductor transitions in highly conducting systems

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

Spivak, B.

2010-04-06

We derive the theory of the quantum (zero temperature) superconductor to metal transition in disordered materials when the resistance of the normal metal near criticality is small compared to the quantum of resistivity. This can occur most readily in situations in which 'Anderson's theorem' does not apply. We explicitly study the transition in superconductor-metal composites, in an swave superconducting film in the presence of a magnetic field, and in a low temperature disordered d-wave superconductor. Near the point of the transition, the distribution of the superconducting order parameter is highly inhomogeneous. To describe this situation we employ a procedure whichmore » is similar to that introduced by Mott for description of the temperature dependence of the variable range hopping conduction. As the system approaches the point of the transition from the metal to the superconductor, the conductivity of the system diverges, and the Wiedemann-Franz law is violated. In the case of d-wave (or other exotic) superconductors we predict the existence of (at least) two sequential transitions as a function of increasing disorder: a d-wave to s-wave, and then an s-wave to metal transition.« less

Methods of Fabricating a Layer of Metallic Glass-Based Material Using Immersion and Pouring Techniques

NASA Technical Reports Server (NTRS)

Hofmann, Douglas (Inventor)

2015-01-01

Systems and methods in accordance with embodiments of the invention implement layers of metallic glass-based materials. In one embodiment, a method of fabricating a layer of metallic glass includes: applying a coating layer of liquid phase metallic glass to an object, the coating layer being applied in a sufficient quantity such that the surface tension of the liquid phase metallic glass causes the coating layer to have a smooth surface; where the metallic glass has a critical cooling rate less than 1000 K/s; and cooling the coating layer of liquid phase metallic glass to form a layer of solid phase metallic glass.

On the thermodynamics of phase transitions in metal hydrides

NASA Astrophysics Data System (ADS)

di Vita, Andrea

2012-02-01

Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier's principle of thermodynamics to a particular phase transition in TiH x , which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H+ ions and of the distance between adjacent H+ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H+ ions (`collective modes') increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H+ ions with collective modes makes a tiny suprathermal fraction of the H+ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.

A Simple, General Synthetic Route toward Nanoscale Transition Metal Borides.

PubMed

Jothi, Palani R; Yubuta, Kunio; Fokwa, Boniface P T

2018-04-01

Most nanomaterials, such as transition metal carbides, phosphides, nitrides, chalcogenides, etc., have been extensively studied for their various properties in recent years. The similarly attractive transition metal borides, on the contrary, have seen little interest from the materials science community, mainly because nanomaterials are notoriously difficult to synthesize. Herein, a simple, general synthetic method toward crystalline transition metal boride nanomaterials is proposed. This new method takes advantage of the redox chemistry of Sn/SnCl 2 , the volatility and recrystallization of SnCl 2 at the synthesis conditions, as well as the immiscibility of tin with boron, to produce crystalline phases of 3d, 4d, and 5d transition metal nanoborides with different morphologies (nanorods, nanosheets, nanoprisms, nanoplates, nanoparticles, etc.). Importantly, this method allows flexibility in the choice of the transition metal, as well as the ability to target several compositions within the same binary phase diagram (e.g., Mo 2 B, α-MoB, MoB 2 , Mo 2 B 4 ). The simplicity and wide applicability of the method should enable the fulfillment of the great potential of this understudied class of materials, which show a variety of excellent chemical, electrochemical, and physical properties at the microscale. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydroxyapatite substituted by transition metals: experiment and theory.

PubMed

Zilm, M E; Chen, L; Sharma, V; McDannald, A; Jain, M; Ramprasad, R; Wei, M

2016-06-28

Bioceramics are versatile materials for hard tissue engineering. Hydroxyapatite (HA) is a widely studied biomaterial for bone grafting and tissue engineering applications. The crystal structure of HA allows for a wide range of substitutions, which allows for tailoring materials properties. Transition metals and lanthanides are of interest since substitution in HA can result in magnetic properties. In this study, experimental results were compared to theoretical calculations of HA substituted with a transition metal. Calculation of a 10 atomic percent substitution of a transition metal ion Mn(2+), Fe(2+), and Co(2+) substituted HA samples lead to magnetic moments of 5, 4, and 3 Bohr magnetons, respectively. Hydroxyapatite substituted by transition metals (MHA) was fabricated through an ion exchange procedure and characterized with X-ray diffraction, Fourier transform infra-red spectroscopy (FTIR), X-ray photoelectron spectroscopy, and vibrating sample magnetometer, and results were compared to theoretical calculations. All the substitutions resulted in phase-pure M(2+)HA with lattice parameters and FTIR spectra in good agreement with calculations. Magnetic measurements revealed that the substitution of Mn(2+) has the greatest effect on the magnetic properties of HA followed by the substitution of Fe(2+) and then Co(2+). The present work underlines the power of synergistic theoretical-experimental work in guiding the rational design of materials.

Hot carrier dynamics in plasmonic transition metal nitrides

NASA Astrophysics Data System (ADS)

Habib, Adela; Florio, Fred; Sundararaman, Ravishankar

2018-06-01

Extraction of non-equilibrium hot carriers generated by plasmon decay in metallic nano-structures is an increasingly exciting prospect for utilizing plasmonic losses, but the search for optimum plasmonic materials with long-lived carriers is ongoing. Transition metal nitrides are an exciting class of new plasmonic materials with superior thermal and mechanical properties compared to conventional noble metals, but their suitability for plasmonic hot carrier applications remains unknown. Here, we present fully first principles calculations of the plasmonic response, hot carrier generation and subsequent thermalization of all group IV, V and VI transition metal nitrides, fully accounting for direct and phonon-assisted transitions as well as electron–electron and electron–phonon scattering. We find the largest frequency ranges for plasmonic response in ZrN, HfN and WN, between those of gold and silver, while we predict strongest absorption in the visible spectrum for the VN, NbN and TaN. Hot carrier generation is dominated by direct transitions for most of the relevant energy range in all these nitrides, while phonon-assisted processes dominate only below 1 eV plasmon energies primarily for the group IV nitrides. Finally, we predict the maximum hot carrier lifetimes to be around 10 fs for group IV and VI nitrides, a factor of 3–4 smaller than noble metals, due to strong electron–phonon scattering. However, we find longer carrier lifetimes for group V nitrides, comparable to silver for NbN and TaN, while exceeding 100 fs (twice that of silver) for VN, making them promising candidates for efficient hot carrier extraction.

Synthesis and Characterization of the 2-Dimensional Transition Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Browning, Robert

In the last 50 years, the semiconductor industry has been scaling the silicon transistor to achieve faster devices, lower power consumption, and improve device performance. Transistor gate dimensions have become so small that short channel effects and gate leakage have become a significant problem. To address these issues, performance enhancement techniques such as strained silicon are used to improve mobility, while new high-k gate dielectric materials replace silicon oxide to reduce gate leakage. At some point the fundamental limit of silicon will be reached and the semiconductor industry will need to find an alternate solution. The advent of graphene led to the discovery of other layered materials such as the transition metal dichalcogenides. These materials have a layered structure similar to graphene and therefore possess some of the same qualities, but unlike graphene, these materials possess sizeable bandgaps between 1-2 eV making them useful for digital electronic applications. Since initially discovered, most of the research on these films has been from mechanically exfoliated flakes, which are easily produced due to the weak van der Waals force binding the layers together. For these materials to be considered for use in mainstream semiconductor technology, methods need to be explored to grow these films uniformly over a large area. In this research, atomic layer deposition (ALD) was employed as the growth technique used to produce large area uniform thin films of several different transition metal dichalcogenides. By optimizing the ALD growth parameters, it is possible to grow high quality films a few to several monolayers thick over a large area with good uniformity. This has been demonstrated and verified using several physical analytical tests such as Raman spectroscopy, photoluminescence, x-ray photoelectron spectroscopy, x-ray diffraction, transmission electron spectroscopy, and scanning electron microscopy, which show that these films possess the

Shuttle orbiter boundary layer transition at flight and wind tunnel conditions

NASA Technical Reports Server (NTRS)

Goodrich, W. D.; Derry, S. M.; Bertin, J. J.

1983-01-01

Hypersonic boundary layer transition data obtained on the windward centerline of the Shuttle orbiter during entry for the first five flights are presented and analyzed. Because the orbiter surface is composed of a large number of thermal protection tiles, the transition data include the effects of distributed roughness arising from tile misalignment and gaps. These data are used as a benchmark for assessing and improving the accuracy of boundary layer transition predictions based on correlations of wind tunnel data taken on both aerodynamically rough and smooth orbiter surfaces. By comparing these two data bases, the relative importance of tunnel free stream noise and surface roughness on orbiter boundary layer transition correlation parameters can be assessed. This assessment indicates that accurate predications of transition times can be made for the orbiter at hypersonic flight conditions by using roughness dominated wind tunnel data. Specifically, times of transition onset and completion is accurately predicted using a correlation based on critical and effective values of a roughness Reynolds number previously derived from wind tunnel data.

Metal-metal bond lengths in complexes of transition metals.

PubMed

Pauling, L

1976-12-01

In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths.

Roles of Engineering Correlations in Hypersonic Entry Boundary Layer Transition Prediction

NASA Technical Reports Server (NTRS)

Campbell, Charles H.; King, Rudolph A.; Kergerise, Michael A.; Berry, Scott A.; Horvath, Thomas J.

2010-01-01

Efforts to design and operate hypersonic entry vehicles are constrained by many considerations that involve all aspects of an entry vehicle system. One of the more significant physical phenomenon that affect entry trajectory and thermal protection system design is the occurrence of boundary layer transition from a laminar to turbulent state. During the Space Shuttle Return To Flight activity following the loss of Columbia and her crew of seven, NASA's entry aerothermodynamics community implemented an engineering correlation based framework for the prediction of boundary layer transition on the Orbiter. The methodology for this implementation relies upon the framework of correlation techniques that have been in use for several decades. What makes the Orbiter boundary layer transition correlation implementation unique is that a statistically significant data set was acquired in multiple ground test facilities, flight data exists to assist in establishing a better correlation and the framework was founded upon state of the art chemical nonequilibrium Navier Stokes flow field simulations. The basic tenets that guided the formulation and implementation of the Orbiter Return To Flight boundary layer transition prediction capability will be reviewed as a recommended format for future empirical correlation efforts. The validity of this approach has since been demonstrated by very favorable comparison of recent entry flight testing performed with the Orbiter Discovery, which will be graphically summarized. These flight data can provide a means to validate discrete protuberance engineering correlation approaches as well as high fidelity prediction methods to higher confidence. The results of these Orbiter engineering and flight test activities only serve to reinforce the essential role that engineering correlations currently exercise in the design and operation of entry vehicles. The framework of information-related to the Orbiter empirical boundary layer transition

Synthesis of Oxides Containing Transition Metals

DTIC Science & Technology

1990-07-09

metal oxide single crystals by the electrolysis of molten salts containing mixtures of the appropriate oxides. Andreiux and Bozon (33-34) were able to...examples of unusual transition metal oxides which can be prepared (usually as single crystals) by electrolysis of fused salts . Summary The methods of...ferrites with the composition MFe 204 involved the thermal decomposition of oxalate (3) or pyridinate salts (1). The synthesis of ferrites from mixed

New chemistry of transition metal oxyhydrides

PubMed Central

Kobayashi, Yoji; Hernandez, Olivier; Tassel, Cédric; Kageyama, Hiroshi

2017-01-01

Abstract In this review we describe recent advances in transition metal oxyhydride chemistry obtained by topochemical routes, such as low temperature reduction with metal hydrides, or high-pressure solid-state reactions. Besides the crystal chemistry, magnetic and transport properties of the bulk powder and epitaxial thin film samples, the remarkable lability of the hydride anion is particularly highlighted as a new strategy to discover unprecedented mixed anion materials. PMID:29383042

Two-dimensional transition metal dichalcogenides as atomically thin semiconductors: opportunities and challenges.

