| 1. |
- Chowdhury, Susmita, et al.
(författare)
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Thermoelectric properties and electronic structure of Cr(Mo,V)Nx thin films studied by synchrotron and lab-based x-ray spectroscopy
- 2023
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Ingår i: Physical Review B. - : AMER PHYSICAL SOC. - 2469-9950 .- 2469-9969. ; 108:20
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Tidskriftsartikel (refereegranskat)abstract
- Chromium-based nitrides are used in hard, resilient coatings and show promise for thermoelectric applications due to their combination of structural, thermal, and electronic properties. Here, we investigate the electronic structures and chemical bonding correlated to the thermoelectric properties of epitaxially grown chromium-based multicomponent nitride Cr(Mo,V)Nx thin films. The small amount of N vacancies causes Cr 3d and N 2p states to appear at the Fermi level and reduces the band gap in Cr0.51N0.49. Incorporating holes by alloying of V in N-deficient CrN results in an enhanced thermoelectric power factor with marginal change in the charge transfer of Cr to N compared with Cr0.51N0.49. Further alloying of Mo, isoelectronic to Cr, increases the density of states at the Fermi level due to hybridization of the (Cr, V) 3d and Mo 4d-N 2p states in Cr(Mo,V)Nx. This hybridization and N off-stoichiometry result in more metal-like electrical resistivity and reduction in Seebeck coefficient. The N deficiency in Cr(Mo,V)Nx also depicts a critical role in reduction of the charge transfer from metal to N site compared with Cr0.51N0.49 and Cr0.50V0.03N0.47. In this paper, we envisage ways for enhancing thermoelectric properties through electronic band engineering by alloying and competing effects of N vacancies.
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| 2. |
- Gangaprasad Rao, Smita, 1992-, et al.
(författare)
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Phase formation and structural evolution of multicomponent (CrFeCo)Ny films
- 2021
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Ingår i: Surface & Coatings Technology. - : ELSEVIER SCIENCE SA. - 0257-8972 .- 1879-3347. ; 412
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Tidskriftsartikel (refereegranskat)abstract
- The Cantor alloy (CoCrFeMnNi) and its variants, in bulk as well as thin films, have been extensively studied. They are known to exhibit cubic crystal structures and thermodynamic stability regardless of their complex chemical composition. Therefore, they may find use as hard, wear-resistant, corrosion and oxidation-resistant coatings. The addition of light elements, such as nitrogen, is known to help improve these properties further through processes such as amorphization and nitride compound formation. Here, we investigate the ternary CrFeCo system to study the effects of nitrogen addition. (CrFeCo)Ny multicomponent thin films are grown on silicon substrates by DC magnetron sputtering. Changes in crystal structure, morphology, mechanical and electrical properties with gradual increases of nitrogen in the film are described and discussed. Increased addition of nitrogen from 14 at.% to 28 at.% in the film leads to a transformation from an fcc to a bcc crystal structure, affects both the mechanical and electrical properties. XPS analysis shows the tendency of nitrogen to bond with Cr over other metals. The films display hardness values between 7 and 11 GPa with resistivities values ranging between 28 and 165 μΩ cm.
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| 3. |
- Gangaprasad Rao, Smita, 1992-, et al.
(författare)
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Plasma diagnostics and film growth of multicomponent nitride thin films with magnetic-field-assisted-dc magnetron sputtering
- 2022
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Ingår i: Vacuum. - : Elsevier. - 0042-207X .- 1879-2715. ; 204
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Tidskriftsartikel (refereegranskat)abstract
- During direct current magnetron sputtering (dcMS) of thin films, the ion energy and flux are complex parameters that influence thin film growth and can be exploited to tailor their properties. The ion energy is generally controlled by the bias voltage applied at the substrate. The ion flux density however is controlled by more complex mechanisms. In this study, we look into magnetic-field-assisted dcMs, where a magnetic field applied in the deposition chamber by use of a solenoid coil at the substrate position, influences the energetic bombardment by Ar ions during deposition. Using this technique, CrFeCoNi multicomponent nitride thin films were grown on Si(100) substrates by varying the bias voltage and magnetic field systematically. Plasma diagnostics were performed by a Langmuir wire probe and a flat probe. On interpreting the data from the current-voltage curves it was confirmed that the ion flux at the substrate increased with increasing coil magnetic field with ion energies corresponding to the applied bias. The increased ion flux assisted by the magnetic field produced by the solenoid coil aids in the stabilization of NaCl B1 crystal structure without introducing Ar ion implantation.
