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Sample records for layered transition-metal ditellurides

  1. Tungsten Ditelluride: a layered semimetal.

    PubMed

    Lee, Chia-Hui; Silva, Eduardo Cruz; Calderin, Lazaro; Nguyen, Minh An T; Hollander, Matthew J; Bersch, Brian; Mallouk, Thomas E; Robinson, Joshua A

    2015-01-01

    Tungsten ditelluride (WTe2) is a transition metal dichalcogenide (TMD) with physical and electronic properties that make it attractive for a variety of electronic applications. Although WTe2 has been studied for decades, its structure and electronic properties have only recently been correctly described. We experimentally and theoretically investigate the structure, dynamics and electronic properties of WTe2, and verify that WTe2 has its minimum energy configuration in a distorted 1T structure (Td structure), which results in metallic-like transport. Our findings unambiguously confirm the metallic nature of WTe2, introduce new information about the Raman modes of Td-WTe2, and demonstrate that Td-WTe2 is readily oxidized via environmental exposure. Finally, these findings confirm that, in its thermodynamically favored Td form, the utilization of WTe2 in electronic device architectures such as field effect transistors may need to be reevaluated. PMID:26066766

  2. Tungsten Ditelluride: a layered semimetal

    NASA Astrophysics Data System (ADS)

    Lee, Chia-Hui; Silva, Eduardo Cruz; Calderin, Lazaro; Nguyen, Minh An T.; Hollander, Matthew J.; Bersch, Brian; Mallouk, Thomas E.; Robinson, Joshua A.

    2015-06-01

    Tungsten ditelluride (WTe2) is a transition metal dichalcogenide (TMD) with physical and electronic properties that make it attractive for a variety of electronic applications. Although WTe2 has been studied for decades, its structure and electronic properties have only recently been correctly described. We experimentally and theoretically investigate the structure, dynamics and electronic properties of WTe2, and verify that WTe2 has its minimum energy configuration in a distorted 1T structure (Td structure), which results in metallic-like transport. Our findings unambiguously confirm the metallic nature of WTe2, introduce new information about the Raman modes of Td-WTe2, and demonstrate that Td-WTe2 is readily oxidized via environmental exposure. Finally, these findings confirm that, in its thermodynamically favored Td form, the utilization of WTe2 in electronic device architectures such as field effect transistors may need to be reevaluated.

  3. Nucleation and growth of noble metals on transition-metal di-tellurides

    NASA Astrophysics Data System (ADS)

    Hla, S. W.; Marinković, V.; Prodan, A.

    1997-04-01

    Transition-metal di-tellurides (α- and β-MoTe 2 and WTe 2) were used as substrates for nucleation and growth studies of noble metals. They represent a group of chemically closely related compounds with different surface topographies. Nucleation and growth of Ag and Au at room temperature were studied by means of UHV-STM, AFM and TEM. The results revealed that the growth and orientation of these metals are influenced by the topography of the substrate surfaces. Contrary to the growth on atomically flat α-MoTe 2, there is an enhanced diffusion and nucleation along the periodic surface troughs on β-MoTe 2 and WTe 2. The topography of their (001) surfaces is responsible for the orientation of metal (112) planes being parallel to the substrate surface.)

  4. Impact Electrochemistry of Layered Transition Metal Dichalcogenides.

    PubMed

    Lim, Chee Shan; Tan, Shu Min; Sofer, Zdeněk; Pumera, Martin

    2015-08-25

    Layered transition metal dichalcogenides (TMDs) exhibit paramount importance in the electrocatalysis of the hydrogen evolution reaction. It is crucial to determine the size of the electrocatalytic particles as well as to establish their electrocatalytic activity, which occurs at the edges of these particles. Here, we show that individual TMD (MoS2, MoSe2, WS2, or WSe2; in general MX2) nanoparticles impacting an electrode surface provide well-defined current "spikes" in both the cathodic and anodic regions. These spikes originate from direct oxidation of the nanoparticles (from M(4+) to M(6+)) at the anodic region and from the electrocatalytic currents generated upon hydrogen evolution in the cathodic region. The positive correlation between the frequency of the impacts and the concentration of TMD nanoparticles is also demonstrated here, enabling determination of the concentration of TMD nanoparticles in colloidal form. In addition, the size of individual TMD nanoparticles can be evaluated using the charge passed during every spike. The capability of detecting both the "indirect" catalytic effect of an impacting TMD nanoparticle as well as "direct" oxidation indicates that the frequency of impacts in both the "indirect" and "direct" scenarios are comparable. This suggests that all TMD nanoparticles, which are electrochemically oxidizable (thus capable of donating electrons to electrodes), are also capable of catalyzing the hydrogen reduction reaction. PMID:26241193

  5. New Layered Ternary Transition-Metal Tellurides

    NASA Astrophysics Data System (ADS)

    Mar, Arthur

    Several new ternary transition-metal tellurides, a class of compounds hitherto largely unexplored, have been synthesized and characterized. These are layered materials whose structures have been determined by single -crystal X-ray diffraction methods. The successful preparation of the compound TaPtTe_5 was crucial in developing an understanding of the MM'Te_5 (M = Nb, Ta; M' = Ni, Pd, Pt) series of compounds, which adopt either of two possible closely-related layered structures. Interestingly, the compound TaPdTe _5 remains unknown. Instead, the compound Ta_4Pd_3Te _{16} has been prepared. Its structure is closely related to that of the previously prepared compound Ta_3Pd _3Te_{14}. The physical properties of these compounds have been measured and correlated with the metal substitutions and interlayer separations. A new series of compounds, MM'Te _4 (M = Nb, Ta; M' = Ru, Os, Rh, Ir), has been discovered. The structure of NbIrTe_4 serves as a prototype: it is an ordered variant of the binary telluride WTe_2. Electronic band-structure calculations have been performed in order to rationalize the trends in metal-metal and tellurium -tellurium bonding observed in WTe_2 and the MM'Te_4 phases. Extension of these studies to include main-group metals has resulted in the synthesis of the new layered ternary germanium tellurides TiGeTe_6, ZrGeTe_4 , and HfGeTe_4. Because germanium can behave ambiguously in its role as a metalloid element, it serves as an anion by capping the metal-centered trigonal prisms and also as a cation in being coordinated in turn by other tellurium atoms in a trigonal pyramidal fashion. Structural relationships among these compounds are illustrated through the use of bicapped trigonal prisms and trigonal pyramids as the basic structural building blocks. The electrical and magnetic properties of these compounds have been measured. Insight into the unusual bonding and physical properties of these germanium-containing compounds has been gained through

  6. Single-layer transition metal sulfide catalysts

    DOEpatents

    Thoma, Steven G.

    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.

  7. A Initio Lcao Electronic Structure Calculations of Layered Transition Metal Compounds.

    NASA Astrophysics Data System (ADS)

    Dawson, William G.

    1987-09-01

    Available from UMI in association with The British Library. In this work the electronic structure of three systems of layered transition metal compounds are examined using an ab initio tight binding (LCAO) method using the Xalpha exchange/correlation approximation: group VI ditellurides, group IV trichalcogenides and quaternary copper oxide defect-perovskites. A chemical pseudopotential argument is presented in order to justify the use of a small basis set of atomic orbitals. The group VI transition metal compounds MoTe_2 and WTe _2 show strong metal-metal interactions and MoTe_2 undergoes an unusual phase transition with the lattice parameter perpendicular to the layers decreasing with increasing temperature. The group IV transition metal trichalcogenides provide a useful series for study due to their quasi-1-dimensional character and the occurrence of two closely related structural variants. The atypical compound ZrTe_3 is given special attention because of its apparent semimetallic nature. The final group of compounds studied are the high Tc superconducting ceramics Ba-La-Cu-O and Ba-Y-Cu-O. The technological importance of compounds with zero resistance and showing the Meissner effect (expelling magnetic fields) above liquid nitrogen temperatures and the, as yet, undefined nature of the mechanism of superconductivity stresses the need to carefully examine the electronic structure of these materials. The role of oxygen vacancies, the charge state of the copper ions and the possibility of structural phase transitions are some of the topics considered here. The use of an atomic-orbital basis allows a comparatively straightforward description of the chemical bonding in a crystal--especially useful when the unit cell contains a large number of atoms.

  8. Exfoliation of large-area transition metal chalcogenide single layers

    PubMed Central

    Magda, Gábor Zsolt; Pető, János; Dobrik, Gergely; Hwang, Chanyong; Biró, László P.; Tapasztó, Levente

    2015-01-01

    Isolating large-areas of atomically thin transition metal chalcogenide crystals is an important but challenging task. The mechanical exfoliation technique can provide single layers of the highest structural quality, enabling to study their pristine properties and ultimate device performance. However, a major drawback of the technique is the low yield and small (typically < 10 μm) lateral size of the produced single layers. Here, we report a novel mechanical exfoliation technique, based on chemically enhanced adhesion, yielding MoS2 single layers with typical lateral sizes of several hundreds of microns. The idea is to exploit the chemical affinity of the sulfur atoms that can bind more strongly to a gold surface than the neighboring layers of the bulk MoS2 crystal. Moreover, we found that our exfoliation process is not specific to MoS2, but can be generally applied for various layered chalcogenides including selenites and tellurides, providing an easy access to large-area 2D crystals for the whole class of layered transition metal chalcogenides. PMID:26443185

  9. Spin and pseudospins in layered transition metal dichalcogenides

    SciTech Connect

    Xu, Xiaodong; Yao, Wang; Xiao, Di; Heinz, Tony F.

    2014-01-01

    The recent emergence of two-dimensional layered materials in particular the transition metal dichalcogenides provides a new laboratory for exploring the internal quantum degrees of freedom of electrons and their potential for new electronics. These degrees of freedom are the real electron spin, the layer pseudospin, and the valley pseudospin. New methods for the quantum control of the spin and these pseudospins arise from the existence of Berry phase-related physical properties and strong spin orbit coupling. The former leads to the versatile control of the valley pseudospin, whereas the latter gives rise to an interplay between the spin and the pseudospins. Here, we provide a brief review of both theoretical and experimental advances in this field.

  10. Comparative study of the synthesis of layered transition metal molybdates

    SciTech Connect

    Mitchell, S.; Gomez-Aviles, A.; Gardner, C.; Jones, W.

    2010-01-15

    Mixed metal oxides (MMOs) prepared by the mild thermal decomposition of layered double hydroxides (LDHs) differ in their reactivity on exposure to aqueous molybdate containing solutions. In this study, we investigate the reactivity of some T-Al containing MMOs (T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates (LTMs) possessing the general formula AT{sub 2}(OH)(MoO{sub 4}){sub 2}.H{sub 2}O, where A=NH{sub 4}{sup +}, Na{sup +} or K{sup +}. The phase selectivity of the reaction was studied with respect to the source of molybdate, the ratio of T to Mo and the reaction pH. LTMs were obtained on reaction of Cu-Al and Zn-Al containing MMOs with aqueous solutions of ammonium heptamolybdate. Rehydration of these oxides in the presence of sodium or potassium molybdate yielded a rehydrated LDH phase as the only crystalline product. The LTM products obtained by the rehydration of MMO precursors were compared with LTMs prepared by direct precipitation from the metal salts in order to study the influence of preparative route on their chemical and physical properties. Differences were noted in the composition, morphology and thermal properties of the resulting products. - Graphical abstract: Mixed metal oxides (MMOs) derived from layered double hydroxide precursors differ in their reactivity on exposure to aqueous molybdate containing solutions. We investigate the influence of the molybdate source, the rehydration pH and the ratio of T/Mo on the reactivity of some T-Al containing MMOs (T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates of general formula AT{sub 2}(OH)(MoO{sub 4}){sub 2}.H{sub 2}O (where A{sup +}=NH{sub 4}{sup +}, K{sup +} or Na{sup +}).

  11. Self-Limiting Layer Synthesis of Transition Metal Dichalcogenides

    PubMed Central

    Kim, Youngjun; Song, Jeong-Gyu; Park, Yong Ju; Ryu, Gyeong Hee; Lee, Su Jeong; Kim, Jin Sung; Jeon, Pyo Jin; Lee, Chang Wan; Woo, Whang Je; Choi, Taejin; Jung, Hanearl; Lee, Han-Bo-Ram; Myoung, Jae-Min; Im, Seongil; Lee, Zonghoon; Ahn, Jong-Hyun; Park, Jusang; Kim, Hyungjun

    2016-01-01

    This work reports the self-limiting synthesis of an atomically thin, two dimensional transition metal dichalcogenides (2D TMDCs) in the form of MoS2. The layer controllability and large area uniformity essential for electronic and optical device applications is achieved through atomic layer deposition in what is named self-limiting layer synthesis (SLS); a process in which the number of layers is determined by temperature rather than process cycles due to the chemically inactive nature of 2D MoS2. Through spectroscopic and microscopic investigation it is demonstrated that SLS is capable of producing MoS2 with a wafer-scale (~10 cm) layer-number uniformity of more than 90%, which when used as the active layer in a top-gated field-effect transistor, produces an on/off ratio as high as 108. This process is also shown to be applicable to WSe2, with a PN diode fabricated from a MoS2/WSe2 heterostructure exhibiting gate-tunable rectifying characteristics. PMID:26725854

  12. Self-Limiting Layer Synthesis of Transition Metal Dichalcogenides.

    PubMed

    Kim, Youngjun; Song, Jeong-Gyu; Park, Yong Ju; Ryu, Gyeong Hee; Lee, Su Jeong; Kim, Jin Sung; Jeon, Pyo Jin; Lee, Chang Wan; Woo, Whang Je; Choi, Taejin; Jung, Hanearl; Lee, Han-Bo-Ram; Myoung, Jae-Min; Im, Seongil; Lee, Zonghoon; Ahn, Jong-Hyun; Park, Jusang; Kim, Hyungjun

    2016-01-01

    This work reports the self-limiting synthesis of an atomically thin, two dimensional transition metal dichalcogenides (2D TMDCs) in the form of MoS2. The layer controllability and large area uniformity essential for electronic and optical device applications is achieved through atomic layer deposition in what is named self-limiting layer synthesis (SLS); a process in which the number of layers is determined by temperature rather than process cycles due to the chemically inactive nature of 2D MoS2. Through spectroscopic and microscopic investigation it is demonstrated that SLS is capable of producing MoS2 with a wafer-scale (~10 cm) layer-number uniformity of more than 90%, which when used as the active layer in a top-gated field-effect transistor, produces an on/off ratio as high as 10(8). This process is also shown to be applicable to WSe2, with a PN diode fabricated from a MoS2/WSe2 heterostructure exhibiting gate-tunable rectifying characteristics. PMID:26725854

  13. Self-Limiting Layer Synthesis of Transition Metal Dichalcogenides

    NASA Astrophysics Data System (ADS)

    Kim, Youngjun; Song, Jeong-Gyu; Park, Yong Ju; Ryu, Gyeong Hee; Lee, Su Jeong; Kim, Jin Sung; Jeon, Pyo Jin; Lee, Chang Wan; Woo, Whang Je; Choi, Taejin; Jung, Hanearl; Lee, Han-Bo-Ram; Myoung, Jae-Min; Im, Seongil; Lee, Zonghoon; Ahn, Jong-Hyun; Park, Jusang; Kim, Hyungjun

    2016-01-01

    This work reports the self-limiting synthesis of an atomically thin, two dimensional transition metal dichalcogenides (2D TMDCs) in the form of MoS2. The layer controllability and large area uniformity essential for electronic and optical device applications is achieved through atomic layer deposition in what is named self-limiting layer synthesis (SLS); a process in which the number of layers is determined by temperature rather than process cycles due to the chemically inactive nature of 2D MoS2. Through spectroscopic and microscopic investigation it is demonstrated that SLS is capable of producing MoS2 with a wafer-scale (~10 cm) layer-number uniformity of more than 90%, which when used as the active layer in a top-gated field-effect transistor, produces an on/off ratio as high as 108. This process is also shown to be applicable to WSe2, with a PN diode fabricated from a MoS2/WSe2 heterostructure exhibiting gate-tunable rectifying characteristics.

  14. Growth of transition metals on cerium tungstate model catalyst layers.

    PubMed

    Skála, T; Tsud, N; Stetsovych, V; Mysliveček, J; Matolín, V

    2016-10-01

    Two model catalytic metal/oxide systems were investigated by photoelectron spectroscopy and scanning tunneling microscopy. The mixed-oxide support was a cerium tungstate epitaxial thin layer grown in situ on the W(1 1 0) single crystal. Active particles consisted of palladium and platinum 3D islands deposited on the tungstate surface at 300 K. Both metals were found to interact weakly with the oxide support and the original chemical state of both support and metals was mostly preserved. Electronic and morphological changes are discussed during the metal growth and after post-annealing at temperatures up to 700 K. Partial transition-metal coalescence and self-cleaning from the CO and carbon impurities were observed. PMID:27494195

  15. Scanning tunneling microscopy of the subsurface structures of tungsten ditelluride and molybdenum ditelluride

    NASA Astrophysics Data System (ADS)

    Tang, S. L.; Kasowski, R. V.; Parkinson, B. A.

    1989-05-01

    The surface structure of the van der Waals faces of tungsten ditelluride (WTe2) and molybdenum ditelluride (2H-MoTe2) have been studied with scanning tunneling microscopy (STM). The hexagonal symmetry observed on the 2H-MoTe2 surface is similar to that observed previously on other transition-metal dichalcogenides. On WTe2, which has a distorted layered structure due to the pairing of the metal atoms, the scanning tunneling micrographs distinctly show the dominance of the metal. Buckled, zig-zag chains of paired atomic rows, which are the signature of the tungsten layer, are observed. These results show for the first time that subsurface atoms can be imaged with the STM. The corrugated surface tellurium layer could not be identified unambiguously in two-dimensional scans. These results are surprising because a first-principles pseudofunction calculation of the surface-electronic charge density around the Fermi energy of the WTe2 surface shows that the calculated spatial distribution of the charge density at the surface has the characteristics of the topmost Te atoms. The experimental observations suggest that, unlike the case of graphite images, a direct comparison of the STM image of this surface with calculated surface charge density is not possible. These observations further suggest that the hexagonal symmetry observed in MoTe2 and other transition-metal dichalcogenides is also due to the metal layer rather than the surface chalcogenides.

  16. Orbital reconstruction in nonpolar tetravalent transition-metal oxide layers

    PubMed Central

    Bogdanov, Nikolay A.; Katukuri, Vamshi M.; Romhányi, Judit; Yushankhai, Viktor; Kataev, Vladislav; Büchner, Bernd; van den Brink, Jeroen; Hozoi, Liviu

    2015-01-01

    A promising route to tailoring the electronic properties of quantum materials and devices rests on the idea of orbital engineering in multilayered oxide heterostructures. Here we show that the interplay of interlayer charge imbalance and ligand distortions provides a knob for tuning the sequence of electronic levels even in intrinsically stacked oxides. We resolve in this regard the d-level structure of layered Sr2IrO4 by electron spin resonance. While canonical ligand-field theory predicts g||-factors less than 2 for positive tetragonal distortions as present in Sr2IrO4, the experiment indicates g|| is greater than 2. This implies that the iridium d levels are inverted with respect to their normal ordering. State-of-the-art electronic-structure calculations confirm the level switching in Sr2IrO4, whereas we find them in Ba2IrO4 to be instead normally ordered. Given the nonpolar character of the metal-oxygen layers, our findings highlight the tetravalent transition-metal 214 oxides as ideal platforms to explore d-orbital reconstruction in the context of oxide electronics. PMID:26105992

  17. Orbital reconstruction in nonpolar tetravalent transition-metal oxide layers.

    PubMed

    Bogdanov, Nikolay A; Katukuri, Vamshi M; Romhányi, Judit; Yushankhai, Viktor; Kataev, Vladislav; Büchner, Bernd; van den Brink, Jeroen; Hozoi, Liviu

    2015-01-01

    A promising route to tailoring the electronic properties of quantum materials and devices rests on the idea of orbital engineering in multilayered oxide heterostructures. Here we show that the interplay of interlayer charge imbalance and ligand distortions provides a knob for tuning the sequence of electronic levels even in intrinsically stacked oxides. We resolve in this regard the d-level structure of layered Sr2IrO4 by electron spin resonance. While canonical ligand-field theory predicts g||-factors less than 2 for positive tetragonal distortions as present in Sr2IrO4, the experiment indicates g|| is greater than 2. This implies that the iridium d levels are inverted with respect to their normal ordering. State-of-the-art electronic-structure calculations confirm the level switching in Sr2IrO4, whereas we find them in Ba2IrO4 to be instead normally ordered. Given the nonpolar character of the metal-oxygen layers, our findings highlight the tetravalent transition-metal 214 oxides as ideal platforms to explore d-orbital reconstruction in the context of oxide electronics. PMID:26105992

  18. Comparative study of the synthesis of layered transition metal molybdates

    NASA Astrophysics Data System (ADS)

    Mitchell, S.; Gómez-Avilés, A.; Gardner, C.; Jones, W.

    2010-01-01

    Mixed metal oxides (MMOs) prepared by the mild thermal decomposition of layered double hydroxides (LDHs) differ in their reactivity on exposure to aqueous molybdate containing solutions. In this study, we investigate the reactivity of some T-Al containing MMOs ( T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates (LTMs) possessing the general formula AT2(OH)(MoO 4) 2·H 2O, where A=NH 4+, Na + or K +. The phase selectivity of the reaction was studied with respect to the source of molybdate, the ratio of T to Mo and the reaction pH. LTMs were obtained on reaction of Cu-Al and Zn-Al containing MMOs with aqueous solutions of ammonium heptamolybdate. Rehydration of these oxides in the presence of sodium or potassium molybdate yielded a rehydrated LDH phase as the only crystalline product. The LTM products obtained by the rehydration of MMO precursors were compared with LTMs prepared by direct precipitation from the metal salts in order to study the influence of preparative route on their chemical and physical properties. Differences were noted in the composition, morphology and thermal properties of the resulting products.

  19. Determination of the thickness and orientation of few-layer tungsten ditelluride using polarized Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Kim, Minjung; Han, Songhee; Kim, Jung Hwa; Lee, Jae-Ung; Lee, Zonghoon; Cheong, Hyeonsik

    2016-09-01

    Orthorhombic tungsten ditelluride (WTe2), with a distorted 1T structure, exhibits a large magnetoresistance that depends on the orientation, and its electrical characteristics changes from semimetallic to insulating as the thickness decreases. Through polarized Raman spectroscopy in combination with transmission electron diffraction, we establish a reliable method to determine the thickness and crystallographic orientation of few-layer WTe2. The Raman spectrum shows a pronounced dependence on the polarization of the excitation laser. We found that the separation between two Raman peaks at ∼90 cm‑1 and at 80–86 cm‑1, depending on thickness, is a reliable fingerprint for determination of the thickness. For determination of the crystallographic orientation, the polarization dependence of the A 1 modes, measured with the 632.8 nm excitation, turns out to be the most reliable. We also discovered that the polarization behaviors of some of the Raman peaks depend on the excitation wavelength as well as thickness, indicating a close interplay between the band structure and anisotropic Raman scattering cross section.

  20. Kondo Effects in Single Layer Transition Metal Dichalcogenides

    NASA Astrophysics Data System (ADS)

    Phillips, Michael; Aji, Vivek

    2015-03-01

    Inversion symmetry breaking and strong spin orbit coupling in two dimensional transition metal dichalcogenides leads to interesting new phenomena such as the valley hall and spin hall effects. They display optical circular dichroism and the ability to generate excitation with valley specificity. In this talk we report on the consequences of these properties on correlated states in hole doped systems focussing on the physics of the screening of magnetic impurities. Unlike typical metals, the breaking of inversion symmetry leads to the mixing of a triplet component to the Kondo cloud. Using a variational wave function approach we determine the nature of the many body state. With the ground state in hand we analyze the excitations generated by valley discriminating perturbations. Graduate Student.

  1. Surface Phonon Dispersion of the Layered Transition-metal Oxides

    NASA Astrophysics Data System (ADS)

    Zhang, J.; Ismail; Matzdorf, R.; Plummer, E. W.; Kimura, T.; Tokura, Y.

    2000-03-01

    Transition-metal oxides exhibit strong coupling between the charge and spin of the electrons and the lattice. Creating a surface by cleaving a single crystal breaks the symmetry of the lattice and disturbs the correlated system without changing the stoichiometry, providing the opportunity to study the response of electronic, structural, and magnetic properties. We have utilized electron-energy loss sprectroscopy (EELS) to study the electronic and lattice excitations of the Sr_2RuO4 and La_0.5Sr_1.5MnO4 surfaces. For both of these materials there are many more than three modes; three dominate surface optical phonons with small dispersion and with higher energies compared to those in the bulk materials. However, these phonons show completely different temperature dependence for different samples. The surface phonons become soft for Sr_2RuO4 while they become stiff for La_0.5Sr_1.5MnO4 with increasing temparature. The change of phonon energy of La_0.5Sr_1.5MnO4 with temperature is also in opposite direction to that of (La, Ca)MnO_4( Zhang et al., Surf. Sci. 393, 64(1997) * LMER Corp. for U.S. DOE under contract No. DE-AC05-96OR22464). These behaviors will be discussed in terms of the electronic, magnetic, and structural properties.

  2. Topological phase transition in layered transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Choe, Duk-Hyun; Sung, Ha-Jun; Chang, Kee Joo

    Despite considerable interests in transition metal dichalcogenides (TMDs), such as MX2 with M = (Mo, W) and X = (S, Se, Te), the physical origin of their topological nature is still in its infancy. The conventional view of topological phase transition (TPT) in TMDs is that the band inversion occurs between the metal d and chalcogen p orbital bands. More precisely, the former is pulled down below the latter. Here we introduce an explicit scheme for analyzing TPT in topological materials and find that the TPT in TMDs is different from the conventional speculation. When the 1T phase undergoes a structural transformation to the 1T' phase in monolayer MX2, the band topology changes from trivial to non-trivial, leading to the TPT. We discuss the exact role of the metal d and chalcogen p orbital bands during the TPT. Our finding would provide clear guidelines for understanding the topological nature not only in TMDs but also in other topological materials yet to be explored.

  3. APCVD Transition Metal Oxides - Functional Layers in "Smart windows"

    NASA Astrophysics Data System (ADS)

    Gesheva, K. A.; Ivanova, T. M.; Bodurov, G. K.

    2014-11-01

    Transition metal oxides (TMO) exhibit electrochromic effect. Under a small voltage they change their optical transmittance from transparent to collored (absorbing) state. The individual material can manifest its electrochromic properties only when it is part of electrochromic (EC) multilayer system. Smart window is controlling the energy of solar flux entering the building or car and makes the interiors comfortable and energy utilization more effective. Recently the efforts of material researchers in this field are directed to price decreasing. APCVD technology is considered as promissing as this process permits flowthrough large-scale production process. The paper presents results on device optimization based on WO3-MoO3 working electrode. Extensive research reveals that WO3-MoO3 structure combines positive features of single oxides: excellent electrochromic performance of WO3 and better kinetic properties of MoO3 deposition. The achieved color efficiency of APCVD WO3-MoO3 films is 200cm2/C and optical modulation of 65-70% are practically favorable electrochromic characteristics. To respond to low cost requirement, the expensive hexacarbonyl can be replaced with acetylacetonate. We have started with this precursor to fabricate mixed WxV1-xO3 films. The films possess excellent surface coverage and high growth-rate. CVD deposition of VO2, a promissing thermochromic thin film material is also presented.

  4. Strong dependence of fluorescence quenching on the transition metal in layered transition metal dichalcogenide nanoflakes for nucleic acid detection.