PubMed

Duan, Xidong; Wang, Chen; Pan, Anlian; Yu, Ruqin; Duan, Xiangfeng

2015-12-21

The discovery of graphene has ignited intensive interest in two-dimensional layered materials (2DLMs). These 2DLMs represent a new class of nearly ideal 2D material systems for exploring fundamental chemistry and physics at the limit of single-atom thickness, and have the potential to open up totally new technological opportunities beyond the reach of existing materials. In general, there are a wide range of 2DLMs in which the atomic layers are weakly bonded together by van der Waals interactions and can be isolated into single or few-layer nanosheets. The van der Waals interactions between neighboring atomic layers could allow much more flexible integration of distinct materials to nearly arbitrarily combine and control different properties at the atomic scale. The transition metal dichalcogenides (TMDs) (e.g., MoS2, WSe2) represent a large family of layered materials, many of which exhibit tunable band gaps that can undergo a transition from an indirect band gap in bulk crystals to a direct band gap in monolayer nanosheets. These 2D-TMDs have thus emerged as an exciting class of atomically thin semiconductors for a new generation of electronic and optoelectronic devices. Recent studies have shown exciting potential of these atomically thin semiconductors, including the demonstration of atomically thin transistors, a new design of vertical transistors, as well as new types of optoelectronic devices such as tunable photovoltaic devices and light emitting devices. In parallel, there have also been considerable efforts in developing diverse synthetic approaches for the rational growth of various forms of 2D materials with precisely controlled chemical composition, physical dimension, and heterostructure interface. Here we review the recent efforts, progress, opportunities and challenges in exploring the layered TMDs as a new class of atomically thin semiconductors.

Transition metal doped (X = V, Cr) CdS monolayer: A DFT study

NASA Astrophysics Data System (ADS)

Deb, Jyotirmoy; Paul, Debolina; Sarkar, Utpal

2018-05-01

In this work based on density functional theory approach with generalized gradient approximation we have investigated the effect doping and co-doping of transition metal atoms in CdS monolayer sheet. On the basis cohesive energy, we have determined the stability of all the transition metal doped systems. CdS monolayer is of nonmagnetic character but the insertion of transition metal atoms introduces the spontaneous spin polarization which results in a significant value of magnetic moment. The band structure analysis reveals that three different types of conducting nature such as spin-select-half-semiconductor, half metallic and metallic nature with total spin polarization has also been observed. The versatile conducting nature of the transition metal doped CdS monolayer predicts the possibility of using these systems in spintronics mainly as a spin filter and also to form metal-semiconductor interface etc. at nanoscale level.

Peruvian perovskite Between Transition-metal to PGM/PlatinumGroupMetal Catalytic Fusion

NASA Astrophysics Data System (ADS)

Maksoed, Wh-

2016-11-01

Strongly correlated electronic materials made of simple building blocks, such as a transition-metal ion in an octahedral oxygen cage forming a perovskite structure- Dagotto & Tokura for examples are the high-temperature superconductivity & the CMR/Colossal Magnetoresistance . Helium-4 denotes from LC Case,ScD: "Catalytic Fusion of Deuterium into Helium-4"- 1998 dealt with gaseous D2- "contacted with a supported metallic catalyst at superatmospheric pressure". The catalyst is a platinum-group metal, at about 0.5% - 1% by weight, on activated C. Accompanies Stephen J Geier, 2010 quotes "transition metal complexes", the Energy thus produced is enormous, and because the deuterium is very cheap in the form of heavy water (less than US 1/g), the fuel cost is very low (<<1 %/KwH). "The oceans contain enough deuterium to satisfy the Earth's energy needs for many millions of year" to keep "maria"/Latin name of seas &Deuteronomy to be eternally preserves. Heartfelt Gratitudes to HE. Mr. Prof. Ir. HANDOJO.

Surface plasmons based terahertz modulator consisting of silicon-air-metal-dielectric-metal layers

NASA Astrophysics Data System (ADS)

Wang, Wei; Yang, Dongxiao; Qian, Zhenhai

2018-05-01

An optically controlled modulator of the terahertz wave, which is composed of a metal-dielectric-metal structure etched with circular loop arrays on both the metal layers and a photoexcited silicon wafer separated by an air layer, is proposed. Simulation results based on experimentally measured complex permittivities predict that modification of complex permittivity of the silicon wafer through excitation laser leads to a significant tuning of transmission characteristics of the modulator, forming the modulation depths of 59.62% and 96.64% based on localized surface plasmon peak and propagating surface plasmon peak, respectively. The influences of the complex permittivity of the silicon wafer and the thicknesses of both the air layer and the silicon wafer are numerically studied for better understanding the modulation mechanism. This study proposes a feasible methodology to design an optically controlled terahertz modulator with large modulation depth, high speed and suitable insertion loss, which is useful for terahertz applications in the future.

Covalence of atoms in the heavier transition metals*

PubMed Central

Pauling, Linus

1977-01-01

The observed magnetic properties of the heavier transition metals permit them to have larger metallic valences than their iron-group congeners. With 0.72 metallic orbital, as found for the iron-group metals, the maximum metallic valence and minimum interatomic distance would occur for 8.28 transargononic electrons. The curves of observed interatomic distances for the close-packed metals of the second and third long periods have minima at this point, supporting the assignment of high valences to these metals. Values of the single-bond radii corresponding to these valences are calculated. PMID:16592407

Near-inertial kinetic energy budget of the mixed layer and shear evolution in the transition layer in the Arabian Sea during the monsoons

NASA Astrophysics Data System (ADS)

Majumder, Sudip; Tandon, Amit; Rudnick, Daniel L.; Thomas Farrar, J.

2015-09-01

We present the horizontal kinetic energy (KE) balance of near-inertial currents in the mixed layer and explain shear evolution in the transition layer using observations from a mooring at 15.26° N in the Arabian Sea during the southwest monsoon. The highly sheared and stratified transition layer at the mixed-layer base varies between 5 m and 35 m and correlates negatively with the wind stress. Results from the mixed layer near-inertial KE (NIKE) balance suggest that wind energy at times can energize the transition layer and at other times is fully utilized within the mixed layer. A simple two layer model is utilized to study the shear evolution in the transition layer and shown to match well with observations. The shear production in this model arises from alignment of wind stress and shear. Although the winds are unidirectional during the monsoon, the shear in the transition layer is predominantly near-inertial. The near-inertial shear bursts in the observations show the same phasing and magnitude at near-inertial frequencies as the wind-shear alignment term.

Hydrogen and dihydrogen bonding of transition metal hydrides

NASA Astrophysics Data System (ADS)

Jacobsen, Heiko

2008-04-01

Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2NO(PH 3) 2 and a small proton donor H 2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H⋯H bond of transition metal hydrides contains both covalent and electrostatic contributions.

A study of low-dimensional quaternary mixed-transition metal chalcogenides

NASA Astrophysics Data System (ADS)

Oledzka, Magdalena Agata

powders. p-Type semiconducting behavior was observed for the samples with rhosbRT of {˜}10sp{-1}Omega{*}cm, and Esba˜ 0.1 eV. The relatively high values of magnetic susceptibility and the weak maximum in the temperature dependence of the magnetic susceptibility above 100 K was attributed to short-range antiferromagnetic interactions. New quaternary layered sulfides: NaCuMSsb2 (M = Mn, Fe, Co, Zn) crystallize in the trigonal CaAlsb2Sisb2-type structure in space group P{bar 3}m1. All the new phases are semiconducting, with rhosb{RT} varying from 6.2× 10sp{-1} to 5× 10sp{-2}Omega{*}cm, depending upon the transition metal M. Magnetic susceptibility measurements indicate the presence of localized Mnsp{2+} ions in NaCuMnSsb2. The NaCuMSsb2 (M = Fe, Co) phases display temperature independent paramagnetism whereas the NaCuZnSsb2 phase is diamagnetic, as expected. In addition, detailed low-temperature magnetic studies of the NaCuFeSsb2 phase revealed spin-glass-type behavior with the freezing temperature Tsbf˜ 50 K.

Shuttle Return To Flight Experimental Results: Cavity Effects on Boundary Layer Transition

NASA Technical Reports Server (NTRS)

Liechty, Derek S.; Horvath, Thomas J.; Berry, Scott A.

2006-01-01

The effect of an isolated rectangular cavity on hypersonic boundary layer transition of the windward surface of the Shuttle Orbiter has been experimentally examined in the Langley Aerothermodynamics Laboratory in support of an agency-wide effort to prepare the Shuttle Orbiter for return to flight. This experimental study was initiated to provide a cavity effects database for developing hypersonic transition criteria to support on-orbit decisions to repair a damaged thermal protection system. Boundary layer transition results were obtained using 0.0075-scale Orbiter models with simulated tile damage (rectangular cavities) of varying length, width, and depth. The database contained within this report will be used to formulate cavity-induced transition correlations using predicted boundary layer edge parameters.

Surface plasmon dispersion engineering via double-metallic AU/AG layers for nitride light-emitting diodes

DOEpatents

Tansu, Nelson; Zhao, Hongping; Zhang, Jing; Liu, Guangyu

2014-04-01

A double-metallic deposition process is used whereby adjacent layers of different metals are deposited on a substrate. The surface plasmon frequency of a base layer of a first metal is tuned by the surface plasmon frequency of a second layer of a second metal formed thereon. The amount of tuning is dependent upon the thickness of the metallic layers, and thus tuning can be achieved by varying the thicknesses of one or both of the metallic layers. In a preferred embodiment directed to enhanced LED technology in the green spectrum regime, a double-metallic Au/Ag layer comprising a base layer of gold (Au) followed by a second layer of silver (Ag) formed thereon is deposited on top of InGaN/GaN quantum wells (QWs) on a sapphire/GaN substrate.

