High-entropy alloy inspired development of compositionally complex superhard (Hf,Ta,Ti,V,Zr)-B-N coatings
In: Materials and design, Band 218, S. 110695
ISSN: 1873-4197
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In: Materials and design, Band 218, S. 110695
ISSN: 1873-4197
We report on the oxidation behaviour of V2AlC coatings up to 800 degrees C, in air. The coatings were deposited at 580 degrees C using magnetron sputtering from a powder metallurgical composite V2AlC target and were subsequently oxidised for 5, 15 and 30 min. The microstructural evolution of the samples was investigated, and X-ray diffraction patterns were collected to track the formation of oxides. The first indications of oxidation appear after just 15 min at 500 degrees C, as V-based oxides grew on the surface of the coatings. Later, the presence of mostly V-based oxides and ternary (V, Al)-oxides was observed starting after 5 min at 600 degrees C. Further analyses confirmed outward diffusion of V and inward diffusion of O, while Al tends to sublimate. alpha-A12O3 was only indexed after 5 min at 800 degrees C. Ex-situ electrical resistivity measurements allowed tracking the oxidation progress of the V2AlC coating. ; Funding Agencies|Euratom research and training programme 2014-2018 [740415]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Foundation Olle Engkvist Byggmastare [184-561]; Swedish research council, VR-RFISwedish Research Council [821-2012-5144, 2017-00646_9]; Swedish Foundation for Strategic Research (SSF)Swedish Foundation for Strategic Research [RIF14-0053]; Swedish Research Council VR Grant [2018-03957]; Swedish Research Council VINNOVA grant [2019-04882]; International Union for Vacuum Science, Technique and Applications through the Medard W. Welch International Scholarship 2019
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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 °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 ∼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 ∼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. ; Funding Agencies|VINNOVA Competence Centre FunMat-II [2016-05156]; VINNOVA research infrastructure grantVinnova [2020-00825]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; M-ERA.net [2013-02355]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [2020.0196]; Electron Microscopy Laboratory at Linkoping University; Swedish Research CouncilSwedish Research CouncilEuropean Commission [VR 2018-04139]; VR-RFI [2017-00646_9]; Swedish Foundation for Strategic Research (SSF)Swedish Foundation for Strategic Research [RIF14-0053]
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Boron-containing materials exhibit a unique combination of ceramic and metallic properties that are sensitively dependent on their given chemical bonding and elemental compositions. However, determining the composition, let alone bonding, with sufficient accuracy is cumbersome with respect to boron, being a light element that bonds in various coordinations. Here, we report on the comprehensive compositional analysis of transition-metal diboride (TMBx) thin films (TM = Ti, Zr, and Hf) by energy-dispersive x-ray spectroscopy (EDX), x-ray photoelectron spectroscopy (XPS), time-of-flight elastic recoil detection analysis (ToF-ERDA), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA). The films are grown on Si and C substrates by dc magnetron sputtering from stoichiometric TMB2 targets and have hexagonal AlB2-type columnar structures. EDX considerably overestimates B/TM ratios, x, compared to the other techniques, particularly for ZrBx. The B concentrations obtained by XPS strongly depend on the energy of Ar+ ions used for removing surface oxides and contaminants prior to analyses and are more reliable for 0.5 keV Ar+. ToF-ERDA, RBS, and NRA yield consistent compositions in TiBx. They also prove TiBx and ZrBx films to be homogeneous with comparable B/TM ratios for each film. However, ToF-ERDA, employing a 36-MeV 127I8+ beam, exhibits challenges in depth resolution and quantification of HfBx due to plural and multiple scattering and associated energy loss straggling effects. Compared to ToF-ERDA, RBS (for the film grown on C substrates) and NRA provide more reliable B/Hf ratios. Overall, a combination of methods is recommended for accurately pinpointing the compositions of borides that contain heavy transition metals. ; Funding agencies: The SwedishResearch Council VR (Grant Nos. 2021-00357, 2018-03957, and642-2013-8020); the Knut and Alice Wallenberg (KAW) Foundation for project funding (No. KAW 2015.0043), the Swedish Energy Agency under Project No. 51201-1, Carl Tryggers Stiftelse (Contract Nos. CTS 15:219, CTS 20:150, and CTS 14:431); the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO Mat LiU No. 2009 00971), the Swedish Research Council VRRFI (No. 2017-00646_9) for supporting the Accelerator based ion technology center; the Swedish Foundation for StrategicResearch (Contract No. RIF14-0053)
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Magnetron sputter deposition of TiBx thin films from a TiB2 target typically results in highly overstoichiometric films due to differences in sputtered-atom ejection angles and gas-phase scattering during transport to the substrate. This study investigates the effects of the magnetron magnetic field strength at the substrate position and the Ar sputtering pressure on the resulting film composition and crystalline quality. It is shown that the B/Ti atomic ratio can be reduced from 2.7 to 2.1 by increasing the Ar pressure from 5 mTorr to 20 mTorr, a trend consistent with previous work. Despite the use of a relatively high Ar pressure, a change to a stronger outer magnetic pole leads to, dense TiB2.1 films of high crystal quality, as shown by X-ray diffraction, scanning transmission electron microscopy, and specific resistivity of 32 mu Omega cm. For epitaxial films deposited at 900 degrees C on Al2O3(001), a TiB2[110]//Al2O3[100] orientational relationship were obtained. ; Funding Agencies|Knut and Alice Wallenberg (KAW) FoundationKnut & Alice Wallenberg Foundation [KAW 2015.0043]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Link_oping University [2009 00971]; VR-RFI (Vetenskapsradet) [821-2012-5144]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [SSF, RIF14-0053]
