Tuning Local Chemical Order and Multiple Properties in High-Entropy Films via Interstitial Filling with Non-Metallic Small Atoms: A Percolation- Theory-Based Perspective
Received date: 2025-11-24
Revised date: 2025-12-23
Online published: 2026-02-12
Supported by
Sino-Russian Cooperative Research Project Funded by the National Natural Science Foundation of China(W2412042);Fundamental Research Funds for the Central Universities(DUT24LAB116)
Interstitial filling with non-metallic small atoms (SAs) provides a crucial pathway for tuning the structure and properties of high-entropy films. Owing to their small atomic size, SAs preferentially occupy interstitial sites and, through their distinct chemical interactions with constituent metallic elements, induce changes in local chemical order (LCO). With increasing SAs content, high-entropy films exhibit a progressive transition from disordered interstitial solid solutions to locally ordered states, and eventually to ordered crystalline or amorphous structures, accompanied by pronounced property variations. Accordingly, this review focuses on high-entropy films and systematically summarizes the effects of SAs filling on crystal structure, LCO, and mechanical, magnetic, and electrical properties. A percolation-theory framework is introduced, in which different LCO types are treated as percolating units with characteristic properties, thereby establishing intrinsic correlations between LCO content and macroscopic property evolution. On this basis, the commonalities and distinctions among different SAs in regulating material properties are summarized and compared. Finally, an outlook on future research directions is provided.
LI Xiaona , WANG Xiao , WANG Dazhe , ZHENG Yuehong , DONG Chuang , P. K. LIAW . Tuning Local Chemical Order and Multiple Properties in High-Entropy Films via Interstitial Filling with Non-Metallic Small Atoms: A Percolation- Theory-Based Perspective[J]. Acta Metall Sin, 2026 , 62(6) : 993 -1008 . DOI: 10.11900/0412.1961.2025.00387
| [1] | Gao T C, Gao J B, Yang S L, et al. Data-driven design of novel lightweight refractory high-entropy alloys with superb hardness and corrosion resistance[J]. npj Comput. Mater., 2024, 10: 256 |
| [2] | Li S, Hou X T, Wang X X, et al. Weldability of high entropy alloys: Microstructure, mechanical property, and corrosion resistance[J]. J. Manuf. Processes, 2023, 99: 209 |
| [3] | Zhu C H, Xu L J, Liu M J, et al. A review on improving mechanical properties of high entropy alloy: Interstitial atom doping[J]. J. Mater. Res. Technol., 2023, 24: 7832 |
| [4] | Yu Q, Qiu S, Jiao Z B. Atomic-scale understanding of interstitial-strengthened high-entropy alloys[J]. Rare Met., 2025, 44: 6002 |
| [5] | Yang Z, Xiang X L, Yang J, et al. High-entropy oxides as energy materials: From complexity to rational design[J]. Mater. Futures, 2024, 3: 042103 |
| [6] | Salian A, Mandal S. Review on the deposition, structure and properties of high entropy oxide films: Current and future perspectives[J]. Bull. Mater. Sci., 2022, 45: 49 |
| [7] | Sharma Y, Mazza A R, Musico B L, et al. Magnetic texture in insulating single crystal high entropy oxide spinel films[J]. ACS Appl. Mater. Interfaces, 2021, 13: 17971 |
