{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,6]],"date-time":"2026-06-06T06:31:02Z","timestamp":1780727462119,"version":"3.54.1"},"reference-count":44,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2025,8,5]],"date-time":"2025-08-05T00:00:00Z","timestamp":1754352000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Science and Technology Council, Taiwan","award":["111-2221-E-019-064"],"award-info":[{"award-number":["111-2221-E-019-064"]}]},{"name":"National Science and Technology Council, Taiwan","award":["112-2221-E-019-014-MY3"],"award-info":[{"award-number":["112-2221-E-019-014-MY3"]}]},{"name":"National Science and Technology Council, Taiwan","award":["113-2224-E-131-001"],"award-info":[{"award-number":["113-2224-E-131-001"]}]},{"name":"National Taiwan Ocean University","award":["111-2221-E-019-064"],"award-info":[{"award-number":["111-2221-E-019-064"]}]},{"name":"National Taiwan Ocean University","award":["112-2221-E-019-014-MY3"],"award-info":[{"award-number":["112-2221-E-019-014-MY3"]}]},{"name":"National Taiwan Ocean University","award":["113-2224-E-131-001"],"award-info":[{"award-number":["113-2224-E-131-001"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>Mixing enthalpy (\u0394Hmix), mixing entropy (\u0394Smix), atomic-size difference (\u03b4), and valence electron concentration (VEC) are the indicators determining the phase structures of multi-principal element alloys. Exploring the relationships between the structures and properties of multi-principal element films is a fundamental study. TiZrHf films with a \u0394Hmix of 0.00 kJ\/mol, \u0394Smix of 9.11 J\/mol\u00b7K (1.10R), \u03b4 of 3.79%, and VEC of 4.00 formed a hexagonal close-packed (HCP) solid solution. Exploring the characterization of TiZrHf films after solving Ta, Y, and Cr atoms with distinct atomic radii is crucial for realizing multi-principal element alloys. This study fabricated TiZrHf, TiZrHfTa, TiZrHfY, and TiZrHfCr films through co-sputtering. The results indicated that TiZrHfTa films formed a single body-centered cubic (BCC) solid solution. In contrast, TiZrHfY films formed a single HCP solid solution, and TiZrHfCr films formed a nanocrystalline BCC solid solution. The crystallization of TiZrHf(Ta, Y, Cr) films and the four indicators mentioned above for multi-principal element alloy structures were correlated. The mechanical properties and thermal stability of the TiZrHf(Ta, Y, Cr) films were investigated.<\/jats:p>","DOI":"10.3390\/ma18153672","type":"journal-article","created":{"date-parts":[[2025,8,5]],"date-time":"2025-08-05T08:46:55Z","timestamp":1754383615000},"page":"3672","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Structural Evolution, Mechanical Properties, and Thermal Stability of Multi-Principal TiZrHf(Ta, Y, Cr) Alloy Films"],"prefix":"10.3390","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0689-5709","authenticated-orcid":false,"given":"Yung-I","family":"Chen","sequence":"first","affiliation":[{"name":"Department of Optoelectronics and Materials Technology, National Taiwan Ocean University, Keelung 202301, Taiwan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tzu-Yu","family":"Ou","sequence":"additional","affiliation":[{"name":"Department of Optoelectronics and Materials Technology, National Taiwan Ocean University, Keelung 202301, Taiwan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2977-4416","authenticated-orcid":false,"given":"Li-Chun","family":"Chang","sequence":"additional","affiliation":[{"name":"Department of Materials Engineering, Ming Chi University of Technology, New Taipei 243303, Taiwan"},{"name":"Center for Plasma and Thin Film Technologies, Ming Chi University of Technology, New Taipei 243303, Taiwan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yan-Zhi","family":"Liao","sequence":"additional","affiliation":[{"name":"Department of Optoelectronics and Materials Technology, National Taiwan Ocean University, Keelung 202301, Taiwan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2025,8,5]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"299","DOI":"10.1002\/adem.200300567","article-title":"Nanostructured high-entropy alloys with multiple principal elements: Novel alloy design concepts and outcomes","volume":"6","author":"Yeh","year":"2004","journal-title":"Adv. Eng. Mater."