    PubMed

    Loo, Adeline Huiling; Bonanni, Alessandra; Pumera, Martin

    2016-08-01

    In recent years, the application of transition metal dichalcogenides for the development of biosensors has been receiving widespread attention from researchers, as demonstrated by the surge in studies present in the field. While different transition metal dichalcogenide materials have been employed for the fabrication of fluorescent biosensors with superior performance, no research has been conducted to draw comparisons across materials containing different transition metals. Herein, the performance of MoS2 and WS2 nanoflakes for the fluorescence detection of nucleic acids is assessed. It is discovered that, at the optimal amount, MoS2 and WS2 nanoflakes exhibit a similar degree of fluorescence quenching, at 75% and 71% respectively. However, MoS2 nanoflakes have better performance in the areas of detection range and selectivity than WS2 nanoflakes. The detection range achieved with MoS2 nanoflakes is 9.60-366 nM while 13.3-143 nM with WS2 nanoflakes. In the context of selectivity, MoS2 nanoflakes display a signal difference of 97.8% between complementary and non-complementary DNA targets, whereas WS2 nanoflakes only exhibit 44.3%. Such research is highly beneficial as it delivers vital insights on how the performance of a fluorescent biosensor can be affected by the transition metal present. Furthermore, these insights can assist in the selection of suitable transition metal dichalcogenide materials for utilization in biosensor development. PMID:27241269

  5. Probing Critical Point Energies of Transition Metal Dichalcogenides: Surprising Indirect Gap of Single Layer WSe2.

    PubMed

    Zhang, Chendong; Chen, Yuxuan; Johnson, Amber; Li, Ming-Yang; Li, Lain-Jong; Mende, Patrick C; Feenstra, Randall M; Shih, Chih-Kang

    2015-10-14

    By using a comprehensive form of scanning tunneling spectroscopy, we have revealed detailed quasi-particle electronic structures in transition metal dichalcogenides, including the quasi-particle gaps, critical point energy locations, and their origins in the Brillouin zones. We show that single layer WSe2 surprisingly has an indirect quasi-particle gap with the conduction band minimum located at the Q-point (instead of K), albeit the two states are nearly degenerate. We have further observed rich quasi-particle electronic structures of transition metal dichalcogenides as a function of atomic structures and spin-orbit couplings. Such a local probe for detailed electronic structures in conduction and valence bands will be ideal to investigate how electronic structures of transition metal dichalcogenides are influenced by variations of local environment. PMID:26389585

  6. Protein Induces Layer-by-Layer Exfoliation of Transition Metal Dichalcogenides.

    PubMed

    Guan, Guijian; Zhang, Shuangyuan; Liu, Shuhua; Cai, Yongqing; Low, Michelle; Teng, Choon Peng; Phang, In Yee; Cheng, Yuan; Duei, Koh Leng; Srinivasan, Bharathi Madurai; Zheng, Yuangang; Zhang, Yong-Wei; Han, Ming-Yong

    2015-05-20

    Here, we report a general and facile method for effective layer-by-layer exfoliation of transition metal dichalcogenides (TMDs) and graphite in water by using protein, bovine serum albumin (BSA) to produce single-layer nanosheets, which cannot be achieved using other commonly used bio- and synthetic polymers. Besides serving as an effective exfoliating agent, BSA can also function as a strong stabilizing agent against reaggregation of single-layer nanosheets for greatly improving their biocompatibility in biomedical applications. With significantly increased surface area, single-layer MoS2 nanosheets also exhibit a much higher binding capacity to pesticides and a much larger specific capacitance. The protein exfoliation process is carefully investigated with various control experiments and density functional theory simulations. It is interesting to find that the nonpolar groups of protein can firmly bind to TMD layers or graphene to expose polar groups in water, facilitating the effective exfoliation of single-layer nanosheets in aqueous solution. The present work will enable to optimize the fabrication of various 2D materials at high yield and large scale, and bring more opportunities to investigate the unique properties of 2D materials and exploit their novel applications. PMID:25936424

  7. Layering effects on low frequency modes in n-layered MX2 transition metal dichalcogenides.

    PubMed

    Cammarata, Antonio; Polcar, Tomas

    2016-02-14

    n-Layered (n = 2, 3, 4) MX2 transition metal dichalcogenides (M = Mo, W; X = S, Se, Te) have been studied using DFT techniques. Long-range van der Waals forces have been modeled using the Grimme correction to capture interlayer interactions. We study the dynamic and electronic dependence of atomic displacement on the number of layers. We find that the displacement patterns mainly affected by a change in the layer number are low-frequency modes at Γ and A k-points; such modes are connected with the intrinsic tribological response. We disentangle electro-phonon coupling by combining orbital polarization, covalency and cophonicity analysis with phonon band calculations. We find that the frequency dependence on the number of layers and the atomic type has a non-trivial relation with the electronic charge distribution in the interlayer region. We show that the interlayer electronic density can be adjusted by appropriately tuning M-X cophonicity, acting as a knob to control vibrational frequencies, hence the intrinsic frictional response. The present results can be exploited to study the electro-phonon coupling effects in TMD-based materials beyond tribological applications. PMID:26806673

  8. Photo-modulation of the spin Hall conductivity of mono-layer transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Sengupta, Parijat; Bellotti, Enrico

    2016-05-01

    We report on a possible optical tuning of the spin Hall conductivity in mono-layer transition metal dichalcogenides. Light beams of frequencies much higher than the energy scale of the system (the off-resonant condition) do not excite electrons but rearrange the band structure. The rearrangement is quantitatively established using the Floquet formalism. For such a system of mono-layer transition metal dichalcogenides, the spin Hall conductivity (calculated with the Kubo expression in presence of disorder) exhibits a drop at higher frequencies and lower intensities. Finally, we compare the spin Hall conductivity of the higher spin-orbit coupled WSe2 to MoS2; the spin Hall conductivity of WSe2 was found to be larger.

  9. Control of electronic properties of 2D carbides (MXenes) by manipulating their transition metal layers

    DOE PAGESBeta

    Anasori, Babak; Shi, Chenyang; Moon, Eun Ju; Xie, Yu; Voigt, Cooper A.; Kent, Paul R. C.; May, Steven J.; Billinge, Simon J. L.; Barsoum, Michel W.; Gogotsi, Yury

    2016-02-24

    In this paper, a transition from metallic to semiconducting-like behavior has been demonstrated in two-dimensional (2D) transition metal carbides by replacing titanium with molybdenum in the outer transition metal (M) layers of M3C2 and M4C3 MXenes. The MXene structure consists of n + 1 layers of near-close packed M layers with C or N occupying the octahedral site between them in an [MX]nM arrangement. Recently, two new families of ordered 2D double transition metal carbides MXenes were discovered, M'2M"C2 and M'2M"2C3 – where M' and M" are two different early transition metals, such as Mo, Cr, Ta, Nb, V, andmore » Ti. The M' atoms only occupy the outer layers and the M" atoms fill the middle layers. In other words, M' atomic layers sandwich the middle M"–C layers. Using X-ray atomic pair distribution function (PDF) analysis on Mo2TiC2 and Mo2Ti2C3 MXenes, we present the first quantitative analysis of structures of these novel materials and experimentally confirm that Mo atoms are in the outer layers of the [MC]nM structures. The electronic properties of these Mo-containing MXenes are compared with their Ti3C2 counterparts, and are found to be no longer metallic-like conductors; instead the resistance increases mildly with decreasing temperatures. Density functional theory (DFT) calculations suggest that OH terminated Mo–Ti MXenes are semiconductors with narrow band gaps. Measurements of the temperature dependencies of conductivities and magnetoresistances have confirmed that Mo2TiC2Tx exhibits semiconductor-like transport behavior, while Ti3C2Tx is a metal. Finally, this finding opens new avenues for the control of the electronic and optical applications of MXenes and for exploring new applications, in which semiconducting properties are required.« less

  10. Performance limits of tunnel transistors based on mono-layer transition-metal dichalcogenides

    SciTech Connect

    Jiang, Xiang-Wei Li, Shu-Shen

    2014-05-12

    Performance limits of tunnel field-effect transistors based on mono-layer transition metal dichalcogenides are investigated through numerical quantum mechanical simulations. The atomic mono-layer nature of the devices results in a much smaller natural length λ, leading to much larger electric field inside the tunneling diodes. As a result, the inter-band tunneling currents are found to be very high as long as ultra-thin high-k gate dielectric is possible. The highest on-state driving current is found to be close to 600 μA/μm at V{sub g} = V{sub d} = 0.5 V when 2 nm thin HfO{sub 2} layer is used for gate dielectric, outperforming most of the conventional semiconductor tunnel transistors. In the five simulated transition-metal dichalcogenides, mono-layer WSe{sub 2} based tunnel field-effect transistor shows the best potential. Deep analysis reveals that there is plenty room to further enhance the device performance by either geometry, alloy, or strain engineering on these mono-layer materials.

  11. Layered transition metal dichalcogenides: promising near-lattice-matched substrates for GaN growth

    PubMed Central

    Gupta, Priti; Rahman, A. A.; Subramanian, Shruti; Gupta, Shalini; Thamizhavel, Arumugam; Orlova, Tatyana; Rouvimov, Sergei; Vishwanath, Suresh; Protasenko, Vladimir; Laskar, Masihhur R.; Xing, Huili Grace; Jena, Debdeep; Bhattacharya, Arnab

    2016-01-01

    Most III-nitride semiconductors are grown on non-lattice-matched substrates like sapphire or silicon due to the extreme difficulty of obtaining a native GaN substrate. We show that several layered transition-metal dichalcogenides are closely lattice-matched to GaN and report the growth of GaN on a range of such layered materials. We report detailed studies of the growth of GaN on mechanically-exfoliated flakes WS2 and MoS2 by metalorganic vapour phase epitaxy. Structural and optical characterization show that strain-free, single-crystal islands of GaN are obtained on the underlying chalcogenide flakes. We obtain strong near-band-edge emission from these layers, and analyse their temperature-dependent photoluminescence properties. We also report a proof-of-concept demonstration of large-area growth of GaN on CVD MoS2. Our results show that the transition-metal dichalcogenides can serve as novel near-lattice-matched substrates for nitride growth. PMID:27025461

  12. Layered transition metal dichalcogenides: promising near-lattice-matched substrates for GaN growth

    NASA Astrophysics Data System (ADS)

    Gupta, Priti; Rahman, A. A.; Subramanian, Shruti; Gupta, Shalini; Thamizhavel, Arumugam; Orlova, Tatyana; Rouvimov, Sergei; Vishwanath, Suresh; Protasenko, Vladimir; Laskar, Masihhur R.; Xing, Huili Grace; Jena, Debdeep; Bhattacharya, Arnab

    2016-03-01

    Most III-nitride semiconductors are grown on non-lattice-matched substrates like sapphire or silicon due to the extreme difficulty of obtaining a native GaN substrate. We show that several layered transition-metal dichalcogenides are closely lattice-matched to GaN and report the growth of GaN on a range of such layered materials. We report detailed studies of the growth of GaN on mechanically-exfoliated flakes WS2 and MoS2 by metalorganic vapour phase epitaxy. Structural and optical characterization show that strain-free, single-crystal islands of GaN are obtained on the underlying chalcogenide flakes. We obtain strong near-band-edge emission from these layers, and analyse their temperature-dependent photoluminescence properties. We also report a proof-of-concept demonstration of large-area growth of GaN on CVD MoS2. Our results show that the transition-metal dichalcogenides can serve as novel near-lattice-matched substrates for nitride growth.

  13. Control of valence and conduction band energies in layered transition metal phosphates via surface functionalization.

    PubMed

    Lentz, Levi C; Kolb, Brian; Kolpak, Alexie M

    2016-05-18

    Layered transition metal phosphates and phosphites (TMPs) are a class of materials composed of layers of 2D sheets bound together via van der Waals interactions and/or hydrogen bonds. Explored primarily for use in proton transfer, their unique chemical tunability also makes TMPs of interest for forming large-scale hybrid materials. Further, unlike many layered materials, TMPs can readily be solution exfoliated to form single 2D sheets or bilayers, making them exciting candidates for a variety of applications. However, the electronic properties of TMPs have largely been unstudied to date. In this work, we use first-principles computations to investigate the atomic and electronic structure of TMPs with a variety of stoichiometries. We demonstrate that there exists a strong linear relationship between the band gap and the ionic radius of the transition metal cation in these materials, and show that this relationship, which opens opportunities for engineering new compositions with a wide range of band gaps, arises from constraints imposed by the phosphorus-oxygen bond geometry. In addition, we find that the energies of the valence and conduction band edges can be systematically tuned over a range of ∼3 eV via modification of the functional group extending from the phosphorus. Based on the Hammett constant of this functional group, we identify a simple, predictive relationship for the ionization potential and electron affinity of layered TMPs. Our results thus provide guidelines for systematic design of TMP-derived functional materials, which may enable new approaches for optimizing charge transfer in electronics, photovoltaics, electrocatalysts, and other applications. PMID:27157509

  14. Charge Transfer Stabilization of Late Transition Metal Oxide Nanoparticles on a Layered Niobate Support.

    PubMed

    Strayer, Megan E; Senftle, Thomas P; Winterstein, Jonathan P; Vargas-Barbosa, Nella M; Sharma, Renu; Rioux, Robert M; Janik, Michael J; Mallouk, Thomas E

    2015-12-30

    Interfacial interactions between late transition metal/metal oxide nanoparticles and oxide supports impact catalytic activity and stability. Here, we report the use of isothermal titration calorimetry (ITC), electron microscopy and density functional theory (DFT) to explore periodic trends in the heats of nanoparticle-support interactions for late transition metal and metal oxide nanoparticles on layered niobate and silicate supports. Data for Co(OH)2, hydroxyiridate-capped IrOx·nH2O, Ni(OH)2, CuO, and Ag2O nanoparticles were added to previously reported data for Rh(OH)3 grown on nanosheets of TBA0.24H0.76Ca2Nb3O10 and a layered silicate. ITC measurements showed stronger bonding energies in the order Ag < Cu ≈ Ni ≈ Co < Rh < Ir on the niobate support, as expected from trends in M-O bond energies. Nanoparticles with exothermic heats of interaction were stabilized against sintering. In contrast, ITC measurements showed endothermic interactions of Cu, Ni, and Rh oxide/hydroxide nanoparticles with the silicate and poor resistance to sintering. These trends in interfacial energies were corroborated by DFT calculations using single-atom and four-atom cluster models of metal/metal oxide nanoparticles. Density of states and charge density difference calculations reveal that strongly bonded metals (Rh, Ir) transfer d-electron density from the adsorbed cluster to niobium atoms in the support; this mixing is absent in weakly binding metals, such as Ag and Au, and in all metals on the layered silicate support. The large differences between the behavior of nanoparticles on niobate and silicate supports highlight the importance of d-orbital interactions between the nanoparticle and support in controlling the nanoparticles' stability. PMID:26651875

  15. Catalytic properties of single layers of transition metal sulfide catalytic materials

    SciTech Connect

    Chianelli, R.R.; Siadati, M.H.; De la Rosa, M.P.; Berhault, G.; Wilcoxon, J.P.; Bearden, R.; Abrams, B.L.

    2006-01-15

    Single layer transition metal sulfides (SLTMS) such as MoS{sub 2}, WS{sub 2}, and ReS{sub 2}, play an important role in catalytic processes such as the hydrofining of petroleum streams, and are involved in at least two of the slurry-catalyst hydroconversion processes that have been proposed for upgrading heavy petroleum feed and other sources of hydrocarbon fuels such as coal and shale oils. Additional promising catalytic applications of the SLTMS are on the horizon. The physical, chemical, and catalytic properties of these materials are reviewed in this report. Also discussed are areas for future research that promise to lead to advanced applications of the SLTMS.

  16. Contacts and transport characteristics of few-layer transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Wang, Junjie; Li, Jing; Shevrin, Jacob; Nguyen, An; Mallouk, Tom; Zhu, J.; Rhodes, Daniel; Balicas, Luis; Watanabe, K.; Taniguchi, T.

    2014-03-01

    Two-dimensional layered transition metal dichalcogenides (TMDs) are potentially useful for electronic and optoelectronic applications. However, the lack of reliable methods to make ohmic contacts has been a major challenge. This work addresses two aspects of this challenge, i.e. interface cleanness and conductivity of the material in the contact area. Using gentle Ar ion milling immediately before the deposition of metal electrodes, we can completely remove polymer residue from prior lithography without significantly damaging the few-layer TMD sheet. Gate stacks made of Au and HfO2 films can inject carriers up to 3 ×1013 cm-2. We make van der Pauw devices of few-layer (< 5 L) TMD (MoS2, WS2, WSe2) sheets using Ti/Au contacts with area < 2 (um)2 and observe contact resistance less than 10 k Ω at high carrier densities, where the sheet conductance is well above 2e2/h. We eliminate hysteresis in the transfer curve of TMD devices by pulsing the gate voltage. Ambipolar conduction is observed in WSe2 devices, with an on/off ratio exceeding 106 for both electrons and holes. WSe2 devices supported on h-BN show field-effect (hole) mobility > 100 cm2/(Vs) at 300K. We discuss the effects of the various approaches taken above.

  17. 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.

  18. 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.

  19. Electronic structure and optical properties of layered ternary transition-metal carbides and nitrides

    NASA Astrophysics Data System (ADS)

    Mo, Yuxiang

    2011-12-01

    The electronic structure and optical properties of Ti3AC 2 (A=Al, Si, Ge), Ti2AC (A=Al, Ga, In; Si, Ge, Sn; P, As; S), Ti2AlN, M2AlC (M=V, Nb, Cr) and Tan+1AlC n (n=1˜4) have been studied using first--principles orthogonalized linear combination of atomic orbitals (OLCAO) method. These layered ternary transition--metal carbides and nitrides are also commonly referred to as "MAX phases". Trends were observed for the calculated density of states (DOS) at Fermi--level, with respect to elemental variations and number of M and X layers. A local minimum of DOS(Ef) was found for Ti3AlC2, Ti2InC and Cr2AlC, predicting relatively high intrinsic structural stability. While a local maximum or an incline was discovered for Ti3GeC2, Ti2GeC, Ti2SnC, Ti 2PC, Nb2AlC, Ta2AlC, Ta4AlC3 and Ta5AlC4, indicating their lower intrinsic structural stability. Inter-band optical conductivities showed anisotropy, but not considerable. The reflectance and colors of the MAX phase compounds were also obtained.

  20. Improved layered mixed transition metal oxides for Li-ion batteries

    SciTech Connect

    Doeff, Marca M.; Conry, Thomas; Wilcox, James

    2010-03-05

    Recent work in our laboratory has been directed towards development of mixed layered transition metal oxides with general composition Li[Ni, Co, M, Mn]O2 (M=Al, Ti) for Li ion battery cathodes. Compounds such as Li[Ni1/3Co1/3Mn1/3]O2 (often called NMCs) are currently being commercialized for use in consumer electronic batteries, but the high cobalt content makes them too expensive for vehicular applications such as electric vehicles (EV), plug-in hybrid electric vehicles (PHEVs), or hybrid electric vehicles (HEVs). To reduce materials costs, we have explored partial or full substitution of Co with Al, Ti, and Fe. Fe substitution generally decreases capacity and results in poorer rate and cycling behavior. Interestingly, low levels of substitution with Al or Ti improve aspects of performance with minimal impact on energy densities, for some formulations. High levels of Al substitution compromise specific capacity, however, so further improvements require that the Ni and Mn content be increased and Co correspondingly decreased. Low levels of Al or Ti substitution can then be used offset negative effects induced by the higher Ni content. The structural and electrochemical characterization of substituted NMCs is presented in this paper.

  1. Low-temperature optical spectroscopy of single-layer transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Plechinger, Gerd; Nagler, Philipp; Schüller, Christian; Korn, Tobias

    In recent years, layered materials beyond graphene have attracted immense interest in the scientific community. Among those, particularly the semiconducting transition metal dichalcogenides (TMDCs) in their monolayer form are in the focus of the current research due to their intriguing optical properties and their potential application in valleytronic-based devices. The optical properties are governed by excitonic features, even at room temperature. The excitons in monolayer TMDCs have unusually large binding energies due to the two-dimensional carrier confinement and weak dielectric screening. Here, we investigate the photoluminescence spectra of monolayer TMDCs at low temperatures. We present clear evidence for the existence of biexcitons in monolayer WS2, exhibiting a superlinear behavior in excitation-power-dependent measurements. Applying a gate-voltage in a FET-configuration, we can identify charge-neutral and negatively charged excitons (trions) in the optical spectrum of different TMDCs. The trion binding energies range in the order of 30 meV. The evolution of the excitonic peaks under the application of external magnetic fields give further insight into the internal structure of these materials.

  2. New chemistry for the growth of first-row transition metal films by atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Klesko, Joseph Peter

    Thin films containing first-row transition metals are widely used in microelectronic, photovoltaic, catalytic, and surface-coating applications. In particular, metallic films are essential for interconnects and seed, barrier, and capping layers in integrated circuitry. Traditional vapor deposition methods for film growth include PVD, CVD, or the use of plasma. However, these techniques lack the requisite precision for film growth at the nanoscale, and thus, are increasingly inadequate for many current and future applications. By contrast, ALD is the favored approach for depositing films with absolute surface conformality and thickness control on 3D architectures and in high aspect ratio features. However, the low-temperature chemical reduction of most first-row transition metal cations to their zero-valent state is very challenging due to their negative electrochemical potentials. A lack of strongly-reducing coreagents has rendered the thermal ALD of metallic films an intractable problem for many elements. Additionally, several established ALD processes for metal films are plagued by low growth rates, impurity incorporation, poor nucleation, high surface roughness, or the need for hazardous coreagents. Finally, stoichiometric control of ternary films grown by ALD is rare, but increasingly important, with emerging applications for metal borate films in catalysis and lithium ion batteries. The research herein is focused toward the development of new ALD processes for the broader application of metal, metal oxide, and metal borate thin films to future nanoscale technologies. These processes display self-limited growth and support the facile nucleation of smooth, continuous, high-purity films. Bis(trimethylsilyl) six-membered rings are employed as strongly-reducing organic coreagents for the ALD of titanium and antimony metal films. Additionally, new processes are developed for the growth of high-purity, low-resistivity cobalt and nickel metal films by exploiting the

  3. 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

  4. Defect-Induced Optoelectronic Response in Single-layer Group-VI Transition-Metal Dichalcogenides

    NASA Astrophysics Data System (ADS)

    Chow, Philippe K.

    The ever-evolving symbiosis between mankind and nanoelectronics-driven technology pushes the limits of its constituent materials, largely due to the dominance of undesirable hetero-interfacial physiochemical behavior at the few-nanometer length scale, which dominates over bulk material characteristics. Driven by such instabilities, research into two-dimensional (2D) van der Waals-layered materials (e.g. graphene, transition metal dichalcogenides (TMDCs), boron nitride), which have characteristically inert surface chemistry, has virtually exploded over the past few years. The discovery of an indirect- to direct-gap conversion in semiconducting group-VI TMDCs (e.g. MoS2) upon thinning to a single atomic layer provided the critical link between metallic and insulating 2D materials. While proof-of-concept demonstrations of single-layer TMDC-based devices for visible-range photodetection, light-emission and solar energy conversion have showed promising results, the exciting qualities are downplayed by poorly-understood defectinduced photocarrier traps, limiting the best-achieved external quantum efficiencies to approximately ~1%. This thesis explores the behavior of defects in atomically-thin TMDC layers in response to optical stimuli using a combination of steady-state photoluminescence, reflectance and Raman spectroscopy at room-temperature. By systematically varying the defect density using plasma-irradiation techniques, an unprecedented room-temperature defect-induced monolayer PL feature was discovered. High-resolution transmission electron microscopy correlated the defect-induced PL with plasma-generation of sulfur vacancy defects while reflectance measurements indicate defect-induced sub-bandgap light absorption. Excitation intensity-dependent PL measurements and exciton rate modeling further help elucidate the origin of the defect-induced PL response and highlights the role of non-radiative recombination on exciton conversion processes. The results in this

  5. 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.

  6. 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

  7. Nonlinear Saturable Absorption of Liquid-Exfoliated Molybdenum/Tungsten Ditelluride Nanosheets.

    PubMed

    Mao, Dong; Du, Bobo; Yang, Dexing; Zhang, Shengli; Wang, Yadong; Zhang, Wending; She, Xiaoyang; Cheng, Huachao; Zeng, Haibo; Zhao, Jianlin

    2016-03-01

    Molybdenum disulfide (MoS2 ) and tungsten disulfide (WS2 ), two representative transition metal dichalcogenide materials, have captured tremendous interest for their unique electronic, optical, and chemical properties. Compared with MoS2 and WS2 , molybdenum ditelluride (MoTe2 ) and tungsten ditelluride (WTe2 ) possess similar lattice structures while having smaller bandgaps (less than 1 eV), which is particularly interesting for applications in the near-infrared wavelength regime. Here, few-layer MoTe2 /WTe2 nanosheets are fabricated by a liquid exfoliation method using sodium deoxycholate bile salt as surfactant, and the nonlinear optical properties of the nanosheets are investigated. The results demonstrate that MoTe2 /WTe2 nanosheets exhibit nonlinear saturable absorption property at 1.55 μm. Soliton mode-locking operations are realized separately in erbium-doped fiber lasers utilizing two types of MoTe2 /WTe2 -based saturable absorbers, one of which is prepared by depositing the nanosheets on side polished fibers, while the other is fabricated by mixing the nanosheets with polyvinyl alcohol and then evaporating them on substrates. Numerous applications may benefit from the nonlinear saturable absorption features of MoTe2 /WTe2 nanosheets, such as visible/near-infrared pulsed laser, materials processing, optical sensors, and modulators. PMID:26800122

  8. Optical absorption by Dirac excitons in single-layer transition-metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Trushin, Maxim; Goerbig, Mark Oliver; Belzig, Wolfgang

    2016-07-01

    We develop an analytically solvable model able to qualitatively explain nonhydrogenic exciton spectra observed recently in two-dimensional (2D) semiconducting transition-metal dichalcogenides. Our exciton Hamiltonian explicitly includes additional angular momentum associated with the pseudospin degree of freedom unavoidable in 2D semiconducting materials with honeycomb structure. We claim that this is the key ingredient for understanding the nonhydrogenic exciton spectra that was missing so far.

  9. Spin transport in n -type single-layer transition-metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Yue, Z.; Tian, Kun; Tiwari, A.; Raikh, M. E.

    2016-05-01

    Valley asymmetry of the electron spectrum in transition-metal dichalcogenides (TMDs) originates from the spin-orbit coupling. Presence of spin-orbit fields of opposite signs for electrons in K and K' valleys in combination with possibility of intervalley scattering result in a nontrivial spin dynamics. This dynamics is reflected in the dependence of nonlocal resistance on external magnetic field (the Hanle curve). We calculate theoretically the Hanle shape in TMDs. It appears that, unlike conventional materials without valley asymmetry, the Hanle shape in TMDs is different for normal and parallel orientations of the external field. For normal orientation, it has two peaks for slow intervalley scattering, while for fast intervalley scattering, the shape is usual. For parallel orientation, the Hanle curve exhibits a cusp at zero field. This cusp is a signature of a slow-decaying valley-asymmetric mode of the spin dynamics.