| [8] | Sharma Y, Zheng Q, Mazza A R, et al. Magnetic anisotropy in single-crystal high-entropy perovskite oxide La(Cr0.2 Mn0.2Fe0.2Co0.2Ni0.2)O3 films[J]. Phys. Rev. Mater., 2020, 4: 014404 |
| [9] | Inoue A, Shibata T, Zhang T. Effect of additional elements on glass transition behavior and glass formation tendency of Zr-Al-Cu-Ni alloys[J]. Mater. Trans., JIM, 1995, 36: 1420 |
| [10] | An Z B, Yang T, Shi C J, et al. Negative enthalpy alloys and local chemical ordering: A concept and route leading to synergy of strength and ductility[J]. Natl. Sci. Rev., 2024, 11: nwae026 |
| [11] | Wu X L. Chemical short-range orders in high-/medium-entropy alloys[J]. J. Mater. Sci. Technol., 2023, 147: 189 |
| [12] | Chen X F, Wang Q, Cheng Z Y, et al. Direct observation of chemical short-range order in a medium-entropy alloy[J]. Nature, 2021, 592: 712 |
| [13] | Wang J, Jiang P, Yuan F P, et al. Chemical medium-range order in a medium-entropy alloy[J]. Nat. Commun., 2022, 13: 1021 |
| [14] | Dasari S, Jagetia A, Sharma A, et al. Tuning the degree of chemical ordering in the solid solution of a complex concentrated alloy and its impact on mechanical properties[J]. Acta Mater., 2021, 212: 116938 |
| [15] | Ding Q Q, Zhang Y, Chen X, et al. Tuning element distribution, structure and properties by composition in high-entropy alloys[J]. Nature, 2019, 574: 223 |
| [16] | Ying H Q, Liu S N, Wu Z D, et al. Phase selection rule of high-entropy metallic glasses with different short-to-medium-range orders[J]. Rare Met., 2022, 41: 2021 |
| [17] | Bonfanti S, Guerra R, Alvarez-Donado R, et al. Quasilocalized modes in crystalline and partially crystalline high-entropy alloys[J]. Phys. Rev. Res., 2024, 6: 013146 |
| [18] | Yang Q, Yang X M, Zhang T, et al. Structure and entropy control of polyamorphous transition in high-entropy metallic glasses[J]. Acta Mater., 2024, 266: 119701 |
| [19] | Luan H W, Zhang X, Ding H Y, et al. High-entropy induced a glass-to-glass transition in a metallic glass[J]. Nat. Commun., 2022, 13: 2183 |
| [20] | Islam M, Young Kim J, Yoo G H, et al. In-depth analysis of structural heterogeneity in high entropy bulk metallic glasses using 4D-STEM[J]. Microsc. Microanal., 2024, 30: ozae044.668 |
| [21] | Zhang X, Luan H, Lou H, et al. Highly variable chemical short-range order in a high-entropy metallic glass[J]. Mater. Today Phys., 2022, 27: 100799 |
| [22] | Luo S F, Khong J C, Huang S, et al. Revealing in situ stress-induced short- and medium-range atomic structure evolution in a multicomponent metallic glassy alloy[J]. Acta Mater., 2024, 272: 119917 |
| [23] | Takeuchi A, Inoue A. Classification of bulk metallic glasses by atomic size difference, heat of mixing and period of constituent elements and its application to characterization of the main alloying element[J]. Mater. Trans., 2005, 46: 2817 |
| [24] | Allred A L. Electronegativity values from thermochemical data[J]. J. Inorg. Nucl. Chem., 1961, 17: 215 |
| [25] | Wang Y H, Jiao M Y, Wu Y, et al. Enhancing properties of high-entropy alloys via manipulation of local chemical ordering[J]. J. Mater. Sci. Technol., 2024, 180: 23 |
| [26] | He Z F, Guo Y X, Sun L F, et al. Interstitial-driven local chemical order enables ultrastrong face-centered cubic multicomponent alloys[J]. Acta Mater., 2023, 243: 118495 |