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| 4. |
- Shu, Rui, 1990-, et al.
(författare)
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Effect of nitrogen content on microstructure and corrosion resistance of sputter-deposited multicomponent (TiNbZrTa)Nx films
- 2020
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Ingår i: Surface & Coatings Technology. - LAUSANNE, SWITZERLAND : Elsevier BV. - 0257-8972 .- 1879-3347. ; 404
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Tidskriftsartikel (refereegranskat)abstract
- Multicomponent (TiNbZrTa)Nx films were deposited on Si(100) substrates at room temperature using magnetron sputtering with a nitrogen flow ratio fN [fN = N2/(Ar + N2)], which was varied from 0 to 30.8%. The nitrogen content in the films varied between 0 and 45.2 at.%, i.e., x = 0 to 0.83. The microstructure was characterized by X-ray diffraction and electron microscopy. The metallic TiNbZrTa film comprised a dominant bcc solid-solution phase, whereas a single NaCl-type face-centred cubic structure was observed in all nitrogen-containing films (TiNbZrTa)Nx. The mechanical, electrical, and electrochemical properties of these films varied with nitrogen content. The maximum hardness was achieved at 22.1 ± 0.3 GPa when N = 43.0 at.%. The resistivities increased from 95 to 424 μΩcm with increasing nitrogen content. A detailed study of the variation of morphology and chemical bonding with nitrogen content was performed and the corrosion resistance of the TiNbZrTa nitride films was explored in 0.1 M H2SO4. While all the films had excellent corrosion resistances at potentials up to 2.0 V vs. Ag/AgCl, the metallic film and the films with low nitrogen contents (x < 0.60) exhibited an almost stable current plateau up to 4.0 V vs. Ag/AgCl. For the films with higher nitrogen contents (x ≥ 0.68), the current plateau was retained up to 2.0 V vs. Ag/AgCl, above which a higher nitrogen content resulted in a higher current. The decrease in the corrosion resistance at these high potentials indicate the presence of a potential-dependent activation effect resulting in an increased oxidation rate of the nitrides (present under the passive oxide film) yielding a release of nitrogen from the films. TEM results indicate that the oxide layer formed after this corrosion measurement was thick and porous for the film with x = 0.76, in very good agreement with the increased corrosion rate for this film. The results demonstrate that an increased nitrogen content in (TiNbZrTa)Nx system improves their mechanical properties with retained high corrosion resistance at potentials up to 2.0 V vs. Ag/AgCl in 0.1 M H2SO4. At even higher potentials, however, the corrosion resistance decreases with increasing nitrogen concentration for films with sufficiently high nitrogen contents (i.e. x ≥ 0.68).
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| 5. |
- Shu, Rui, 1990-, et al.
(författare)
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Effects of alloying and deposition temperature on phase formation and superconducting properties of TiZrTaNb-based high entropy-alloy films
- 2022
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Ingår i: Applied Physics Letters. - : American Institute of Physics (AIP). - 0003-6951 .- 1077-3118. ; 120:15
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Tidskriftsartikel (refereegranskat)abstract
- A variety of bulk high-entropy alloy superconductors have been recently discovered; however, for thin films, only the TaNbHfZrTi highentropy alloy system has been investigated for its superconducting properties. Here, (TiZrNbTa)1-xWx and (TiZrNbTa)1-xVx superconducting films have been produced by DC magnetron sputtering at different growth temperatures. The phase formation and superconducting behavior of these films depend on the content of alloying x and deposition temperature. A single body-centered cubic (bcc) phase can be formed in the low x range with enough driving energy for crystallinity, but phase transition between amorphous or two bcc structures is observed when increasing x. The highest superconducting transition temperature Tc reaches 8.0 K for the TiZrNbTa film. The superconducting transition temperature Tc of these films deposited at the same temperature decreases monotonically as a function of x. Increasing deposition temperature to 400 °C can enhance Tc for these films while retaining nearly equivalent compositions. Our experimental observations suggest that Tc of superconducting high entropy alloys relate to the atomic radii difference and electronegativity difference of involved elements beyond the valence electron number.