  10. Optical Limiting and Theoretical Modelling of Layered Transition Metal Dichalcogenide Nanosheets.

    PubMed

    Dong, Ningning; Li, Yuanxin; Feng, Yanyan; Zhang, Saifeng; Zhang, Xiaoyan; Chang, Chunxia; Fan, Jintai; Zhang, Long; Wang, Jun

    2015-01-01

    Nonlinear optical property of transition metal dichalcogenide (TMDC) nanosheet dispersions, including MoS2, MoSe2, WS2, and WSe2, was performed by using Z-scan technique with ns pulsed laser at 1064 nm and 532 nm. The results demonstrate that the TMDC dispersions exhibit significant optical limiting response at 1064 nm due to nonlinear scattering, in contrast to the combined effect of both saturable absorption and nonlinear scattering at 532 nm. Selenium compounds show better optical limiting performance than that of the sulfides in the near infrared. A liquid dispersion system based theoretical modelling is proposed to estimate the number density of the nanosheet dispersions, the relationship between incident laser fluence and the size of the laser generated micro-bubbles, and hence the Mie scattering-induced broadband optical limiting behavior in the TMDC dispersions. PMID:26415562

  11. Optical Limiting and Theoretical Modelling of Layered Transition Metal Dichalcogenide Nanosheets

    PubMed Central

    Dong, Ningning; Li, Yuanxin; Feng, Yanyan; Zhang, Saifeng; Zhang, Xiaoyan; Chang, Chunxia; Fan, Jintai; Zhang, Long; Wang, Jun

    2015-01-01

    Nonlinear optical property of transition metal dichalcogenide (TMDC) nanosheet dispersions, including MoS2, MoSe2, WS2, and WSe2, was performed by using Z-scan technique with ns pulsed laser at 1064 nm and 532 nm. The results demonstrate that the TMDC dispersions exhibit significant optical limiting response at 1064 nm due to nonlinear scattering, in contrast to the combined effect of both saturable absorption and nonlinear scattering at 532 nm. Selenium compounds show better optical limiting performance than that of the sulfides in the near infrared. A liquid dispersion system based theoretical modelling is proposed to estimate the number density of the nanosheet dispersions, the relationship between incident laser fluence and the size of the laser generated micro-bubbles, and hence the Mie scattering-induced broadband optical limiting behavior in the TMDC dispersions. PMID:26415562

  12. Atomic-Resolution Visualization of Distinctive Chemical Mixing Behavior of Ni, Co and Mn with Li in Layered Lithium Transition-Metal Oxide Cathode Materials

    SciTech Connect

    Yan, Pengfei; Zheng, Jianming; Lv, Dongping; Wei, Yi; Zheng, Jiaxin; Wang, Zhiguo; Kuppan, Saravanan; Yu, Jianguo; Luo, Langli; Edwards, Danny J.; Olszta, Matthew J.; Amine, Khalil; Liu, Jun; Xiao, Jie; Pan, Feng; Chen, Guoying; Zhang, Jiguang; Wang, Chong M.

    2015-07-06

    Capacity and voltage fading of layer structured cathode based on lithium transition metal oxide is closely related to the lattice position and migration behavior of the transition metal ions. However, it is scarcely clear about the behavior of each of these transition metal ions. We report direct atomic resolution visualization of interatomic layer mixing of transition metal (Ni, Co, Mn) and lithium ions in layer structured oxide cathodes for lithium ion batteries. Using chemical imaging with aberration corrected scanning transmission electron microscope (STEM) and DFT calculations, we discovered that in the layered cathodes, Mn and Co tend to reside almost exclusively at the lattice site of transition metal (TM) layer in the structure or little interlayer mixing with Li. In contrast, Ni shows high degree of interlayer mixing with Li. The fraction of Ni ions reside in the Li layer followed a near linear dependence on total Ni concentration before reaching saturation. The observed distinctively different behavior of Ni with respect to Co and Mn provides new insights on both capacity and voltage fade in this class of cathode materials based on lithium and TM oxides, therefore providing scientific basis for selective tailoring of oxide cathode materials for enhanced performance.

  13. Surface Recombination Limited Lifetimes of Photoexcited Carriers in Few-Layer Transition Metal Dichalcogenide MoS₂.

    PubMed

    Wang, Haining; Zhang, Changjian; Rana, Farhan

    2015-12-01

    We present results on photoexcited carrier lifetimes in few-layer transition metal dichalcogenide MoS2 using nondegenerate ultrafast optical pump-probe technique. Our results show a sharp increase of the carrier lifetimes with the number of layers in the sample. Carrier lifetimes increase from few tens of picoseconds in monolayer samples to more than a nanosecond in 10-layer samples. The inverse carrier lifetime was found to scale according to the probability of the carriers being present at the surface layers, as given by the carrier wave function in few layer samples, which can be treated as quantum wells. The carrier lifetimes were found to be largely independent of the temperature, and the inverse carrier lifetimes scaled linearly with the photoexcited carrier density. These observations are consistent with defect-assisted carrier recombination, in which the capture of electrons and holes by defects occurs via Auger scatterings. Our results suggest that carrier lifetimes in few-layer samples are surface recombination limited due to the much larger defect densities at surface layers compared with the inner layers. PMID:26535607

  14. Design of Efficient Catalysts with Double Transition Metal Atoms on C2N Layer.

    PubMed

    Li, Xiyu; Zhong, Wenhui; Cui, Peng; Li, Jun; Jiang, Jun

    2016-05-01

    Heterogeneous catalysis often involves molecular adsorptions to charged catalyst site and reactions triggered by catalyst charges. Here we use first-principles simulations to design oxygen reduction reaction (ORR) catalyst based on double transition metal (TM) atoms stably supported by 2D crystal C2N. It not only holds characters of low cost and high durability but also effectively accumulates surface polarization charges on TMs and later deliveries to adsorbed O2 molecule. The Co-Co, Ni-Ni, and Cu-Cu catalysts exhibit high adsorption energies and extremely low dissociation barriers for O2, as compared with their single-atom counterparts. Co-Co on C2N presents less than half the value of the reaction barrier of bulk Pt catalysts in the ORR rate-determining steps. These catalytic improvements are well explained by the dependences of charge polarization on various systems, which opens up a new strategy for optimizing TM catalytic performance with the least metal atoms on porous low-dimensional materials. PMID:27093364

  15. Nickel-rich layered lithium transition-metal oxide for high-energy lithium-ion batteries.

    PubMed

    Liu, Wen; Oh, Pilgun; Liu, Xien; Lee, Min-Joon; Cho, Woongrae; Chae, Sujong; Kim, Youngsik; Cho, Jaephil

    2015-04-01

    High energy-density lithium-ion batteries are in demand for portable electronic devices and electrical vehicles. Since the energy density of the batteries relies heavily on the cathode material used, major research efforts have been made to develop alternative cathode materials with a higher degree of lithium utilization and specific energy density. In particular, layered, Ni-rich, lithium transition-metal oxides can deliver higher capacity at lower cost than the conventional LiCoO2 . However, for these Ni-rich compounds there are still several problems associated with their cycle life, thermal stability, and safety. Herein the performance enhancement of Ni-rich cathode materials through structure tuning or interface engineering is summarized. The underlying mechanisms and remaining challenges will also be discussed. PMID:25801735

  16. Visualization and quantification of transition metal atomic mixing in Mo1−xWxS2 single layers

    PubMed Central

    Dumcenco, Dumitru O; Kobayashi, Haruka; Liu, Zheng; Huang, Ying-Sheng; Suenaga, Kazu

    2013-01-01

    The alloying behaviour of materials is a well-known problem in all kinds of compounds. Revealing the heteroatomic distributions in two-dimensional crystals is particularly critical for their practical use as nano-devices. Here we obtain statistics of the homo- and heteroatomic coordinates in single-layered Mo1−xWxS2 from the atomically resolved scanning transmission electron microscope images and successfully quantify the degree of alloying for the transition metal elements (Mo or W). The results reveal the random alloying of this mixed dichalcogenide system throughout the chemical compositions (x=0 to 1). Such a direct route to gain an insight into the alloying degree on individual atom basis will find broad applications in characterizing low-dimensional heterocompounds and become an important complement to the existing theoretical methods. PMID:23322039

  17. Investigation of the Spatially Resolved Electronic Structure of Single Layer WS2 on Transition Metal Oxide Surfaces

    NASA Astrophysics Data System (ADS)

    Katoch, Jyoti; Ulstrup, Søren; Koch, Roland; Schwarz, Daniel; Singh, Simranjeet; McCreary, Kathy; Keun Yoo, Hyang; Xu, Jinsong; Jonker, Berry; Kawakami, Roland; Bostwick, Aaron; Rotenberg, Eli; Jozwiak, Chris

    The family of semiconducting single layer (SL) transition metal dichalcogenides (TMDs) have lately been intensely studied, owing to the strong coupling between spin and valley degrees of freedom as well as the presence of strongly bound excitons. The choice of supporting substrate is known to strongly influence these properties. We set out to investigate the electronic properties of CVD grown SL WS2 transferred onto the dielectric oxide materials SrTiO3 and TiO2. By using a combination of photoemission electron microscopy (PEEM) and angle-resolved photoemission (ARPES) with micrometer focus we obtain simultaneous spatial, momentum and energy-resolved information about SL WS2 on a polar (SrTiO3) and a nonpolar (TiO2) surface for the first time.

  18. n-Type Transition Metal Oxide as a Hole Extraction Layer in PbS Quantum Dot Solar Cells

    SciTech Connect

    Gao, Jianbo; Perkins, Craig L.; Luther, Joseph M.; Hanna, Mark C.; Chen, Hsiang-Yu; Semonin, Octavi E.; Nozik, Arthur J.; Ellingson, Randy J.; Beard, Matthew C.

    2011-08-10

    The n-type transition metal oxides (TMO) consisting of molybdenum oxide (MoO{sub x}) and vanadium oxide (V₂O{sub x}) are used as an efficient hole extraction layer (HEL) in heterojunction ZnO/PbS quantum dot solar cells (QDSC). A 4.4% NREL-certified device based on the MoO{sub x} HEL is reported with Al as the back contact material, representing a more than 65% efficiency improvement compared with the case of Au contacting the PbS quantum dot (QD) layer directly. We find the acting mechanism of the hole extraction layer to be a dipole formed at the MoO{sub x} and PbS interface enhancing band bending to allow efficient hole extraction from the valence band of the PbS layer by MoO{sub x}. The carrier transport to the metal anode is likely enhanced through shallow gap states in the MoO{sub x} layer.

  19. Large-scale delamination of multi-layers transition metal carbides and carbonitrides “MXenes”

    SciTech Connect

    Naguib, Michael; Unocic, Raymond R.; Armstrong, Beth L.; Nanda, Jagjit

    2015-04-17

    Herein we report on a general approach to delaminate multi-layered MXenes using an organic base to induce swelling that in turn weakens the bonds between the MX layers. Simple agitation or mild sonication of the swollen MXene in water resulted in the large-scale delamination of the MXene layers. The delamination method is demonstrated for vanadium carbide, and titanium carbonitrides MXenes.

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

    SciTech Connect

    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 materials 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.

  1. Low-frequency Raman modes as fingerprints of layer stacking configurations of transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Liang, Liangbo; Puretzky, Alexander; Sumpter, Bobby; Meunier, Vincent; Geohegan, David; David B. Geohegan Team; Vincent Meunier Team

    The tunable optoelectronic properties of stacked two-dimensional (2D) crystal monolayers are determined by their stacking orientation, order, and atomic registry. Atomic-resolution Z-contrast scanning transmission electron microscopy (AR-Z-STEM) can be used to determine the exact atomic registration between different layers in few-layer 2D stacks; however, fast and relatively inexpensive optical characterization techniques are essential for rapid development of the field. Using two- and three-layer MoSe2 and WSe2 crystals synthesized by chemical vapor deposition, we show that the generally unexplored low-frequency (LF) Raman modes (<50 cm-1) that originate from interlayer vibrations can serve as fingerprints to characterize not only the number of layers, but also their stacking configurations [Puretzky and Liang et al, ACS Nano 2015, 9, 6333]. First-principles Raman calculations and group theory analysis corroborate the experimental assignments determined by AR-Z-STEM and show that the calculated LF mode fingerprints are related to the 2D crystal symmetries. Our combined experimental/theoretical work demonstrates the LF Raman modes potentially more effective than HF Raman modes to probe the layer stacking and interlayer interaction for 2D materials. The authors acknowledge support from Eugene P. Wigner Fellowship at the Oak Ridge National Laboratory and the Center for Nanophase Materials Sciences, a DOE Office of Science User Facility.

  2. Electronic and thermoelectric properties of few-layer transition metal dichalcogenides

    SciTech Connect

    Wickramaratne, Darshana; Lake, Roger K.; Zahid, Ferdows

    2014-03-28

    The electronic and thermoelectric properties of one to four monolayers of MoS{sub 2}, MoSe{sub 2}, WS{sub 2}, and WSe{sub 2} are calculated. For few layer thicknesses, the near degeneracies of the conduction band K and Σ valleys and the valence band Γ and K valleys enhance the n-type and p-type thermoelectric performance. The interlayer hybridization and energy level splitting determine how the number of modes within k{sub B}T of a valley minimum changes with layer thickness. In all cases, the maximum ZT coincides with the greatest near-degeneracy within k{sub B}T of the band edge that results in the sharpest turn-on of the density of modes. The thickness at which this maximum occurs is, in general, not a monolayer. The transition from few layers to bulk is discussed. Effective masses, energy gaps, power-factors, and ZT values are tabulated for all materials and layer thicknesses.

  3. Effective Control of the Charge and Magnetic States of Transition-Metal Atoms on Single-Layer Boron Nitride

    SciTech Connect

    Huang, B.; Xiang, H. J.; Yu, J. J.; Wei, S. H.

    2012-05-18

    Developing approaches to effectively control the charge and magnetic states is critical to the use of magnetic nanostructures in quantum information devices but is still challenging. Here we suggest that the magnetic and charge states of transition-metal (TM) doped single-layer boron-nitride (SLBN) systems can be easily controlled by the (internal) defect engineering and (external) electric fields (E{sub ext}). The relative positions and symmetries of the in-gap levels induced by defect engineering and the TM d-orbital energy levels effectively determine the charge states and magnetic properties of the TM/SLBN system. Remarkably, the application of an E{sub ext} can easily control the size of the crystal field splitting of the TM d orbitals and thus, leading to the spin crossover in TM/SLBN, which could be used as E{sub ext}-driven nonvolatile memory devices. Our conclusion obtained from TM/SLBN is valid generally in other TM adsorbed layered semiconductors.

  4. Giant magneto-optical Raman effect in a layered transition metal compound

    PubMed Central

    Ji, Jianting; Zhang, Anmin; Fan, Jiahe; Li, Yuesheng; Wang, Xiaoqun; Zhang, Jiandi; Plummer, E. W.; Zhang, Qingming

    2016-01-01

    We report a dramatic change in the intensity of a Raman mode with applied magnetic field, displaying a gigantic magneto-optical effect. Using the nonmagnetic layered material MoS2 as a prototype system, we demonstrate that the application of a magnetic field perpendicular to the layers produces a dramatic change in intensity for the out-of-plane vibrations of S atoms, but no change for the in-plane breathing mode. The distinct intensity variation between these two modes results from the effect of field-induced broken symmetry on Raman scattering cross-section. A quantitative analysis on the field-dependent integrated Raman intensity provides a unique method to precisely determine optical mobility. Our analysis is symmetry-based and material-independent, and thus the observations should be general and inspire a new branch of inelastic light scattering and magneto-optical applications. PMID:26884198

  5. Giant magneto-optical Raman effect in a layered transition metal compound.

    PubMed

    Ji, Jianting; Zhang, Anmin; Fan, Jiahe; Li, Yuesheng; Wang, Xiaoqun; Zhang, Jiandi; Plummer, E W; Zhang, Qingming

    2016-03-01

    We report a dramatic change in the intensity of a Raman mode with applied magnetic field, displaying a gigantic magneto-optical effect. Using the nonmagnetic layered material MoS2 as a prototype system, we demonstrate that the application of a magnetic field perpendicular to the layers produces a dramatic change in intensity for the out-of-plane vibrations of S atoms, but no change for the in-plane breathing mode. The distinct intensity variation between these two modes results from the effect of field-induced broken symmetry on Raman scattering cross-section. A quantitative analysis on the field-dependent integrated Raman intensity provides a unique method to precisely determine optical mobility. Our analysis is symmetry-based and material-independent, and thus the observations should be general and inspire a new branch of inelastic light scattering and magneto-optical applications. PMID:26884198

  6. Anisotropic optical properties of few-layer transition metal dichalcogenide ReS2

    NASA Astrophysics Data System (ADS)

    Li, Zhenglu; Cao, Ting; da Jornada, Felipe H.; Wu, Meng; Louie, Steven G.

    We present first-principles (DFT, GW and GW-BSE) calculations of the electronic and optical properties of few-layer rhenium disulfide (ReS2). Monolayer ReS2 shows strong many-electron effects with a fundamental quasiparticle band gap of 2.38 eV based on G0W0 calculation and a large exciton binding energy of 690 meV based on solving the Bethe-Salpeter equation. Highly anisotropic linear-polarized optical absorptions are revealed for few-layer and bulk ReS2. The band gap shows a decreasing trend with the optical polarization direction near the absorption edge gradually rotating from around 67 degree in the monolayer to 85 degree in the bulk, referencing to the Re-chain. Our calculations are consistent with recent experimental data and theoretical studies, and provide a systematic understanding of the electronic and optical properties in few-layer ReS2. This work was supported by National Science Foundation Grant No. DMR15-1508412 and the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. Computational resources have been provided by DOE at Lawrence Berkeley National Laboratory's NERSC facility.

  7. 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

    2016-04-01

    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 (CH3NH3PbI3-xClx) 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. PMID:26947400

  8. One-Step Synthesis of MoS₂/WS₂ Layered Heterostructures and Catalytic Activity of Defective Transition Metal Dichalcogenide Films.

    PubMed

    Woods, John M; Jung, Yeonwoong; Xie, Yujun; Liu, Wen; Liu, Yanhui; Wang, Hailiang; Cha, Judy J

    2016-02-23

    Transition metal dichalcogenides (TMDCs) are a promising class of two-dimensional (2D) materials for use in applications such as 2D electronics, optoelectronics, and catalysis. Due to the van der Waals (vdW) bonding between layers, vdW heterostructures can be constructed between two different species of TMDCs. Most studies employ exfoliation or co-vapor growth schemes, which are limited by the small size and uneven distribution of heterostructures on the growth substrate. In this work we demonstrate a one-step synthesis procedure for large-area vdW heterostructures between horizontal TMDCs MoS2 and WS2. The synthesis procedure is scalable and provides patterning ability, which is critical for electronic applications in integrated circuits. We demonstrate rectification characteristics of large-area MoS2/WS2 stacks. In addition, hydrogen evolution reaction performance was measured in these horizontal MoS2 and WS2 thin films, which indicate that, in addition to the catalytically active sulfur edge sites, defect sites may serve as catalyst sites. PMID:26836122

  9. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    NASA Astrophysics Data System (ADS)

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2016-01-01

    In this work, a detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented for select MXenes-a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Herein we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, sbnd O, sbnd OH and sbnd F, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. From XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.

  10. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    DOE PAGESBeta

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2015-12-01

    A detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented in this work for select MXenes—a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Thus we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, single bondO, single bondOHmore » and single bondF, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. Moreover, from XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.« less

  11. X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes)

    SciTech Connect

    Halim, Joseph; Cook, Kevin M.; Naguib, Michael; Eklund, Per; Gogotsi, Yury; Rosen, Johanna; Barsoum, Michel W.

    2015-12-01

    A detailed high resolution X-ray photoelectron spectroscopy (XPS) analysis is presented in this work for select MXenes—a recently discovered family of two-dimensional (2D) carbides and carbonitrides. Given their 2D nature, understanding their surface chemistry is paramount. Thus we identify and quantify the surface groups present before, and after, sputter-cleaning as well as freshly prepared vs. aged multi-layered cold pressed discs. The nominal compositions of the MXenes studied here are Ti3C2Tx, Ti2CTx, Ti3CNTx, Nb2CTx and Nb4C3Tx, where T represents surface groups that this work attempts to quantify. In all the cases, the presence of three surface terminations, single bondO, single bondOH and single bondF, in addition to OH-terminations relatively strongly bonded to H2O molecules, was confirmed. Moreover, from XPS peak fits, it was possible to establish the average sum of the negative charges of the terminations for the aforementioned MXenes. Based on this work, it is now possible to quantify the nature of the surface terminations. This information can, in turn, be used to better design and tailor these novel 2D materials for various applications.

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

    PubMed Central

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

    2016-01-01

    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. PMID:27601195

  13. Anti-Ambipolar Field-Effect Transistors Based On Few-Layer 2D Transition Metal Dichalcogenides.

    PubMed

    Li, Yongtao; Wang, Yan; Huang, Le; Wang, Xiaoting; Li, Xingyun; Deng, Hui-Xiong; Wei, Zhongming; Li, Jingbo

    2016-06-22

    Two-dimensional (2D) materials and their related van der Waals heterostructures have attracted considerable interest for their fascinating new properties. There are still many challenges in realizing the potential of 2D semiconductors in practical (opto)electronics such as signal transmission and logic circuit, etc. Herein, we report the gate-tunable anti-ambipolar devices on the basis of few-layer transition metal dichalcogenides (TMDs) heterostructures to gain higher information storage density. Our study shows that carrier concentration regulated by the gate voltage plays a major role in the "anti-ambipolar" behavior, where the drain-source current can only pass through in specific range of gate voltage (Vg) and it will be restrained if the Vg goes beyond the range. Several improved strategies were theoretically discussed and experimentally adopted to obtain higher current on/off ratio for the anti-ambipolar devices, such as choosing suitable p-/n-pair, increasing carrier concentration by using thicker-layer TMDs, and so on. The modified SnS2/WSe2 device with the current on/off ratio exceeding 200 and on-state Vg ranging from -20 to 0 V was successfully achieved. On the basis of the anti-ambipolar field-effect transistors (FETs), we also reveal the potential of three-channel device unit for signal processing and information storage. With the equal quantity N of device units, 3(N) digital signals can be obtained from such three-channel devices, which are much larger than 2(N) ones obtained from traditional two-channel complementary metal oxide semiconductors (CMOS). PMID:27258569

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

    PubMed

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

    2016-01-01

    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. PMID:27601195

  15. Determining layer number of two-dimensional flakes of transition-metal dichalcogenides by the Raman intensity from substrates.

    PubMed

    Li, Xiao-Li; Qiao, Xiao-Fen; Han, Wen-Peng; Zhang, Xin; Tan, Qing-Hai; Chen, Tao; Tan, Ping-Heng

    2016-04-01

    Transition-metal dichalcogenide (TMD) semiconductors have been widely studied due to their distinctive electronic and optical properties. The property of TMD flakes is a function of their thickness, or layer number (N). How to determine the N of ultrathin TMD materials is of primary importance for fundamental study and practical applications. Raman mode intensity from substrates has been used to identify the N of intrinsic and defective multilayer graphenes up to N = 100. However, such analysis is not applicable to ultrathin TMD flakes due to the lack of a unified complex refractive index (ñ) from monolayer to bulk TMDs. Here, we discuss the N identification of TMD flakes on the SiO2/Si substrate by the intensity ratio between the Si peak from 100 nm (or 89 nm) SiO2/Si substrates underneath TMD flakes and that from bare SiO2/Si substrates. We assume the real part of ñ of TMD flakes as that of monolayer TMD and treat the imaginary part of ñ as a fitting parameter to fit the experimental intensity ratio. An empirical ñ, namely, ñ(eff), of ultrathin MoS2, WS2 and WSe2 flakes from monolayer to multilayer is obtained for typical laser excitations (2.54 eV, 2.34 eV or 2.09 eV). The fitted ñ(eff) of MoS2 has been used to identify the N of MoS2 flakes deposited on 302 nm SiO2/Si substrate, which agrees well with that determined from their shear and layer-breathing modes. This technique of measuring Raman intensity from the substrate can be extended to identify the N of ultrathin 2D flakes with N-dependent ñ. For application purposes, the intensity ratio excited by specific laser excitations has been provided for MoS2, WS2 and WSe2 flakes and multilayer graphene flakes deposited on Si substrates covered by a 80-110 nm or 280-310 nm SiO2 layer. PMID:26906625

  16. 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.

  17. Pressure-driven dome-shaped superconductivity and electronic structural evolution in tungsten ditelluride

    NASA Astrophysics Data System (ADS)

    Pan, Xing-Chen; Chen, Xuliang; Liu, Huimei; Feng, Yanqing; Wei, Zhongxia; Zhou, Yonghui; Chi, Zhenhua; Pi, Li; Yen, Fei; Song, Fengqi; Wan, Xiangang; Yang, Zhaorong; Wang, Baigeng; Wang, Guanghou; Zhang, Yuheng

    2015-07-01

    Tungsten ditelluride has attracted intense research interest due to the recent discovery of its large unsaturated magnetoresistance up to 60 T. Motivated by the presence of a small, sensitive Fermi surface of 5d electronic orbitals, we boost the electronic properties by applying a high pressure, and introduce superconductivity successfully. Superconductivity sharply appears at a pressure of 2.5 GPa, rapidly reaching a maximum critical temperature (Tc) of 7 K at around 16.8 GPa, followed by a monotonic decrease in Tc with increasing pressure, thereby exhibiting the typical dome-shaped superconducting phase. From theoretical calculations, we interpret the low-pressure region of the superconducting dome to an enrichment of the density of states at the Fermi level and attribute the high-pressure decrease in Tc to possible structural instability. Thus, tungsten ditelluride may provide a new platform for our understanding of superconductivity phenomena in transition metal dichalcogenides.

  18. Pressure-driven dome-shaped superconductivity and electronic structural evolution in tungsten ditelluride

    PubMed Central

    Pan, Xing-Chen; Chen, Xuliang; Liu, Huimei; Feng, Yanqing; Wei, Zhongxia; Zhou, Yonghui; Chi, Zhenhua; Pi, Li; Yen, Fei; Song, Fengqi; Wan, Xiangang; Yang, Zhaorong; Wang, Baigeng; Wang, Guanghou; Zhang, Yuheng

    2015-01-01

    Tungsten ditelluride has attracted intense research interest due to the recent discovery of its large unsaturated magnetoresistance up to 60 T. Motivated by the presence of a small, sensitive Fermi surface of 5d electronic orbitals, we boost the electronic properties by applying a high pressure, and introduce superconductivity successfully. Superconductivity sharply appears at a pressure of 2.5 GPa, rapidly reaching a maximum critical temperature (Tc) of 7 K at around 16.8 GPa, followed by a monotonic decrease in Tc with increasing pressure, thereby exhibiting the typical dome-shaped superconducting phase. From theoretical calculations, we interpret the low-pressure region of the superconducting dome to an enrichment of the density of states at the Fermi level and attribute the high-pressure decrease in Tc to possible structural instability. Thus, tungsten ditelluride may provide a new platform for our understanding of superconductivity phenomena in transition metal dichalcogenides. PMID:26203922

  19. Novel properties of Tungsten ditelluride

    NASA Astrophysics Data System (ADS)

    Liu, Huimei; National Laboratory of Solid State Microstructures, School of Physics, Collaborative Innovation Cent Collaboration

    Tungsten ditelluride has attracted intense research interest due to the recent discovery of its large unsaturated magnetoresistance up to 60 Tesla. By using density functional theory calculations, we qualitatively reproduced the observed spin texture. Since the spin texture would forbid back scatterings that are directly involved in the resistivity, we suggest that the SOC and the related spin and orbital angular momentum textures may play an important role in the anomalously large magnetoresistance of WTe2. Motivated by the presence of a small, sensitive Fermi surface of 5d electronic orbitals, we also boost the electronic properties by applying a high pressure, and introduce superconductivity successfully.

  20. Incorporation of transition metals into Mg Al layered double hydroxides: Coprecipitation of cations vs. their pre-complexation with an anionic chelator

    NASA Astrophysics Data System (ADS)

    Tsyganok, Andrey; Sayari, Abdelhamid

    2006-06-01

    A comparative study on two different methods for preparing Mg-Al layered double hydroxides (LDH) containing various divalent transition metals M ( M=Co, Ni, Cu) has been carried out. The first (conventional) method involved coprecipitation of divalent metals M(II) with Mg(II) and Al(III) cations using carbonate under basic conditions. The second approach was based on the ability of transition metals to form stable anionic chelates with edta 4- (edta 4-=ethylenediaminetetraacetate) that were synthesized and further introduced into LDH by coprecipitation with Mg and Al. The synthesized LDHs were characterized by X-ray diffraction (XRD) and X-ray fluorescence (XRF) methods, thermogravimetry with mass-selective detection of decomposition products (TG-MSD), Fourier transform infrared (FTIR) and Raman spectroscopy techniques. The results obtained were discussed in terms of efficiency of transition metal incorporation into the LDH structure, thermal stability of materials and the ability of metal chelates to intercalate the interlayer space of Mg-Al LDH. Vibrational spectroscopy studies confirmed that the integrity of the metal chelates was preserved upon incorporation into the LDH.