| [27] | Lei Z F, Liu X J, Wu Y, et al. Enhanced strength and ductility in a high-entropy alloy via ordered oxygen complexes[J]. Nature, 2018, 563: 546 |
| [28] | Zhao D D, Yang Q, Wang D W, et al. Ordered nitrogen complexes overcoming strength-ductility trade-off in an additively manufactured high-entropy alloy[J]. Virtual Phys. Prototyping, 2020, 15: 532 |
| [29] | Jiao M Y, Lei Z F, Wu Y, et al. Manipulating the ordered oxygen complexes to achieve high strength and ductility in medium-entropy alloys[J]. Nat. Commun., 2023, 14: 806 |
| [30] | Wang Q, Wang Z H, Zhang Q X, et al. Achieving high damping capacity in oxygen-enhanced BCC Zr-Hf-Ti-Nb multi-principal-element alloys with low Young's modulus[J]. Adv. Sci., 2025, 12: 2501068 |
| [31] | Shi L X, Shao Y, Fan Z Y, et al. Connecting the composition, structure, and magnetic property in high-entropy metallic glasses[J]. Acta Mater., 2023, 254: 118983 |
| [32] | Wu Y, Cao D, Yao Y L, et al. Substantially enhanced plasticity of bulk metallic glasses by densifying local atomic packing[J]. Nat. Commun., 2021, 12: 6582 |
| [33] | Zallen R. The Physics of Amorphous Solids[M]. New York: John Wiley & Sons, Inc, 1998: 135 |
| [34] | Stauffer D, Aharony A. Introduction to Percolation Theory[M]. 2nd Ed., London: Taylor & Francis, 2003: 15 |
| [35] | Scher H, Zallen R. Critical density in percolation processes[J]. J. Chem. Phys., 1970, 53: 3759 |
| [36] | Rost C M, Sachet E, Borman T, et al. Entropy-stabilized oxides[J]. Nat. Commun., 2015, 6: 8485 |
| [37] | Takeuchi A, Yubuta K, Wada T. Critically percolated states in high-entropy alloys with exact equi-atomicity[J]. Mater. Trans., 2019, 60: 330 |
| [38] | Takeuchi A, Wada T. Os-free Fe12Ir20Re20Rh20Ru28 high-entropy alloy with single hcp structure including Fe from late transition metals[J]. Mater. Trans., 2022, 63: 7 |
| [39] | Lun Z, Ouyang B, Kwon D H, et al. Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries[J]. Nat. Mater., 2021, 20: 214 |
| [40] | Kim H K, Ahn J P, Lee B J, et al. Role of atomic-scale chemical heterogeneities in improving the plasticity of Cu-Zr-Ag bulk amorphous alloys[J]. Acta Mater., 2018, 157: 209 |
| [41] | Hasmy A, Ispas S, Hehlen B. Percolation transitions in compressed SiO2 glasses[J]. Nature, 2021, 599: 62 |
| [42] | Mora-Barzaga G, Urbassek H M, Deluigi O R, et al. Chemical short-range order increases the phonon heat conductivity in a refractory high-entropy alloy[J]. Sci. Rep., 2024, 14: 20628 |
| [43] | Kirnbauer A, Spadt C, Koller C M, et al. High-entropy oxide thin films based on Al-Cr-Nb-Ta-Ti[J]. Vacuum, 2019, 168: 108850 |
| [44] | Fritze S, Malinovskis P, Riekehr L, et al. Hard and crack resistant carbon supersaturated refractory nanostructured multicomponent coatings[J]. Sci. Rep., 2018, 8: 14508 |
| [45] | Liu C, Lu W J, Xia W Z, et al. Massive interstitial solid solution alloys achieve near-theoretical strength[J]. Nat. Commun., 2022, 13: 1102 |
| [46] | Yan X H, Zhu B H, Zhang Y, et al. Phase formation and unusual interstitial solid-solution strengthening behavior of (CoCrFeMnNi)Nx high-entropy ceramic films[J]. Surf. Coat. Technol., 2024, 477: 130392 |
| [47] | Bi L X, Li X N, Li Z M, et al. Performance and local structure evolution of NbMoTaWV entropy-stabilized oxide thin films with variable oxygen content[J]. Surf. Coat. Technol., 2020, 402: 126326 |