Influence of Passivation Layers for Metal Grating-Based Quantum Well Infrared Photodetectors

NASA Astrophysics Data System (ADS)

Liu, Dong; Fu, Yong-Qi; Yang, Le-Chen; Zhang, Bao-Shun; Li, Hai-Jun; Fu, Kai; Xiong, Min

2012-06-01

To improve absorption of quantum well infrared photodetectors (QWIPs), a coupling layer with metallic grating is designed and fabricated above the quantum well. The metal grating is composed of 100 nm Au film on top, and a 20-nm Ti thin layer between the Au film and the sapphire substrate is coated as an adhesion/buffer layer. To protect the photodetector from oxidation and to decrease leakage, a SiO2 film is deposited by means of plasma-enhanced chemical vapor deposition. A value of about 800 nm is an optimized thickness for the SiO2 applied in the metallic grating-based mid-infrared QWIP. In addition, a QWIP passivation layer is studied experimentally. The results demonstrate that the contribution from the layer is positive for metal grating coupling with the quantum well. The closer the permittivity of the two dielectric layers (SiO2 and the passivation layers), and the closer the two transmission peaks, the greater the QWIP enhancement will be.

Electrochemical Characteristics of Layered Transition Metal Oxide Cathode Materials for Lithium Ion Batteries: Surface, Bulk Behavior, and Thermal Properties.

PubMed

Tian, Chixia; Lin, Feng; Doeff, Marca M

2018-01-16

Layered lithium transition metal oxides, in particular, NMCs (LiNi x Co y Mn z O 2 ) represent a family of prominent lithium ion battery cathode materials with the potential to increase energy densities and lifetime, reduce costs, and improve safety for electric vehicles and grid storage. Our work has focused on various strategies to improve performance and to understand the limitations to these strategies, which include altering compositions, utilizing cation substitutions, and charging to higher than usual potentials in cells. Understanding the effects of these strategies on surface and bulk behavior and correlating structure-performance relationships advance our understanding of NMC materials. This also provides information relevant to the efficacy of various approaches toward ensuring reliable operation of these materials in batteries intended for demanding traction and grid storage applications. In this Account, we start by comparing NMCs to the isostructural LiCoO 2 cathode, which is widely used in consumer batteries. Effects of changing the metal content (Ni, Mn, Co) upon structure and performance of NMCs are briefly discussed. Our early work on the effects of partial substitution of Al, Fe, and Ti for Co on the electrochemical and bulk structural properties is then covered. The original aim of this work was to reduce the Co content (and thus the raw materials cost) and to determine the effect of the substitutions on the electrochemical and bulk structural properties. More recently, we have turned to the application of synchrotron and advanced microscopy techniques to understand both bulk and surface characteristics of the NMCs. Via nanoscale-to-macroscale spectroscopy and atomically resolved imaging techniques, we were able to determine that the surfaces of NMC undergo heterogeneous reconstruction from a layered structure to rock salt under a variety of conditions. Interestingly, formation of rock salt also occurs under abuse conditions. The surface

Role of phonons in the metal-insulator phase transition.

NASA Technical Reports Server (NTRS)

Langer, W. D.

1972-01-01

Review, for the transition series oxides, of the Mattis and Lander model, which is one of electrons interacting with lattice vibrations (electron and phonon interaction). The model displays superconducting, insulating, and metallic phases. Its basic properties evolve from a finite crystallographic distortion associated with a dominant phonon mode and the splitting of the Brillouin zone into two subzones, a property of simple cubic and body centered cubic lattices. The order of the metal-insulator phase transition is examined. The basic model has a second-order phase transition and the effects of additional mechanisms on the model are calculated. The way in which these mechanisms affect the magnetically ordered transition series oxides as described by the Hubbard model is discussed.

Electronic, magnetic and transport properties of transition metal-doped holely C2N-h2D nanoribbons

NASA Astrophysics Data System (ADS)

He, Jing-Jing; Guo, Yan-Dong; Yan, Xiao-Hong; Zeng, Hong-Li

2018-01-01

A novel layered two-dimensional graphene-like material C2N-h2D with evenly distributed holes and nitrogen atoms has been synthesized via a bottom-up wet-chemical reaction [Nat. Commun. 6, 6486 (2015)]. The presence of holes provides a ground for further functionalization by doping. By performing a first-principles study, we have doped transition metals at the center of the holes of C2N-h2D nanoribbons and explored their doping effects on electronic, magnetic and transport properties. It is found that the doping can essentially regulate the electronic properties of C2N-h2D nanoribbons. The metallic zigzag ribbon is tuned into a semiconductor for Mn, Fe and Co-doped cases, but half-metal for Ni-doping. This transition is derived from the peculiar band morphology which has a big band gap between the edge state and the higher band, so when the energy of the edge state is reduced by the impurity state, the band gap falls too and crosses the Fermi level. In contrast, the pristine semiconducting armchair C2N-h2D nanoribbon is changed into metallic. Different from the zigzag case, its physical mechanism originates from the hybridization of 3 d orbitals of transition metal atoms and the p orbitals of carbon and nitrogen atoms which introduces several resonant peaks at the Fermi level in the density of states. Furthermore, the magnetic moments of all doped materials are enhanced compared to the pristine structures but decrease as the atomic number of the transition metal atom increases. And the spin polarization of armchair C2N-h2D nanoribbon is increased, while that of the zigzag structure is decreased except the Ni-doped one which is completely spin-polarized suggesting great prospects in the future of spintronics and nanoelectronics.

The Electronic Structure of Transition Metal Coated Fullerenes

NASA Astrophysics Data System (ADS)

Patton, David C.; Pederson, Mark R.; Kaxiras, Efthimios

1998-03-01

Clusters composed of fullerene molecules with an outer shell of transition metal atoms in the composition C_60M_62 (M being a transition metal) have been produced with laser vaporisation techniques(F. Tast, N. Malinowski, S. Frank, M. Heinebrodt, I.M.L. Billas, and T. P. Martin, Z. Phys D 40), 351 (1997).. We have studied several of these very large systems with a parallel version of the all-electron NRLMOL cluster code. Optimized geometries of the metal encased fullerenes C_60Ti_62 and C_60V_62 are presented along with their HOMO-LUMO gaps, electron affinities, ionization energies, and cohesive energies. We compare the stability of these clusters to relaxed met-car structures (e.g. Ti_8C_12) and to relaxed rocksalt metal-carbide fragments (TiC)n with n=8 and 32. In addition to metal-coated fullerenes we consider the possibility of a trilayered structure consisting of a small shell of metal atoms enclosed by a metal coated fullerene. The nature of bonding in these systems is analyzed by studying the electronic charge distributions.

Metal Thio- and Selenophosphates as Multifunctional van der Waals Layered Materials.

PubMed

Susner, Michael A; Chyasnavichyus, Marius; McGuire, Michael A; Ganesh, Panchapakesan; Maksymovych, Petro

2017-10-01

Since the discovery of Dirac physics in graphene, research in 2D materials has exploded with the aim of finding new materials and harnessing their unique and tunable electronic and optical properties. The follow-on work on 2D dielectrics and semiconductors has led to the emergence and development of hexagonal boron nitride, black phosphorus, and transition metal disulfides. However, the spectrum of good insulating materials is still very narrow. Likewise, 2D materials exhibiting correlated phenomena such as superconductivity, magnetism, and ferroelectricity have yet to be developed or discovered. These properties will significantly enrich the spectrum of functional 2D materials, particularly in the case of high phase-transition temperatures. They will also advance a fascinating fundamental frontier of size and proximity effects on correlated ground states. Here, a broad family of layered metal thio(seleno)phosphate materials that are moderate- to wide-bandgap semiconductors with incipient ionic conductivity and a host of ferroic properties are reviewed. It is argued that this material class has the potential to merge the sought-after properties of complex oxides with electronic functions of 2D and quasi-2D electronic materials, as well as to create new avenues for both applied and fundamental materials research in structural and magnetic correlations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Boundary Layer Transition Flight Experiment Overview

NASA Technical Reports Server (NTRS)

Berger, Karen T.; Anderson, Brian P.; Campbell, Charles H.; Garske, Michael T.; Saucedo, Luis A.; Kinder, Gerald R.; Micklos, Ann M.

2011-01-01

In support of the Boundary Layer Transition Flight Experiment (BLT FE) Project, a manufactured protuberance tile was installed on the port wing of Space Shuttle Orbiter Discovery for STS-119, STS-128, STS-131 and STS-133 as well as Space Shuttle Endeavour for STS-134. Additional instrumentation was installed in order to obtain more spatially resolved measurements downstream of the protuberance. This paper provides an overview of the BLT FE Project with emphasis on the STS-131 and STS-133 results. A high-level overview of the in-situ flight data is presented, along with a summary of the comparisons between pre- and post-flight analysis predictions and flight data. Comparisons show that empirically correlated predictions for boundary layer transition onset time closely match the flight data, while predicted surface temperatures were significantly higher than observed flight temperatures. A thermocouple anomaly observed on a number of the missions is discussed as are a number of the mitigation actions that will be taken on the final flight, STS-134, including potential alterations of the flight trajectory and changes to the flight instrumentation.

Superconductivity and bandwidth-controlled Mott metal-insulator transition in 1T-TaS2-xSex

NASA Astrophysics Data System (ADS)

Ang, R.; Miyata, Y.; Ieki, E.; Nakayama, K.; Sato, T.; Liu, Y.; Lu, W. J.; Sun, Y. P.; Takahashi, T.

2013-09-01

We have performed high-resolution angle-resolved photoemission spectroscopy (ARPES) of layered chalcogenide 1T-TaS2-xSex to elucidate the electronic states especially relevant to the occurrence of superconductivity. We found a direct evidence for a Ta-5d-derived electron pocket associated with the superconductivity, which is fragile against a Mott-gap opening observed in the insulating ground state for S-rich samples. In particular, a strong electron-electron interaction-induced Mott gap driven by a Ta 5d orbital also exists in the metallic ground state for Se-rich samples, while finite ARPES intensity near the Fermi level likely originating from a Se 4p orbital survives, indicative of the orbital-selective nature of the Mott transition. Present results suggest that effective electron correlation and p-d hybridization play a crucial role to tune the superconductivity and Mott metal-insulator transition.

An Alternative Approach to the Teaching of Systematic Transition Metal Chemistry.