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| 6. |
- Shu, Rui, 1990-, et al.
(författare)
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Influence of Metal Substitution and Ion Energy on Microstructure Evolution of High-Entropy Nitride (TiZrTaMe)N1-x (Me = Hf, Nb, Mo, or Cr) Films
- 2021
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Ingår i: ACS APPLIED ELECTRONIC MATERIALS. - : American Chemical Society (ACS). - 2637-6113. ; 3:6, s. 2748-2756
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Tidskriftsartikel (refereegranskat)abstract
- Multicomponent or high-entropy ceramics show unique combinations of mechanical, electrical, and chemical properties of importance in coating applications. However, generalizing controllable thin-film processes for these complex materials remains a challenge. Here, understoichiometric (TiZrTaMe)N1-x (Me = Hf, Nb, Mo, or Cr, 0.12 <= x <= 0.30) films were deposited on Si(100) substrates at 400 degrees C by reactive magnetron sputtering using single elemental targets. The influence of ion energy during film growth was investigated by varying the negative substrate bias voltage from similar to 10 V (floating potential) to 130 V. The nitrogen content for the samples determined by elastic recoil detection analysis varied from 34.9 to 43.8 at. % (0.12 <= x <= 0.30), and the metal components were near-equimolar and not affected by the bias voltage. On increasing the substrate bias, the phase structures of (TiZrTaMe)N1-x (Me = Hf, Nb, or Mo) films evolved from a polycrystalline fcc phase to a (002) preferred orientation along with a change in surface morphology from faceted triangular features to a dense and smooth structure with nodular mounds. All the four series of (TiZrTaMe)N1-x (Me = Hf, Nb, Mo, or Cr) films exhibited increasing intrinsic stress with increasing negative bias. The maximum compressive stress reached similar to 3.1 GPa in Hf- and Cr-containing films deposited at -130 V. The hardness reached a maximum value of 28.0 +/- 1.0 GPa at a negative bias >= 100 V for all the four series of films. The effect of bias on the mechanical properties of (TiNbZrMe)N1-x films can thus guide the design of protective high-entropy nitride films.
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| 7. |
- Shu, Rui, 1990-
(författare)
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Nonstoichiometric Multicomponent Nitride Thin Films
- 2020
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- High entropy ceramics have rapidly developed as a class of materials based on high entropy alloys; the latter being materials that contain five or more elements in near-equal proportions. Their unconventional compositions and chemical structures hold promise for achieving unprecedented combinations of mechanical, electrical and chemical properties. In this thesis, high entropy ceramic films, (TiNbZrTa)Nx were deposited using reactive magnetron sputtering with segmented targets. The stoichiometry x was tuned with two deposition parameters, i.e., substrate temperature and nitrogen flow ratio fN, their effect on microstructure and mechanical, electric, and electrochemical properties were investigated.Understoichiometric MeNx (Me = TiNbZrTa, 0.25 ≤ x ≤ 0.59) films were synthesized at a constant fN when substrate temperature was varied from room temperature (RT) to 700 °C. For low-temperature deposition, the coatings exhibited fcc solid-solution polycrystalline structures. A NaCl-type structure with (001) preferred orientation was observed in MeN0.46 coating deposited at 400 ºC, while an hcp structure was found for the coatings deposited above 500 ºC. The maximum hardness value of 26 GPa as well as the highest and values (0.12 and 0.34 GPa) were obtained for the MeN0.46 coating. These films exhibited low RT electrical resistivities. In 0.1 M H2SO4 aqueous solution, the most corrosion resistant film was MeN0.46 featured dense structure and low roughness.The MeNx films (x=0, 0.57 < x ≤ 0.83) were deposited with different fN. The maximum hardness was achieved at 22.1 GPa for MeN0.83 film. Their resistivities increased from 95 to 424 μΩcm with increasing nitrogen content. The corrosion resistance is related to the amount of nitrogen in the films. The corrosion current density was around 10-8 A/cm2, while the films with lower nitrogen contents (x < 0.60) exhibited a nearly stable current plateau up to 4.0 V, similar to the metallic films, while the films with a higher nitrogen content only featured a plateau up to 2.0 V, above which a higher nitrogen content resulted in higher currents. The reason was that the oxidation of these films at potentials above about 2.0 V vs. Ag/AgCl resulted in the formation of porous oxide layers as significant fraction of the generated N2 was lost to the electrolyte.Hence, these observed effects of deposition temperature and nitrogen content on the overall properties of nonstoichiometric MeNx films provide insights regarding protective multicomponent nitride films, e.g. as corrosion resistant coatings on metallic bipolar plates in fuel cells or batteries.