| [48] | Li H, Jiang N, Li J L, et al. Hard and tough (NbTaMoW)Nx high entropy nitride films with sub-stoichiometric nitrogen[J]. J. Alloys Compd., 2021, 889: 161713 |
| [49] | Li Y T, Jiang X, Wang X T, et al. Integration of hardness and toughness in (CuNiTiNbCr)Nx high entropy films through nitrogen-induced nanocomposite structure[J]. Scr. Mater., 2024, 238: 115763 |
| [50] | Liu W, Wang C T, Zhao S C, et al. Enhancing wear resistance: In-situ ceramic phase precipitation for strengthening and toughening FeCoNiCrNx high-entropy alloy films[J]. Surf. Coat. Technol., 2024, 478: 130466 |
| [51] | Scavini M, Coduri M, Allieta M, et al. Percolating hierarchical defect structures drive phase transformation in Ce1-xGdxO2-x/2: A total scattering study[J]. IUCrJ, 2015, 2: 511 |
| [52] | Sha C H, Zhou Z F, Xie Z H, et al. FeMnNiCoCr-based high entropy alloy coatings: Effect of nitrogen additions on microstructural development, mechanical properties and tribological performance[J]. Appl. Surf. Sci., 2020, 507: 145101 |
| [53] | Chen Y J, Ma J S, Lin Y C, et al. Interstitial engineering enabling superior mechanical properties of nitrogen-supersaturated Fe50Mn30-Co10Cr10 high-entropy alloys[J]. Acta Mater., 2024, 277: 120214 |
| [54] | Sha C H, Zhou Z F, Xie Z H, et al. Extremely hard, α-Mn type high entropy alloy coatings[J]. Scr. Mater., 2020, 178: 477 |
| [55] | Sha C H, Zhou Z F, Xie Z H, et al. High entropy alloy FeMnNiCoCr coatings: Enhanced hardness and damage-tolerance through a dual-phase structure and nanotwins[J]. Surf. Coat. Technol., 2020, 385: 125435 |
| [56] | Feng X B, Zhang J Y, Wang Y Q, et al. Size effects on the mechanical properties of nanocrystalline NbMoTaW refractory high entropy alloy thin films[J]. Int. J. Plast., 2017, 95: 264 |
| [57] | Zhao Y M, Chen S N, Chen Y J, et al. Super-hard and anti-corrosion (AlCrMoSiTi)Nx high entropy nitride coatings by multi-arc cathodic vacuum magnetic filtration deposition[J]. Vacuum, 2022, 195: 110685 |
| [58] | Wang X, Li X N, Li Z M, et al. Utilizing cluster percolation theory to analyze electrical resistivity jumps in high-entropy alloy thin films containing small atoms[J]. Scr. Mater., 2024, 238: 115727 |
| [59] | Zhang F Y, Ma H L, Zhao R B, et al. Microstructure, mechanical and corrosion performance of magnetron sputtered (Al0.5CoCrFeNi)Nx high-entropy alloy nitride films[J]. J. Alloys Compd., 2023, 968: 172158 |
| [60] | Lin Y C, Hsu S Y, Lai Y T, et al. Effect of the N2/(Ar + N2) ratio on mechanical properties of high entropy nitride (Cr0.35Al0.25Nb0.12Si0.08-V0.20)Nx films[J]. Mater. Chem. Phys., 2021, 274: 125195 |
| [61] | Zhang C X, Lu X L, Wang C, et al. Tailoring the microstructure, mechanical and tribocorrosion performance of (CrNbTiAlV)Nx high-entropy nitride films by controlling nitrogen flow[J]. J. Mater. Sci. Technol., 2022, 107: 172 |
| [62] | Chen L Q, Li W, Liu P, et al. Microstructure and mechanical properties of (AlCrTiZrV)Nx high-entropy alloy nitride films by reactive magnetron sputtering[J]. Vacuum, 2020, 181: 109706 |
| [63] | El Garah M, Touaibia D E, Achache S, et al. Effect of nitrogen content on structural and mechanical properties of AlTiZrTaHf(-N) high entropy films deposited by reactive magnetron sputtering[J]. Surf. Coat. Technol., 2022, 432: 128051 |