ERIC Educational Resources Information Center

Hathaway, Brian

1979-01-01

Presents an alternative approach to teaching Systematic Transition Metal Chemistry with the transition metal chemistry skeleton features of interest. The "skeleton" is intended as a guide to predicting the chemistry of a selected compound. (Author/SA)

Meteoric metal layers in the atmosphere of Mars

NASA Astrophysics Data System (ADS)

Plane, John; Whalley, Charlotte

Radio occultation measurements from several spacecraft (e.g., Mars Express, Mars Global Sur-veyor) have revealed the presence of a "third" ion layer in the Martian atmosphere, which occurs sporadically around 90 km. Because this is the aerobraking region of the atmosphere, and the layers resemble sporadic E layers observed in the terrestrial atmosphere, it has been proposed that these layers consist of metallic ions (principally Fe+ and Mg+ ). A major problem with this hypothesis is that we have shown recently that metallic ions re-combine rapidly in a CO2 -rich atmosphere, both because of the efficiency of CO2 as the "third body" and because of the very low temperatures (about 140 K). In fact, both Fe+ and Mg+ form CO2 cluster ions about 200 times faster than current Mars models predict. These cluster ions should rapidly be destroyed by dissociative recombination with electrons, so that sporadic layers containing metallic ions would have lifetimes of only minutes. We will present a new laboratory study of all the reactions that appear to be required to solve this problem. Most importantly, we will show that the reactions of molecular magnesium ions (Mg+ .CO2 , MgO2 + and MgO+ ) with atomic O are about 20 times faster than expected. The laboratory will then be used to construct a new model of the Martian upper atmosphere, which demonstrates that the sporadic third layers must largely be composed of Mg+ and not Fe+ . These layers should then have lifetimes of more than 10 hours, in accord with observations from Mars Express made on successive orbits.

Shuttle Return To Flight Experimental Results: Protuberance Effects on Boundary Layer Transition

NASA Technical Reports Server (NTRS)

Liechty, Derek S.; Berry, Scott A.; Horvath, Thomas J.

2006-01-01

The effect of isolated roughness elements on the windward boundary layer of the Shuttle Orbiter has been experimentally examined in the Langley Aerothermodynamic Laboratory in support of an agency-wide effort to prepare the Shuttle Orbiter for return to flight. This experimental effort was initiated to provide a roughness effects database for developing transition criteria to support on-orbit decisions to repair damage to the thermal protection system. Boundary layer transition results were obtained using trips of varying heights and locations along the centerline and attachment lines of 0.0075-scale models. Global heat transfer images using phosphor thermography of the Orbiter windward surface and the corresponding heating distributions were used to infer the state of the boundary layer (laminar, transitional, or turbulent). The database contained within this report will be used to formulate protuberance-induced transition correlations using predicted boundary layer edge parameters.

Metal-insulator and charge ordering transitions in oxide nanostructures

NASA Astrophysics Data System (ADS)

Singh, Sujay Kumar

Strongly correlated oxides are a class of materials wherein interplay of various degrees of freedom results in novel electronic and magnetic phenomena. Vanadium oxides are widely studied correlated materials that exhibit metal-insulator transitions (MIT) in a wide temperature range from 70 K to 380 K. In this Thesis, results from electrical transport measurements on vanadium dioxide (VO2) and vanadium oxide bronze (MxV 2O5) (where M: alkali, alkaline earth, and transition metal cations) are presented and discussed. Although the MIT in VO2 has been studied for more than 50 years, the microscopic origin of the transition is still debated since a slew of external parameters such as light, voltage, and strain are found to significantly alter the transition. Furthermore, recent works on electrically driven switching in VO2 have shown that the role of Joule heating to be a major cause as opposed to electric field. We explore the mechanisms behind the electrically driven switching in single crystalline nanobeams of VO2 through DC and AC transport measurements. The harmonic analysis of the AC measurement data shows that non-uniform Joule heating causes electronic inhomogeneities to develop within the nanobeam and is responsible for driving the transition in VO2. Surprisingly, field assisted emission mechanisms such as Poole-Frenkel effect is found to be absent and the role of percolation is also identified in the electrically driven transition. This Thesis also provides a new insight into the mechanisms behind the electrolyte gating induced resistance modulation and the suppression of MIT in VO2. We show that the metallic phase of VO2 induced by electrolyte gating is due to an electrochemical process and can be both reversible and irreversible under different conditions. The kinetics of the redox processes increase with temperature; a complete suppression of the transition and the stabilization of the metallic phase are achievable by gating in the rutile metallic phase

Phase diagram of the ultrafast photoinduced insulator-metal transition in vanadium dioxide

NASA Astrophysics Data System (ADS)

Cocker, T. L.; Titova, L. V.; Fourmaux, S.; Holloway, G.; Bandulet, H.-C.; Brassard, D.; Kieffer, J.-C.; El Khakani, M. A.; Hegmann, F. A.

2012-04-01

We use time-resolved terahertz spectroscopy to probe the ultrafast dynamics of the insulator-metal phase transition induced by femtosecond laser pulses in a nanogranular vanadium dioxide (VO2) film. Based on the observed thresholds for characteristic transient terahertz dynamics, a phase diagram of critical pump fluence versus temperature for the insulator-metal phase transition in VO2 is established for the first time over a broad range of temperatures down to 17 K. We find that both Mott and Peierls mechanisms are present in the insulating state and that the photoinduced transition is nonthermal. We propose a critical-threshold model for the ultrafast photoinduced transition based on a critical density of electrons and a critical density of coherently excited phonons necessary for the structural transition to the metallic state. As a result, evidence is found at low temperatures for an intermediate metallic state wherein the Mott state is melted but the Peierls distortion remains intact, consistent with recent theoretical predictions. Finally, the observed terahertz conductivity dynamics above the photoinduced transition threshold reveal nucleation and growth of metallic nanodomains over picosecond time scales.

Quantum size effects in layered VX{sub 2} (X = S, Se) materials: Manifestation of metal to semimetal or semiconductor transition

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

Wasey, A. H. M. Abdul; Chakrabarty, Soubhik; Das, G. P., E-mail: msgpd@iacs.res.in

2015-02-14

Most of the two dimensional (2D) transition metal dichalcogenides (TMDC) are nonmagnetic in pristine form. However, 2D pristine VX{sub 2} (X = S, Se, Te) materials are found to be ferromagnetic. Using spin polarized density functional theory (DFT) calculations, we have studied the electronic, magnetic, and surface properties of this class of materials in both trigonal prismatic H- and octahedral T-phase. Our calculations reveal that they exhibit materially different properties in those two polymorphs. Most importantly, detailed investigation of electronic structure explored the quantum size effect in H-phase of these materials thereby leading to metal to semimetal (H-VS{sub 2}) or semiconductor (H-VSe{submore » 2}) transition when downsizing from bilayer to corresponding monolayer.« less

Evaluating transition-metal catalysis in gas generation from the Permian Kupferschiefer by hydrous pyrolysis

USGS Publications Warehouse

Lewan, M.D.; Kotarba, M.J.; Wieclaw, D.; Piestrzynski, A.

2008-01-01

Transition metals in source rocks have been advocated as catalysts in determining extent, composition, and timing of natural gas generation (Mango, F. D. (1996) Transition metal catalysis in the generation of natural gas. Org. Geochem.24, 977–984). This controversial hypothesis may have important implications concerning gas generation in unconventional shale-gas accumulations. Although experiments have been conducted to test the metal-catalysis hypothesis, their approach and results remain equivocal in evaluating natural assemblages of transition metals and organic matter in shale. The Permian Kupferschiefer of Poland offers an excellent opportunity to test the hypothesis with immature to marginally mature shale rich in both transition metals and organic matter. Twelve subsurface samples containing similar Type-II kerogen with different amounts and types of transition metals were subjected to hydrous pyrolysis at 330° and 355 °C for 72 h. The gases generated in these experiments were quantitatively collected and analyzed for molecular composition and stable isotopes. Expelled immiscible oils, reacted waters, and spent rock were also quantitatively collected. The results show that transition metals have no effect on methane yields or enrichment. δ13C values of generated methane, ethane, propane and butanes show no systematic changes with increasing transition metals. The potential for transition metals to enhance gas generation and oil cracking was examined by looking at the ratio of the generated hydrocarbon gases to generated expelled immiscible oil (i.e., GOR), which showed no systematic change with increasing transition metals. Assuming maximum yields at 355 °C for 72 h and first-order reaction rates, pseudo-rate constants for methane generation at 330 °C were calculated. These rate constants showed no increase with increasing transition metals. The lack of a significant catalytic effect of transition metals on the extent, composition, and timing of

Metal-metal bond lengths in complexes of transition metals*

PubMed Central

Pauling, Linus

1976-01-01

In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths. PMID:16592368

Transition metal sulfide loaded catalyst

DOEpatents

Maroni, Victor A.; Iton, Lennox E.; Pasterczyk, James W.; Winterer, Markus; Krause, Theodore R.

1994-01-01

A zeolite based catalyst for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C.sub.2 + hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

Comparison of turbulence in a transitional boundary layer to turbulence in a developed boundary layer*

NASA Astrophysics Data System (ADS)

Park, G. I.; Wallace, J.; Wu, X.; Moin, P.

2010-11-01

Using a recent DNS of a flat-plate boundary layer, statistics of turbulence in transition at Reθ= 500 where spots merge (distributions of the mean velocity, rms velocity and vorticity fluctuations, Reynolds shear stress, kinetic energy production and dissipation rates and enstrophy) have been compared to these statistics for the developed boundary layer turbulence at Reθ= 1850. When the distributions in the transitional region, determined in narrow planes 0.03 Reθ wide, exclude regions and times when the flow is not turbulent, they closely resemble those in the developed turbulent state at the higher Reynolds number, especially in the buffer and sublayers. The skin friction coefficient, determined in this conditional manner in the transitional flow is, of course, much larger than that obtained by including both turbulent and non-turbulent information there, and is consistent with a value obtained by extrapolating from the developed turbulent region. We are attempting to perform this data analysis even further upstream in the transitioning flow at Reθ= 300 where the turbulent spots are individuated. These results add further evidence to support the view that the structure of a developed turbulent boundary layer is little different from its structure in its embryonic form in turbulent spots. *CTR 2010 Summer Program research.

Metal aminocarboxylate coordination polymers with chain and layered structures.

PubMed

Dan, Meenakshi; Rao, C N R

2005-11-18

The synthesis and structures of metal aminocarboxylates prepared in acidic, neutral, or alkaline media have been explored with the purpose of isolating coordination polymers with linear chain and two-dimensional layered structures. Metal glycinates of the formulae [CoCl2(H2O)2(CO2CH2NH3)] (I), [MnCl2(CO2CH2NH3)2] (II), and [Cd3Cl6(CO2CH2NH3)4] (III) with one-dimensional chain structures have been obtained by the reaction of the metal salts with glycine in an acidic medium under hydro/solvothermal conditions. These chain compounds contain glycine in the zwitterionic form. 4-Aminobutyric acid transforms to a cyclic amide under such reaction conditions, and the amide forms a chain compound of the formula [CdBr2(C4H7NO)2] (IV). Glycine in the zwitterionic form also forms a two-dimensional layered compound of the formula [Mn(H2O)2(CO2CH2NH3)2]Br2 (V). 6-Aminocaproic acid under alkaline conditions forms layered compounds with metals at room temperature, the metal being coordinated both by the amino nitrogen and the carboxyl oxygen atoms. Of the two layered compounds [Cd{CO2(CH2)5NH2}2]2 H2O (VI) and [Cu{CO2(CH2)5NH2}2]2 H2O (VII), the latter has voids in which water molecules reside.