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In: Materials and design, Band 224, S. 111323
ISSN: 1873-4197
Multicomponent TixNbCrAl nitride films were deposited on Si(100) substrates by reactive direct current magnetron sputtering (dcMS) and high power impulse magnetron sputtering (HiPIMS) in the absence of substrate heating and bias. Three single Ti, Nb, and Cr50Al50 targets were either driven by three de or three HiPIMS power supplies. The Ti content in the films was varied by tuning the power applied to the Ti target. The composition was determined by ion beam analysis. The nitrogen content is nearly stoichiometric (48-50 at.%) in the HiPIMS series, while the dcMS are understoichiometric (39-45 at.%). The crystal structure, stress and density of the studied film were investigated by X-ray techniques and the microstructure was examined by scanning electron microscopy. All the Ti-containing films for both series exhibit an fcc NaCl-type phase structure. In particular, the dcMS series shows a (111) preferred orientation, resulting in a faceted surface morphology compared to a dense and smooth microstructure of the HiPIMS films. The compressive stress of the HiPIMS series (> 2.0 GPa) is significantly larger than the values of the dcMS series (<0.5 GPa). Nanoindentation measurements show a maximum hardness of 29.9 GPa and Youngs modulus of 304 GPa were obtained in the HiPIMS series. The results may promote HiPIMS techniques for the synthesis of complex multicomponent films for the application aspect to protective and hard coatings. ; Funding Agencies|VINNOVA Competence Centre FunMat-II [2016-05156]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; M - ERA. net (project MC2) [2013-02355]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [2020.0196, KAW 2015.0043]; Electron Microscopy Laboratory at Linkoping University; Swedish Research CouncilSwedish Research CouncilEuropean Commission [VR 2018-04139]; Swedish Research Council VR-RFISwedish Research Council [2019-00191]; Swedish Foundation for Strategic ResearchSwedish Foundation for Strategic Research [RIF14-0053]; National Natural Science Foundation of ChinaNational Natural Science Foundation of China (NSFC) [51805102]; Guizhou Provincial Natural Science Foundation [[2020]1Y228]; China Scholarship Council (CSC)China Scholarship Council
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In: Materials and design, Band 142, S. 203-211
ISSN: 1873-4197
Direct growth of orthorhombic Ta3N5-type Ta-O-N compound thin films, specifically Ta3-xN5-yOy, on Si and sapphire substrates with various atomic fractions is realized by unbalanced magnetron sputtering. Low-degree fiber-textural Ta3-xN5-yOy films were grown through reactive sputtering of Ta in a gas mixture of N-2, Ar, and O-2 with keeping a partial pressure ratio of 3:2:0.1 in a total working pressure range of 5-30 mTorr. With increasing total pressure from 5 to 30 mTorr, the atomic fraction of O in the as-grown Ta3-xN5-yOy films was found to increase from 0.02 to 0.15 while that of N and Ta decrease from 0.66 to 0.54 and 0.33 to 0.31, respectively, leading to a decrease in b lattice constant up to around 1.3%. Metallic TaNx phases were formed without oxygen. For a working pressure of 40 mTorr, an amorphous, O-rich Ta-N-O compound film with a high O fraction of similar to 0.48, was formed, mixed with non-stoichiometric TaON and Ta2O5. By analyzing the plasma discharge, the increasing O incorporation is associated with oxide formation on top of the Ta target due to a higher reactivity of Ta with O than with N. The increase of O incorporation in the films also leads to a optical bandgap widening from similar to 2.22 to similar to 2.96 eV, which is in agreement with the compositional and structural changes from a crystalline Ta3-xN5-yOy to an amorphous O-rich Ta-O-N compound. ; Funding Agencies|Vetenskapseddet [2018-04198]; Energimyndigheten [46658-1]; Stiftelsen 011e Engkvist Byggmastare [197-0210]; Linkoping University Library; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]; VR-RFI [821-2012-5144, 2017-00646_9]; Swedish Foundation for Strategic Research (SSF)Swedish Foundation for Strategic Research [RIF14-0053, 5E13-0333]
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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). ; Funding agencies: VINNOVA Competence Centre FunMat-II (grant no. 2016-05156), The Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU No. 2009 00971), M – ERA.net (project MC2 grant no. 2013-02355), The Knut and Alice Wallenberg Foundation through the Wallenberg Academy Fellows program (P.E.) and the Electron Microscopy Laboratory at Linköping University, The Swedish Research Council VR Grant 2018-03957, The VINNOVA Grant 2018-04290, The Åforsk Foundation Grant 16-359, Carl Tryggers Stiftelse contract CTS 17:166, VR-RFI (contracts #821-2012-5144 & #2017-00646_9), The Swedish Foundation for Strategic Research (SSF, contract RIF14-0053)
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