| [64] | Cui P P, Li W, Liu P, et al. Effects of nitrogen content on microstructures and mechanical properties of (AlCrTiZrHf)N high-entropy alloy nitride films[J]. J. Alloys Compd., 2020, 834: 155063 |
| [65] | Hsueh H T, Shen W J, Tsai M H, et al. Effect of nitrogen content and substrate bias on mechanical and corrosion properties of high-entropy films (AlCrSiTiZr)100-xNx[J]. Surf. Coat. Technol., 2012, 206: 4106 |
| [66] | Li Y T, Chen X M, Zeng X K, et al. Hard yet tough and self-lubricating (CuNiTiNbCr)Cx high-entropy nanocomposite films: Effects of carbon content on structure and properties[J]. J. Mater. Sci. Technol., 2024, 173: 20 |
| [67] | Zendejas Medina L, Tavares da Costa M V, Paschalidou E M, et al. Enhancing corrosion resistance, hardness, and crack resistance in magnetron sputtered high entropy CoCrFeMnNi coatings by adding carbon[J]. Mater. Des., 2021, 205: 109711 |
| [68] | Jhong Y S, Huang C W, Lin S J. Effects of CH4 flow ratio on the structure and properties of reactively sputtered (CrNbSiTiZr)Cx coatings[J]. Mater. Chem. Phys., 2018, 210: 348 |
| [69] | Liu W, Wang C, Yang K, et al. Carbon-driven microstructural tuning enhances tribological and corrosion performance in FeCoNiCrCx high-entropy alloy films[J]. Carbon, 2025, 238: 120237 |
| [70] | Khan N A, Akhavan B, Zheng Z, et al. Nanostructured AlCoCrCu0.5FeNi high entropy oxide (HEO) thin films fabricated using reactive magnetron sputtering[J]. Appl. Surf. Sci., 2021, 553: 149491 |
| [71] | Lin M I, Tsai M H, Shen W J, et al. Evolution of structure and properties of multi-component (AlCrTaTiZr)Ox films[J]. Thin Solid Films, 2010, 518: 2732 |
| [72] | Lee C Y, Chien C H, Yeh J W, et al. Effects of the carbon-to-nitrogen ratio on the microstructure and properties of (CrNbSiTiZr)CxNy high-entropy carbonitride films[J]. Mater. Chem. Phys., 2022, 277: 125374 |
| [73] | Chang S Y, Lin S Y, Huang Y C. Microstructures and mechanical properties of multi-component (AlCrTaTiZr)NxCy nanocomposite coatings[J]. Thin Solid Films, 2011, 519: 4865 |
| [74] | Zok F W, Miserez A. Property maps for abrasion resistance of materials[J]. Acta Mater., 2007, 55: 6365 |
| [75] | Ling Y C, Yu X, Yuan S J, et al. Flexomagnetic effect enhanced ferromagnetism and magnetoelectrochemistry in freestanding high-entropy alloy films[J]. ACS Nano, 2023, 17: 17299 |
| [76] | Pavithra C L P, Janardhana R K S K, Reddy K M, et al. An advancement in the synthesis of unique soft magnetic CoCuFeNiZn high entropy alloy thin films[J]. Sci. Rep., 2021, 11: 8836 |
| [77] | Chaudhary V, Chaudhary R, Banerjee R, et al. Accelerated and conventional development of magnetic high entropy alloys[J]. Mater. Today, 2021, 49: 231 |
| [78] | Chen J W, Chen S H, Shafer P, et al. Role of the structure order in the transport and magnetic properties of high-entropy alloy films[J]. NPG Asia Mater., 2024, 15: 72 |
| [79] | Mazza A R, Skoropata E, Sharma Y, et al. Designing magnetism in high entropy oxides[J]. Adv. Sci., 2022, 9: 2200391 |
| [80] | Sarkar A, Kruk R, Hahn H. Magnetic properties of high entropy oxides[J]. Dalton Trans., 2021, 50: 1973 |
| [81] | Ogale S B, Venkatesan T V, Blamire M G. Functional Metal Oxides: New Science and Novel Applications[M]. Germany: John Wiley & Sons, Inc, 2013: 26 |