  1. Surface group modification and carrier transport properties of layered transition metal carbides (Ti2CTx, T: -OH, -F and -O)

    NASA Astrophysics Data System (ADS)

    Lai, Shen; Jeon, Jaeho; Jang, Sung Kyu; Xu, Jiao; Choi, Young Jin; Park, Jin-Hong; Hwang, Euyheon; Lee, Sungjoo

    2015-11-01

    In spite of recent significant research into various two-dimensional (2D) materials after the emergence of graphene, the development of a new 2D material that provides both high mobility and an appropriate energy band gap (which are crucial for various device applications) remains elusive. In this report, we demonstrate that the carrier transport behaviour of 2D Ti2CTx, which belongs to the family of 2D transition metal carbides and nitrides, can be tuned by modifying the surface group Tx (-OH, -F, and -O). Our results show that 2D Ti2C(OH)xFy and Ti2COx films can be obtained via simple chemical treatment, thermal annealing, and mechanical exfoliation processes. For the first time, we study the carrier transport properties of 2D Ti2CTx field effect transistors (FETs), obtaining the high field effect carrier mobilities of 104 cm2 V-1 s-1 at room temperature. The temperature dependent resistivity of the Ti2COx film exhibits semiconductor like Arrhenius behaviour at zero gate voltage, from which we estimate the energy gap of 80 meV. One interesting feature of the FETs based on transition metal carbides is that the field effect mobility at room temperature is less sensitive to the measured transport gaps, which may arise from the dominant charge transport of activated carriers over the narrow energy gaps of the transition metal carbides. Our results open up the possibility that new 2D materials with high mobilities and appropriate band gaps can be achieved, and broaden the range of electronic device applications of Ti2CTx films.In spite of recent significant research into various two-dimensional (2D) materials after the emergence of graphene, the development of a new 2D material that provides both high mobility and an appropriate energy band gap (which are crucial for various device applications) remains elusive. In this report, we demonstrate that the carrier transport behaviour of 2D Ti2CTx, which belongs to the family of 2D transition metal carbides and nitrides

  2. Synthesis-Microstructure-Performance Relationship of Layered Transition Metal Oxides as Cathode for Rechargeable Sodium Batteries Prepared by High-Temperature Calcination

    SciTech Connect

    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

    2014-09-05

    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.

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

    PubMed

    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

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

    NASA Astrophysics Data System (ADS)

    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.

  5. 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

  6. Oligocyclopentadienyl transition metal complexes

    SciTech Connect

    de Azevedo, Cristina G.; Vollhardt, K. Peter C.

    2002-01-18

    Synthesis, characterization, and reactivity studies of oligocyclopentadienyl transition metal complexes, namely those of fulvalene, tercyclopentadienyl, quatercyclopentadienyl, and pentacyclopentadienyl(cyclopentadienyl) are the subject of this account. Thermal-, photo-, and redox chemistries of homo- and heteropolynuclear complexes are described.

  7. Transition Metal Nitride Coated with Atomic Layers of Pt as a Low-Cost, Highly Stable Electrocatalyst for the Oxygen Reduction Reaction.

    PubMed

    Tian, Xinlong; Luo, Junming; Nan, Haoxiong; Zou, Haobin; Chen, Rong; Shu, Ting; Li, Xiuhua; Li, Yingwei; Song, Huiyu; Liao, Shijun; Adzic, Radoslav R

    2016-02-10

    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 of 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. PMID:26796872

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

    DOE PAGESBeta

    Tian, Xinlong; Adzic, Radoslav R.; Luo, Junming; Nan, Haoxiong; Zou, Haobin; Chen, Rong; Shu, Ting; Li, Xiuhua; Li, Yingwei; Song, Huiyi; et al

    2016-01-21

    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

  9. Wall energy and wall thickness of exchange-coupled rare-earth transition-metal triple layer stacks

    SciTech Connect

    Raasch, D.; Mathieu, C.

    1997-08-01

    The room-temperature wall energy {sigma}{sub w}=4.0{times}10{sup {minus}3}J/m{sup 2} of an exchange-coupled Tb{sub 19.6}Fe{sub 74.7}Co{sub 5.7}/Dy{sub 28.5}Fe{sub 43.2}Co{sub 28.3} double layer stack can be reduced by introducing a soft magnetic intermediate layer in between both layers exhibiting a significantly smaller anisotropy compared to Tb{endash}FeCo and Dy{endash}FeCo. {sigma}{sub w} will decrease linearly with increasing intermediate layer thickness, d{sub IL}, until the wall is completely located within the intermediate layer for d{sub IL}{ge}d{sub w}, where d{sub w} denotes the wall thickness. Thus, d{sub w} can be obtained from the plot {sigma}{sub w} versus d{sub IL}. We determined {sigma}{sub w} and d{sub w} on Gd{endash}FeCo intermediate layers with different anisotropy behavior (perpendicular and in-plane easy axis) and compared the results with data obtained from Brillouin light-scattering measurements, where exchange stiffness, A, and uniaxial anisotropy, K{sub u}, could be determined. With the knowledge of A and K{sub u}, wall energy and thickness were calculated and showed an excellent agreement with the magnetic measurements. A ten times smaller perpendicular anisotropy of Gd{sub 28.1}Fe{sub 71.9} in comparison to Tb{endash}FeCo and Dy{endash}FeCo resulted in a much smaller {sigma}{sub w}=1.1{times}10{sup {minus}3}J/m{sup 2} and d{sub w}=24nm at 300 K. A Gd{sub 34.1}Fe{sub 61.4}Co{sub 4.5} with in-plane anisotropy at room temperature showed a further reduced {sigma}{sub w}=0.3{times}10{sup {minus}3}J/m{sup 2} and d{sub w}=17nm. The smaller wall energy was a result of a different wall structure compared to perpendicular layers. {copyright} {ital 1997 American Institute of Physics.}

  10. 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. PMID:25470356

  11. Flexible n-type thermoelectric materials by organic intercalation of layered transition metal dichalcogenide TiS2.

    PubMed

    Wan, Chunlei; Gu, Xiaokun; Dang, Feng; Itoh, Tomohiro; Wang, Yifeng; Sasaki, Hitoshi; Kondo, Mami; Koga, Kenji; Yabuki, Kazuhisa; Snyder, G Jeffrey; Yang, Ronggui; Koumoto, Kunihito

    2015-06-01

    Organic semiconductors are attracting increasing interest as flexible thermoelectric materials owing to material abundance, easy processing and low thermal conductivity. Although progress in p-type polymers and composites has been reported, their n-type counterpart has fallen behind owing to difficulties in n-type doping of organic semiconductors. Here, we present an approach to synthesize n-type flexible thermoelectric materials through a facile electrochemical intercalation method, fabricating a hybrid superlattice of alternating inorganic TiS2 monolayers and organic cations. Electrons were externally injected into the inorganic layers and then stabilized by organic cations, providing n-type carriers for current and energy transport. An electrical conductivity of 790 S cm(-1) and a power factor of 0.45 mW m(-1) K(-2) were obtained for a hybrid superlattice of TiS2/[(hexylammonium)x(H2O)y(DMSO)z], with an in-plane lattice thermal conductivity of 0.12 ± 0.03 W m(-1) K(-1), which is two orders of magnitude smaller than the thermal conductivities of the single-layer and bulk TiS2. High power factor and low thermal conductivity contributed to a thermoelectric figure of merit, ZT, of 0.28 at 373 K, which might find application in wearable electronics. PMID:25849369

  12. Al capping layers for nondestructive x-ray photoelectron spectroscopy analyses of transition-metal nitride thin films

    SciTech Connect

    Greczynski, Grzegorz Hultman, Lars; Petrov, Ivan; Greene, J. E.

    2015-09-15

    X-ray photoelectron spectroscopy (XPS) compositional analyses of materials that have been air exposed typically require ion etching in order to remove contaminated surface layers. However, the etching step can lead to changes in sample surface and near-surface compositions due to preferential elemental sputter ejection and forward recoil implantation; this is a particular problem for metal/gas compounds and alloys such as nitrides and oxides. Here, the authors use TiN as a model system and compare XPS analysis results from three sets of polycrystalline TiN/Si(001) films deposited by reactive magnetron sputtering in a separate vacuum chamber. The films are either (1) air-exposed for ≤10 min prior to insertion into the ultrahigh-vacuum (UHV) XPS system; (2) air-exposed and subject to ion etching, using different ion energies and beam incidence angles, in the XPS chamber prior to analysis; or (3) Al-capped in-situ in the deposition system prior to air-exposure and loading into the XPS instrument. The authors show that thin, 1.5–6.0 nm, Al capping layers provide effective barriers to oxidation and contamination of TiN surfaces, thus allowing nondestructive acquisition of high-resolution core-level spectra representative of clean samples, and, hence, correct bonding assignments. The Ti 2p and N 1s satellite features, which are sensitive to ion bombardment, exhibit high intensities comparable to those obtained from single-crystal TiN/MgO(001) films grown and analyzed in-situ in a UHV XPS system and there is no indication of Al/TiN interfacial reactions. XPS-determined N/Ti concentrations acquired from Al/TiN samples agree very well with Rutherford backscattering and elastic recoil analysis results while ion-etched air-exposed samples exhibit strong N loss due to preferential resputtering. The intensities and shapes of the Ti 2p and N 1s core level signals from Al/TiN/Si(001) samples do not change following long-term (up to 70 days) exposure to ambient conditions

  13. Rapid synthesis of transition metal dichalcogenide few-layer thin crystals by the microwave-induced-plasma assisted method

    NASA Astrophysics Data System (ADS)

    Chaturvedi, Apoorva; Slabon, Adam; Hu, Peng; Feng, Shuanglong; Zhang, Ke-ke; Prabhakar, Rajiv Ramanujam; Kloc, Christian

    2016-09-01

    Few-layer thin crystals of WS2, MoS2, WSe2, MoSe2 and ReS2 were synthesized via the microwave-induced-plasma-assisted method. The synthesis was accomplished in plasma that was formed inside sealed quartz ampoules heated by plasma surrounding the sealed ampoule. Powder X-ray diffraction, Raman spectroscopy and Transmission Electron Microscopy indicate thin crystals of high-quality. The proposed method is rapid, reproducible and environmentally friendly. It is applicable to practically every direct reaction between metals and nonmetals if the nonmetal vapor pressure can reach a pressure of a few torr, which is required for plasma formation inside a sealed ampoule.

  14. Towards understanding the rate capability of layered transition metal oxides LiNiyMnyCo1-2yO2

    NASA Astrophysics Data System (ADS)

    Li, Zheng; Ban, Chunmei; Chernova, Natasha A.; Wu, Zhuangchun; Upreti, Shailesh; Dillon, Anne; Whittingham, M. Stanley

    2014-12-01

    This work attempts to understand the rate capability of layered transition metal oxides LiNiyMnyCo1-2yO2 (0.33 ≤ y ≤ 0.5). The rate capability of LiNiyMnyCo1-2yO2 increase with increasing Co in the compounds and with increasing amount of carbon additives in the electrodes. The lithium diffusion coefficients and electronic conductivities of LixNiyMnyCo1-2yO2 are investigated and compared. The 333 compound has higher diffusivity and electronic conductivity and thus better rate performance than 550. Chemical diffusion coefficients for both delithiation and lithiation of LixNiyMnyCo1-2yO2 investigated by GITT and PITT experiments are calculated to be around 10-10 cm2 s-1, lower than that of LixCoO2. The electronic conductivity of LixNiyMnyCo1-2yO2 is inferior compared to LixCoO2 at same temperature and delithiation stage. However, the LixNiyMnyCo1-2yO2 are able to deliver 55%-80% of theoretical capacity at 5 C with good electronic wiring in the composite electrode that make them very promising candidates for electric propulsion in terms of rate capability.

  15. Multidimensional transition metal complexes based on 3-amino-1H-1,2,4-triazole-5-carboxylic acid: from discrete mononuclear complexes to layered materials.

    PubMed

    Liu, Bing; Fernandes, José A; Tomé, João P C; Paz, Filipe A Almeida; Cunha-Silva, Luís

    2015-01-01

    The synthesis and structural characterization of five transition metal complexes with different dimensionality and incorporating residues of 3-amino-1H-1,2,4-triazole-5-carboxylic acid (H2atrc) is reported: [Zn(Hatrc)2(H2O)] (1), [Mn(Hatrc)2(H2O)2]·2H2O (2), [Fe2(Hatrc)4(OH)2]·6H2O (3), [Cd(Hatrc)2(H2O)]n (4), and [Mn(atrc)(H2O)]n·nH2O (5). These materials could be prepared from solution (1-3), diffusion (4), or hydrothermal reactions (5) with various anions and L:M ratios. Structural details were revealed by single crystal X-ray diffraction. The discrete units composing compounds 1-3, the polymeric 1D chain of 4 and the 2D layer of 5 are further extended into 3D supramolecular architectures through the formation of hydrogen bonds. PMID:26198221

  16. 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. PMID:25562378

  17. 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. PMID:25666075

  18. Method of boronizing transition-metal surfaces

    SciTech Connect

    Koyama, K.; Shimotake, H.

    1981-08-28

    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/sup 0/C and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface.

  19. 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.

  20. 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.

  1. Enhancement of band-to-band tunneling in mono-layer transition metal dichalcogenides two-dimensional materials by vacancy defects

    SciTech Connect

    Jiang, Xiang-Wei; Li, Shu-Shen; Gong, Jian; Xu, Nuo; Zhang, Jinfeng; Hao, Yue; Wang, Lin-Wang

    2014-01-13

    The band-to-band tunneling of monolayer transition metal dichalcogenides nano-junction is investigated using atomistic ab initio quantum transport simulations. From the simulation, it is found that the transition metal vacancy defect in the two-dimensional MX{sub 2} (M = Mo,W; X = S,Se) band-to-band tunneling diode can dramatically boost the on-state current up to 10 times while maintaining the device sub-threshold swing. The performance enhancement mechanism is discussed in detail by examining partial density of states of the system. It is found that the transition metal vacancy induces band-gap states, which reduce the effective length of the tunneling transition region.

  2. Transition Metal Switchable Mirror

    SciTech Connect

    2009-01-01

    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

  3. Transition Metal Switchable Mirror

    ScienceCinema

    None

    2010-01-08

    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.

  4. Transition Metal Switchable Mirror

    ScienceCinema

    None

    2013-05-29

    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

  5. Transition Metal Switchable Mirror

    SciTech Connect

    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.

  6. Selenophene transition metal complexes

    SciTech Connect

    White, C.J.

    1994-07-27

    This research shows that selenophene transition metal complexes have a chemistry that is similar to their thiophene analogs. Selenophene coordination has been demonstrated and confirmed by molecular structure in both the {eta}{sup 5}- and the {eta}{sup 1}(Se)-coordination modes. The reaction chemistry of selenophene complexes closely resembles that of the analogous thiophene complexes. One major difference, however, is that selenophene is a better donor ligand than thiophene making the selenophene complexes more stable than the corresponding thiophene complexes. The {sup 77}Se NMR chemical shift values for selenophene complexes fall within distinct regions primarily depending on the coordination mode of the selenophene ligand. In the final paper, the C-H bond activation of {eta}{sup 1}(S)-bound thiophenes, {eta}{sup 1}(S)-benzothiophene and {eta}{sup 1}(Se)-bound selenophenes has been demonstrated. The deprotonation and rearrangement of the {eta}{sup 1}(E)-bound ligand to the carbon bound L-yl complex readily occurs in the presence of base. Reprotonation with a strong acid gives a carbene complex that is unreactive towards nucleophilic attack at the carbene carbon and is stable towards exposure to air. The molecular structure of [Cp(NO)(PPh{sub 3})Re(2-benzothioenylcarbene)]O{sub 3}SCF{sub 3} was determined and contains a Re-C bond with substantial double bond character. Methyl substitution for the thienylcarbene or selenylcarbene gives a carbene that rearranges thermally to give back the {eta}{sup 1}(E)-bound complex. Based on these model reactions, a new mechanism for the H/D exchange of thiophene over the hydrodesulfurization catalyst has been proposed.

  7. 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

  8. Raman scattering and anomalous Stokes–anti-Stokes ratio in MoTe2 atomic layers

    PubMed Central

    Goldstein, Thomas; Chen, Shao-Yu; Tong, Jiayue; Xiao, Di; Ramasubramaniam, Ashwin; Yan, Jun

    2016-01-01

    Stokes and anti-Stokes Raman scattering are performed on atomic layers of hexagonal molybdenum ditelluride (MoTe2), a prototypical transition metal dichalcogenide (TMDC) semiconductor. The data reveal all six types of zone center optical phonons, along with their corresponding Davydov splittings, which have been challenging to see in other TMDCs. We discover that the anti-Stokes Raman intensity of the low energy layer-breathing mode becomes more intense than the Stokes peak under certain experimental conditions, and find the effect to be tunable by excitation frequency and number of atomic layers. These observations are interpreted as a result of resonance effects arising from the C excitons in the vicinity of the Brillouin zone center in the photon-electron-phonon interaction process. PMID:27324297

  9. 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…

  10. 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.

  11. Dimensional diversity in transition metal trihalides

    SciTech Connect

    Jianhua Lin; Miller, G.J. )

    1993-04-14

    Structural variations of the second- and third-row transition metal trihalides are rationalized via tight-binding band calculations and evaluation of Madelung energetic factors. The observed structure for a given metal halide is controlled by both the coordination geometry at the anion and the d electron configuration at the metal. As the polarizability of the halide increases, the M-X-M angle, in general, decreases so that three-dimensional frameworks occur for the fluorides, while layer and chain structures are found for the chlorides, bromides, and iodides. Within a particular halide system, systematic structural trends also occur as the d electron configuration changes. 56 refs., 23 figs., 4 tabs.

  12. Strain Engineering of Transition Metal Dichalcogenides

    NASA Astrophysics Data System (ADS)

    Dadgar, Ali; Pasupathy, Abhay; Herman, Irving; Wang, Dennis; Kang, Kyungnam; Yang, Eui-Hyeok

    The application of strain to materials can cause changes to bandwidth, effective masses, degeneracies and even structural phases. In the case of the transition metal dichalcogenide (TMD) semiconductors, small strain (around 1 percent) is expected to change band gaps and mobilities, while larger strains are expected to cause phase changes from the triangular 2H phase to orthorhombic 1T' phases. We will describe experimental techniques to apply small and large (around 10 percent) strains to one or few layer samples of the TMD semiconductors, and describe the effect of the strain using optical (Raman, photoluminescence) and cryogenic transport techniques.

  13. A General Method for Constructing Two-Dimensional Layered Mesoporous Mono- and Binary-Transition-Metal Nitride/Graphene as an Ultra-Efficient Support to Enhance Its Catalytic Activity and Durability for Electrocatalytic Application.

    PubMed

    Liu, Baocang; Huo, Lili; Si, Rui; Liu, Jian; Zhang, Jun

    2016-07-27

    We constructed a series of two-dimensional (2D) layered mesoporous mono- and binary-transition-metal nitride/graphene nanocomposites (TMN/G, TM = Ti, Cr, W, Mo, TiCr, TiW, and TiMo) via an efficient and versatile nanocasting strategy for the first time. The 2D layered mesoporous TMN/G is constituted of small TMN nanoparticles composited with graphene nanosheets and has a large surface area with high porosity. Through decoration with well-dispersed Pt nanoparticles, 2D layered mesoporous Pt/TMN/G catalysts can be obtained that display excellent catalytic activity and stability for methanol electro-oxidation reactions (MOR) and oxygen reduction reactions (ORR) in both acidic and alkaline media. The 2D layered mesoporous binary-Pt/TMN/G catalysts possess catalytic activity superior to that of mono-Pt/TMN/G, graphene free Pt/TMN, Pt/G, and Pt/C catalysts. Encouragingly, the 2D layered mesoporous Pt/Ti0.5Cr0.5N/G catalyst exhibits the best electrocatalytic performance for both MOR and ORR. The outstanding electrocatalytic performance of the Pt/Ti0.5Cr0.5N/G catalyst is rooted in its large surface area, high porosity, strong interaction among Pt, Ti0.5Cr0.5N, and graphene, an excellent electron transfer property facilitated by N-doped graphene, and the small size of Pt and Ti0.5Cr0.5N nanocrystals. The outstanding catalytic performance provides the 2D layered mesoporous Pt/Ti0.5Cr0.5N/G catalyst with a wide range of application prospects in direct methanol fuel cells in both acidic and alkaline media. The synthetic method may be available for constructing other 2D layered mesoporous metal nitrides, carbides, and phosphides. PMID:27356463

  14. 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

    NASA Astrophysics Data System (ADS)

    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

    2015-01-01

    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.

  15. 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. PMID:25612725

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

    SciTech Connect

    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 E-mail: hchahm@kist.re.kr; Ham, Hyung Chul E-mail: hchahm@kist.re.kr

    2015-01-21

    The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt{sub 3}M 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/Pt{sub 3}M 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/Pt{sub 3}M 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 Pt{sub 3}M 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.

  17. Synthesis of transition metal borides layers under pulsed electron-beams treatment in a vacuum for surface hardening of instrumental steels

    NASA Astrophysics Data System (ADS)

    Milonov, A. S.; Danzheev, B. A.; Smirnyagina, N. N.; Dasheev, D. E.; Kim, T. B.; Semenov, A. P.

    2015-11-01

    The saturation of the surface layers of metals and alloys with boron is conducted for increasing their surface hardness, wear resistance, etc. Multicomponent layers containing in its composition borides of refractory metals, as a rule, are formed by the methods of chemical- thermal processing in the interaction of boriding component with refractory one or by the method of saturation of refractory metal impurities or alloy with boron. In this work, we studied the features of vanadium and iron borides formation on the surface of instrumental steels U8A and R18 under the influence of intense electron beams in continuous and pulse modes.

  18. Flexible transition metal dichalcogenide nanosheets for band-selective photodetection

    PubMed Central

    Velusamy, Dhinesh Babu; Kim, Richard Hahnkee; Cha, Soonyoung; Huh, June; Khazaeinezhad, Reza; Kassani, Sahar Hosseinzadeh; Song, Giyoung; Cho, Suk Man; Cho, Sung Hwan; Hwang, Ihn; Lee, Jinseong; Oh, Kyunghwan; Choi, Hyunyoug; Park, Cheolmin

    2015-01-01

    The photocurrent conversions of transition metal dichalcogenide nanosheets are unprecedentedly impressive, making them great candidates for visible range photodetectors. Here we demonstrate a method for fabricating micron-thick, flexible films consisting of a variety of highly separated transition metal dichalcogenide nanosheets for excellent band-selective photodetection. Our method is based on the non-destructive modification of transition metal dichalcogenide sheets with amine-terminated polymers. The universal interaction between amine and transition metal resulted in scalable, stable and high concentration dispersions of a single to a few layers of numerous transition metal dichalcogenides. Our MoSe2 and MoS2 composites are highly photoconductive even at bending radii as low as 200 μm on illumination of near infrared and visible light, respectively. More interestingly, simple solution mixing of MoSe2 and MoS2 gives rise to blended composite films in which the photodetection properties were controllable. The MoS2/MoSe2 (5:5) film showed broad range photodetection suitable for both visible and near infrared spectra. PMID:26333531

  19. O3-type layered transition metal oxide Na(NiCoFeTi)1/4O2 as a high rate and long cycle life cathode material for sodium ion batteries

    DOE PAGESBeta

    Yue, Ji -Li; Yang, Xiao -Qing; Zhou, Yong -Ning; Yu, Xiqian; Bak, Seong -Min; Fu, Zheng -Wen

    2015-10-09

    High rate capability and long cycle life are challenging goals for the development of room temperature sodium-ion batteries. Here we report a new single phase quaternary O3-type layer-structured transition metal oxide Na(NiCoFeTi)1/4O2 synthesized by a simple solid-state reaction as a new cathode material for sodium-ion batteries. It can deliver a reversible capacity of 90.6 mA h g–1 at a rate as high as 20C. At 5C, 75.0% of the initial specific capacity can be retained after 400 cycles with a capacity-decay rate of 0.07% per cycle, demonstrating a superior long-term cyclability at high current density. X-ray diffraction and absorption characterizationmore » revealed reversible phase transformations and electronic structural changes during the Na+ deintercalation/intercalation process. Ni, Co and Fe ions contribute to charge compensation during charge and discharge. Although Ti ions do not contribute to the charge transfer, they play a very important role in stabilizing the structure during charge and discharge by suppressing the Fe migration. Additionally, Ti substitution can also smooth the charge–discharge plateaus effectively, which provides a potential advantage for the commercialization of this material for room temperature sodium-ion batteries.« less

  20. O3-type layered transition metal oxide Na(NiCoFeTi)1/4O2 as a high rate and long cycle life cathode material for sodium ion batteries

    SciTech Connect

    Yue, Ji -Li; Yang, Xiao -Qing; Zhou, Yong -Ning; Yu, Xiqian; Bak, Seong -Min; Fu, Zheng -Wen

    2015-10-09

    High rate capability and long cycle life are challenging goals for the development of room temperature sodium-ion batteries. Here we report a new single phase quaternary O3-type layer-structured transition metal oxide Na(NiCoFeTi)1/4O2 synthesized by a simple solid-state reaction as a new cathode material for sodium-ion batteries. It can deliver a reversible capacity of 90.6 mA h g–1 at a rate as high as 20C. At 5C, 75.0% of the initial specific capacity can be retained after 400 cycles with a capacity-decay rate of 0.07% per cycle, demonstrating a superior long-term cyclability at high current density. X-ray diffraction and absorption characterization revealed reversible phase transformations and electronic structural changes during the Na+ deintercalation/intercalation process. Ni, Co and Fe ions contribute to charge compensation during charge and discharge. Although Ti ions do not contribute to the charge transfer, they play a very important role in stabilizing the structure during charge and discharge by suppressing the Fe migration. Additionally, Ti substitution can also smooth the charge–discharge plateaus effectively, which provides a potential advantage for the commercialization of this material for room temperature sodium-ion batteries.

  1. Raman spectroscopy of transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Saito, R.; Tatsumi, Y.; Huang, S.; Ling, X.; Dresselhaus, M. S.

    2016-09-01

    Raman spectroscopy of transition metal dichalcogenides (TMDs) is reviewed based on our recent theoretical and experimental works. First, we discuss the semi-classical and quantum mechanical description for the polarization dependence of Raman spectra of TMDs in which the optical dipole transition matrix elements as a function of laser excitation energy are important for understanding the polarization dependence of the Raman intensity and Raman tensor. Overviewing the symmetry of TMDs, we discuss the dependence of the Raman spectra of TMDs on layer thickness, polarization, laser energy and the structural phase. Furthermore, we discuss the Raman spectra of twisted bilayer and heterostructures of TMDs. Finally, we give our perspectives on the Raman spectroscopy of TMDs.

  2. Raman spectroscopy of transition metal dichalcogenides.

    PubMed

    Saito, R; Tatsumi, Y; Huang, S; Ling, X; Dresselhaus, M S

    2016-09-01

    Raman spectroscopy of transition metal dichalcogenides (TMDs) is reviewed based on our recent theoretical and experimental works. First, we discuss the semi-classical and quantum mechanical description for the polarization dependence of Raman spectra of TMDs in which the optical dipole transition matrix elements as a function of laser excitation energy are important for understanding the polarization dependence of the Raman intensity and Raman tensor. Overviewing the symmetry of TMDs, we discuss the dependence of the Raman spectra of TMDs on layer thickness, polarization, laser energy and the structural phase. Furthermore, we discuss the Raman spectra of twisted bilayer and heterostructures of TMDs. Finally, we give our perspectives on the Raman spectroscopy of TMDs. PMID:27388703

  3. 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.