Metallicity of Ca 2Cu 6P 5 with single and double copper-pnictide layers

DOE PAGES

Li, Li; Parker, David; Chi, Miaofang; ...

2016-02-16

We report thermodynamic and transport properties, and also theoretical calculations, for Cu-based compound Ca 2Cu 6P 5 and compare with CaCu 2-δP 2. Both materials have layers of edge-sharing copper pnictide tetrahedral CuP 4, similar to Fe–As and Fe–Se layers (with FeAs 4, FeSe 4) in the iron-based superconductors. Despite the presence of this similar transition-metal pnictide layer, we find that both Ca 2Cu 6P 5 and CaCu 2-δP 2 have temperature-independent magnetic susceptibility and show metallic behavior with no evidence of either magnetic ordering or superconductivity down to 1.8 K CaCu 2-δP 2 is slightly off-stoichiometric, with δ =more » 0.14. Theoretical calculations suggest that unlike Fe 3d-based magnetic materials with a large density of states (DOS) at the Fermi surface, Cu have comparatively low DOS, with the majority of the 3d spectral weight located well below Fermi level. The room-temperature resistivity value of Ca 2Cu 6P 5 is only 9 μΩ-cm, due to a substantial plasma frequency and an inferred electron-phonon coupling λ of 0.073 (significantly smaller than that of metallic Cu). Also, microscopy result shows that Cu–Cu distance along the c-axis within the double layers can be very short (2.5 Å), even shorter than metallic elemental copper bond (2.56 Å). The value of dρ/dT for CaCu 2-δP 2 at 300 K is approximately three times larger than in Ca 2Cu 6P 5, which suggests the likelihood of stronger electron-phonon coupling. Lastly, this study shows that the details of Cu–P layers and bonding are important for their transport characteristics. In addition, it emphasizes the remarkable character of the DOS of ‘122’ iron-based materials, despite much structural similarities.« less

Understanding the Intrinsic Electrochemistry of Ni-Rich Layered Cathodes

NASA Astrophysics Data System (ADS)

Sallis, Shawn

The demand for energy is continually increasing overtime and the key to meeting future demand in a sustainable way is with energy storage. Li-ion batteries employing layered transition metal oxide cathodes are one of the most technologically important energy storage technologies. However, current Li-ion batteries are unable to access their full theoretical capacity and suffer from performance limiting degradation over time partially originating from the cathode and partially from the interface with the electrolyte. Understanding the fundamental limitations of layered transition metal oxide cathodes requires a complete understanding of the surface and bulk of the materials in their most delithiated state. In this thesis, we employ LiNi0.8Co0.15Al 0.05O2 (NCA) as a model system for Ni-rich layered oxide cathodes. Unlike its parent compound, LiCoO2, NCA is capable of high states of delithiation with minimal structural transitions. Furthermore, commercially available NCA has little to no transition metals in the Li layer. X-ray spectroscopies are an ideal tool for studying cathodes at high states of delithiation due their elemental selectivity, range of probing depths, and sensitivity to both chemical and electronic state information. The oxidation state of the transition metals at the surface can be probed via X-ray photoelectron spectroscopy (XPS) while both bulk and surface oxidation states as well as changes in metal oxygen bonding can be probed using X-ray absorption spectroscopy (XAS). Using X-ray spectroscopy in tandem with electrochemical, transport and microscopy measurements of the same materials, the impedance growth with increasing delithiation was correlated with the formation of a disordered NiO phase on the surface of NCA which was precipitated by the release of oxygen. Furthermore, the surface degradation was strongly impacted by the type of Li salt used in the electrolyte, with the standard commercial salt LiPF6 suffering from exothermic decomposition

Transition metal-substituted cobalt ferrite nanoparticles for biomedical applications.

PubMed

Sanpo, Noppakun; Berndt, Christopher C; Wen, Cuie; Wang, James

2013-03-01

Transition metals of copper, zinc, chromium and nickel were substituted into cobalt ferrite nanoparticles via a sol-gel route using citric acid as a chelating agent. The microstructure and elemental composition were characterized using scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. Phase analysis of transition metal-substituted cobalt ferrite nanoparticles was performed via X-ray diffraction. Surface wettability was measured using the water contact angle technique. The surface roughness of all nanoparticles was measured using profilometry. Moreover, thermogravimetric analysis and differential scanning calorimetry were performed to determine the temperature at which the decomposition and oxidation of the chelating agents took place. Results indicated that the substitution of transition metals influences strongly the microstructure, crystal structure and antibacterial property of the cobalt ferrite nanoparticles. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Growth and sacrificial oxidation of transition metal nanolayers

NASA Astrophysics Data System (ADS)

Tsarfati, Tim; Zoethout, Erwin; van de Kruijs, Robbert; Bijkerk, Fred

2009-04-01

Growth and oxidation of Au, Pt, Pd, Rh, Cu, Ru, Ni and Co layers of 0.3-4.3 nm thickness on Mo have been investigated with ARPES and AFM. Co and Ni layers oxidize while the Mo remains metallic. For nobler metals, the on top O and oxidation state of subsurface Mo increase, suggesting sacrificial e - donation by Mo. Au and Cu, in spite of their significantly lower surface free energy, grow in islands on Mo and actually promote Mo oxidation. Applications of the sacrificial oxidation in nanometer thin layers exist in a range of nanoscopic devices, such as nano-electronics and protection of e.g. multilayer X-ray optics for astronomy, medicine and lithography.

Transition metal sulfide loaded catalyst

DOEpatents

Maroni, V.A.; Iton, L.E.; Pasterczyk, J.W.; Winterer, M.; Krause, T.R.

1994-04-26

A zeolite-based catalyst is described for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C[sub 2]+ hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

Fabrication of carbon nanotube films from alkyne-transition metal complexes

DOEpatents

Iyer, Vivekanantan S [Delft, NL; Vollhardt, K Peter C. [Oakland, CA

2007-08-28

A simple method for the production or synthesis of carbon nanotubes as free-standing films or nanotube mats by the thermal decomposition of transition metal complexed alkynes with aryl, alkyl, alkenyl, or alkynyl substituents. In particular, transition metal (e.g. Co, Ni, Fe, Mo) complexes of diarylacetylenes, e.g. diphenylacetylene, and solid mixtures of these complexes with suitable, additional carbon sources are heated in a vessel. More specifically, the heating of the transition metal complex is completed at a temperature between 400-800.degree. C. and more particularly 550-700.degree. C. for between 0.1 to 24 hours and more particularly 0.5-3 hours in a sealed vessel under a partial pressure of argon or helium.

Porous nanoarchitectures of spinel-type transition metal oxides for electrochemical energy storage systems.

PubMed

Park, Min-Sik; Kim, Jeonghun; Kim, Ki Jae; Lee, Jong-Won; Kim, Jung Ho; Yamauchi, Yusuke

2015-12-14

Transition metal oxides possessing two kinds of metals (denoted as AxB3-xO4, which is generally defined as a spinel structure; A, B = Co, Ni, Zn, Mn, Fe, etc.), with stoichiometric or even non-stoichiometric compositions, have recently attracted great interest in electrochemical energy storage systems (ESSs). The spinel-type transition metal oxides exhibit outstanding electrochemical activity and stability, and thus, they can play a key role in realising cost-effective and environmentally friendly ESSs. Moreover, porous nanoarchitectures can offer a large number of electrochemically active sites and, at the same time, facilitate transport of charge carriers (electrons and ions) during energy storage reactions. In the design of spinel-type transition metal oxides for energy storage applications, therefore, nanostructural engineering is one of the most essential approaches to achieving high electrochemical performance in ESSs. In this perspective, we introduce spinel-type transition metal oxides with various transition metals and present recent research advances in material design of spinel-type transition metal oxides with tunable architectures (shape, porosity, and size) and compositions on the micro- and nano-scale. Furthermore, their technological applications as electrode materials for next-generation ESSs, including metal-air batteries, lithium-ion batteries, and supercapacitors, are discussed.

Pronounced Photovoltaic Response from Multilayered Transition-Metal Dichalcogenides PN-Junctions.

PubMed

Memaran, Shahriar; Pradhan, Nihar R; Lu, Zhengguang; Rhodes, Daniel; Ludwig, Jonathan; Zhou, Qiong; Ogunsolu, Omotola; Ajayan, Pulickel M; Smirnov, Dmitry; Fernández-Domínguez, Antonio I; García-Vidal, Francisco J; Balicas, Luis

2015-11-11

Transition metal dichalcogenides (TMDs) are layered semiconductors with indirect band gaps comparable to Si. These compounds can be grown in large area, while their gap(s) can be tuned by changing their chemical composition or by applying a gate voltage. The experimental evidence collected so far points toward a strong interaction with light, which contrasts with the small photovoltaic efficiencies η ≤ 1% extracted from bulk crystals or exfoliated monolayers. Here, we evaluate the potential of these compounds by studying the photovoltaic response of electrostatically generated PN-junctions composed of approximately 10 atomic layers of MoSe2 stacked onto the dielectric h-BN. In addition to ideal diode-like response, we find that these junctions can yield, under AM-1.5 illumination, photovoltaic efficiencies η exceeding 14%, with fill factors of ~70%. Given the available strategies for increasing η such as gap tuning, improving the quality of the electrical contacts, or the fabrication of tandem cells, our study suggests a remarkable potential for photovoltaic applications based on TMDs.

Photoelectrolysis at the oxide-electrolyte interface as interpreted through the 'transition' layer model

NASA Astrophysics Data System (ADS)

Kalia, R. K.; Weber, Michael F.; Schumacher, L.; Dignam, M. J.

1980-12-01

A transition layer model of the oxide-electrolyte interface, proposed earlier by one of us, is outlined and then examined in the light of experimental data relating primarily to photoelectrolysis of water at semiconducting oxide electrodes. The model provides useful insight into the behaviour of the system and allows a calculation of thc minimum bias potential needed for photoelectrolysis, thus illuminating the origin of the requirement for such an external bias. In order to electrolyse water without a bias, the model requires an n-type oxide to be sufficiently reduced so that it is thermodynamically capable of chemically reducing water to produce hydrogen at 1 atm pressure. Similarly, for bias-free operation, a p-type metal oxide must be thermodynamically unstable with respect to the release of oxygen at 1 atm pressure. In the face of these requirements it is apparent that oxide stability is bound to be in general a serious problem for nonstoichiometric single metal oxides.