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"1153","DOI":"10.1126\/science.1254581","article-title":"A fracture-resistant high-entropy alloy for cryogenic applications","volume":"345","author":"Gludovatz","year":"2014","journal-title":"Science"},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"Sahlberg, M., Karlsson, D., Zlotea, C., and Jansson, U. (2016). Superior hydrogen storage in high entropy alloys. Sci. Rep., 6.","DOI":"10.1038\/srep36770"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"107","DOI":"10.1016\/j.actamat.2020.08.029","article-title":"Thermodynamic route for self-forming 1.5 nm V-Nb-Mo-Ta-W high-entropy alloy barrier layer: Roles of enthalpy and mixing entropy","volume":"199","author":"Hsiao","year":"2020","journal-title":"Acta Mater."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"170166","DOI":"10.1016\/j.jallcom.2023.170166","article-title":"A new design rule for high entropy alloy diffusion barriers in Cu metallization","volume":"953","author":"Gruber","year":"2023","journal-title":"J. Alloys Compd."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"794","DOI":"10.1007\/s11837-021-05107-w","article-title":"Structure and properties of high-entropy amorphous thin films: A review","volume":"74","author":"Zhang","year":"2022","journal-title":"JOM"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"65","DOI":"10.1016\/j.scriptamat.2016.10.028","article-title":"Novel TiNbTaZrMo high-entropy alloys for metallic biomaterials","volume":"129","author":"Todai","year":"2017","journal-title":"Scr. Mater."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"110959","DOI":"10.1016\/j.msec.2020.110959","article-title":"Design of high-ductile medium entropy alloys for dental implants","volume":"113","author":"Wang","year":"2020","journal-title":"Mater. Sci. Eng. C"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"534","DOI":"10.1002\/adem.200700240","article-title":"Solid-solution phase formation rules for multi-component alloys","volume":"10","author":"Zhang","year":"2008","journal-title":"Adv. Eng. Mater."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"103505","DOI":"10.1063\/1.3587228","article-title":"Effect of valence electron concentration on stability of fcc or bcc phase in high entropy alloys","volume":"109","author":"Guo","year":"2011","journal-title":"J. Appl. Phys."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"225","DOI":"10.1080\/21663831.2019.1584592","article-title":"Formation, structure and properties of biocompatible TiZrHfNbTa high-entropy alloys","volume":"7","author":"Yuan","year":"2019","journal-title":"Mater. Res. Lett."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"164849","DOI":"10.1016\/j.jallcom.2022.164849","article-title":"Phase stability of Ti-containing high-entropy alloys with a bcc or hcp structure","volume":"911","author":"Yanao","year":"2022","journal-title":"J. Alloys Compd."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Chen, Y.I., Chen, Y.J., Lai, C.Y., and Chang, L.C. (2022). Mechanical and Anticorrosive Properties of TiNbTa and TiNbTaZr Films on Ti-6Al-4V Alloy. Coatings, 12.","DOI":"10.3390\/coatings12121985"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"4475","DOI":"10.1016\/j.actamat.2007.04.024","article-title":"Theory-guided bottom-up design of \u03b2-titanium alloys as biomaterials based on first principles calculations: Theory and experiments","volume":"55","author":"Raabe","year":"2007","journal-title":"Acta Mater."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"574","DOI":"10.1016\/j.msec.2015.12.071","article-title":"Biocompatibility of new Ti\u2013Nb\u2013Ta base alloys","volume":"61","author":"Hussein","year":"2016","journal-title":"Mater. Sci. Eng. C"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1700645","DOI":"10.1002\/adem.201700645","article-title":"High-entropy alloys: Potential candidates for high-temperature applications\u2013an overview","volume":"20","author":"Praveen","year":"2018","journal-title":"Adv. Eng. Mater."