  4. Synthesis of transition metal carbonitrides

    DOEpatents

    Munir, Zuhair A. R.; Eslamloo-Grami, Maryam

    1994-01-01

    Transition metal carbonitrides (in particular, titanium carbonitride, TiC.sub.0.5 N.sub.0.5) are synthesized by a self-propagating reaction between the metal (e.g., titanium) and carbon in a nitrogen atmosphere. Complete conversion to the carbonitride phase is achieved with the addition of TiN as diluent and with a nitrogen pressure .gtoreq.0.6 MPa. Thermodynamic phase-stability calculations and experimental characterizations of quenched samples provided revealed that the mechanism of formation of the carbonitride is a two-step process. The first step involves the formation of the nonstoichiometric carbide, TiC.sub.0.5, and is followed by the formation of the product by the incorporation of nitrogen in the defect-structure carbide.

  5. Inherited (In)stabilities in Transition Metal Superlattices

    NASA Astrophysics Data System (ADS)

    Rudin, Sven

    2011-03-01

    Many transition metals exhibit a solid phase with a body-centered cubic (bcc) crystal structure. For some elements, e.g., tungsten (W), bcc is the only solid phase; for others, e.g., titanium (Ti), the bcc phase only appears at high temperatures. Titanium's high-temperature bcc phase exhibits soft phonon modes. These reflect the atomic movements upon transformation into the low-temperature phases. One such mode shows atomic displacements that also appear in the top few layers of tungsten's surface reconstruction. Superlattices constructed from alternating nanometer-thick layers of W and Ti would allow the two displacement patterns to interact. The work presented here uses density functional theory calculations to predict how the structure and mechanical response of such superlattices depends on the choice of transition metal elements and the layer thicknesses.

  6. Engineering skyrmions in transition-metal multilayers for spintronics

    NASA Astrophysics Data System (ADS)

    Dupé, B.; Bihlmayer, G.; Böttcher, M.; Blügel, S.; Heinze, S.

    2016-06-01

    Magnetic skyrmions are localized, topologically protected spin structures that have been proposed for storing or processing information due to their intriguing dynamical and transport properties. Important in terms of applications is the recent discovery of interface stabilized skyrmions as evidenced in ultra-thin transition-metal films. However, so far only skyrmions at interfaces with a single atomic layer of a magnetic material were reported, which greatly limits their potential for application in devices. Here we predict the emergence of skyrmions in [4d/Fe2/5d]n multilayers, that is, structures composed of Fe biatomic layers sandwiched between 4d and 5d transition-metal layers. In these composite structures, the exchange and the Dzyaloshinskii-Moriya interactions that control skyrmion formation can be tuned separately by the two interfaces. This allows engineering skyrmions as shown based on density functional theory and spin dynamics simulations.

  7. Engineering skyrmions in transition-metal multilayers for spintronics.

    PubMed

    Dupé, B; Bihlmayer, G; Böttcher, M; Blügel, S; Heinze, S

    2016-01-01

    Magnetic skyrmions are localized, topologically protected spin structures that have been proposed for storing or processing information due to their intriguing dynamical and transport properties. Important in terms of applications is the recent discovery of interface stabilized skyrmions as evidenced in ultra-thin transition-metal films. However, so far only skyrmions at interfaces with a single atomic layer of a magnetic material were reported, which greatly limits their potential for application in devices. Here we predict the emergence of skyrmions in [4d/Fe2/5d]n multilayers, that is, structures composed of Fe biatomic layers sandwiched between 4d and 5d transition-metal layers. In these composite structures, the exchange and the Dzyaloshinskii-Moriya interactions that control skyrmion formation can be tuned separately by the two interfaces. This allows engineering skyrmions as shown based on density functional theory and spin dynamics simulations. PMID:27257020

  8. Engineering skyrmions in transition-metal multilayers for spintronics

    PubMed Central

    Dupé, B.; Bihlmayer, G.; Böttcher, M.; Blügel, S.; Heinze, S.

    2016-01-01

    Magnetic skyrmions are localized, topologically protected spin structures that have been proposed for storing or processing information due to their intriguing dynamical and transport properties. Important in terms of applications is the recent discovery of interface stabilized skyrmions as evidenced in ultra-thin transition-metal films. However, so far only skyrmions at interfaces with a single atomic layer of a magnetic material were reported, which greatly limits their potential for application in devices. Here we predict the emergence of skyrmions in [4d/Fe2/5d]n multilayers, that is, structures composed of Fe biatomic layers sandwiched between 4d and 5d transition-metal layers. In these composite structures, the exchange and the Dzyaloshinskii–Moriya interactions that control skyrmion formation can be tuned separately by the two interfaces. This allows engineering skyrmions as shown based on density functional theory and spin dynamics simulations. PMID:27257020

  9. 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.

  10. 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.

  11. Transition metals activate TFEB in overexpressing cells

    PubMed Central

    Peña, Karina A.; Kiselyov, Kirill

    2015-01-01

    Transition metal toxicity is an important factor in the pathogenesis of numerous human disorders, including neurodegenerative diseases. Lysosomes have emerged as important factors in transition metal toxicity because they handle transition metals via endocytosis, autophagy, absorption from the cytoplasm and exocytosis. Transcription factor EB (TFEB) regulates lysosomal biogenesis and the expression of lysosomal proteins in response to lysosomal and/or metabolic stresses. Since transition metals cause lysosomal dysfunction, we proposed that TFEB may be activated to drive gene expression in response to transition metal exposure and that such activation may influence transition metal toxicity. We found that transition metals copper (Cu) and iron (Fe) activate recombinant TFEB and stimulate the expression of TFEB-dependent genes in TFEB-overexpressing cells. In cells that show robust lysosomal exocytosis, TFEB was cytoprotective at moderate levels of Cu exposure, decreasing oxidative stress as reported by the expression of heme oxygenase-1 (HMOX1) gene. However, at high levels of Cu exposure, particularly in cells with low levels of lysosomal exocytosis, activation of overexpressed TFEB was toxic, increasing oxidative stress and mitochondrial damage. Based on these data, we conclude that TFEB-driven gene network is a component of the cellular response to transition metals. These data suggest limitations and disadvantages of TFEB overexpression as a therapeutic approach. PMID:26251447

  12. Finding new ternary transition metal selenides and sulphides

    NASA Astrophysics Data System (ADS)

    Narayan, Awadhesh; Bhutani, Ankita; Eckstein, James N.; Shoemaker, Daniel P.; Wagner, Lucas K.

    The transition metal oxides exhibit many interesting physical properties, and have been explored in detail over time. Recently, the transition metal chalchogenides including selenium and sulfur have been of interest because of their correlated electron properties, as seen in the iron based superconductors and the layered transition metal dichalchogenides. However, the chalchogenides are much less explored than the oxides, and there is an open question of whether there may be new materials heretofore undiscovered. We perform a systematic combined theoretical and experimental search over ternary phase diagrams that are empty in the Inorganic Crystal Structure Database containing cations, transition metals, and one of selenium or sulfur. In these 27 ternary systems, we use a probabilistic model to reduce the likelihood of false negative predictions, which results in a list of 24 candidate materials. We then conduct a variety of synthesis experiments to check the candidate materials for stability. While the prediction method did obtain compositions that are stable, none of the candidate materials formed in our experiments. We come to the conclusion that these phase diagrams are either truly empty or have unusual structures or synthesis requirements. This work was supported by the Center for Emergent Superconductivity, Department of Energy Frontier Research Center under Grant No. DEAC0298CH1088.

  13. Piperazine pivoted transition metal dithiocarbamates

    NASA Astrophysics Data System (ADS)

    Khan, Sadaf; Nami, Shahab A. A.; Siddiqi, K. S.

    2008-03-01

    A quadridentate ligand disodium bis(2,2'-dithiopiperazinato-2,2'-diamino diethylamine) Na 2L 2 and its self assembled transition metal complexes of the type, M 2(L 2) 2 {M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II)} have been reported. The piperazine pivoted homodinuclear complexes have been characterized by a range of spectral, thermal, microanalytical and conductometric techniques. On the basis of IR and 1HNMR data a symmetrical bidentate coordination of the dithiocarbamato moiety has been observed in all the cases. The TGA profile of the ligand exhibits two stage thermolytic pattern although the complexes decompose in three steps, respectively. Metal sulfide is found to be the end product. The formation of homodinuclear complexes has been ascertained on the basis of FAB mass spectral data and a probable fragmentation pattern has been proposed. On the basis of UV-visible spectroscopic results and room temperature magnetic moment data a tetrahedral geometry has been proposed for all the complexes except for the Ni(II) and Cu(II) which are found to be square-planar.

  14. Polytypism in superhard transition-metal triborides

    PubMed Central

    Liang, Yongcheng; Yang, Jiong; Yuan, Xun; Qiu, Wujie; Zhong, Zheng; Yang, Jihui; Zhang, Wenqing

    2014-01-01

    The quest of novel compounds with special structures and unusual functionalities continues to be a central challenge to modern materials science. Even though their exact structures have puzzled scientists for decades, superhard transition-metal borides (TMBs) have long been believed to exist only in simple crystal structures. Here, we report on a polytypic phenomenon in superhard WB3 and MoB3 with a series of energetically degenerate structures due to the random stacking of metal layers amongst the interlocking boron layers. Such polytypism can create a multiphase solid-solution compound with a large number of interfaces amongst different polytypes, and these interfaces will strongly hinder the interlayer sliding movement within each polytype, thereby further increase the hardness of this particular material. Furthermore, in contrast to the conventional knowledge that intrinsically strong chemical bonds in superhard materials should lead to high lattice thermal conductivity, the polytypic TMB3 manifest anomalously low lattice thermal conductivity due to structural disorders and phonon folding. These findings promise to open a new avenue to searching for novel superhard materials with additional functionalities. PMID:24863493

  15. Patterning Superatom Dopants on Transition Metal Dichalcogenides.

    PubMed

    Yu, Jaeeun; Lee, Chul-Ho; Bouilly, Delphine; Han, Minyong; Kim, Philip; Steigerwald, Michael L; Roy, Xavier; Nuckolls, Colin

    2016-05-11

    This study describes a new and simple approach to dope two-dimensional transition metal dichalcogenides (TMDCs) using the superatom Co6Se8(PEt3)6 as the electron dopant. Semiconducting TMDCs are wired into field-effect transistor devices and then immersed into a solution of these superatoms. The degree of doping is determined by the concentration of the superatoms in solution and by the length of time the films are immersed in the dopant solution. Using this chemical approach, we are able to turn mono- and few-layer MoS2 samples from moderately to heavily electron-doped states. The same approach applied on WSe2 films changes their characteristics from hole transporting to electron transporting. Moreover, we show that the superatom doping can be patterned on specific areas of TMDC films. To illustrate the power of this technique, we demonstrate the fabrication of a lateral p-n junction by selectively doping only a portion of the channel in a WSe2 device. Finally, encapsulation of the doped films with crystalline hydrocarbon layers stabilizes their properties in an ambient environment. PMID:27082448

  16. Meyer Neldel rule application to silicon supersaturated with transition metals

    NASA Astrophysics Data System (ADS)

    García-Hemme, Eric; García-Hernansanz, Rodrigo; Olea, Javier; Pastor, David; del Prado, Alvaro; Mártil, Ignacio; González-Díaz, Germán

    2015-02-01

    This paper presents the results for the transverse conductance across a bilayer formed by supersaturating with diverse transition metals a thin layer of a silicon wafer. The layer is formed by ion implantation and annealed by pulsed laser melting. The transverse conductance is exponentially activated, obtaining values ranging from 0.018 to 0.7 eV for the activation energy and pre-exponential factors of 10-2-1012 S depending on the annealing energy density. A semi-logarithmic plot of the pre-exponential factor versus activation energy shows an almost perfect linear behaviour as stated by the Meyer Neldel rule. The Meyer Neldel energy obtained for implantation with different transition metals and also annealed in different conditions is 22 meV, which is within the range of silicon phonons, thus confirming the hypothesis of the multi excitation entropy theory.

  17. Exciton complexes in low dimensional transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Thilagam, A.

    2014-08-01

    We examine the excitonic properties of layered configurations of low dimensional transition metal dichalcogenides (LTMDCs) using the fractional dimensional space approach. The binding energies of the exciton, trion, and biexciton in LTMDCs of varying layers are analyzed, and linked to the dimensionality parameter α, which provides insight into critical electro-optical properties (relative oscillator strength, absorption spectrum, exciton-exciton interaction) of the material systems. The usefulness of α is highlighted by its independence of the physical mechanisms underlying the confinement effects of geometrical structures. Our estimates of the binding energies of exciton complexes for the monolayer configuration of transition metal dichalcogenides suggest a non-collinear structure for the trion and a positronium-molecule-like square structure for the biexciton.

  18. Exciton complexes in low dimensional transition metal dichalcogenides

    SciTech Connect

    Thilagam, A.

    2014-08-07

    We examine the excitonic properties of layered configurations of low dimensional transition metal dichalcogenides (LTMDCs) using the fractional dimensional space approach. The binding energies of the exciton, trion, and biexciton in LTMDCs of varying layers are analyzed, and linked to the dimensionality parameter α, which provides insight into critical electro-optical properties (relative oscillator strength, absorption spectrum, exciton-exciton interaction) of the material systems. The usefulness of α is highlighted by its independence of the physical mechanisms underlying the confinement effects of geometrical structures. Our estimates of the binding energies of exciton complexes for the monolayer configuration of transition metal dichalcogenides suggest a non-collinear structure for the trion and a positronium-molecule-like square structure for the biexciton.

  19. Transition Metal Phosphide Hydroprocessing Catalysts: A review

    SciTech Connect

    Oyama, S.; Gott, T; Zhao, H; Lee, Y

    2009-01-01

    The diminishing quality of oil feedstocks coupled with increasingly more stringent environmental regulations limiting the content of sulfur in transportation fuels have given rise to a need for improved hydroprocessing technology. This review begins with a summary of the major improvements in hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) catalysts and processes that have been reported in recent years. It then describes a new class of hydroprocessing catalysts, the transition metal phosphides, which have emerged as a promising group of high-activity, stable catalysts. The phosphides have physical properties resembling ceramics, so are strong and hard, yet retain electronic and magnetic properties similar to metals. Their crystal structures are based on trigonal prisms, yet they do not form layered structures like the sulfides. They display excellent performance in HDS and HDN, with the most active phosphide, Ni{sub 2}P, having activity surpassing that of promoted sulfides on the basis of sites titrated by chemisorption (CO for the phosphides, O{sub 2} for the sulfides). In the HDS of difficult heteroaromatics like 4,6-dimethyldibenzothiophene Ni{sub 2}P operates by the hydrogenation pathway, while in the HDN of substituted nitrogen compounds like 2-methylpiperidine it carries out nucleophilic substitution. The active sites for hydrogenation in Ni{sub 2}P have a square pyramidal geometry, while those for direct hydrodesulfurization have a tetrahedral geometry. Overall, Ni{sub 2}P is a promising catalyst for deep HDS in the presence of nitrogen and aromatic compounds.

  20. Thermomechanical properties of 3d transition metals

    SciTech Connect

    Karaoglu, B.; Rahman, S.M.M. . Dept. of Physics)

    1994-05-15

    The authors have investigated the density variation of the Einstein temperatures and elastic constants of the 3d transition metals. In this respect they have employed the transition metal (TM) pair potentials involving the sp contribution with an appropriate exchange and correlation function, the d-band broadening contribution and the d-band hybridization term. These calculations are aimed at testing the TM pair potentials in generating the quasilocal and local thermomechanical properties.

  1. Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Mak, Kin Fai; Shan, Jie

    2016-04-01

    Recent advances in the development of atomically thin layers of van der Waals bonded solids have opened up new possibilities for the exploration of 2D physics as well as for materials for applications. Among them, semiconductor transition metal dichalcogenides, MX2 (M = Mo, W; X = S, Se), have bandgaps in the near-infrared to the visible region, in contrast to the zero bandgap of graphene. In the monolayer limit, these materials have been shown to possess direct bandgaps, a property well suited for photonics and optoelectronics applications. Here, we review the electronic and optical properties and the recent progress in applications of 2D semiconductor transition metal dichalcogenides with emphasis on strong excitonic effects, and spin- and valley-dependent properties.

  2. Observation of Interlayer Phonons in Transition Metal Dichalcogenide Heterostructures

    NASA Astrophysics Data System (ADS)

    He, Rui; Ye, Zhipeng; Ji, Chao; Means-Shively, Casie; Anderson, Heidi; Kidd, Tim; Chiu, Kuan-Chang; Chou, Cheng-Tse; Wu, Jenn-Ming; Lee, Yi-Hsien; Andersen, Trond; Lui, Chun Hung

    Interlayer phonon modes in transition metal dichalcogenide (TMD) heterostructures are observed for the first time. We measured the low-frequency Raman response of MoS2/WSe2 and MoSe2/MoS2 heterobilayers. We discovered a distinct Raman mode (30 - 35 cm-1) that cannot be found in any individual monolayers. By comparing with Raman spectra of Bernal bilayer (2L) MoS2, 2L MoSe2 and 2L WSe2, we identified the new Raman mode as the layer breathing vibration arising from the vertical displacement of the two TMD layers. The layer breathing mode (LBM) only emerges in bilayer regions with atomically close layer-layer proximity and clean interface. In addition, the LBM frequency exhibits noticeable dependence on the rotational angle between the two TMD layers, which implies a change of interlayer separation and interlayer coupling strength with the layer stacking.

  3. Microwave-assisted synthesis of transition metal phosphide

    SciTech Connect

    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.

  4. Pristine and intercalated transition metal dichalcogenide superconductors

    NASA Astrophysics Data System (ADS)

    Klemm, Richard A.

    2015-07-01

    Transition metal dichalcogenides (TMDs) are quasi-two-dimensional layered compounds that exhibit strongly competing effects of charge-density wave (CDW) formation and superconductivity (SC). The weak van der Waals interlayer bonding between hexagonal layers of octahedral or trigonal prismatic TMD building blocks allows many polytypes to form. In the single layer 1 T polytype materials, one or more CDW states can form, but the pristine TMDs are not superconducting. The 2 H polytypes have two or more Fermi surfaces and saddle bands, allowing for dual orderings, which can be coexisting CDW and SC orderings, two SC gaps as in MgB2, two CDW gaps, and possibly even pseudogaps above the onset TCDW s of CDW orderings. Higher order polytypes allow for multiple CDW gaps and at least one superconducting gap. The CDW transitions TCDW s usually greatly exceed the superconducting transitions at their low Tc values, their orbital order parameters (OPs) are generally highly anisotropic and can even contain nodes, and the SC OPs can be greatly affected by their simultaneous presence. The properties of the CDWs ubiquitously seen in TMDs are remarkably similar to those of the pseudogaps seen in the high-Tc cuprates. In 2H-NbSe2, for example, the CDW renders its general s-wave SC OP orbital symmetry to be highly anisotropic and strongly reduces its Josephson coupling strength (IcRn) with the conventional SC, Pb. Hence, the pristine TMDs are highly "unconventional" in comparison with Pb, but are much more "conventional" than are the ferromagnetic superconductors such as URhGe. Applied pressure and intercalation generally suppress the TMD CDWs, allowing for enhanced SC formation, even in the 1 T polytype materials. The misfit intercalation compound (LaSe)1.14(NbSe2) and many 2 H -TMDs intercalated with organic Lewis base molecules, such as TaS2(pyridine)1/2, have completely incoherent c-axis transport, dimensional-crossover effects, and behave as stacks of intrinsic Josephson junctions

  5. Transition metal catalysis in confined spaces.

    PubMed

    Leenders, Stefan H A M; Gramage-Doria, Rafael; de Bruin, Bas; Reek, Joost N H

    2015-01-21

    Transition metal catalysis plays an important role in both industry and in academia where selectivity, activity and stability are crucial parameters to control. Next to changing the structure of the ligand, introducing a confined space as a second coordination sphere around a metal catalyst has recently been shown to be a viable method to induce new selectivity and activity in transition metal catalysis. In this review we focus on supramolecular strategies to encapsulate transition metal complexes with the aim of controlling the selectivity via the second coordination sphere. As we will discuss, catalyst confinement can result in selective processes that are impossible or difficult to achieve by traditional methods. We will describe the template-ligand approach as well as the host-guest approach to arrive at such supramolecular systems and discuss how the performance of the catalyst is enhanced by confining it in a molecular container. PMID:25340992

  6. Roles of transition metals interchanging with lithium in electrode materials.

    PubMed

    Kawaguchi, Tomoya; Fukuda, Katsutoshi; Tokuda, Kazuya; Sakaida, Masashi; Ichitsubo, Tetsu; Oishi, Masatsugu; Mizuki, Jun'ichiro; Matsubara, Eiichiro

    2015-06-01

    Roles of antisite transition metals interchanging with Li atoms in electrode materials of Li transition-metal complex oxides were clarified using a newly developed direct labeling method, termed powder diffraction anomalous fine structure (P-DAFS) near the Ni K-edge. We site-selectively investigated the valence states and local structures of Ni in Li0.89Ni1.11O2, where Ni atoms occupy mainly the NiO2 host-layer sites and partially the interlayer Li sites in-between the host layers, during electrochemical Li insertion/extraction in a lithium-ion battery (LIB). The site-selective X-ray near edge structure evaluated via the P-DAFS method revealed that the interlayer Ni atoms exhibited much lower electrochemical activity as compared to those at the host-layer site. Furthermore, the present analyses of site-selective extended X-ray absorption fine structure performed using the P-DAFS method indicates local structural changes around the residual Ni atoms at the interlayer space during the initial charge; it tends to gather to form rock-salt NiO-like domains around the interlayer Ni. The presence of the NiO-like domains in the interlayer space locally diminishes the interlayer distance and would yield strain energy because of the lattice mismatch, which retards the subsequent Li insertion both thermodynamically and kinetically. Such restrictions on the Li insertion inevitably make the NiO-like domains electrochemically inactive, resulting in an appreciable irreversible capacity after the initial charge but an achievement of robust linkage of neighboring NiO2 layers that tend to be dissociated without the Li occupation. The P-DAFS characterization of antisite transition metals interchanging with Li atoms complements the understanding of the detailed charge-compensation and degradation mechanisms in the electrode materials. PMID:25959625

  7. 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'. PMID:27501969

  8. Electronics and optoelectronics of two-dimensional transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    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 MoS2, MoSe2, WS2 and WSe2 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.

  9. Protein-Transition Metal Ion Networks

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Proteins obtained from agricultural sources were blended with divalent metal ions. Feather keratin, egg albumin, and wheat gluten showed increases of 2-3 times in modulus with addition of divalent transition metal ions Cu2+ and Zn2+. Increasing concentrations of ions resulted in increased stiffnes...

  10. High Pressure Synthesis of Transition Metal Carbonyls.

    ERIC Educational Resources Information Center

    Hagen, A. P.; And Others

    1979-01-01

    Presents an experiment which uses readily available starting materials and inexpensive equipment for synthesis of transition metal carbonyls at 1000 atm and which is intended to give students experience in techniques used in research and industry. Safety precautions are emphasized. (Author/SA)

  11. Functionalization of Two-Dimensional Transition-Metal Dichalcogenides.

    PubMed

    Chen, Xin; McDonald, Aidan R

    2016-07-01

    Two-dimensional (2D) layered transition-metal dichalcogenides (TMDs) are a fascinating class of nanomaterials that have the potential for application in catalysis, electronics, photonics, energy storage, and sensing. TMDs are rather inert, and thus pose problems for chemical derivatization. However, to further modify the properties of TMDs and fully harness their capabilities, routes towards their chemical functionalization must be identified. Herein, recent efforts toward the chemical (bond-forming) functionalization of 2D TMDs are critically reviewed. Recent successes are highlighted, along with areas where further detailed analyses and experimentation are required. This burgeoning field is very much in its infancy but has already provided several important breakthroughs. PMID:26848815

  12. Band engineering in transition metal dichalcogenides: Stacked versus lateral heterostructures

    NASA Astrophysics Data System (ADS)

    Guo, Yuzheng; Robertson, John

    2016-06-01

    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.

  13. Signaling Mechanisms and Disrupted Cytoskeleton in the Diphenyl Ditelluride Neurotoxicity

    PubMed Central

    Pessoa-Pureur, Regina; Heimfarth, Luana; Rocha, João B.

    2014-01-01

    Evidence from our group supports that diphenyl ditelluride (PhTe)2 neurotoxicity depends on modulation of signaling pathways initiated at the plasma membrane. The (PhTe)2-evoked signal is transduced downstream of voltage-dependent Ca2+ channels (VDCC), N-methyl-D-aspartate receptors (NMDA), or metabotropic glutamate receptors activation via different kinase pathways (protein kinase A, phospholipase C/protein kinase C, mitogen-activated protein kinases (MAPKs), and Akt signaling pathway). Among the most relevant cues of misregulated signaling mechanisms evoked by (PhTe)2 is the cytoskeleton of neural cells. The in vivo and in vitro exposure to (PhTe)2 induce hyperphosphorylation/hypophosphorylation of neuronal and glial intermediate filament (IF) proteins (neurofilaments and glial fibrillary acidic protein, resp.) in different brain structures of young rats. Phosphorylation of IFs at specific sites modulates their association/disassociation and interferes with important physiological roles, such as axonal transport. Disrupted cytoskeleton is a crucial marker of neurodegeneration and is associated with reactive astrogliosis and apoptotic cell death. This review focuses the current knowledge and important results on the mechanisms of (PhTe)2 neurotoxicity with special emphasis on the cytoskeletal proteins and their differential regulation by kinases/phosphatases and Ca2+-mediated mechanisms in developmental rat brain. We propose that the disrupted cytoskeletal homeostasis could support brain damage provoked by this neurotoxicant. PMID:25050142

  14. Signaling mechanisms and disrupted cytoskeleton in the diphenyl ditelluride neurotoxicity.

    PubMed

    Pessoa-Pureur, Regina; Heimfarth, Luana; Rocha, João B

    2014-01-01

    Evidence from our group supports that diphenyl ditelluride (PhTe)2 neurotoxicity depends on modulation of signaling pathways initiated at the plasma membrane. The (PhTe)2-evoked signal is transduced downstream of voltage-dependent Ca(2+) channels (VDCC), N-methyl-D-aspartate receptors (NMDA), or metabotropic glutamate receptors activation via different kinase pathways (protein kinase A, phospholipase C/protein kinase C, mitogen-activated protein kinases (MAPKs), and Akt signaling pathway). Among the most relevant cues of misregulated signaling mechanisms evoked by (PhTe)2 is the cytoskeleton of neural cells. The in vivo and in vitro exposure to (PhTe)2 induce hyperphosphorylation/hypophosphorylation of neuronal and glial intermediate filament (IF) proteins (neurofilaments and glial fibrillary acidic protein, resp.) in different brain structures of young rats. Phosphorylation of IFs at specific sites modulates their association/disassociation and interferes with important physiological roles, such as axonal transport. Disrupted cytoskeleton is a crucial marker of neurodegeneration and is associated with reactive astrogliosis and apoptotic cell death. This review focuses the current knowledge and important results on the mechanisms of (PhTe)2 neurotoxicity with special emphasis on the cytoskeletal proteins and their differential regulation by kinases/phosphatases and Ca(2+)-mediated mechanisms in developmental rat brain. We propose that the disrupted cytoskeletal homeostasis could support brain damage provoked by this neurotoxicant. PMID:25050142

  15. Chemical vapour deposition: Transition metal carbides go 2D

    NASA Astrophysics Data System (ADS)

    Gogotsi, Yury

    2015-11-01

    The unique properties of 2D materials, such as graphene or transition metal dichalcogenides, have been attracting much attention in the past decade. Now, metallically conductive and even superconducting transition metal carbides are entering the game.