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| 8. |
- Shu, Rui, 1990-
(författare)
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Refractory High-entropy Alloy and Nitride Thin Films
- 2022
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis focuses on understanding the process-structure-property relation-ships for several refractory-metal-based high-entropy alloys and nitrides synthesized by magnetron sputtering. The thesis begins with the growth of TiZrNbTaNx understoichiometric nitrides by controlling substrate temperature and nitrogen flow ratio fN. Their effects on microstructure and mechanical, electric, and electrochemical properties were investigated. TiZrNbTaN0.46 deposited at 400 ºC shows a NaCl-type structure with (001) preferred orientation and exhibits the highest corrosion resistance in 0.1 M H2SO4 aqueous solution. A stable passive region up to 3.0 V vs. Ag/AgCl could be achieved when x< 0.64. The densification effects were explored by ion energy for (TiZrTaMe)N1–x (Me = Hf, Nb, Mo, or Cr) films and by high-power impulse magnetron sputtering technique for TiNbCrAl films.The local chemical distortions in the TiZrTaNb-based system with different nitrogen content were investigated by X-ray absorption fine structure spectros-copy. The influence of crystallinity on superconducting transition behavior was studied in (TiZrHf)x(TaNb)1-x, (TiZrNbTa)1-xWx, and (TiZrNbTa)1-xVx systems. The highest superconducting transition temperature (Tc) reaches 8.05 K for the TiZrNbTa film (x=0). The superconducting transition temperature Tc of these films deposited at the fixed temperature decreases monotonically as a function of x, and Tc can be increased by elevating the deposition temperature. Furthermore, the structural stability and elemental segregation under Xe-ion irradiation of TiZrNbTaV-based HEA and HEN films, and high-entropy TiZrN-bTa/CrFeCoNi metallic and nitride multilayer coatings were investigated. The microstructure of TiZrNbTaVN film remain stable after irradiation at room temperature and 500 °C. The as-deposited TiZrNbTaV film exhibited an amorphous structure and became a bcc phase structure after irradiation at 500 °C. Thermal-induced and irradiation-induced grain growth resulted in a grain-size distribution. For the multilayer coatings, the microstructure of metallic multilayers was not stable and the interdiffusion or mixing of the constituent elements is prominent under ion irradiation and/or heat treatment. no diffusion and phase trans-formation were observed for the nitride multilayers after irradiation at 500 °C.
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| 9. |
- Shu, Rui, 1990-, et al.
(författare)
-
Stoichiometry Effects on the Chemical Ordering and Superconducting Properties in TiZrTaNbNx Refractory High Entropy Nitrides
- 2023
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Ingår i: Annalen der Physik. - : Wiley-VCH Verlagsgesellschaft. - 0003-3804 .- 1521-3889.
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Tidskriftsartikel (refereegranskat)abstract
- High-entropy materials, an exciting new class of structural materials involvingfive or more elements, are emerging as unexplored ground forsuperconductors. Here, the effects of nitrogen stoichiometry are investigatedon local chemical structure of TiZrNbTa-based thin films by variousX-ray-based techniques. Lattice distortion and short-range order of a set ofTiZrNbTaNxsamples, including bond lengths of different atomic pairs andcoordination numbers of substituting atoms are quantitatively studied. Themaximum superconducting transition temperature Tcis found at 10 K for anear-stoichiometric (TiZrNbTa)N1.08film, which is>8 K measured for ametallic TiZrNbTa film. The underlying electronic structure and chemicalbonding in these high entropy nitrides thus influence the superconductingmacroscopic properties.
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