Ultrafast photo-induced dynamics across the metal-insulator transition of VO2

NASA Astrophysics Data System (ADS)

Wang, Siming; Ramírez, Juan Gabriel; Jeffet, Jonathan; Bar-Ad, Shimshon; Huppert, Dan; Schuller, Ivan K.

2017-04-01

The transient reflectivity of VO2 films across the metal-insulator transition clearly shows that with low-fluence excitation, when insulating domains are dominant, energy transfer from the optically excited electrons to the lattice is not instantaneous, but precedes the superheating-driven expansion of the metallic domains. This implies that the phase transition in the coexistence regime is lattice-, not electronically-driven, at weak laser excitation. The superheated phonons provide the latent heat required for the propagation of the optically-induced phase transition. For VO2 this transition path is significantly different from what has been reported in the strong-excitation regime. We also observe a slow-down of the superheating-driven expansion of the metallic domains around the metal-insulator transition, which is possibly due to the competition among several co-existing phases, or an emergent critical-like behavior.

Tellurium tetrachloride and diphenyl ditelluride cause cytotoxicity in rat hippocampal astrocytes.

PubMed

Roy, Shalini; Hardej, Diane

2011-10-01

Tellurium tetrachloride (TeCl(4)) and diphenyl ditelluride (DPDT) cytotoxicity, was investigated in rat astrocytes. Concentrations of 0.24-250μM (24h) were tested for viability using MTT(3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide) and trypan blue exclusion. MTT showed significant decreases at all concentrations tested for both compounds. Significant decreases in viability were seen in 1.95-250μM of DPDT and 0.97-250μM of TeCl(4) with trypan blue exclusion. The LC(50) for both compounds was 62.5μM. Light and scanning microscopy confirm toxicity observed at higher concentrations. Thiobarbituric acid reactive substances (TBARs) assay, TUNEL, cytochrome c and caspase release were carried out. No significant increase in TBARS with either agent was observed (15.625-62.5μM). TUNEL and cytochrome c assays demonstrated apoptosis in TeCl(4) treated cells (31.25-125μM). Non-apoptotic cells were observed in DPDT treated cells. Studies of caspase 3/7 and caspase 9 indicated increased activity in TeCl(4) but not in DPDT treated cells. Optical Emission Spectroscopy of DPDT and TeCl(4) treated cells demonstrated significant accumulation of elemental tellurium in all treatment groups (31.25-125μM). We conclude that DPDT and TeCl(4) are cytotoxic to astrocytes. TeCl(4) treated cells die via the intrinsic apoptotic pathway. Accumulation of tellurium occurs with both compounds, but results in different mechanisms of cell death. Copyright © 2011 Elsevier Ltd. All rights reserved.

Recent advances in transition-metal dichalcogenides based electrochemical biosensors: A review.

PubMed

Wang, Yi-Han; Huang, Ke-Jing; Wu, Xu

2017-11-15

Layered transition metal dichalcogenides (TMDCs) comprise a category of two-dimensional (2D) materials that offer exciting properties, including large surface area, metallic and semi-conducting electrical capabilities, and intercalatable morphologies. Biosensors employ biological molecules to recognize the target and utilize output elements which can translate the biorecognition event into electrical, optical or mass-sensitive signals to determine the quantities of the target. TMDCs nanomaterials have been widely applied in various electrochemical biosensors with high sensitivity and selectivity. The marriage of TMDCs and electrochemical biosensors has created many productive sensing strategies for applications in the areas of clinical diagnosis, environmental monitoring and food safety. In recent years, an increasing number of TMDCs-based electrochemical biosensors are reported, suggesting TMDCs offers new possibilities of improving the performance of electrochemical biosensors. This review summarizes recent advances in electrochemical biosensors based on TMDCs for detection of various inorganic and organic analytes in the last five years, including glucose, proteins, DNA, heavy metal, etc. In addition, we also point out the challenges and future perspectives related to the material design and development of TMDCs-based electrochemical biosensors. Copyright © 2017 Elsevier B.V. All rights reserved.

Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses

NASA Astrophysics Data System (ADS)

Das, Santanu; Choudhary, Kamal; Chernatynskiy, Aleksandr; Choi Yim, Haein; Bandyopadhyay, Asis K.; Mukherjee, Sundeep

2016-06-01

High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe-Co metallic glass system of composition [(Co1-x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent ‘Stoner type’ magnetization for the amorphous alloys in contrast to ‘Heisenberg type’ in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study.

Characterization of structural response to hypersonic boundary-layer transition

DOE PAGES

Riley, Zachary B.; Deshmukh, Rohit; Miller, Brent A.; ...

2016-05-24

The inherent relationship between boundary-layer stability, aerodynamic heating, and surface conditions makes the potential for interaction between the structural response and boundary-layer transition an important and challenging area of study in high-speed flows. This paper phenomenologically explores this interaction using a fundamental two-dimensional aerothermoelastic model under the assumption of an aluminum panel with simple supports. Specifically, an existing model is extended to examine the impact of transition onset location, transition length, and transitional overshoot in heat flux and fluctuating pressure on the structural response of surface panels. Transitional flow conditions are found to yield significantly increased thermal gradients, and theymore » can result in higher maximum panel temperatures compared to turbulent flow. Results indicate that overshoot in heat flux and fluctuating pressure reduces the flutter onset time and increases the strain energy accumulated in the panel. Furthermore, overshoot occurring near the midchord can yield average temperatures and peak displacements exceeding those experienced by the panel subject to turbulent flow. Lastly, these results suggest that fully turbulent flow does not always conservatively predict the thermo-structural response of surface panels.« less

Pure electronic metal-insulator transition at the interface of complex oxides

DOE PAGES

Meyers, D.; Liu, Jian; Freeland, J. W.; ...

2016-06-21

We observed complex materials in electronic phases and transitions between them often involve coupling between many degrees of freedom whose entanglement convolutes understanding of the instigating mechanism. Metal-insulator transitions are one such problem where coupling to the structural, orbital, charge, and magnetic order parameters frequently obscures the underlying physics. We demonstrate a way to unravel this conundrum by heterostructuring a prototypical multi-ordered complex oxide NdNiO3 in ultra thin geometry, which preserves the metal-to-insulator transition and bulk-like magnetic order parameter, but entirely suppresses the symmetry lowering and long-range charge order parameter. Furthermore, these findings illustrate the utility of heterointerfaces as amore » powerful method for removing competing order parameters to gain greater insight into the nature of the transition, here revealing that the magnetic order generates the transition independently, leading to an exceptionally rare purely electronic metal-insulator transition with no symmetry change.« less

Modified Oxygen Defect Chemistry at Transition Metal Oxide Heterostructures Probed by Hard X-ray Photoelectron Spectroscopy and X-ray Diffraction

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

Chen, Yan; Fong, Dillon D.; Herbert, F. William

Transition metal oxide hetero-structures are interesting due to the distinctly different properties that can arise from their interfaces, such as superconductivity, high catalytic activity and magnetism. Oxygen point defects can play an important role at these interfaces in inducing potentially novel properties. The design of oxide hetero-structures in which the oxygen defects are manipulated to attain specific functionalities requires the ability to resolve the state and concentration of local oxygen defects across buried interfaces. In this work, we utilized a novel combination of hard x-ray photoelectron spectroscopy (HAXPES) and high resolution xray diffraction (HRXRD) to probe the local oxygen defectmore » distribution across the buried interfaces of oxide heterolayers. This approach provides a non-destructive way to qualitatively probe locally the oxygen defects in transition metal oxide hetero-structures. We studied two trilayer structures as model systems - the La 0.8Sr 0.2CoO 3-δ/(La 0.5Sr 0.5) 2CoO 4/La 0.8Sr 0.2CoO 3-δ (LSC 113/LSC 214) and the La 0.8Sr 0.2CoO 3-δ/La 2NiO 4+δ/La 0.8Sr 0.2CoO 3-δ (LSC 113/LNO 214) on SrTiO 3(001) single crystal substrates. We found that the oxygen defect chemistry of these transition metal oxides was strongly impacted by the presence of interfaces and the properties of the adjacent phases. Under reducing conditions, the LSC 113 in the LSC 113/LNO 214 tri-layer had less oxygen vacancies than the LSC 113 in the LSC 113/LSC 214 tri-layer and the LSC 113 single phase film. On the other hand, LSC 214 and LNO 214 were more reduced in the two tri-layer structures when in contact with the LSC 113 layer compared to their single phase counterparts. Furthermore, the results point out a potential way to modify the local oxygen defect states at oxide hetero-interfaces.« less

Modified Oxygen Defect Chemistry at Transition Metal Oxide Heterostructures Probed by Hard X-ray Photoelectron Spectroscopy and X-ray Diffraction

DOE PAGES

Chen, Yan; Fong, Dillon D.; Herbert, F. William; ...

2018-04-17

Transition metal oxide hetero-structures are interesting due to the distinctly different properties that can arise from their interfaces, such as superconductivity, high catalytic activity and magnetism. Oxygen point defects can play an important role at these interfaces in inducing potentially novel properties. The design of oxide hetero-structures in which the oxygen defects are manipulated to attain specific functionalities requires the ability to resolve the state and concentration of local oxygen defects across buried interfaces. In this work, we utilized a novel combination of hard x-ray photoelectron spectroscopy (HAXPES) and high resolution xray diffraction (HRXRD) to probe the local oxygen defectmore » distribution across the buried interfaces of oxide heterolayers. This approach provides a non-destructive way to qualitatively probe locally the oxygen defects in transition metal oxide hetero-structures. We studied two trilayer structures as model systems - the La 0.8Sr 0.2CoO 3-δ/(La 0.5Sr 0.5) 2CoO 4/La 0.8Sr 0.2CoO 3-δ (LSC 113/LSC 214) and the La 0.8Sr 0.2CoO 3-δ/La 2NiO 4+δ/La 0.8Sr 0.2CoO 3-δ (LSC 113/LNO 214) on SrTiO 3(001) single crystal substrates. We found that the oxygen defect chemistry of these transition metal oxides was strongly impacted by the presence of interfaces and the properties of the adjacent phases. Under reducing conditions, the LSC 113 in the LSC 113/LNO 214 tri-layer had less oxygen vacancies than the LSC 113 in the LSC 113/LSC 214 tri-layer and the LSC 113 single phase film. On the other hand, LSC 214 and LNO 214 were more reduced in the two tri-layer structures when in contact with the LSC 113 layer compared to their single phase counterparts. Furthermore, the results point out a potential way to modify the local oxygen defect states at oxide hetero-interfaces.« less

Hund's rule in superatoms with transition metal impurities.