  16. 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.

  17. (Electronic structure and reactivities of transition metal clusters)

    SciTech Connect

    Not Available

    1992-01-01

    The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

  18. Corrosion behavior of mesoporous transition metal nitrides

    SciTech Connect

    Yang, Minghui; Allen, Amy J.; Nguyen, Minh T.; Ralston, Walter T.; MacLeod, Michelle J.; DiSalvo, Francis J.

    2013-09-15

    Transition metal nitrides (TMN) have many desirable characteristics such as high hardness and good thermal stability under reducing conditions. This work reports an initial survey of the chemical stability of mesoporous TMNs (TM=Nb, V, Cr and Ti) in water at 80 °C at neutral, acidic and alkaline pH. The mesoporous TMNs had specific surface areas of 25–60 m{sup 2}/g with average pore sizes ranging from 10 to 50 nm. The high surface areas of these materials enhance the rate of corrosion per unit mass over that of a bulk material, making detection of corrosion much easier. The products were characterized by Rietveld refinement of powder X-ray diffraction (PXRD) patterns and by scanning electron microscopy (SEM). Several nitrides have corrosion rates that are, within error, not distinguishable from zero (±1 Å/day). Of the nitrides examined, CrN appears to be the most corrosion resistant under acidic conditions. None of the nitrides studied are corrosion resistant under alkaline conditions. - Graphical abstract: Corrosion behavior of mesoporous transition metal nitrides (TM=Nb, V, Cr and Ti) in acidic and alkaline solutions at 80 °C for 2 weeks. Display Omitted - highlights: • Corrosion rates of mesoporous transition metal nitrides in aqueous solution is reported. • The mesoporous TMNs had surface areas of 25–60 m{sup 2}/g. • CrN is the most corrosion resistant under the conditions studied.

  19. Aging of Transition Metal Dichalcogenide Monolayers.

    PubMed

    Gao, Jian; Li, Baichang; Tan, Jiawei; Chow, Phil; Lu, Toh-Ming; Koratkar, Nikhil

    2016-02-23

    Two-dimensional sheets of transition metal dichalcogenides are an emerging class of atomically thin semiconductors that are considered to be "air-stable", similar to graphene. Here we report that, contrary to current understanding, chemical vapor deposited transition metal dichalcogenide monolayers exhibit poor long-term stability in air. After room-temperature exposure to the environment for several months, monolayers of molybdenum disulfide and tungsten disulfide undergo dramatic aging effects including extensive cracking, changes in morphology, and severe quenching of the direct gap photoluminescence. X-ray photoelectron and Auger electron spectroscopy reveal that this effect is related to gradual oxidation along the grain boundaries and the adsorption of organic contaminants. These results highlight important challenges associated with the utilization of transition metal dichalcogenide monolayers in electronic and optoelectronic devices. We also demonstrate a potential solution to this problem, featuring encapsulation of the monolayer sheet by a 10-20 nm thick optically transparent polymer (parylene C). This strategy is shown to successfully prevent the degradation of the monolayer material under accelerated aging (i.e., high-temperature, oxygen-rich) conditions. PMID:26808328

  20. 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

  1. Tightly Bound Trions in Transition Metal Dichalcogenide Heterostructures.

    PubMed

    Bellus, Matthew Z; Ceballos, Frank; Chiu, Hsin-Ying; Zhao, Hui

    2015-06-23

    We report the observation of trions at room temperature in a van der Waals heterostructure composed of MoSe2 and WS2 monolayers. These trions are formed by excitons excited in the WS2 layer and electrons transferred from the MoSe2 layer. Recombination of trions results in a peak in the photoluminescence spectra, which is absent in monolayer WS2 that is not in contact with MoSe2. The trion origin of this peak is further confirmed by the linear dependence of the peak position on excitation intensity. We deduced a zero-density trion binding energy of 62 meV. The trion formation facilitates electrical control of exciton transport in transition metal dichalcogenide heterostructures, which can be utilized in various optoelectronic applications. PMID:26046238

  2. Chemical Trends for Transition Metal Compound Bonding to Graphene

    NASA Astrophysics Data System (ADS)

    Lange, Bjoern; Blum, Volker

    2015-03-01

    Transition metal compounds are of interest as catalysts for the hydrogen evolution reaction (HER). However, a perfect candidate to replace expensive platinum has not yet been identified. To tailor a specific compound, several properties come into play. One is the bonding to the underlying substrate, for which π-bonded carbon nanostructures are promising candidates. Here we analyze the bonding of small transition metal compound nanoclusters to a graphene layer for a range of chemical compositions: MxAy (M = Mo, Ti; A = S, O, B, N, C). The clusters are generated by an unbiased random search algorithm. We perform total energy calculations based on density functional theory to identify lowest energy clusters. We calculate binding energies using the PBE and HSE functionals with explicit van der Waals treatment and benchmark those against RPA cluster calculations. Our results indicate that molybdenum-carbides and -nitrides tend to bond tightly to graphene. Mo-oxides and -sulfides show small binding energies, indicating van der Waals bonding.

  3. Vibrational scaling factors for transition metal carbonyls

    NASA Astrophysics Data System (ADS)

    Assefa, M. K.; Devera, J. L.; Brathwaite, A. D.; Mosley, J. D.; Duncan, M. A.

    2015-11-01

    Vibrational frequencies for a selected set of transition metal carbonyl complexes are computed with various forms of density functional theory (B3LYP, BP86, M06, and M06-L), employing several different basis sets. The computed frequencies for the carbonyl stretches are compared to the experimental values obtained from gas phase infrared spectra of isolated neutrals and ions. Recommended carbonyl-stretch scaling factors which are developed vary significantly for different functionals, but there is little variation with basis set. Scaled frequencies compared to experimental spectra for cobalt and tantalum carbonyl cations reveal additional variations in multiplet patterns and relative band intensities for different functionals.

  4. Electrical Conduction in Transition-Metal Salts

    NASA Astrophysics Data System (ADS)

    Grado-Caffaro, M. A.; Grado-Caffaro, M.

    2016-04-01

    We predict that a given transition-metal salt as, for example, a K2CuCl4·2H2O-type compound, can behave as an electrical conductor in the paramagnetic case. In fact, we determine the electrical conductance in a salt of this type. This conductance is found to be quantised in agreement with previous well-known results. Related mathematical expressions in the context of superexchange interaction are obtained. In addition, we determine the corresponding (macroscopically viewed) current density and the associated electron wave functions.

  5. Electronic doping of transition metal oxide perovskites

    NASA Astrophysics Data System (ADS)

    Cammarata, Antonio; Rondinelli, James M.

    2016-05-01

    CaFeO3 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 CaFeO3. 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.

  6. Transition-Metal-Catalyzed Bioorthogonal Cycloaddition Reactions.

    PubMed

    Yang, Maiyun; Yang, Yi; Chen, Peng R

    2016-02-01

    In recent years, bioorthogonal reactions have emerged as a powerful toolbox for specific labeling and visualization of biomolecules, even within the highly complex and fragile living systems. Among them, copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction is one of the most widely studied and used biocompatible reactions. The cytotoxicity of Cu(I) ions has been greatly reduced due to the use of Cu(I) ligands, which enabled the CuAAC reaction to proceed on the cell surface, as well as within an intracellular environment. Meanwhile, other transition metals such as ruthenium, rhodium and silver are now under development as alternative sources for catalyzing bioorthogonal cycloadditions. In this review, we summarize the development of CuAAC reaction as a prominent bioorthogonal reaction, discuss various ligands used in reducing Cu(I) toxicity while promoting the reaction rate, and illustrate some of its important biological applications. The development of additional transition metals in catalyzing cycloaddition reactions will also be briefly introduced. PMID:27572985

  7. Transition Metal Nitrides: A First Principles Study

    NASA Astrophysics Data System (ADS)

    Pathak, Ashish; Singh, A. K.

    2016-04-01

    The present work describes the structural stability and electronic and mechanical properties of transition metal nitrides (TmNs: B1 cubic structure (cF8, Fm ‾ overline 3 m)) using first principles density functional theory (DFT) within generalized gradient approximation (GGA). The lattice constant of TmNs increases with increasing the atomic radii of the transition metals. Stability of the TmNs decreases from IVB to VIB groups due to increase in formation energy/atom. The bonding characteristics of these nitrides have been explained based on electronic density of states and charge density. All the TmNs satisfy Born stability criteria in terms of elastic constants except CrN and MoN that do not exist in equilibrium binary phase diagrams. The groups IVB and V-VIB nitrides are associated with brittle and ductile behaviour based on G/B ratios, respectively. The estimated melting temperatures of these nitrides exhibit reasonably good agreement with calculated with B than those of the C11 for all nitrides.

  8. Thermodynamic Hydricity of Transition Metal Hydrides.

    PubMed

    Wiedner, Eric S; Chambers, Matthew B; Pitman, Catherine L; Bullock, R Morris; Miller, Alexander J M; Appel, Aaron M

    2016-08-10

    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 bond-breaking 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 H2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H2 in the presence of a base, and the potential-pKa 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. Methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO2, and the production and oxidation of hydrogen. PMID:27483171

  9. Methyl Complexes of the Transition Metals.

    PubMed

    Campos, Jesús; López-Serrano, Joaquín; Peloso, Riccardo; Carmona, Ernesto

    2016-05-01

    Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, that is, based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition-metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition-metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last five years. After a panoramic overview on M-CH3 compounds of Groups 3 to 11, which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity. PMID:26991740

  10. Iodide effects in transition metal catalyzed reactions.

    PubMed

    Maitlis, Peter M; Haynes, Anthony; James, Brian R; Catellani, Marta; Chiusoli, Gian Paolo

    2004-11-01

    The unique properties of I(-) allow it to be involved in several different ways in reactions catalyzed by the late transition metals: in the oxidative addition, the migration, and the coupling/reductive elimination steps, as well as in substrate activation. Most steps are accelerated by I(-)(for example through an increased nucleophilicity of the metal center), but some are retarded, because a coordination site is blocked. The "soft" iodide ligand binds more strongly to soft metals (low oxidation state, electron rich, and polarizable) such as the later and heavier transition metals, than do the other halides, or N- and O-centered ligands. Hence in a catalytic cycle that includes the metal in a formally low oxidation state there will be less tendency for the metal to precipitate (and be removed from the cycle) in the presence of I(-) than most other ligands. Iodide is a good nucleophile and is also easily and reversibly oxidized to I(2). In addition, I(-) can play key roles in purely organic reactions that occur as part of a catalytic cycle. Thus to understand the function of iodide requires careful analysis, since two or sometimes more effects occur in different steps of one single cycle. Each of these topics is illustrated with examples of the influence of iodide from homogeneous catalytic reactions in the literature: methanol carbonylation to acetic acid and related reactions; CO hydrogenation; imine hydrogenation; and C-C and C-N coupling reactions. General features are summarised in the Conclusions. PMID:15510253

  11. 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.

  12. Doping dependent plasmon dispersion in 2 H -transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Müller, Eric; Büchner, Bernd; Habenicht, Carsten; König, Andreas; Knupfer, Martin; Berger, Helmuth; Huotari, Simo

    2016-07-01

    We report the behavior of the charge carrier plasmon of 2 H -transition metal dichalcogenides (TMDs) as a function of intercalation with alkali metals. Intercalation and concurrent doping of the TMD layers have a substantial impact on plasmon energy and dispersion. While the plasmon energy shifts are related to the intercalation level as expected within a simple homogeneous electron gas picture, the plasmon dispersion changes in a peculiar manner independent of the intercalant and the TMD materials. Starting from a negative dispersion, the slope of the plasmon dispersion changes sign and grows monotonously upon doping. Quantitatively, the increase of this slope depends on the orbital character (4 d or 5 d ) of the conduction bands, which indicates a decisive role of band structure effects on the plasmon behavior.

  13. Stacking dependent electronic structures of transition metal dichalcogenides heterobilayer

    NASA Astrophysics Data System (ADS)

    Lee, Yea-Lee; Park, Cheol-Hwan; Ihm, Jisoon

    The systematic study of the electronic structures and optical properties of the transition metal dichalcogenides (TMD) heterobilayers can significantly improve the designing of new electronic and optoelectronic devices. Here, we theoretically study the electronic structures and optical properties of TMD heterobilayers using the first-principles methods. The band structures of TMD heterobilayer are shown to be determined by the band alignments of the each layer, the weak interlayer interactions, and angle dependent stacking patterns. The photoluminescence spectra are investigated using the calculated band structures, and the optical absorption spectra are examined by the GW approximations including the electron-hole interaction through the solution of the Bethe-Salpeter equation. It is expected that the weak interlayer interaction gives rise to the substantial interlayer optical transition which will be corresponding to the interlayer exciton.

  14. Transition Metal Dichalcogenide Growth via Close Proximity Precursor Supply

    PubMed Central

    O'Brien, Maria; McEvoy, Niall; Hallam, Toby; Kim, Hye-Young; Berner, Nina C.; Hanlon, Damien; Lee, Kangho; Coleman, Jonathan N.; Duesberg, Georg S.

    2014-01-01

    Reliable chemical vapour deposition (CVD) of transition metal dichalcogenides (TMDs) is currently a highly pressing research field, as numerous potential applications rely on the production of high quality films on a macroscopic scale. Here, we show the use of liquid phase exfoliated nanosheets and patterned sputter deposited layers as solid precursors for chemical vapour deposition. TMD monolayers were realized using a close proximity precursor supply in a CVD microreactor setup. A model describing the growth mechanism, which is capable of producing TMD monolayers on arbitrary substrates, is presented. Raman spectroscopy, photoluminescence, X-ray photoelectron spectroscopy, atomic force microscopy, transmission electron microscopy, scanning electron microscopy and electrical transport measurements reveal the high quality of the TMD samples produced. Furthermore, through patterning of the precursor supply, we achieve patterned growth of monolayer TMDs in defined locations, which could be adapted for the facile production of electronic device components. PMID:25487822

  15. Transition Metal Dichalcogenide Growth via Close Proximity Precursor Supply

    NASA Astrophysics Data System (ADS)

    O'Brien, Maria; McEvoy, Niall; Hallam, Toby; Kim, Hye-Young; Berner, Nina C.; Hanlon, Damien; Lee, Kangho; Coleman, Jonathan N.; Duesberg, Georg S.

    2014-12-01

    Reliable chemical vapour deposition (CVD) of transition metal dichalcogenides (TMDs) is currently a highly pressing research field, as numerous potential applications rely on the production of high quality films on a macroscopic scale. Here, we show the use of liquid phase exfoliated nanosheets and patterned sputter deposited layers as solid precursors for chemical vapour deposition. TMD monolayers were realized using a close proximity precursor supply in a CVD microreactor setup. A model describing the growth mechanism, which is capable of producing TMD monolayers on arbitrary substrates, is presented. Raman spectroscopy, photoluminescence, X-ray photoelectron spectroscopy, atomic force microscopy, transmission electron microscopy, scanning electron microscopy and electrical transport measurements reveal the high quality of the TMD samples produced. Furthermore, through patterning of the precursor supply, we achieve patterned growth of monolayer TMDs in defined locations, which could be adapted for the facile production of electronic device components.

  16. Synthesis of millimeter-scale transition metal dichalcogenides single crystals

    DOE PAGESBeta

    Gong, Yongji; Ye, Gonglan; Lei, Sidong; Shi, Gang; Vajtai, Robert; Pantelides, Sokrates T.; Zhou, Wu; Li, Bo; Ajayan, Pullikel M.

    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 MoSe2 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 can also bemore » 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 cm2 V-1 s-1, for back-gated MoSe2 transistors. This generic synthesis approach is also demonstrated for other TMD layers such as millimeter-scale WSe2 single crystals.« less

  17. Observation of anomalous Stokes versus anti-Stokes ratio in MoTe2 atomic layers

    NASA Astrophysics Data System (ADS)

    Goldstein, Thomas; Chen, Shao-Yu; Xiao, Di; Ramasubramaniam, Ashwin; Yan, Jun

    We grow hexagonal molybdenum ditelluride (MoTe2), a prototypical transition metal dichalcogenide (TMDC) semiconductor, with chemical vapor transport methods and investigate its atomic layers with Stokes and anti-Stokes Raman scattering. We report observation of all six types of zone center optical phonons. Quite remarkably, the anti-Stokes Raman intensity of the low energy layer-breathing mode becomes more intense than the Stokes peak under certain experimental conditions, creating an illusion of 'negative temperature'. This effect is tunable, and can be switched from anti-Stokes enhancement to suppression by varying the excitation wavelength. We interpret this observation to be a result of resonance effects arising from the C excitons in the vicinity of the Brillouin zone center, which are robust even for multiple layers of MoTe2. The intense anti-Stokes Raman scattering provides a cooling channel for the crystal and opens up opportunities for laser cooling of atomically thin TMDC semiconductor devices. Supported by the University of Massachusetts Amherst, the National Science Foundation Center for Hierarchical Manufacturing (CMMI-1025020) and Office of Emerging Frontiers in Research and Innovation (EFRI-1433496).

  18. Smoothing of ultrathin silver films by transition metal seeding

    NASA Astrophysics Data System (ADS)

    Anders, André; Byon, Eungsun; Kim, Dong-Ho; Fukuda, Kentaro; Lim, Sunnie H. N.

    2006-11-01

    The nucleation and coalescence of silver islands on coated glass was investigated by in situ measurements of the sheet resistance. Sub-monolayer amounts of niobium and other transition metals were deposited prior to the deposition of silver. It was found that in some cases, the transition metals lead to coalescence of silver at nominally thinner films with smoother topology. The smoothing or roughening effects by the presence of the transition metal can be explained by kinetically limited transition metal islands growth and oxidation, followed by defect-dominated nucleation of silver.

  19. Main-group elements as transition metals.

    PubMed

    Power, Philip P

    2010-01-14

    The last quarter of the twentieth century and the beginning decade of the twenty-first witnessed spectacular discoveries in the chemistry of the heavier main-group elements. The new compounds that were synthesized highlighted the fundamental differences between their electronic properties and those of the lighter elements to a degree that was not previously apparent. This has led to new structural and bonding insights as well as a gradually increasing realization that the chemistry of the heavier main-group elements more resembles that of transition-metal complexes than that of their lighter main-group congeners. The similarity is underlined by recent work, which has shown that many of the new compounds react with small molecules such as H(2), NH(3), C(2)H(4) or CO under mild conditions and display potential for applications in catalysis. PMID:20075912

  20. Catabolism of hyaluronan: involvement of transition metals

    PubMed Central

    Šoltés, Ladislav; Kogan, Grigorij

    2009-01-01

    One of the very complex structures in the vertebrates is the joint. The main component of the joint is the synovial fluid with its high-molar-mass glycosaminoglycan hyaluronan, which turnover is approximately twelve hours. Since the synovial fluid does not contain any hyaluronidases, the fast hyaluronan catabolism is caused primarily by reductive-oxidative processes. Eight transition metals – V23, Mn25, Fe26, Co27, Ni28, Cu29, Zn30, and Mo42 – naturally occurring in living organism are essential for the control of various metabolic and signaling pathways. They are also the key elements in catabolism of hyaluronan in the joint. In this overview, the role of these metals in physiological and pathophysiological catabolism of hyaluronan is described. The participation of these metals in the initiation and propagation of the radical degradation hyaluronan is critically reviewed. PMID:21217859

  1. Radiation damage of transition metal carbides

    SciTech Connect

    Dixon, G.

    1991-01-01

    In this grant period we have investigated electrical properties of transition metal carbides and radiation-induced defects produced by low-temperature electron irradiation in them. Special attention has been given to the composition VC[sub 0.88] in which the vacancies on the carbon sublattice of this fcc crystal order to produce a V[sub 8]C[sub 7] superlattice. The existence of this superlattice structure was found to make the crystal somewhat resistant to radiation damage at low doses and/or at ambient temperature. At larger doses significant changes in the resistivity are produced. Annealing effects were observed which we believe to be connected with the reconstitution of the superlattice structure.

  2. Multifunctional Ligands in Transition Metal Catalysis

    SciTech Connect

    Crabtree, Robert H

    2011-01-01

    Sophisticated ligands are now being designed that do far more than just fulfil their traditional spectator roles by binding to the metal and providing a sterically-defined binding pocket for the substrate in homogeneous transition metal catalysis. This Focus review emphasizes selected cases in which ligands carry additional functional groups that change the properties of the ligand as a result of an external stimulus or undergo catalytically-relevant ligand-based reactivity. These include proton responsive ligands capable of gaining or losing one or more protons, ligands having a hydrogen bonding function, electroresponsive ligands capable of gaining or losing one or more electrons, and photoresponsive ligands capable of undergoing a useful change of properties upon irradiation. Molecular recognition ligands and proton coupled electron transfer (PCET) are briefly discussed.

  3. Excited Biexcitons in Transition Metal Dichalcogenides

    NASA Astrophysics Data System (ADS)

    Zhang, David

    Recently, experimental measurements and theoretical modeling have been in a disagreement concerning the binding energy of biexctions in transition metal dichalcogenides. While theory predicts a smaller binding energy (~20 meV) that is, as logically expected, lower than that of the trion, experiment finds values much larger (~60 meV), actually exceeding those for the trion. In this work, we show that there exists an excited state of the biexciton which yields binding energies that match well with experimental findings and thus gives a plausible explanation for the apparent discrepancy. Furthermore, it is shown that the electron-hole correlation functions of the ground state biexciton and trion are remarkably similar, possibly explaining why a distinct signature of ground state biexcitons would not have been noticed experimentally.

  4. Trion dynamics in Transition Metal Dichalcogenide Monolayers

    NASA Astrophysics Data System (ADS)

    Singh, Akshay; Tran, Kha; Wu, Sanweng; Ross, Jason; Moody, Galan; Xu, Xiaodong; Li, Elaine

    2015-03-01

    Transition Metal Dichalcogenides (TMD's) in the monolayer limit, exhibit interesting phenomena including increased photoluminescence, spin-valley coupling and many-body effects. Excitons (bound electron-hole pairs) and trions (charged excitons) in these materials have unusually large binding energy and dominate the optical response near the band gap. In particular, trions can drift under application of an electric field and have higher spin lifetimes increasing applications in quantum spin models. We study the temporal dynamics of excitons and trions including their formation and lifetimes using time resolved two-color pump-probe spectroscopy on a monolayer TMD (MoSe2). Trions are observed to have vastly different temporal dynamics with much slower decay than excitons. We also observe rapid formation of trions when resonantly pumped while a slow rise (in temporal response) is seen for other excitation energies. We suggest that localization of trions needs to be taken into account to explain these observations.

  5. Excited Biexcitons in Transition Metal Dichalcogenides.

    PubMed

    Zhang, David K; Kidd, Daniel W; Varga, Kálmán

    2015-10-14

    The Stochastic Variational Method (SVM) is used to show that the effective mass model correctly estimates the binding energies of excitons and trions but fails to predict the experimental binding energy of the biexciton. Using high-accuracy variational calculations, it is demonstrated that the biexciton binding energy in transition metal dichalcogenides is smaller than the trion binding energy, contradicting experimental findings. It is also shown that the biexciton has bound excited states and that the binding energy of the L = 0 excited state is in very good agreement with experimental data. This excited state corresponds to a hole attached to a negative trion and may be a possible resolution of the discrepancy between theory and experiment. PMID:26422057

  6. Energy bands in some transition metals

    NASA Astrophysics Data System (ADS)

    Laurent, D. G.

    1981-08-01

    Self consistent linear combination of Gaussian orbitals energy band calculations were performed for the two paramagnetic 3d transition metals, chromium and vanadium. The energy bands densities of states and Fermi surfaces were obtained using the two most popular local exchange correlation potentials (Kohn-Sham-Gaspar and von Barth-Hedin) for chromium and the Kohn-Sham-Gaspar potential alone for vanadium. A comparison was made with the available experimental data. New interpretations for some of the neutron scattering data are made in the chromium case. Results are also presented for the Compton profiles and optical conductivities. These correlate well with the experiments if appropriate angular averages (for the Compton profile) and lifetime effcts (for the optical conductivity) are included. The electron energy loss spectrum, computed over the range 0-6.5 eV agreed well with experiment.

  7. Spin-orbit damping in transition metals

    NASA Astrophysics Data System (ADS)

    Gilmore, Keith

    2008-03-01

    Magnetization dynamics are routinely described with the Landau-Lifshitz-Gilbert (LLG) equation. However, it is expected that the LLG equation fails to properly describe the large amplitude dynamics that occur during magnetization reversal. Improving switching speeds in nanoscale devices by tailoring materials requires both a qualitative understanding of the relaxation processes that contribute to damping and the ability to quantitatively calculate the resulting damping rates. We consider small amplitude LLG damping in transition metals as a prelude to approaching the more complicated mechanisms expected in complete reversal events. LLG damping rates in pure transition metal systems have non-monotonic temperature dependencies that have been empirically shown by Heinrich et al. [1] to have one part proportional to the conductivity and one part proportional to the resistivity. Kambersky [2] postulated that both contributions result from a torque between the spin and orbital moments. We have conducted first-principles calculations that validate this claim for single element systems [3]. Our calculations for Fe, Co, and Ni both qualitatively match the two trends observed in measurements and quantitatively agree with the observed damping rates. We will discuss how the spin-orbit interaction produces two contributions to damping with nearly opposite temperature dependencies and compare calculations of the damping rate versus resistivity with experimental results. [1] B. Heinrich, D.J. Meredith, and J.F. Cochran, J. Appl. Phys., 50(11), 7726 (1979). [2] V. Kambersky, Czech. J. Phys. B, 26, 1366 (1976). [3] K. Gilmore, Y.U. Idzerda, and M.D. Stiles, Phys. Rev. Lett., 99, 027204 (2007).

  8. Superconductivity emerging from a suppressed large magnetoresistant state in tungsten ditelluride

    PubMed Central

    Kang, Defen; Zhou, Yazhou; Yi, Wei; Yang, Chongli; Guo, Jing; Shi, Youguo; Zhang, Shan; Wang, Zhe; Zhang, Chao; Jiang, Sheng; Li, Aiguo; Yang, Ke; Wu, Qi; Zhang, Guangming; Sun, Liling; Zhao, Zhongxian

    2015-01-01

    The recent discovery of large magnetoresistance in tungsten ditelluride provides a unique playground to find new phenomena and significant perspective for potential applications. The large magnetoresistance effect originates from a perfect balance of hole and electron carriers, which is sensitive to external pressure. Here we report the suppression of the large magnetoresistance and emergence of superconductivity in pressurized tungsten ditelluride via high-pressure synchrotron X-ray diffraction, electrical resistance, magnetoresistance and alternating current magnetic susceptibility measurements. Upon increasing pressure, the positive large magnetoresistance effect is gradually suppressed and turned off at a critical pressure of 10.5 GPa, where superconductivity accordingly emerges. No structural phase transition is observed under the pressure investigated. In situ high-pressure Hall coefficient measurements at low temperatures demonstrate that elevating pressure decreases the population of hole carriers but increases that of the electron ones. Significantly, at the critical pressure, a sign change of the Hall coefficient is observed. PMID:26203807

  9. Superconductivity emerging from a suppressed large magnetoresistant state in tungsten ditelluride

    NASA Astrophysics Data System (ADS)

    Kang, Defen; Zhou, Yazhou; Yi, Wei; Yang, Chongli; Guo, Jing; Shi, Youguo; Zhang, Shan; Wang, Zhe; Zhang, Chao; Jiang, Sheng; Li, Aiguo; Yang, Ke; Wu, Qi; Zhang, Guangming; Sun, Liling; Zhao, Zhongxian

    2015-07-01

    The recent discovery of large magnetoresistance in tungsten ditelluride provides a unique playground to find new phenomena and significant perspective for potential applications. The large magnetoresistance effect originates from a perfect balance of hole and electron carriers, which is sensitive to external pressure. Here we report the suppression of the large magnetoresistance and emergence of superconductivity in pressurized tungsten ditelluride via high-pressure synchrotron X-ray diffraction, electrical resistance, magnetoresistance and alternating current magnetic susceptibility measurements. Upon increasing pressure, the positive large magnetoresistance effect is gradually suppressed and turned off at a critical pressure of 10.5 GPa, where superconductivity accordingly emerges. No structural phase transition is observed under the pressure investigated. In situ high-pressure Hall coefficient measurements at low temperatures demonstrate that elevating pressure decreases the population of hole carriers but increases that of the electron ones. Significantly, at the critical pressure, a sign change of the Hall coefficient is observed.