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"96","DOI":"10.1016\/j.intermet.2013.05.002","article-title":"More than entropy in high-entropy alloys: Forming solid solutions or amorphous phase","volume":"41","author":"Guo","year":"2013","journal-title":"Intermetallics"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"2183","DOI":"10.1016\/S0025-5408(01)00715-2","article-title":"Effect of the atomic size distribution on glass forming ability of amorphous metallic alloys","volume":"36","author":"Senkov","year":"2001","journal-title":"Mater. Res. Bull."},{"key":"ref_19","unstructured":"Cullity, B.D., and Stock, S.R. (2001). Elements of X-Ray Diffraction, Prentice Hall. [3rd ed.]."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1564","DOI":"10.1557\/JMR.1992.1564","article-title":"An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments","volume":"7","author":"Oliver","year":"1992","journal-title":"J. Mater. Res."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1858","DOI":"10.1016\/j.tsf.2008.07.014","article-title":"Celebrating the 100th anniversary of the Stoney equation for film stress: Developments from polycrystalline steel strips to single crystal silicon wafers","volume":"517","author":"Janssen","year":"2009","journal-title":"Thin Solid Films"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"305","DOI":"10.1016\/j.pnsc.2014.06.001","article-title":"Solid solution or amorphous phase formation in TiZr-based ternary to quinternary multi-principal-element films","volume":"24","author":"Braic","year":"2014","journal-title":"Prog. Nat. Sci."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"14257","DOI":"10.1016\/j.ceramint.2016.06.055","article-title":"Structural, electro-optical, and mechanical properties of reactively sputtered (TiZrHf)N coatings","volume":"42","author":"Tsai","year":"2016","journal-title":"Ceram. Int."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"56","DOI":"10.1016\/j.nimb.2019.07.010","article-title":"Effect of Zr content on structure and mechanical properties of (CrTaNbMoV)Zrx films","volume":"457","author":"Feng","year":"2019","journal-title":"Nucl. Instrum. Methods Phys. Res. Sect. B-Beam Interact. Mater. At."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"130410","DOI":"10.1016\/j.surfcoat.2024.130410","article-title":"Effects of nitrogen flow ratio on the mechanical and anticorrosive properties of cosputtered (TiZrHfTa)Nx films","volume":"477","author":"Ou","year":"2024","journal-title":"Surf. Coat. Technol."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"130815","DOI":"10.1016\/j.surfcoat.2024.130815","article-title":"Characterization of cosputtered (TiZrHfY)Nx films","volume":"483","author":"Ou","year":"2024","journal-title":"Surf. Coatings Technol."},{"key":"ref_27","first-page":"111123","article-title":"Novel Ti\u2013Zr\u2013Hf\u2013Nb\u2013Fe refractory high-entropy alloys for potential biomedical applications","volume":"223","author":"Wang","year":"2022","journal-title":"Mater. Des."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"106845","DOI":"10.1016\/j.intermet.2020.106845","article-title":"Bio-corrosion behavior and in vitro biocompatibility of equimolar TiZrHfNbTa high-entropy alloy","volume":"124","author":"Yang","year":"2020","journal-title":"Intermetallics"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"63","DOI":"10.1016\/j.elecom.2018.11.009","article-title":"Corrosion behavior of Hf0.5Nb0.5Ta0.5T1.5Zr refractory high-entropy alloy in aqueous chloride solutions","volume":"98","author":"Zhou","year":"2019","journal-title":"Electrochem. Commun."},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Wang, X., Hu, T., Ma, T., Yang, X., Zhu, D., Dong, D., Xiao, J., and Yang, X. (2022). Mechanical, corrosion, and wear properties of TiZrTaNbSn biomedical high-entropy alloys. Coatings, 12.","DOI":"10.3390\/coatings12121795"},{"key":"ref_31","doi-asserted-by":"crossref","unstructured":"Wei, Z., Attarilar, S., Ebrahimi, M., and Li, J. (2024). Corrosion and wear behavior of additively manufactured metallic parts in biomedical applications. Metals, 14.","DOI":"10.3390\/met14010096"},{"key":"ref_32","first-page":"112898","article-title":"Effect of in-situ formed oxide and carbide phases on microstructure, thermal stability, hardness, and corrosion behavior of Zr\/Y-doped CoCrFeNi high-entropy alloys","volume":"218","author":"Zhang","year":"2023","journal-title":"Corros. Sci."