PubMed

Medel, Victor M; Reveles, Jose Ulises; Khanna, Shiv N; Chauhan, Vikas; Sen, Prasenjit; Castleman, A Welford

2011-06-21

The quantum states in metal clusters bunch into supershells with associated orbitals having shapes resembling those in atoms, giving rise to the concept that selected clusters could mimic the characteristics of atoms and be classified as superatoms. Unlike atoms, the superatom orbitals span over multiple atoms and the filling of orbitals does not usually exhibit Hund's rule seen in atoms. Here, we demonstrate the possibility of enhancing exchange splitting in superatom shells via a composite cluster of a central transition metal and surrounding nearly free electron metal atoms. The transition metal d states hybridize with superatom D states and result in enhanced splitting between the majority and minority sets where the moment and the splitting can be controlled by the nature of the central atom. We demonstrate these findings through studies on TMMg(n) clusters where TM is a 3d atom. The clusters exhibit Hund's filling, opening the pathway to superatoms with magnetic shells.

Recognition- and reactivity-based fluorescent probes for studying transition metal signaling in living systems.

PubMed

Aron, Allegra T; Ramos-Torres, Karla M; Cotruvo, Joseph A; Chang, Christopher J

2015-08-18

Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed "recognition" and "reactivity". Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give three recent

Critical behavior at a dynamic vortex insulator-to-metal transition

DOE PAGES

Poccia, Nicola; Baturina, Tatyana I.; Coneri, Francesco; ...

2015-09-10

An array of superconducting islands placed on a normal metal film offers a tunable realization of nanopatterned superconductivity. This system enables elucidating open questions concerning the nature of competing vortex states and phase transitions between them. A square array creates the egg crate potential in which magnetic field-induced vortices are frozen into a vortex insulator. We observe a vortex insulator-to-vortex metal transition driven by the applied electric current and determine critical exponents strikingly coinciding with those for thermodynamic liquid-gas transition. Lastly, our findings offer a comprehensive description of dynamic critical behavior and establish a deep connection between equilibrium and nonequilibriummore » phase transitions.« less

Critical behavior at a dynamic vortex insulator-to-metal transition.

PubMed

Poccia, Nicola; Baturina, Tatyana I; Coneri, Francesco; Molenaar, Cor G; Wang, X Renshaw; Bianconi, Ginestra; Brinkman, Alexander; Hilgenkamp, Hans; Golubov, Alexander A; Vinokur, Valerii M

2015-09-11

An array of superconducting islands placed on a normal metal film offers a tunable realization of nanopatterned superconductivity. This system enables investigation of the nature of competing vortex states and phase transitions between them. A square array creates the eggcrate potential in which magnetic field-induced vortices are frozen into a vortex insulator. We observed a vortex insulator-vortex metal transition driven by the applied electric current and determined critical exponents that coincided with those for thermodynamic liquid-gas transition. Our findings offer a comprehensive description of dynamic critical behavior and establish a deep connection between equilibrium and nonequilibrium phase transitions. Copyright © 2015, American Association for the Advancement of Science.

Hall effect at a tunable metal-insulator transition

NASA Astrophysics Data System (ADS)

Teizer, W.; Hellman, F.; Dynes, R. C.

2003-03-01

Using a rotating magnetic field, the Hall effect in three-dimensional amorphous GdxSi1-x has been measured in the critical regime of the metal-insulator transition for a constant total magnetic field. The Hall coefficient R0 is negative, indicating electronlike conductivity, with a magnitude that increases with decreasing conductivity. R0 diverges at the metal-insulator transition, and displays critical behavior with exponent -1 [R0˜(H-HC)-1]. This dependence is interpreted as a linear decrease in the density of mobile carriers n˜R-10˜H-HC, indicative of the dominant influence of interaction effects.

Correlation of nosetip boundary-layer transition data measured in ballistics-range experiments

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

Reda, D.C.

1979-11-01

Preablated nosetips of various carbonaceous materials were tested in a ballistics range. Surface-temperature contours, measured with image-converter cameras, were used to define boundary-layer transition-fron contours. Measurements of surface roughness, surface temperature, average transition-calculations of nosetip flowfields, and with calculations of laminar boundary-layer development in these flowfields, to transform all data into various dimensionless parameters. These parameters were defined by previous attempts to correlate existing wind-tunnel data for transition on rough/blunt bodies.

Spectral observations of hole injection with transition metal oxides for an efficient organic light-emitting diode

NASA Astrophysics Data System (ADS)

Chiu, Tien-Lung; Chuang, Ya-Ting

2015-02-01

Transition metal oxides, such as molybdenum trioxide (MoO3), tungsten trioxide (WO3) and vanadium pent-oxide (V2O5), are well-known hole injection materials used for organic electronic devices. These materials promote work functions of anodes, reduce energy barriers, and facilitate hole transport at the interface between the inorganic anode and organic hole-transporting layer (HTL). In this study, we characterized the transmittance spectra and work function of these materials. Furthermore, we employed a hole-injection layer (HIL) in a blue phosphorescent organic light-emitting diode (OLED) to evaluate their hole-injection capacity by detecting the variation in the emission spectra. Thus, we utilized an OLED structure that has fast electron transporting dynamics to establish the recombination zone located at emitting layer and a partial HTL close to the anode. We used these three transition metal oxides individually as HILs sandwiched between the ITO anode and HTL and concluded that the strength of emissive light from the HTL was determined by their hole-injection capacity, depending on work function. The small amount of HTL emission light of the V2O5 OLED was explained by the high work function of 5.8 eV for the V2O5 film. However, the V2O5 OLED demonstrated the least favorable optoelectrical performance because of its low transmittance and high resistance of the V2O5 film. Ultimately, the 5 nm-MoO3 OLED exhibited the highest device performance because of its high material conductivity and transparency in the visible band.

Transition Delay in Hypersonic Boundary Layers via Optimal Perturbations

NASA Technical Reports Server (NTRS)

Paredes, Pedro; Choudhari, Meelan M.; Li, Fei

2016-01-01

The effect of nonlinear optimal streaks on disturbance growth in a Mach 6 axisymmetric flow over a 7deg half-angle cone is investigated in an e ort to expand the range of available techniques for transition control. Plane-marching parabolized stability equations are used to characterize the boundary layer instability in the presence of azimuthally periodic streaks. The streaks are observed to stabilize nominally planar Mack mode instabilities, although oblique Mack mode disturbances are destabilized. Experimentally measured transition onset in the absence of any streaks correlates with an amplification factor of N = 6 for the planar Mack modes. For high enough streak amplitudes, the transition threshold of N = 6 is not reached by the Mack mode instabilities within the length of the cone, but subharmonic first mode instabilities, which are destabilized by the presence of the streaks, reach N = 6 near the end of the cone. These results suggest a passive flow control strategy of using micro vortex generators to induce streaks that would delay transition in hypersonic boundary layers.

Inorganic-Organic Coating via Molecular Layer Deposition Enables Long Life Sodium Metal Anode.

PubMed

Zhao, Yang; Goncharova, Lyudmila V; Zhang, Qian; Kaghazchi, Payam; Sun, Qian; Lushington, Andrew; Wang, Biqiong; Li, Ruying; Sun, Xueliang

2017-09-13

Metallic Na anode is considered as a promising alternative candidate for Na ion batteries (NIBs) and Na metal batteries (NMBs) due to its high specific capacity, and low potential. However, the unstable solid electrolyte interphase layer caused by serious corrosion and reaction in electrolyte will lead to big challenges, including dendrite growth, low Coulombic efficiency and even safety issues. In this paper, we first demonstrate the inorganic-organic coating via advanced molecular layer deposition (alucone) as a protective layer for metallic Na anode. By protecting Na anode with controllable alucone layer, the dendrites and mossy Na formation have been effectively suppressed and the lifetime has been significantly improved. Moreover, the molecular layer deposition alucone coating shows better performances than the atomic layer deposition Al 2 O 3 coating. The novel design of molecular layer deposition protected Na metal anode may bring in new opportunities to the realization of the next-generation high energy-density NIBs and NMBs.

Atomic layer deposition of ZrO2 on W for metal-insulator-metal capacitor application

NASA Astrophysics Data System (ADS)

Lee, Sang-Yun; Kim, Hyoungsub; McIntyre, Paul C.; Saraswat, Krishna C.; Byun, Jeong-Soo

2003-04-01

A metal-insulator-metal (MIM) capacitor using ZrO2 on tungsten (W) metal bottom electrode was demonstrated and characterized in this letter. Both ZrO2 and W metal were synthesized by an atomic layer deposition (ALD) method. High-quality 110˜115 Å ZrO2 films were grown uniformly on ALD W using ZrCl4 and H2O precursors at 300 °C, and polycrystalline ZrO2 in the ALD regime could be obtained. A 13˜14-Å-thick interfacial layer between ZrO2 and W was observed after fabrication, and it was identified as WOx through angle-resolved x-ray photoelectron spectroscopy analysis with wet chemical etching. The apparent equivalent oxide thickness was 20˜21 Å. An effective dielectric constant of 22˜25 including an interfacial WOx layer was obtained by measuring capacitance and thickness of MIM capacitors with Pt top electrodes. High capacitance per area (16˜17 fF/μm2) and low leakage current (10-7 A/cm2 at ±1 V) were achieved.

Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni.

PubMed

Higgs, T D C; Bonetti, S; Ohldag, H; Banerjee, N; Wang, X L; Rosenberg, A J; Cai, Z; Zhao, J H; Moler, K A; Robinson, J W A

2016-07-22

Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. The results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

DOE PAGES

Higgs, T. D. C.; Bonetti, S.; Ohldag, H.; ...

2016-07-22

Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using themore » element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. In conclusion, the results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.« less

Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

NASA Astrophysics Data System (ADS)

Higgs, T. D. C.; Bonetti, S.; Ohldag, H.; Banerjee, N.; Wang, X. L.; Rosenberg, A. J.; Cai, Z.; Zhao, J. H.; Moler, K. A.; Robinson, J. W. A.

2016-07-01

Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. The results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

A numerical method for the prediction of high-speed boundary-layer transition using linear theory

NASA Technical Reports Server (NTRS)

Mack, L. M.

1975-01-01

A method is described of estimating the location of transition in an arbitrary laminar boundary layer on the basis of linear stability theory. After an examination of experimental evidence for the relation between linear stability theory and transition, a discussion is given of the three essential elements of a transition calculation: (1) the interaction of the external disturbances with the boundary layer; (2) the growth of the disturbances in the boundary layer; and (3) a transition criterion. The computer program which carried out these three calculations is described. The program is first tested by calculating the effect of free-stream turbulence on the transition of the Blasius boundary layer, and is then applied to the problem of transition in a supersonic wind tunnel. The effects of unit Reynolds number and Mach number on the transition of an insulated flat-plate boundary layer are calculated on the basis of experimental data on the intensity and spectrum of free-stream disturbances. Reasonable agreement with experiment is obtained in the Mach number range from 2 to 4.5.

Covalent bonds against magnetism in transition metal compounds

PubMed Central

Streltsov, Sergey V.; Khomskii, Daniel I.