  10. Transport studies in 2D transition metal dichalcogenides and black phosphorus

    NASA Astrophysics Data System (ADS)

    Du, Yuchen; Neal, Adam T.; Zhou, Hong; Ye, Peide D.

    2016-07-01

    Two-dimensional (2D) materials are a new family of materials with interesting physical properties, ranging from insulating hexagonal boron nitride, semiconducting or semi-metallic transition metal dichalcogenides, to gapless metallic graphene. In this review, we provide a brief discussion of transport studies in transition metal dichalcogenides, including both semiconducting and semi-metallic phases, as well as a discussion of the newly emerged narrow bandgap layered material, black phosphorus, in terms of its electrical and quantum transport properties at room and cryogenic temperatures. Ultra-thin layered channel materials with atomic layer thickness in the cross-plane direction, together with relatively high carrier mobility with appropriate passivation techniques, provide the promise for new scientific discoveries and broad device applications.

  11. Transport studies in 2D transition metal dichalcogenides and black phosphorus.

    PubMed

    Du, Yuchen; Neal, Adam T; Zhou, Hong; Ye, Peide D

    2016-07-01

    Two-dimensional (2D) materials are a new family of materials with interesting physical properties, ranging from insulating hexagonal boron nitride, semiconducting or semi-metallic transition metal dichalcogenides, to gapless metallic graphene. In this review, we provide a brief discussion of transport studies in transition metal dichalcogenides, including both semiconducting and semi-metallic phases, as well as a discussion of the newly emerged narrow bandgap layered material, black phosphorus, in terms of its electrical and quantum transport properties at room and cryogenic temperatures. Ultra-thin layered channel materials with atomic layer thickness in the cross-plane direction, together with relatively high carrier mobility with appropriate passivation techniques, provide the promise for new scientific discoveries and broad device applications. PMID:27187790

  12. Properties of molecular beam epitaxy grown Eu{sub x}(transition metal){sub y} films (transition metals: Mn, Cr)

    SciTech Connect

    Balin, K.; Nowak, A.; Gibaud, A.; Szade, J.; Celinski, Z.

    2011-04-01

    The electronic and crystallographic structures, as well as the magnetic properties, of Eu{sub x}(transition metal){sub y} (transition metals: Mn, Cr) thin films grown by molecular beam epitaxy were studied. Relative changes of the Eu/Mn and Eu/Cr ratios derived from the XPS lines, as well as x-ray reflectivity, indicate mixing of the Eu/Mn and Eu/Cr layers. Valency transitions from Eu{sup 2+} to Eu{sup 3+} were observed in both systems for most studied stoichiometries. A transition to a magnetically ordered phase was observed at 15 K, 40 K, and 62 K for selected films in the Eu-Mn system, and at 50 K for the film with a Eu/Cr ratio of 0.5.

  13. 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…

  14. 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.

  15. (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

  16. Electronic structure origins of the extremely large magnetoresistance in tungsten ditelluride

    NASA Astrophysics Data System (ADS)

    Pletikosic, Ivo; Ali, Mazhar; Cava, Robert; Valla, Tonica

    2015-03-01

    WTe2 is a layered transition metal dichalcogenide showing a structural reduction to one-dimensional tellurium-surrounded tungsten chains. The material exhibits an extremely large positive anisotropic magnetoresistance of a few million percent that increases as the square of the field and shows no saturation up to 60 T. We explored the possible electronic structure origins of the magnetoresistance by means of angle-resolved photoelectron spectroscopy (ARPES) and found electron and hole pockets of equal size along the direction of tungsten chains, forming a highly anisotropic quasi-twodimensional Fermi surface. The perfect carrier compensation at low temperatures has been identified as the primary source of the magnetoresistive effect, and the change of the Fermi surface shape as well as a high-density-of-states band slightly below the Fermi level recognized as the cause of its diminishing at rising temperatures.

  17. Energetic characteristics of transition metal complexes.

    PubMed

    Wojewódka, Andrzej; Bełzowski, Janusz; Wilk, Zenon; Staś, Justyna

    2009-11-15

    Ten transition metal nitrate and perchlorate complexes of hydrazine and ethylenediamine were synthesized, namely [Cu(EN)(2)](ClO(4))(2), [Co(EN)(3)](ClO(4))(3), [Ni(EN)(3)](ClO(4))(2), [Hg(EN)(2)](ClO(4))(2), [Cr(N(2)H(4))(3)](ClO(4))(3), [Cd(N(2)H(4))(3)](ClO(4))(2), [Ni(N(2)H(4))(3)](NO(3))(2), [Co(N(2)H(4))(3)](NO(3))(3), [Zn(N(2)H(4))(3)](NO(3))(2), and [Cd(N(2)H(4))(3)](NO(3))(2) based on the lines of the literature reported methods. All of them were tested with applying underwater detonation test and further compared to the typical blasting explosives: RDX, HMX, TNT and PETN. From the above presented complexes [Ni(N(2)H(4))(3)](NO(3))(2) (called NHN) and [Co(N(2)H(4))(3)](NO(3))(3) (called CoHN) are known as primary explosives and can be used as the standard explosives. Explosion parameters, such as shock wave overpressure, shock wave energy equivalent and bubble energy equivalent, were determined. Evaluated energetic characteristics of the tested compounds are comparable to those of the classic high explosives and are even enhanced in some cases. PMID:19631466

  18. Properties of Transition Metal Doped Alumina

    NASA Astrophysics Data System (ADS)

    Nykwest, Erik; Limmer, Krista; Brennan, Ray; Blair, Victoria; Ramprasad, Rampi

    Crystallographic texture can have profound effects on the properties of a material. One method of texturing is through the application of an external magnetic field during processing. While this method works with highly magnetic systems, doping is required to couple non-magnetic systems with the external field. Experiments have shown that low concentrations of rare earth (RE) dopants in alumina powders have enabled this kind of texturing. The magnetic properties of RE elements are directly related to their f orbital, which can have as many as 7 unpaired electrons. Since d-block elements can have as many as 5 unpaired electrons the effects of substitutional doping of 3d transition metals (TM) for Al in alpha (stable) and theta (metastable) alumina on the local structure and magnetic properties, in addition to the energetic cost, have been calculated by performing first-principles calculations based on density functional theory. This study has led to the development of general guidelines for the magnetic moment distribution at and around the dopant atom, and the dependence of this distribution on the dopant atom type and its coordination environment. It is anticipated that these findings can aid in the selection of suitable dopants help to guide parallel experimental efforts. This project was supported in part by an internship at the Army Research Laboratory, administered by the Oak Ridge Institute for Science and Education, along with a grant of computer time from the DoD High Performance Computing Modernization Program.

  19. Transition metal-free olefin polymerization catalyst

    DOEpatents

    Sen, Ayusman; Wojcinski, II, Louis M.; Liu, Shengsheng

    2001-01-01

    Ethylene and/or propylene are polymerized to form high molecular weight, linear polymers by contacting ethylene and/or propylene monomer, in the presence of an inert reaction medium, with a catalyst system which consists essentially of (1) an aluminum alkyl component, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum and diethylaluminum hydride and (2) a Lewis acid or Lewis acid derivative component, such as B (C.sub.6 F.sub.5).sub.3, [(CH.sub.3).sub.2 N (H) (C.sub.6 H.sub.5)].sup.+ [B (C.sub.6 F.sub.5)4].sup.-, [(C.sub.2 H.sub.5).sub.3 NH].sup.+ [B C.sub.6 F.sub.5).sub.4 ],.sup.-, [C(C.sub.6 F.sub.5).sub.3 ].sup.+ [B(C.sub.6 F.sub.5).sub.4 ].sup.-, (C.sub.2 H.sub.5).sub.2 Al(OCH.sub.3), (C.sub.2 H.sub.5).sub.2 Al(2,6-di-t-butyl-4-methylphenoxide), (C.sub.2 H.sub.5)Al(2,6 -di-t-butylphenoxide).sub.2, (C.sub.2 H.sub.5).sub.2 Al(2,6-di-t-butylphonoxide) , 2,6 -di-t-butylphenol.multidot.methylaluminoxane or an alkylaluminoxane, and which may be completely free any transition metal component(s).

  20. Tunable magnetocaloric effect in transition metal alloys.

    PubMed

    Belyea, Dustin D; Lucas, M S; Michel, E; Horwath, J; Miller, Casey W

    2015-01-01

    The unpredictability of geopolitical tensions and resulting supply chain and pricing instabilities make it imperative to explore rare earth free magnetic materials. As such, we have investigated fully transition metal based "high entropy alloys" in the context of the magnetocaloric effect. We find the NiFeCoCrPdx family exhibits a second order magnetic phase transition whose critical temperature is tunable from 100 K to well above room temperature. The system notably displays changes in the functionality of the magnetic entropy change depending on x, which leads to nearly 40% enhancement of the refrigerant capacity. A detailed statistical analysis of the universal scaling behavior provides direct evidence that heat treatment and Pd additions reduce the distribution of exchange energies in the system, leading to a more magnetically homogeneous alloy. The general implications of this work are that the parent NiFeCoCr compound can be tuned dramatically with FCC metal additives. Together with their relatively lower cost, their superior mechanical properties that aid manufacturability and their relative chemical inertness that aids product longevity, NiFeCoCr-based materials could ultimately lead to commercially viable magnetic refrigerants. PMID:26507636

  1. Exciton formation in monolayer transition metal dichalcogenides.

    PubMed

    Ceballos, Frank; Cui, Qiannan; Bellus, Matthew Z; Zhao, Hui

    2016-06-01

    Two-dimensional transition metal dichalcogenides provide a unique platform to study excitons in confined structures. Recently, several important aspects of excitons in these materials have been investigated in detail. However, the formation process of excitons from free carriers has yet to be understood. Here we report time-resolved measurements on the exciton formation process in monolayer samples of MoS2, MoSe2, WS2, and WSe2. The free electron-hole pairs, injected by an ultrashort laser pulse, immediately induce a transient absorption signal of a probe pulse tuned to the exciton resonance. The signal quickly drops by about a factor of two within 1 ps and is followed by a slower decay process. In contrast, when excitons are resonantly injected, the fast decay component is absent. Based both on its excitation excess energy and intensity dependence, this fast decay process is attributed to the formation of excitons from the electron-hole pairs. This interpretation is also consistent with a model that shows how free electron-hole pairs can be about twice more effective than excitons in altering the exciton absorption strength. From our measurements and analysis of our results, we determined that the exciton formation times in these monolayers to be shorter than 1 ps. PMID:27219022

  2. Trion formation in monolayer transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Kezerashvili, Roman Ya.; Tsiklauri, Shalva M.

    We present three-body calculations for trions binding energy in monolayer transition metal dichalcogenides using the method of hyperspherical harmonics (HH). In numerical calculations for a proper treatment of Coulomb screening in two dimensions we assume that electrons and holes are interacted via Keldysh potential. The convergences of binding energy calculations for the ground state of the trion as a function of the grand angular momentum are studied. For the trion binding energy in MoS2 we obtain 19.2 mev. This value is remarkably close to the experimental one of 18 meV. A comparison with results of other calculations are presented. We also study solutions of a hyperradial equation in a minimal approximation for the ground angular momentum to examine two regimes: a long range and a short range cases when the inter particle distance is much greater and much less than the screening length. For these cases, we find analytical expressions for the energy and wave function for trion states

  3. Tunable magnetocaloric effect in transition metal alloys

    PubMed Central

    Belyea, Dustin D.; Lucas, M. S.; Michel, E.; Horwath, J.; Miller, Casey W.

    2015-01-01

    The unpredictability of geopolitical tensions and resulting supply chain and pricing instabilities make it imperative to explore rare earth free magnetic materials. As such, we have investigated fully transition metal based “high entropy alloys” in the context of the magnetocaloric effect. We find the NiFeCoCrPdx family exhibits a second order magnetic phase transition whose critical temperature is tunable from 100 K to well above room temperature. The system notably displays changes in the functionality of the magnetic entropy change depending on x, which leads to nearly 40% enhancement of the refrigerant capacity. A detailed statistical analysis of the universal scaling behavior provides direct evidence that heat treatment and Pd additions reduce the distribution of exchange energies in the system, leading to a more magnetically homogeneous alloy. The general implications of this work are that the parent NiFeCoCr compound can be tuned dramatically with FCC metal additives. Together with their relatively lower cost, their superior mechanical properties that aid manufacturability and their relative chemical inertness that aids product longevity, NiFeCoCr-based materials could ultimately lead to commercially viable magnetic refrigerants. PMID:26507636

  4. Tunable magnetocaloric effect in transition metal alloys

    NASA Astrophysics Data System (ADS)

    Belyea, Dustin D.; Lucas, M. S.; Michel, E.; Horwath, J.; Miller, Casey W.

    2015-10-01

    The unpredictability of geopolitical tensions and resulting supply chain and pricing instabilities make it imperative to explore rare earth free magnetic materials. As such, we have investigated fully transition metal based “high entropy alloys” in the context of the magnetocaloric effect. We find the NiFeCoCrPdx family exhibits a second order magnetic phase transition whose critical temperature is tunable from 100 K to well above room temperature. The system notably displays changes in the functionality of the magnetic entropy change depending on x, which leads to nearly 40% enhancement of the refrigerant capacity. A detailed statistical analysis of the universal scaling behavior provides direct evidence that heat treatment and Pd additions reduce the distribution of exchange energies in the system, leading to a more magnetically homogeneous alloy. The general implications of this work are that the parent NiFeCoCr compound can be tuned dramatically with FCC metal additives. Together with their relatively lower cost, their superior mechanical properties that aid manufacturability and their relative chemical inertness that aids product longevity, NiFeCoCr-based materials could ultimately lead to commercially viable magnetic refrigerants.

  5. Defect-Tolerant Monolayer Transition Metal Dichalcogenides.

    PubMed

    Pandey, Mohnish; Rasmussen, Filip A; Kuhar, Korina; Olsen, Thomas; Jacobsen, Karsten W; Thygesen, Kristian S

    2016-04-13

    Localized electronic states formed inside the band gap of a semiconductor due to crystal defects can be detrimental to the material's optoelectronic properties. Semiconductors with a lower tendency to form defect induced deep gap states are termed defect-tolerant. Here we provide a systematic first-principles investigation of defect tolerance in 29 monolayer transition metal dichalcogenides (TMDs) of interest for nanoscale optoelectronics. We find that the TMDs based on group VI and X metals form deep gap states upon creation of a chalcogen (S, Se, Te) vacancy, while the TMDs based on group IV metals form only shallow defect levels and are thus predicted to be defect-tolerant. Interestingly, all the defect sensitive TMDs have valence and conduction bands with a very similar orbital composition. This indicates a bonding/antibonding nature of the gap, which in turn suggests that dangling bonds will fall inside the gap. These ideas are made quantitative by introducing a descriptor that measures the degree of similarity of the conduction and valence band manifolds. Finally, the study is generalized to nonpolar nanoribbons of the TMDs where we find that only the defect sensitive materials form edge states within the band gap. PMID:27027786

  6. Exciton formation in monolayer transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Ceballos, Frank; Cui, Qiannan; Bellus, Matthew Z.; Zhao, Hui

    2016-06-01

    Two-dimensional transition metal dichalcogenides provide a unique platform to study excitons in confined structures. Recently, several important aspects of excitons in these materials have been investigated in detail. However, the formation process of excitons from free carriers has yet to be understood. Here we report time-resolved measurements on the exciton formation process in monolayer samples of MoS2, MoSe2, WS2, and WSe2. The free electron-hole pairs, injected by an ultrashort laser pulse, immediately induce a transient absorption signal of a probe pulse tuned to the exciton resonance. The signal quickly drops by about a factor of two within 1 ps and is followed by a slower decay process. In contrast, when excitons are resonantly injected, the fast decay component is absent. Based both on its excitation excess energy and intensity dependence, this fast decay process is attributed to the formation of excitons from the electron-hole pairs. This interpretation is also consistent with a model that shows how free electron-hole pairs can be about twice more effective than excitons in altering the exciton absorption strength. From our measurements and analysis of our results, we determined that the exciton formation times in these monolayers to be shorter than 1 ps.

  7. New Gallides and Germanides of Transition Metals

    NASA Astrophysics Data System (ADS)

    Popova, S. V.

    1982-01-01

    The analysis of the average atomic volumes (AAV) of the intermediate phases from the concentration was done in many two-component systems. It was shown that in some systems (namely transition metal with non-transition element from the IIIrd or IVth group of the periodic table) the AAV of the intermediate phases are much more less than the sum of the volumes of the pure components. It means that the formation of the intermediate phases in such systems is accompanied by a rather large decreasing of the volume in comparison with the mixture of elements. For this reason the high pressure conditions are favourable for the formation of the intermediate phases in such systems from the thermodynamical point of view. On the ground of these data the systems W-Ga, W-Ge, Re-Ga, Os-Ga, Sc-Ga, Ta-Ga, were investigated at high pressures and temperatures. It was found that many new phases are crystallised in these systems. All of them are metastable at room pressure. The composition and crystal structures of these phases were investigated at ordinary conditions.

  8. Transition-metal substitutions in iron chalcogenides

    NASA Astrophysics Data System (ADS)

    Bezusyy, V. L.; Gawryluk, D. J.; Malinowski, A.; Cieplak, Marta Z.

    2015-03-01

    The a b -plane resistivity and Hall effect are studied in Fe1 -yMyTe0.65Se0.35 single crystals doped with two transition-metal elements, M = Co or Ni, over a wide doping range, 0 ≤y ≤0.2 . The superconducting transition temperature, Tc, reaches zero for Co at y ≃0.14 and for Ni at y ≃0.032 , while the resistivity at the Tc onset increases weakly with Co doping, and strongly with Ni doping. The Hall coefficient RH, positive for y =0 , remains so at high temperatures for all y , while it changes sign to negative at low T for y >0.135 (Co) and y >0.06 (Ni). The analysis based on a two-band model suggests that at high T residual hole pockets survive the doping, but holes get localized upon the lowering of T , so that the effect of the electron doping on the transport becomes evident. The suppression of the Tc by Co impurity is related to electron doping, while in the case of the Ni impurity strong electron localization most likely contributes to fast decrease of the Tc.

  9. RKKY interaction in transition-metal dichalcogenide nanoflakes

    NASA Astrophysics Data System (ADS)

    Avalos-Ovando, Oscar; Mastrogiuseppe, Diego; Ulloa, Sergio

    2015-03-01

    Transition metal dichalcogenides (TMDs) are layered crystals with unique electronic and optical properties, and are promising candidates for a new generation of semiconductor-based devices, mainly when exfoliated to one or a few layers. The process of exfoliation often produces nanoscale samples -flakes- with different shapes and boundaries. These flakes might have applications as quantum dots with novel characteristics. One interesting topic relates to the presence of magnetic impurities and their interaction. In combination with strong spin-orbit coupling and valley degrees of freedom, TMDs might have a great impact in the field of spintronics. Using an effective low-energy two-orbital tight-binding model, we study the Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction between two magnetic impurities in 2D TMD nanoflakes. We consider different geometries and terminations, analyzing the effect of the sample size. Our results show the behavior of the interaction for impurities sitting at different positions in the flake, and its possible tunability with the electron/hole concentration. The magnetic impurities can be intrinsic to the sample production process or can be introduced extrinsically. Our results can be tested with local probes, such as spin-polarized STM. Supported by NSF DMR MWN/CIAM.

  10. 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. PMID:24862644

  11. Hyperfine structure studies of transition metals

    SciTech Connect

    Young, L.; Kurtz, C.; Hasegawa, S.

    1995-08-01

    This past year our studies of hyperfine structure (hfs) in metastable states of transition metals concentrated on the analysis of hfs in the four-valence electron system, Nb II. Earlier, we measured hfs intervals using the laser-rf double resonance and laser-induced fluorescence methods in a fast-ion beam of Nb{sup +}. The resulting experimental magnetic dipole and electric quadrupole interaction constants are compared to those calculated by a relativistic configuration interaction approach. These are the first hfs data on this refractory element. Theoretically, it is found that the most important contributions to the energy are the pair excitations, valence single excitations and core polarization from the shallow core. However, the inner core polarization is found to be crucial for hfs, albeit unimportant for energy. For the J=2 level at 12805 cm{sup -1}, 4d{sup 4} {sup 3}F. the theoretical relativistic configuration A-value is in agreement with the experimental result to an accuracy of 4%. Other calculated A-values are expected to be of the same accuracy. A paper describing these results was accepted for publication. Experimental studies of the four-valence electron system V{sup +} in the (4s+3d){sup 4} manifold are complete. The theoretical difficulties for the 3d manifold, noted earlier for the three-valence electron Ti{sup +}, as compared to the 4d manifold appear to be repeated in the case of the four-valence electron systems (Nb{sup +} and V{sup +}). Relativistic configuration interaction calculations are underway, after which a paper will be published.

  12. New pathways for organic synthesis. Practical applications of transition metals

    SciTech Connect

    Colquhoun, H.M.; Holton, J.; Thompson, D.J.; Twigg, M.V.

    1984-01-01

    This book contains a considerable number of transition-metal-based procedures that have genuine applications in synthesis, and which are arranged according to the nature of the organic product or synthetic transformation being carried out. The objective is to provide those engaged in the preparation of pharmaceuticals, natural products, herbicides, dyestuffs, and other organic chemicals with a practical guide to the application of transition metals in organic synthesis. Topics considered include the formation of carbon-carbon bonds, the formation of carbocyclic compounds, the formation of heterocyclic compounds, the isomerization of alkenes, the direct introduction and removal of carbonyl groups, reduction, oxidation, and preparing and handling transition metal catalysts.

  13. Nutritional immunity: transition metals at the pathogen-host interface

    PubMed Central

    Hood, M. Indriati; Skaar, Eric P.

    2013-01-01

    Transition metals occupy an essential niche in biological systems. Their electrostatic properties stabilize substrates or reaction intermediates in the active sites of enzymes, while their heightened reactivity is harnessed for catalysis. However, the latter property renders transition metals toxic at high concentrations. Bacteria, like all living organisms, must regulate the levels of these elements to satisfy their physiological needs while avoiding harm. It is therefore not surprising that the host capitalizes on both the essentiality and toxicity of transition metals to defend against bacterial invaders. This review will discuss established and emerging paradigms in nutrient metal homeostasis at the pathogen-host interface. PMID:22796883

  14. Electrolytic separation of crystals of transition-metal oxides

    NASA Technical Reports Server (NTRS)

    Arnott, R. J.; Feretti, A.; Kunnamann, W.

    1969-01-01

    Versatile flux system grows large, well-formed, stoichiometric single crystals of mixed oxides of the transition-metal elements. These crystals have important uses in the microwave field, and applications as lasers and masers in communications.

  15. Electrical properties of transition metal hydrogen complexes in silicon

    SciTech Connect

    Weber, J.

    1998-12-31

    A summary is given on the electrical properties of transition-metal hydrogen complexes in silicon. Contrary to the general understanding, hydrogen leads not only to passivation of deep defect levels but also creates several new levels in the band gap due to electrically active transition-metal complexes. The author presents detailed data for Pt-H complexes and summarize briefly the results on the transition metals Ti, Co, Ni, Pd, and Ag. The introduction of hydrogen at room temperature by wet chemical etching, followed by specific annealing steps allows us to study the formation of the different complexes. In particular, depth profiles of the defect concentrations give an estimate of the number of hydrogen atoms involved in the complexes. Transition-metals binding up to four hydrogen atoms are identified.

  16. Mechanisms of transition-metal gettering in silicon

    SciTech Connect

    MYERS JR.,SAMUEL M.; SEIBT,M.; SCHROTER,W.

    2000-03-23

    The atomic process, kinetics, and equilibrium thermodynamics underlying the gettering of transition-metal impurities in Si are reviewed from a mechanistic perspective. Methods for mathematical modeling of gettering are reviewed and illustrated. Needs for further research are discussed.

  17. Ab initio tight-binding Hamiltonian for transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Fang, Shiang; Kuate Defo, Rodrick; Shirodkar, Sharmila N.; Lieu, Simon; Tritsaris, Georgios A.; Kaxiras, Efthimios

    2015-11-01

    We present an accurate ab initio tight-binding Hamiltonian for the transition metal dichalcogenides, MoS2, MoSe2, WS2, WSe2, with a minimal basis (the d orbitals for the metal atoms and p orbitals for the chalcogen atoms) based on a transformation of the Kohn-Sham density functional theory Hamiltonian to a basis of maximally localized Wannier functions. The truncated tight-binding Hamiltonian, with only on-site, first, and partial second neighbor interactions, including spin-orbit coupling, provides a simple physical picture and the symmetry of the main band-structure features. Interlayer interactions between adjacent layers are modeled by transferable hopping terms between the chalcogen p orbitals. The full-range tight-binding Hamiltonian can be reduced to hybrid-orbital k .p effective Hamiltonians near the band extrema that capture important low-energy excitations. These ab initio Hamiltonians can serve as the starting point for applications to interacting many-body physics including optical transitions and Berry curvature of bands, of which we give some examples.

  18. Green's function approach to edge states in transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Farmanbar, Mojtaba; Amlaki, Taher; Brocks, Geert

    2016-05-01

    The semiconducting two-dimensional transition metal dichalcogenides MX 2 show an abundance of one-dimensional metallic edges and grain boundaries. Standard techniques for calculating edge states typically model nanoribbons, and require the use of supercells. In this paper, we formulate a Green's function technique for calculating edge states of (semi-)infinite two-dimensional systems with a single well-defined edge or grain boundary. We express Green's functions in terms of Bloch matrices, constructed from the solutions of a quadratic eigenvalue equation. The technique can be applied to any localized basis representation of the Hamiltonian. Here, we use it to calculate edge states of MX 2 monolayers by means of tight-binding models. Aside from the basic zigzag and armchair edges, we study edges with a more general orientation, structurally modifed edges, and grain boundaries. A simple three-band model captures an important part of the edge electronic structures. An 11-band model comprising all valence orbitals of the M and X atoms is required to obtain all edge states with energies in the MX 2 band gap. Here, states of odd symmetry with respect to a mirror plane through the layer of M atoms have a dangling-bond character, and tend to pin the Fermi level.

  19. Exciton-polariton condensation in transition metal dichalcogenide bilayer heterostructure

    NASA Astrophysics Data System (ADS)

    Lee, Ki Hoon; Jeong, Jae-Seung; Min, Hongki; Chung, Suk Bum

    For the bilayer heterostructure system in an optical microcavity, the interplay of the Coulomb interaction and the electron-photon coupling can lead to the emergence of quasiparticles consisting of the spatially indirect exciton and cavity photons known as dipolariton, which can form the Bose-Einstein condensate above a threshold density. Additional physics comes into play when each layer of the bilayer system consists of the transition metal dichalcogenide (TMD) monolayer. The TMD monolayer band structure in the low energy spectrum has two valley components with nontrivial Berry phase, which gives rise to a selection rule in the exciton-polariton coupling, e.g. the exciton from one (the other) valley can couple only to the clockwise (counter-clockwise) polarized photon. We investigate possible condensate phases of exciton-polariton in the bilayer TMD microcavity changing relevant parameters such as detuning, excitation density and interlayer distance. This work was supported in part by the Institute for Basic Science of Korea (IBS) under Grant IBS-R009-Y1 and by the National Research Foundation of Korea (NRF) under the Basic Science Research Program Grant No. 2015R1D1A1A01058071.