| [82] | Roth W L. Magnetic structures of MnO, FeO, CoO, and NiO[J]. Phys. Rev., 1958, 110: 1333 |
| [83] | Hillebrecht F U, Ohldag H, Weber N B, et al. Magnetic moments at the surface of antiferromagnetic NiO(100)[J]. Phys. Rev. Lett., 2001, 86: 3419 |
| [84] | Srdi? V V, Cveji? Z, Milanovi? M, et al. Metal Oxide Structure, Crystal Chemistry, and Magnetic Properties[M]. Amsterdam: Elsevier, 2018: 313 |
| [85] | Teillet J, Bouree F, Krishnan R. Magnetic structure of CoFe2O4[J]. J. Magn. Magn. Mater., 1993, 123: 93 |
| [86] | Bouferrache K, Charifi Z, Baaziz H, et al. Electronic structure, magnetic and optic properties of spinel compound NiFe2O4[J]. Semicond. Sci. Technol., 2020, 35: 095013 |
| [87] | Ke W E, Chen J W, Liu C E, et al. Crystalline magnetic anisotropy in high entropy (Fe, Co, Ni, Cr, Mn)3O4 oxide driven by single-element orbital anisotropy[J]. Adv. Funct. Mater., 2024, 34: 2312856 |
| [88] | Wang H L, Huang H L, Feng Y P, et al. Enhanced exchange bias in epitaxial high-entropy oxide heterostructures[J]. ACS Appl. Mater. Interfaces, 2023, 15: 58643 |
| [89] | Mayandi J, Dias M, Stange M, et al. Partial oxidation of high entropy alloys: A route toward nanostructured ferromagnets[J]. Materialia, 2021, 20: 101250 |
| [90] | Zhang J Y, Wang X, Li X N, et al. Native oxidation and complex magnetic anisotropy-dominated soft magnetic CoCrFeNi-based high-entropy alloy thin films[J]. Adv. Sci., 2022, 9: 2203139 |
| [91] | Minouei H, Kheradmandfard M, Saboktakin Rizi M, et al. Formation mechanism of high-entropy spinel thin film and its mechanical and magnetic properties: Linking high-entropy alloy to high-entropy ceramic[J]. Appl. Surf. Sci., 2022, 576: 151719 |
| [92] | Bachani S K, Wang C J, Lou B S, et al. Fabrication of TiZrNb-TaFeN high-entropy alloys coatings by HiPIMS: Effect of nitrogen flow rate on the microstructural development, mechanical and tribological performance, electrical properties and corrosion characteristics[J]. J. Alloys Compd., 2021, 873: 159605 |
| [93] | Xia A, Dedoncker R, Glushko O, et al. Influence of the nitrogen content on the structure and properties of MoNbTaVW high entropy alloy thin films[J]. J. Alloys Compd., 2021, 850: 156740 |
| [94] | Wang X, Li X N, Li Z M, et al. Percolation theory analysis on the variation of magnetic and electrical properties in oxygen-containing CoCrFeNi high-entropy films[J]. Acta Mater., 2025, 293: 121123 |
| [95] | Yu R S, Huang R H, Lee C M, et al. Synthesis and characterization of multi-element oxynitride semiconductor film prepared by reactive sputtering deposition[J]. Appl. Surf. Sci., 2012, 263: 58 |
| [96] | Chen T K, Wong M S. Hard transparent conducting hex-element complex oxide films by reactive sputtering[J]. J. Mater. Res., 2008, 23: 3075 |
| [97] | Pristá? G, Gruber G C, Orendá? M, et al. Multiple transition temperature enhancement in superconducting TiNbMoTaW high entropy alloy films through tailored N incorporation[J]. Acta Mater., 2024, 262: 119428 |
| [98] | Hu R W, Bozin E S, Warren J B, et al. Superconductivity, magnetism, and stoichiometry of single crystals of Fe1+y (Te1-xSx)z[J]. Phys. Rev., 2009, 80B: 214514 |
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