2016-01-01

Magnetism in transition metal compounds is usually considered starting from a description of isolated ions, as exact as possible, and treating their (exchange) interaction at a later stage. We show that this standard approach may break down in many cases, especially in 4d and 5d compounds. We argue that there is an important intersite effect—an orbital-selective formation of covalent metal–metal bonds that leads to an “exclusion” of corresponding electrons from the magnetic subsystem, and thus strongly affects magnetic properties of the system. This effect is especially prominent for noninteger electron number, when it results in suppression of the famous double exchange, the main mechanism of ferromagnetism in transition metal compounds. We study this mechanism analytically and numerically and show that it explains magnetic properties of not only several 4d–5d materials, including Nb2O2F3 and Ba5AlIr2O11, but can also be operative in 3d transition metal oxides, e.g., in CrO2 under pressure. We also discuss the role of spin–orbit coupling on the competition between covalency and magnetism. Our results demonstrate that strong intersite coupling may invalidate the standard single-site starting point for considering magnetism, and can lead to a qualitatively new behavior. PMID:27601669

Effect of Surface Waviness on Transition in Three-Dimensional Boundary-Layer Flow

NASA Technical Reports Server (NTRS)

Masad, Jamal A.

1996-01-01

The effect of a surface wave on transition in three-dimensional boundary-layer flow over an infinite swept wing was studied. The mean flow computed using interacting boundary-layer theory, and transition was predicted using linear stability theory coupled with the empirical eN method. It was found that decreasing the wave height, sweep angle, or freestream unit Reynolds number, and increasing the freestream Mach number or suction level all stabilized the flow and moved transition onset to downstream locations.

Temperature dependent current-voltage characteristics of Au/n-Si Schottky barrier diodes and the effect of transition metal oxides as an interface layer

NASA Astrophysics Data System (ADS)

Mahato, Somnath; Puigdollers, Joaquim

2018-02-01

Temperature dependent current-voltage (I‒V) characteristics of Au/n-type silicon (n-Si) Schottky barrier diodes have been investigated. Three transition metal oxides (TMO) are used as an interface layer between gold and silicon. The basic Schottky diode parameters such as ideality factor (n), barrier height (ϕb 0) and series resistance (Rs) are calculated and successfully explained by the thermionic emission (TE) theory. It has been found that ideality factor decreased and barrier height increased with increased of temperature. The conventional Richardson plot of ln(I0/T2) vs. 1000/T is determined the activation energy (Ea) and Richardson constant (A*). Whereas value of 'A*' is much smaller than the known theoretical value of n-type Si. The temperature dependent I-V characteristics obtained the mean value of barrier height (ϕb 0 bar) and standard deviation (σs) from the linear plot of ϕap vs. 1000/T. From the modified Richardson plot of ln(I0/T2) ˗ (qσ)2/2(kT)2 vs. 1000/T gives Richardson constant and homogeneous barrier height of Schottky diodes. Main observation in this present work is the barrier height and ideality factor shows a considerable change but the series resistance value exhibits negligible change due to TMO as an interface layer.

Electrocatalysis using transition metal carbide and oxide nanocrystals

NASA Astrophysics Data System (ADS)

Regmi, Yagya N.

Carbides are one of the several families of transition metal compounds that are considered economic alternatives to catalysts based on noble metals and their compounds. Phase pure transition metal carbides of group 4-6 metals, in the first three periods, were synthesized using a common eutectic salt flux synthesis method, and their electrocatalytic activities compared under uniform electrochemical conditions. Mo2C showed highest hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) activities among the nine metal carbides investigated, but all other metal carbides also showed substantial activities. All the metal carbides showed remarkable enhancement in catalytic activities as supports, when compared to traditional graphitic carbon as platinum support. Mo2C, the most active transition metal carbide electrocatalyst, was prepared using four different synthesis routes, and the synthesis route dependent activities compared. Bifunctional Mo 2C that is HER as well as oxygen evolution reaction (OER) active, was achieved when the carbide was templated on a multiwalled carbon nanotube using carbothermic reduction method. Bimetallic carbides of Fe, Co, and Ni with Mo or W were prepared using a common carbothermic reduction method. Two different stoichiometries of bimetallic carbides were obtained for each system within a 60 °C temperature window. While the bimetallic carbides showed relatively lower electrocatalytic activities towards HER and ORR in comparison to Mo2C and WC, they revealed remarkably higher OER activities than IrO2 and RuO2, the state-of-the-art OER catalysts. Bimetallic oxides of Fe, Co, and Ni with Mo and W were also prepared using a hydrothermal synthesis method and they also revealed OER activities that are much higher than RuO2 and IrO2. Additionally, the OER activities were dependent on the degree and nature of hydration in the bimetallic oxide crystal lattice, with the completely hydrated, as synthesized, cobalt molybdate and nickel

Ultrafast photophysics of transition metal complexes.

PubMed

Chergui, Majed

2015-03-17

The properties of transition metal complexes are interesting not only for their potential applications in solar energy conversion, OLEDs, molecular electronics, biology, photochemistry, etc. but also for their fascinating photophysical properties that call for a rethinking of fundamental concepts. With the advent of ultrafast spectroscopy over 25 years ago and, more particularly, with improvements in the past 10-15 years, a new area of study was opened that has led to insightful observations of the intramolecular relaxation processes such as internal conversion (IC), intersystem crossing (ISC), and intramolecular vibrational redistribution (IVR). Indeed, ultrafast optical spectroscopic tools, such as fluorescence up-conversion, show that in many cases, intramolecular relaxation processes can be extremely fast and even shorter than time scales of vibrations. In addition, more and more examples are appearing showing that ultrafast ISC rates do not scale with the magnitude of the metal spin-orbit coupling constant, that is, that there is no heavy-atom effect on ultrafast time scales. It appears that the structural dynamics of the system and the density of states play a crucial role therein. While optical spectroscopy delivers an insightful picture of electronic relaxation processes involving valence orbitals, the photophysics of metal complexes involves excitations that may be centered on the metal (called metal-centered or MC) or the ligand (called ligand-centered or LC) or involve a transition from one to the other or vice versa (called MLCT or LMCT). These excitations call for an element-specific probe of the photophysics, which is achieved by X-ray absorption spectroscopy. In this case, transitions from core orbitals to valence orbitals or higher allow probing the electronic structure changes induced by the optical excitation of the valence orbitals, while also delivering information about the geometrical rearrangement of the neighbor atoms around the atom of

Transition-metal impurities in semiconductors and heterojunction band lineups

NASA Astrophysics Data System (ADS)

Langer, Jerzy M.; Delerue, C.; Lannoo, M.; Heinrich, Helmut

1988-10-01

The validity of a recent proposal that transition-metal impurity levels in semiconductors may serve as a reference in band alignment in semiconductor heterojunctions is positively verified by using the most recent data on band offsets in the following lattice-matched heterojunctions: Ga1-xAlxAs/GaAs, In1-xGaxAsyP1-y/InP, In1-xGaxP/GaAs, and Cd1-xHgxTe/CdTe. The alignment procedure is justified theoretically by showing that transition-metal energy levels are effectively pinned to the average dangling-bond energy level, which serves as the reference level for the heterojunction band alignment. Experimental and theoretical arguments showing that an increasingly popular notion on transition-metal energy-level pinning to the vacuum level is unjustified and must be abandoned in favor of the internal-reference rule proposed recently [J. M. Langer and H. Heinrich, Phys. Rev. Lett. 55, 1414 (1985)] are presented.

New Insight into the Solar System’s Transition Disk Phase Provided by the Metal-rich Carbonaceous Chondrite Isheyevo

NASA Astrophysics Data System (ADS)

Morris, Melissa A.; Garvie, Laurence A. J.; Knauth, L. Paul

2015-03-01

Many aspects of planet formation are controlled by the amount of gas remaining in the natal protoplanetary disks (PPDs). Infrared observations show that PPDs undergo a transition stage at several megayears, during which gas densities are reduced. Our Solar System would have experienced such a stage. However, there is currently no data that provides insight into this crucial time in our PPD’s evolution. We show that the Isheyevo meteorite contains the first definitive evidence for a transition disk stage in our Solar System. Isheyevo belongs to a class of metal-rich meteorites whose components have been dated at almost 5 Myr after formation of Ca, Al-rich inclusions, and exhibits unique sedimentary layers that imply formation through gentle sedimentation. We show that such layering can occur via the gentle sweep-up of material found in the impact plume resulting from the collision of two planetesimals. Such sweep-up requires gas densities consistent with observed transition disks (10-12-10-11 g cm-3). As such, Isheyevo presents the first evidence of our own transition disk and provides new constraints on the evolution of our solar nebula.

Unintentional carbide formation evidenced during high-vacuum magnetron sputtering of transition metal nitride thin films

NASA Astrophysics Data System (ADS)

Greczynski, G.; Mráz, S.; Hultman, L.; Schneider, J. M.

2016-11-01

Carbide signatures are ubiquitous in the surface analyses of industrially sputter-deposited transition metal nitride thin films grown with carbon-less source materials in typical high-vacuum systems. We use high-energy-resolution photoelectron spectroscopy to reveal details of carbon temporal chemical state evolution, from carbide formed during film growth to adventitious carbon adsorbed upon contact with air. Using in-situ grown Al capping layers that protect the as-deposited transition metal nitride surfaces from oxidation, it is shown that the carbide forms during film growth rather than as a result of post deposition atmosphere exposure. The XPS signature of carbides is masked by the presence of adventitious carbon contamination, appearing as soon as samples are exposed to atmosphere, and eventually disappears after one week-long storage in lab atmosphere. The concentration of carbon assigned to carbide species varies from 0.28 at% for ZrN sample, to 0.25 and 0.11 at% for TiN and HfN, respectively. These findings are relevant for numerous applications, as unintentionally formed impurity phases may dramatically alter catalytic activity, charge transport and mechanical properties by offsetting the onset of thermally-induced phase transitions. Therefore, the chemical state of C impurities in PVD-grown films should be carefully investigated.

Rare earth zirconium oxide buffer layers on metal substrates

DOEpatents

Williams, Robert K.; Paranthaman, Mariappan; Chirayil, Thomas G.; Lee, Dominic F.; Goyal, Amit; Feenstra, Roeland

2001-01-01

A laminate article comprises a substrate and a biaxially textured (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer over the substrate, wherein 0layer can be deposited using sol-gel or metal-organic decomposition. The laminate article can include a layer of YBCO over the (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer. A layer of CeO.sub.2 between the YBCO layer and the (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer can also be include. Further included can be a layer of YSZ between the CeO.sub.2 layer and the (RE.sub.x A.sub.(1-x)).sub.2 O.sub.2-(x/2) buffer layer. The substrate can be a biaxially textured metal, such as nickel. A method of forming the laminate article is also disclosed.