  20. Magnetic ground state of semiconducting transition-metal trichalcogenide monolayers

    SciTech Connect

    Sivadas, Nikhil; Daniels, Matthew W.; Swendsen, Robert H.; Okamoto, Satoshi; Xiao, Di

    2015-06-16

    Layered transition-metal trichalcogenides with the chemical formula ABX3 have attracted recent interest as potential candidates for two-dimensional magnets. Using first-principles calculations within density functional theory, we investigate the magnetic ground states of monolayers of Mn- and Cr-based semiconducting trichalcogenides.We show that the second and third nearest-neighbor exchange interactions (J2 and J3) between magnetic ions, which have been largely overlooked in previous theoretical studies, are crucial in determining the magnetic ground state. Specifically, we find that monolayer CrSiTe3 is an antiferromagnet with a zigzag spin texture due to significant contribution from J3, whereas CrGeTe3 is a ferromagnet with a Curie temperature of 106 K. Monolayers of Mn compounds (MnPS3 and MnPSe3) always show antiferromagnetic N eel order. We identify the physical origin of various exchange interactions, and demonstrate that strain can be an effective knob for tuning the magnetic properties. Possible magnetic ordering in the bulk is also discussed. In conclusion, our study suggests that ABX3 can be a promising platform to explore two-dimensional magnetic phenomena.

  1. Magnetic ground state of semiconducting transition-metal trichalcogenide monolayers

    DOE PAGESBeta

    Sivadas, Nikhil; Daniels, Matthew W.; Swendsen, Robert H.; Okamoto, Satoshi; Xiao, Di

    2015-06-16

    Layered transition-metal trichalcogenides with the chemical formula ABX3 have attracted recent interest as potential candidates for two-dimensional magnets. Using first-principles calculations within density functional theory, we investigate the magnetic ground states of monolayers of Mn- and Cr-based semiconducting trichalcogenides.We show that the second and third nearest-neighbor exchange interactions (J2 and J3) between magnetic ions, which have been largely overlooked in previous theoretical studies, are crucial in determining the magnetic ground state. Specifically, we find that monolayer CrSiTe3 is an antiferromagnet with a zigzag spin texture due to significant contribution from J3, whereas CrGeTe3 is a ferromagnet with a Curie temperaturemore » of 106 K. Monolayers of Mn compounds (MnPS3 and MnPSe3) always show antiferromagnetic N eel order. We identify the physical origin of various exchange interactions, and demonstrate that strain can be an effective knob for tuning the magnetic properties. Possible magnetic ordering in the bulk is also discussed. In conclusion, our study suggests that ABX3 can be a promising platform to explore two-dimensional magnetic phenomena.« less

  2. Exciton radiative lifetimes in two-dimensional transition metal dichalcogenides.

    PubMed

    Palummo, Maurizia; Bernardi, Marco; Grossman, Jeffrey C

    2015-05-13

    Light emission in two-dimensional (2D) transition metal dichalcogenides (TMDs) changes significantly with the number of layers and stacking sequence. While the electronic structure and optical absorption are well understood in 2D-TMDs, much less is known about exciton dynamics and radiative recombination. Here, we show first-principles calculations of intrinsic exciton radiative lifetimes at low temperature (4 K) and room temperature (300 K) in TMD monolayers with the chemical formula MX2 (X = Mo, W, and X = S, Se), as well as in bilayer and bulk MoS2 and in two MX2 heterobilayers. Our results elucidate the time scale and microscopic origin of light emission in TMDs. We find radiative lifetimes of a few picoseconds at low temperature and a few nanoseconds at room temperature in the monolayers and slower radiative recombination in bulk and bilayer than in monolayer MoS2. The MoS2/WS2 and MoSe2/WSe2 heterobilayers exhibit very long-lived (∼20-30 ns at room temperature) interlayer excitons constituted by electrons localized on the Mo-based and holes on the W-based monolayer. The wide radiative lifetime tunability, together with the ability shown here to predict radiative lifetimes from computations, hold unique potential to manipulate excitons in TMDs and their heterostructures for application in optoelectronics and solar energy conversion. PMID:25798735

  3. Defect engineering of two-dimensional transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Lin, Zhong; Carvalho, Bruno R.; Kahn, Ethan; Lv, Ruitao; Rao, Rahul; Terrones, Humberto; Pimenta, Marcos A.; Terrones, Mauricio

    2016-06-01

    Two-dimensional transition metal dichalcogenides (TMDs), an emerging family of layered materials, have provided researchers a fertile ground for harvesting fundamental science and emergent applications. TMDs can contain a number of different structural defects in their crystal lattices which significantly alter their physico-chemical properties. Having structural defects can be either detrimental or beneficial, depending on the targeted application. Therefore, a comprehensive understanding of structural defects is required. Here we review different defects in semiconducting TMDs by summarizing: (i) the dimensionalities and atomic structures of defects; (ii) the pathways to generating structural defects during and after synthesis and, (iii) the effects of having defects on the physico-chemical properties and applications of TMDs. Thus far, significant progress has been made, although we are probably still witnessing the tip of the iceberg. A better understanding and control of defects is important in order to move forward the field of Defect Engineering in TMDs. Finally, we also provide our perspective on the challenges and opportunities in this emerging field.

  4. Strain engineering of electronic properties of transition metal dichalcogenide monolayers

    NASA Astrophysics Data System (ADS)

    Maniadaki, Aristea E.; Kopidakis, Georgios; Remediakis, Ioannis N.

    2016-02-01

    We present Density Functional Theory (DFT) results for the electronic and dielectric properties of single-layer (2D) semiconducting transition metal dichalcogenides MX2 (M=Mo, W; X=S, Se, Te) under isotropic, uniaxial (along the zigzag and armchair directions), and shear strain. Electronic band gaps decrease while dielectric constants increase for heavier chalcogens X. The direct gaps of equilibrium structures often become indirect under certain types of strain, depending on the material. The effects of strain and of broken symmetry on the band structure are discussed. Gaps reach maximum values at small compressive strains or in equilibrium, and decrease with larger strains. In-plane dielectric constants generally increase with strain, reaching a minimum value at small compressive strains. The out-of-plane constants exhibit a similar behavior under shear strain but under isotropic and uniaxial strain they increase with compression and decrease with tension, thus exhibiting a monotonic behavior. These DFT results are theoretically explained using only structural parameters and equilibrium dielectric constants. Our findings are consistent with available experimental data.

  5. Interactions between lasers and two-dimensional transition metal dichalcogenides.

    PubMed

    Lu, Junpeng; Liu, Hongwei; Tok, Eng Soon; Sow, Chorng-Haur

    2016-05-01

    The recent increasing research interest in two-dimensional (2D) layered materials has led to an explosion of in the discovery of novel physical and chemical phenomena in these materials. Among the 2D family, group-VI transition metal dichalcogenides (TMDs), such as represented by MoS2 and WSe2, are remarkable semiconductors with sizable energy band gaps, which make the TMDs promising building blocks for new generation optoelectronics. On the other hand, the specificity and tunability of the band gaps can generate particularly strong light-matter interactions between TMD crystals and specific photons, which can trigger complex and interesting phenomena such as photo-scattering, photo-excitation, photo-destruction, photo-physical modification, photochemical reaction and photo-oxidation. Herein, we provide an overview of the phenomena explained by various interactions between lasers and the 2D TMDs. Characterizations of the optical fundamentals of the TMDs via laser spectroscopies are reviewed. Subsequently, photoelectric conversion devices enabled by laser excitation and the functionality extension and performance improvement of the TMDs materials via laser modification are comprehensively summarized. Finally, we conclude the review by discussing the prospects for further development in this research area. PMID:27141556

  6. 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

  7. 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

  8. First-principles prediction of redox potentials in transition-metal compounds with LDA+U

    NASA Astrophysics Data System (ADS)

    Zhou, F.; Cococcioni, M.; Marianetti, C. A.; Morgan, D.; Ceder, G.

    2004-12-01

    First-principles calculations within the local density approximation (LDA) or generalized gradient approximation (GGA), though very successful, are known to underestimate redox potentials, such as those at which lithium intercalates in transition metal compounds. We argue that this inaccuracy is related to the lack of cancellation of electron self-interaction errors in LDA/GGA and can be improved by using the DFT+U method with a self-consistent evaluation of the U parameter. We show that, using this approach, the experimental lithium intercalation voltages of a number of transition metal compounds, including the olivine LixMPO4 ( M=Mn , Fe Co, Ni), layered LixMO2 ( x=Co , Ni) and spinel-like LixM2O4 ( M=Mn , Co), can be reproduced accurately.

  9. 2D crystals of transition metal dichalcogenide and their iontronic functionalities

    NASA Astrophysics Data System (ADS)

    Zhang, Y. J.; Yoshida, M.; Suzuki, R.; Iwasa, Y.

    2015-12-01

    2D crystals based on transition metal dichalcogenides (TMDs) provide a unique platform of novel physical properties and functionalities, including photoluminescence, laser, valleytronics, spintronics, piezoelectric devices, field effect transistors (FETs), and superconductivity. Among them, FET devices are extremely useful because of voltage-tunable carrier density and Fermi energy. In particular, high density charge accumulation in electric double layer transistor (EDLT), which is a FET device driven by ionic motions, is playing key roles for expanding the functionalities of TMD based 2D crystals. Here, we report several device concepts which were realized by introducing EDLTs in TMDs, taking the advantage of their extremely unique band structures and phase transition phenomena realized simply by thinning to the monolayer level. We address two kinds of TMDs based on group VI and group V transition metals, which basically yield semiconductors and metals, respectively. For each system, we first introduce peculiar characteristics of TMDs achieved by thinning the crystals, followed by the related FET functionalities.

  10. Magnetism and electronic phase transitions in monoclinic transition metal dichalcogenides with transition metal atoms embedded

    NASA Astrophysics Data System (ADS)

    Lin, Xianqing; Ni, Jun

    2016-08-01

    First-principles calculations have been performed to study the energetic, electronic, and magnetic properties of substitutional 3d transition metal dopants in monoclinic transition metal dichalcogenides (TMDs) as topological insulators ( 1 T ' - MX 2 with M = (Mo, W) and X = (S, Se)). We find various favorite features in these doped systems to introduce magnetism and other desirable electronic properties: (i) The Mn embedded monoclinic TMDs are magnetic, and the doped 1 T ' - MoS 2 still maintains the semiconducting character with high concentration of Mn, while an electronic phase transition occurs in other Mn doped monoclinic TMDs with an increasing concentration of Mn. Two Mn dopants prefer the ferromagnetic coupling except for substitution of the nearest Mo atoms in 1 T ' - MoS 2 , and the strength of exchange interaction shows anisotropic behavior with dopants along one Mo zigzag chain having much stronger coupling. (ii) The substitutional V is a promising hole dopant, which causes little change to the energy dispersion around the conduction and valence band edges in most systems. In contrast, parts of the conduction band drop for the electron dopants Co and Ni due to the large structural distortion. Moreover, closing band gaps of the host materials are observed with increasing carrier concentration. (iii) Single Fe dopant has a magnetic moment, but it also dopes electrons. When two Fe dopants have a small distance, the systems turn into nonmagnetic semiconductors. (iv) The formation energies of all dopants are much lower than those in hexagonal TMDs and are all negative in certain growth conditions, suggesting possible realization of the predicted magnetism, electronic phase transitions as well as carrier doping in 1 T ' - MX 2 based topological devices.

  11. Magnetization and compensation temperature in transition metal -- rare earth multilayers: a mean-field approach

    NASA Astrophysics Data System (ADS)

    Tornau, E. E.; Šmakov, J.; Lapinskas, S.; Rosengren, A.

    1998-03-01

    Mean-field theory is used to explain the magnetization as a function of layer thickness in transition metal -- rare earth multilayers. Long-range dipole interactions are included along with FM nearest neighbor interactions within the layers and AF nearest neighbor interactions at the interface. The obtained dependencies of saturation magnetization and compensation temperature on layer thickness agree with experimental data on Tb/Co multilayers( L. Ertl, G. Endl, and H. Hoffmann, J. Magn. Magn. Mater. 113, 227 (1992).). The saturation magnetization is constant for very thin films (the behavior characteristic to Tb - Co alloys) but it decreases with increase of layer thickness. At thick enough films the magnetization starts to increase again confirming the importance of the long - range forces. The compensation temperature also decreases with layer thickness. The proposed theory is extended to calculate the magnetization of FM/AFM layers with a spacer layer in between.

  12. Electron Scattering at Surfaces and Interfaces of Transition Metals

    NASA Astrophysics Data System (ADS)

    Zheng, Pengyuan

    The effect of surfaces on the electron transport at reduced scales is attracting continuous interest due to its broad impact on both the understanding of materials properties and their application for nanoelectronics. The size dependence of for conductor's electrical resistivity rho due to electron surface scattering is most commonly described within the framework of Fuchs and Sondheimer (FS) and their various extensions, which uses a phenomenological scattering parameter p to define the probability of electrons being elastically (i.e. specularly) scattered by the surface without causing an increase of rho at reduced size. However, a basic understanding of what surface chemistry and structure parameters determine the specularity p is still lacking. In addition, the assumption of a spherical Fermi surface in the FS model is too simple for transition metals to give accurate account of the actual surface scattering effect. The goal of this study is to develop an understanding of the physics governing electron surface/interface scattering in transition metals and to study the significance of their Fermi surface shape on surface scattering. The advancement of the scientific knowledge in electron surface and interface scattering of transition metals can provide insights into how to design high-conductivity nanowires that will facilitate the viable development of advanced integrated circuits, thermoelectric power generation and spintronics. Sequential in situ and ex situ transport measurements as a function of surface chemistry demonstrate that electron surface/interface scattering can be engineered by surface doping, causing a decrease in the rho. For instance, the rho of 9.3-nm-thick epitaxial and polycrystalline Cu is reduced by 11--13% when coated with 0.75 nm Ni. This is due to electron surface scattering which exhibits a specularity p = 0.7 for the Cu-vacuum interface that transitions to completely diffuse (p = 0) when exposed to air. In contrast, Ni-coated surfaces

  13. Second harmonic generation in nanoscale films of transition metal chalcogenides: Taking into account multibeam interference

    NASA Astrophysics Data System (ADS)

    Lavrov, S. D.; Kudryavtsev, A. V.; Shestakova, A. P.; Kulyuk, L.; Mishina, E. D.

    2016-05-01

    Second harmonic generation is studied in structures containing nanoscale layers of transition metal chalcogenides that are two-dimensional semiconductors and deposited on a SiO2/Si substrate. The second harmonic generation intensity is calculated with allowance for multibeam interference in layers of dichalcogenide and silicon oxide. The coefficient of reflection from the SiO2-layer-based Fabry-Perot cavity is subsequently calculated for pump wave fields initiating nonlinear polarization at every point of dichalcogenide, which is followed by integration of all second harmonic waves generated by this polarization. Calculated second harmonic intensities are presented as functions of dichalcogenide and silicon oxide layer thicknesses. The dependence of the second harmonic intensity on the MoS2 layer thickness is studied experimentally in the layer of 2-140 nm. A good coincidence of the experimental data and numerical simulation results has been obtained.

  14. Chemistry of Two-Dimensional Transition Metal Carbides (MXenes)

    NASA Astrophysics Data System (ADS)

    Mashtalir, Olha

    With consumer trends pushing toward smaller, faster, more flexible, multitasking devices, researchers striving to meet these needs have targeted two-dimensional (2D) materials---and graphene in particular---as holding the most promise for use in advanced applications. But in 2011, a significant interest has been triggered by a newly discovered family of novel 2D materials---layered transitional metal carbides and carbonitrides, named MXenes. Those compounds were of general formula Mn+1 XnTx, where M stands for metal atom, X is C and/or N, n = 1, 2 or 3, and Tx represents surface groups. Being initially suggested as a material for electrical energy storage systems, MXenes' properties and their potential applications have not been explored. This work is the first complete study of MXenes' chemistry that sheds light on the chemical composition, structure and properties of these novel materials and possible routes of its modification. The research was focused on 2D titanium carbide, Ti3C2Tx, chosen as the representative of the MXene family. The kinetic study of Ti 3C2Tx synthesis discovered the main synthesis parameters, viz. temperature, time and particle size, that affect the etching process and define the quality of final product. MXenes were found to be able to spontaneously accommodate various ions and small organic molecules between the layers leading to preopening of the structure. A major challenge of large scale production of delaminated, atomically thin 2D MXene layers was solved with two delamination techniques involving dimethyl sulfoxide and isopropyl amine pre-intercalation followed by sonication in water. Ti3C2Tx was also found to possess adsorptive and photocatalytic properties, revealing its potential for environmental applications. It also showed limited stability in water and in the presence of oxygen, providing important practical information on proper handling and storage of MXene materials. Completion of this work allowed the performance of energy

  15. Three-fold rotational defects in two-dimensional transition metal dichalcogenides

    PubMed Central

    Lin, Yung-Chang; Björkman, Torbjörn; Komsa, Hannu-Pekka; Teng, Po-Yuan; Yeh, Chao-Hui; Huang, Fei-Sheng; Lin, Kuan-Hung; Jadczak, Joanna; Huang, Ying-Sheng; Chiu, Po-Wen; Krasheninnikov, Arkady V.; Suenaga, Kazu

    2015-01-01

    As defects frequently govern the properties of crystalline solids, the precise microscopic knowledge of defect atomic structure is of fundamental importance. We report a new class of point defects in single-layer transition metal dichalcogenides that can be created through 60° rotations of metal–chalcogen bonds in the trigonal prismatic lattice, with the simplest among them being a three-fold symmetric trefoil-like defect. The defects, which are inherently related to the crystal symmetry of transition metal dichalcogenides, can expand through sequential bond rotations, as evident from in situ scanning transmission electron microscopy experiments, and eventually form larger linear defects consisting of aligned 8–5–5–8 membered rings. First-principles calculations provide insights into the evolution of rotational defects and show that they give rise to p-type doping and local magnetic moments, but weakly affect mechanical characteristics of transition metal dichalcogenides. Thus, controllable introduction of rotational defects can be used to engineer the properties of these materials. PMID:25832503

  16. Three-fold rotational defects in two-dimensional transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Lin, Yung-Chang; Björkman, Torbjörn; Komsa, Hannu-Pekka; Teng, Po-Yuan; Yeh, Chao-Hui; Huang, Fei-Sheng; Lin, Kuan-Hung; Jadczak, Joanna; Huang, Ying-Sheng; Chiu, Po-Wen; Krasheninnikov, Arkady V.; Suenaga, Kazu

    2015-04-01

    As defects frequently govern the properties of crystalline solids, the precise microscopic knowledge of defect atomic structure is of fundamental importance. We report a new class of point defects in single-layer transition metal dichalcogenides that can be created through 60° rotations of metal-chalcogen bonds in the trigonal prismatic lattice, with the simplest among them being a three-fold symmetric trefoil-like defect. The defects, which are inherently related to the crystal symmetry of transition metal dichalcogenides, can expand through sequential bond rotations, as evident from in situ scanning transmission electron microscopy experiments, and eventually form larger linear defects consisting of aligned 8-5-5-8 membered rings. First-principles calculations provide insights into the evolution of rotational defects and show that they give rise to p-type doping and local magnetic moments, but weakly affect mechanical characteristics of transition metal dichalcogenides. Thus, controllable introduction of rotational defects can be used to engineer the properties of these materials.

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

    SciTech Connect

    Heimfarth, Luana; Loureiro, Samanta Oliveira; Dutra, Márcio Ferreira; Andrade, Cláudia; Pettenuzzo, Letícia; Guma, Fátima T. Costa Rodrigues; Gonçalves, Carlos Alberto Saraiva; Batista Teixeira da Rocha, João; Pessoa-Pureur, Regina

    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){sub 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 Akt

  18. 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.

  19. Hybrid uranium-transition-metal oxide cage clusters.

    PubMed

    Ling, Jie; Hobbs, Franklin; Prendergast, Steven; Adelani, Pius O; Babo, Jean-Marie; Qiu, Jie; Weng, Zhehui; Burns, Peter C

    2014-12-15

    Transition-metal based polyoxometalate clusters have been known for decades, whereas those built from uranyl peroxide polyhedra have more recently emerged as a family of complex clusters. Here we report the synthesis and structures of six nanoscale uranyl peroxide cage clusters that contain either tungstate or molybdate polyhedra as part of the cage, as well as phosphate tetrahedra. These transition-metal-uranium hybrid clusters exhibit unique polyhedral connectivities and topologies that include 6-, 7-, 8-, 10-, and 12-membered rings of uranyl polyhedra and uranyl ions coordinated by bidentate peroxide in both trans and cis configurations. The transition-metal polyhedra appear to stabilize unusual units built of uranyl polyhedra, rather than templating their formation. PMID:25434424

  20. 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. PMID:23137676

  1. Superhardness effect in transition-metal diborides films

    NASA Astrophysics Data System (ADS)

    Bazhin, A. I.; Goncharov, A. A.; Pogrebnyak, A. D.; Stupak, V. A.; Goncharova, S. A.

    2016-06-01

    The structure, composition, and properties of transition-metal diboride films have been studied. It was shown that they are characterized by a wide range of structural states, namely from amorphous-like to nanocrystalline with crystallite sizes of 1-50 nm. The characteristic peculiarity of the structure of film transition-metal diborides with high physical and mechanical properties is the formation of a nanocrystalline (columnar) structure with the growth texture in plane [00.1] and a nanocrystallite size of 20-50 nm. The element composition of a superhard highly textured film transition-metal diborides was studied by ion mass spectrometry and Auger electron spectroscopy. The overstoichiometry effect in nanocrystalline transitionmetal diboride films is explained. It was shown that this effect is related to the formation of an additional B⎯B covalent bond, which is realized at subgrain boundaries and leads to the appearance of superhardness in the formed coatings.

  2. Nanodisperse transition metal electrodes (NTME) for electrochemical cells

    SciTech Connect

    Striebel, Kathryn A.; Wen, Shi-Jie

    1998-12-01

    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.

  3. Binding of transition metals to S100 proteins.

    PubMed

    Gilston, Benjamin A; Skaar, Eric P; Chazin, Walter J

    2016-08-01

    The S100 proteins are a unique class of EF-hand Ca(2+) binding proteins distributed in a cell-specific, tissue-specific, and cell cycle-specific manner in humans and other vertebrates. These proteins are distinguished by their distinctive homodimeric structure, both intracellular and extracellular functions, and the ability to bind transition metals at the dimer interface. Here we summarize current knowledge of S100 protein binding of Zn(2+), Cu(2+) and Mn(2+) ions, focusing on binding affinities, conformational changes that arise from metal binding, and the roles of transition metal binding in S100 protein function. PMID:27430886

  4. Trion formation dynamics in monolayer transition metal dichalcogenides

    NASA Astrophysics Data System (ADS)

    Singh, Akshay; Moody, Galan; Tran, Kha; Scott, Marie E.; Overbeck, Vincent; Berghäuser, Gunnar; Schaibley, John; Seifert, Edward J.; Pleskot, Dennis; Gabor, Nathaniel M.; Yan, Jiaqiang; Mandrus, David G.; Richter, Marten; Malic, Ermin; Xu, Xiaodong; Li, Xiaoqin

    2016-01-01

    We report charged exciton (trion) formation dynamics in doped monolayer transition metal dichalcogenides, specifically molybdenum diselenide (MoS e2 ), 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.

  5. Trion formation dynamics in monolayer transition metal dichalcogenides

    DOE PAGESBeta

    Singh, Akashay; Moody, Galan; Schaibley, John R.; Yan, Jiaqiang; Mandrus, David G.; Xu, Xiaodong; Li, Xiaoqun; Tran, Kha; Scott, Marie E.; Overbeck, Vincent; et al

    2016-01-05

    Here, we report charged exciton (trion) formation dynamics in doped monolayer transition metal dichalcogenides, specifically molybdenum diselenide (MoSe2), 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.

  6. Structural and Electrochemical Characterization of Lithium Transition Metal Phosphates

    NASA Astrophysics Data System (ADS)

    Hashambhoy, Ayesha Maria

    The lithium ion battery has emerged as one of the most promising hybrid vehicle energy storage systems of the future. Of the potential cathode chemistries explored, lithium transition metal phosphates have generated a significant amount of interest due to their low-cost precursors, potential ease of synthesis, stability, and their environmentally friendly nature. This is in contrast to layered oxide systems such as LiCoO2, which have long been considered state of the art, but are now being reevaluated due to their structural instability at elevated temperatures, and higher cost. In particular, LiFePO4 has an operating potential comparable to those batteries available on the market (˜3.5V vs. Li/Li+), and higher theoretical specific capacity (170mAh/g vs. that of LiCoO2 which is 140mAh/g). The manganese analog to LiFePO4, LiMnPO4, exhibits a higher operating potential (˜4.1V v Li/Li+), and the same theoretical capacity, however Li-ion diffusion through this structure is much more rate limited and its theoretical capacity cannot be realized at rates suitable for commercial applications. The purpose of this work was threefold: 1) To explore the impact of Fe substitution on Mn sites in LiMnPO 4. 2) To examine the effects of alterations to the particle/electrolyte interface on rate capability. 3) To explore a novel fabrication route for LiMnPO4 using microwaves, and determine an optimal power and time combination for best performance. The coexistence of Fe and Mn on the transition metal site M, of LiMPO 4 resulted in an improved apparent Li-ion diffusivity in both Fe and Mn regimes as compared to that observed for LiFePO4 and LiMnPO 4 respectively. Calculations made from two different analysis methods, cyclic voltammetry (CV) and galvanostatic intermittent titration (GITT) drew this same conclusion. The signature characteristics observed from the CVs pertaining to single and dual phase reactions led to a delithiation model of LiFe0.5Mn0.5PO4 proposing the localization

  7. Establishing dual electrogenerated chemiluminescence and multicolor electrochromism in functional ionic transition-metal complexes.

    PubMed

    Puodziukynaite, Egle; Oberst, Justin L; Dyer, Aubrey L; Reynolds, John R

    2012-01-18

    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 with 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(max) ranging from 680 to 722 nm and luminance up to 135 cd/m(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. PMID:22239285

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

    SciTech Connect

    Puodziukynaite, Egle; Oberst, Justin L.; Dyer, Aubrey L.; Reynolds, John R.

    2011-12-29

    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 with 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.

  9. Tuning magnetic anisotropy by interfacially engineering the oxygen coordination environment in a transition metal oxide

    NASA Astrophysics Data System (ADS)

    Kan, Daisuke; Aso, Ryotaro; Sato, Riko; Haruta, Mitsutaka; Kurata, Hiroki; Shimakawa, Yuichi

    2016-04-01

    Strong correlations between electrons, spins and lattices--stemming from strong hybridization between transition metal d and oxygen p orbitals--are responsible for the functional properties of transition metal oxides. Artificial oxide heterostructures with chemically abrupt interfaces provide a platform for engineering bonding geometries that lead to emergent phenomena. Here we demonstrate the control of the oxygen coordination environment of the perovskite, SrRuO3, by heterostructuring it with Ca0.5Sr0.5TiO3 (0-4 monolayers thick) grown on a GdScO3 substrate. We found that a Ru-O-Ti bond angle of the SrRuO3 /Ca0.5Sr0.5TiO3 interface can be engineered by layer-by-layer control of the Ca0.5Sr0.5TiO3 layer thickness, and that the engineered Ru-O-Ti bond angle not only stabilizes a Ru-O-Ru bond angle never seen in bulk SrRuO3, but also tunes the magnetic anisotropy in the entire SrRuO3 layer. The results demonstrate that interface engineering of the oxygen coordination environment allows one to control additional degrees of freedom in functional oxide heterostructures.

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

    SciTech Connect

    Puodziukynaite, Egle; Oberst, Justin L.; Dyer, Aubrey L.; Reynolds, John R.

    2012-01-18

    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 with 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.