},{"key":"ref_33","doi-asserted-by":"crossref","unstructured":"Liu, Y., Xiang, D., Wang, K., and Yu, T. (2022). Corrosion of laser cladding high-entropy alloy coatings: A review. Coatings, 12.","DOI":"10.3390\/coatings12111669"},{"key":"ref_34","first-page":"134","article-title":"Evolution in microstructure and corrosion behavior of AlCoCrxFeNi high-entropy alloy coatings prepared by laser cladding","volume":"133","author":"Chen","year":"2018","journal-title":"Corros. Sci."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"79","DOI":"10.1016\/j.intermet.2018.04.023","article-title":"Phase stability of a ductile single-phase BCC Hf0.5Nb0.5Ta0.5Ti1.5Zr refractory high-entropy alloy","volume":"98","author":"Yao","year":"2018","journal-title":"Intermetallics"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"50","DOI":"10.1016\/j.scriptamat.2018.08.032","article-title":"Phase transformations of HfNbTaTiZr high-entropy alloy at intermediate temperatures","volume":"158","author":"Chen","year":"2019","journal-title":"Scr. Mater."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"2403632","DOI":"10.1002\/adma.202403632","article-title":"Accelerated discovery of (TiZrHf )x(NbTa)1\u2212x high-entropy alloys with superior thermal stability and a new crystallization mechanism","volume":"36","author":"Cheng","year":"2024","journal-title":"Adv. Mater."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"666","DOI":"10.1116\/1.1312732","article-title":"Influence of apparatus geometry and deposition conditions on the structure and topography of thick sputtered coatings","volume":"11","author":"Thornton","year":"1974","journal-title":"J. Vac. Sci. Technol."},{"key":"ref_39","doi-asserted-by":"crossref","unstructured":"Barin, I. (1995). Thermochemical Data of Pure Substances, VCH. [3rd ed.].","DOI":"10.1002\/9783527619825"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"2539","DOI":"10.1111\/j.1151-2916.1994.tb04641.x","article-title":"Hardness\u2013Grain-Size Relations in Ceramics","volume":"77","author":"Rice","year":"1994","journal-title":"J. Am. Ceram. Soc."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"636","DOI":"10.1016\/j.surfcoat.2018.03.092","article-title":"Effects of post-deposition annealing on the chemical composition, microstructure, optical and mechanical properties of Y2O3 film","volume":"344","author":"Xu","year":"2018","journal-title":"Surf. Coat. Technol."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"37","DOI":"10.1016\/S0040-6090(00)01381-X","article-title":"Influence of process parameters on the structure and the properties of ZrO2 coatings deposited by reactive pulsed magnetron sputtering (PMS)","volume":"377\u2013378","author":"Goedicke","year":"2000","journal-title":"Thin Solid Films"},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"303","DOI":"10.1016\/S0257-8972(99)00501-0","article-title":"Properties of zirconium oxide thin films deposited by pulsed reactive magnetron sputtering","volume":"120\u2013121","author":"Koski","year":"1999","journal-title":"Surf. Coat. Technol."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"125821","DOI":"10.1016\/j.surfcoat.2020.125821","article-title":"Influence of substrate bias voltage on structure, mechanical and corrosion properties of ZrO2 thin films deposited by reactive magnetron sputter deposition","volume":"393","author":"Zegtoul","year":"2020","journal-title":"Surf. Coat. Technol."}],"container-title":["Materials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1996-1944\/18\/15\/3672\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T18:23:18Z","timestamp":1760034198000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1996-1944\/18\/15\/3672"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,8,5]]},"references-count":44,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2025,8]]}},"alternative-id":["ma18153672"],"URL":"https:\/\/doi.org\/10.3390\/ma18153672","relation":{},"ISSN":["1996-1944"],"issn-type":[{"value":"1996-1944","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,8,5]]}}}